A method for the selective oxidation of a thioether

Abstract

The present application relates to a kind of method for selective oxidation of sulfide, which includes the following steps: in the presence of oxygen, the mixed raw material containing sulfide, aldehyde compound and alcohol compound is contacted with catalyst to carry out oxidation reaction;The catalyst includes metal nanoparticles and molecular sieve composite catalytic material, the composite catalytic material includes full-silica molecular sieve and metal element M dispersed in the intracrystalline of full-silica molecular sieve;The metal element M is metal element capable of forming oxide aggregate;The method uses metal-containing hierarchical porous molecular sieve for selective oxidation of sulfide, and high conversion rate and sulfoxide or sulfone selectivity can be obtained under relatively mild conditions.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic chemical industry, in particular, to a method for selective oxidation of sulfide. BACKGROUND

[0002] Sulfoxide is an important sulfur-containing substance. For example, dimethyl sulfoxide (DMSO) can be used as an organic solvent, a reaction medium and an organic synthesis intermediate, and can also be used as a dyeing solvent, a dye removal agent, a dyeing carrier for synthetic fibers, and an absorbent for recovering acetylene and sulfur dioxide. Dimethyl sulfoxide is an extremely important aprotic polar solvent that is soluble in both water and organic solvents, and is widely used as a solvent and a reaction reagent, and has a very high selective extraction capacity. Dimethyl sulfoxide itself has the effects of relieving inflammation, relieving pain, diuresis and sedation, and can be directly used as a raw material and a carrier for certain drugs in the pharmaceutical industry, and is known as a "panacea", and is often added as an active component of pain relieving drugs.

[0003] As another type of sulfur-containing compound, sulfone also has a wide range of uses. For example, dimethyl sulfone is a high-tech, high-value fine chemical product, which is a high-temperature solvent and a high-purity reagent for drug synthesis, dye intermediates and food additives, a chromatographic stationary liquid and an analytical reagent. Dimethyl sulfone is also a necessary substance for human collagen protein synthesis, and is applied as a health care product, and is a main drug for maintaining the balance of biological sulfur elements in the human body. It can regulate gastrointestinal function, promote nutrient absorption, treat arthritis, skin diseases, gastrointestinal diseases, skin care and health care functions, and has attracted attention abroad, and is widely used as a health care product, and the demand has increased rapidly in the past two years.

[0004] Sulfoxide / sulfone is generally prepared by sulfide oxidation. Depending on the oxidizing agent and the oxidation method used, the oxidation method generally includes nitric acid oxidation, peroxide oxidation, ozone oxidation, anodic oxidation and nitrogen dioxide oxidation. The disadvantages of nitric acid oxidation are that the reaction is not easy to control, the equipment is severely corroded, and the environment is heavily polluted. The problem of low conversion rate of sulfide exists in ozone oxidation. Anodic oxidation is not suitable for large-scale implementation. Nitrogen dioxide oxidation also has the problem of environmental pollution. The most commonly used oxidizing agent in peroxide method is hydrogen peroxide, which is usually provided in the form of an aqueous solution. Although water can act as a solvent, the solubility of sulfide as a reactant in water is still limited, thereby reducing the yield of sulfide. SUMMARY

[0005] The purpose of the present disclosure is to provide a method for selective oxidation of sulfide, which uses a metal-containing hierarchical pore molecular sieve for selective oxidation of sulfide, and can obtain high conversion rate of sulfide and high selectivity of sulfoxide or sulfone under relatively mild conditions, and has high industrial application value.

[0006] To achieve the above object, the first aspect of the present disclosure provides a method for selective oxidation of sulfide, comprising the following steps:

[0007] In the presence of oxygen, a mixed raw material containing sulfide compounds, aldehyde compounds and alcohol compounds is contacted with a catalyst to perform an oxidation reaction;

[0008] The catalyst is a composite catalytic material, which comprises a full-silica molecular sieve and a metal element M dispersed in the intracrystalline of the full-silica molecular sieve; the metal element M is a metal element capable of forming an oxide aggregate.

[0009] Optionally, the composite catalytic material has the following H2-TPR characteristics:

[0010] The reduction peak temperature of the composite catalytic material in the H2-TPR test is T1,

[0011] The reduction peak temperature of the oxide aggregate in the H2-TPR test is T2,

[0012] T0 defined by the following formula (1) is any value between 350℃ and 600℃;

[0013] T0 = T1-T2 Formula (1);

[0014] Preferably, the value of T0 is any value between 350℃ and 550℃.

[0015] Optionally, the sulfide compounds are selected from one or more of alkyl sulfide, benzene ring-containing sulfide and derivatives thereof;

[0016] Optionally, the aldehyde compounds are selected from one or more of alkyl aldehyde with carbon atom number of 4-10 or aryl aldehyde with carbon atom number of 7-12;

[0017] The alcohol compounds are selected from one or more of alkyl alcohol with carbon atom number of 4-10 or aryl alcohol with carbon atom number of 7-12;

[0018] The molar ratio of the sulfide compounds: aldehyde compounds: alcohol compounds is 1:(1-6):(0.001-2); preferably 1:(1-5):(0.001-2).

[0019] Optionally, the conditions of the oxidation reaction include: reaction temperature of 40-100℃, preferably 60-80℃; time of 1-48h, preferably 2-24h; oxygen pressure of 0.1-0.5MPa, preferably 0.1-0.3MPa;

[0020] The weight ratio of the catalyst to the sulfide compounds is 1:(1-20); preferably 1:(1-10);

[0021] Optionally, the reactor for the oxidation reaction comprises any one of a tank reactor, a fixed bed reactor, a moving bed reactor, a suspended bed reactor and a slurry bed reactor.

[0022] Optionally, the all-silica molecular sieve in the composite catalytic material is at least one of MFI structure molecular sieve, MEL structure molecular sieve, BEA structure molecular sieve, MWW structure molecular sieve, two-dimensional hexagonal structure molecular sieve, MOR structure molecular sieve and TUN structure molecular sieve and other structure of silica molecular sieve; preferably one or several selected from MFI structure molecular sieve, MEL structure molecular sieve, BEA structure molecular sieve, MCM structure molecular sieve and SBA structure molecular sieve; further preferably one or several of MFI structure molecular sieve, MEL structure molecular sieve and BEA structure molecular sieve; further preferably MFI structure molecular sieve;

[0023] The metal M is selected from one or several of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold.

[0024] Optionally, when the metal M is Co, the oxide aggregate is Co3O4 aggregate;

[0025] When the metal M is Mn, the oxide aggregate is MnO2 aggregate;

[0026] When the metal M is Fe, the oxide aggregate is Fe2O3 aggregate;

[0027] When the metal M is Ni, the oxide aggregate is NiO aggregate;

[0028] When the metal M is Pd, the oxide aggregate is PdO aggregate;

[0029] When the metal M is Pt, the oxide aggregate is PtO2 aggregate; or,

[0030] When the metal M is Cu, the oxide aggregate is CuO aggregate.

[0031] Optionally, in the composite catalytic material, the molar ratio of metal M element to silicon element is (0.001-0.22):1, preferably (0.001-0.15):1.

[0032] Optionally, the BET specific surface area of the composite catalytic material is 400-800 m 2The total pore volume is 0.3-0.65 mL / g, the micropore volume is 0.1-0.19 mL / g, the mesopore volume is 0.2-0.46 mL / g, and the metal element M exists in the form of metal nanoparticles, and the average particle size of the metal nanoparticles is 0.5-10 nm.

[0033] Optionally, the catalyst is prepared by a preparation method comprising the following steps:

[0034] S1, mixing a template agent, a silicon source, water, a metal M precursor, a silylation reagent and a peroxide to obtain a reaction mixture, wherein the silylation reagent comprises at least one coordination group complexed with metal M ions;

[0035] S2, performing hydrothermal crystallization treatment and calcination treatment on the reaction mixture.

[0036] Optionally, in step S1, the molar ratio of the silicon source: template agent: water: metal element M: silylation reagent is 1:(0.001-1):(5-100):(0.001-0.22):(0.025-0.4), preferably 1:(0.001-1):(5-50):(0.001-0.15):(0.025-0.3), wherein the silicon source is calculated as SiO2; the molar ratio of the peroxide to the metal element M is (0.5-5):1, preferably (0.5-3):1.

[0037] Optionally, step S1 comprises:

[0038] a, mixing a template agent, a silicon source and water to obtain a hydrolyzed solution of silicon;

[0039] b, adding a peroxide to an aqueous solution of a metal M precursor to obtain a first mixture after mixing; mixing the first mixture with the hydrolyzed solution of silicon to obtain a second mixture;

[0040] c, adding a silylation reagent to the second mixture to obtain the reaction mixture after mixing;

[0041] Preferably, the mixing conditions in step c include stirring at 20-80°C for 0.5-2 hours.

[0042] Optionally, in step S1, the silicon source is selected from at least one of organosilicone grease, solid silica gel, white carbon black and silica sol; preferably, it is selected from at least one of organosilicone grease, solid silica gel and white carbon black;

[0043] Further preferably, the organosilicone grease has a general formula as shown in the following formula (A):

[0044]

[0045] wherein R a , R b , R c , R d each independently is selected from an alkyl group having 1 to 6 carbon atoms, which alkyl group is a branched or straight chain alkyl group; preferably, R a , R b , R c , R d each independently is selected from a straight chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms; further preferably, the R a , R b , R c , R d each independently is selected from a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, a sec-butyl group, an iso-butyl group or a tert-butyl group; further preferably, the organosilicon grease is selected from one or more of tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate, dimethyldiethyl silicate.

[0046] Optionally, in step S1, the template agent is an organic base, preferably at least one selected from a quaternary ammonium base, an aliphatic amine and an aliphatic alcohol amine; further preferably, the template agent has a general formula selected from at least one of the quaternary ammonium bases represented by the following formula (B):

[0047] R1, R2, R3and R4each is selected from an alkyl group having 1 to 4 carbon atoms, preferably a straight chain alkyl group having 1 to 4 carbon atoms and a branched alkyl group having 3 to 4 carbon atoms, more preferably R1, R2, R3and R4each is selected from a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, a sec-butyl group, an iso-butyl group or a tert-butyl group;

[0048] Further preferably, the molecular sieve in the composite catalytic material is an MFI type molecular sieve, the template agent is tetrapropyl ammonium hydroxide or is a mixture of tetrapropyl ammonium hydroxide and one or more selected from tetrapropyl ammonium chloride, tetrapropyl ammonium bromide; or

[0049] The molecular sieve in the composite catalytic material is an MEL type molecular sieve, the template agent is tetrabutyl ammonium hydroxide or is a mixture of tetrabutyl ammonium hydroxide and one or more selected from tetrabutyl ammonium chloride, tetrabutyl ammonium bromide; or

[0050] The molecular sieve in the composite catalytic material is a Beta type molecular sieve, the template agent is tetraethyl ammonium hydroxide or is a mixture of tetraethyl ammonium hydroxide and one or more selected from tetraethyl ammonium chloride, tetraethyl ammonium bromide.

[0051] Optionally, in step a, the silicon source is an organosilicon grease, and the method further comprises a hydrolysis alcohol-removing treatment after mixing the template agent, the organosilicon grease and water, to obtain the hydrolytic solution of silicon.

[0052] The conditions of the hydrolysis alcohol-removing treatment include stirring and hydrolyzing at 0-95℃ for 2-10 hours; preferably stirring and hydrolyzing at 50-95℃ for 2-8 hours.

[0053] Optionally, in step S1, the metal M precursor is one or more of inorganic metal compounds and organic metal compounds; the inorganic metal compound is a water-soluble inorganic salt of metal M; the water-soluble inorganic salt of metal M is selected from one or more of chloride, hydrated chloride, sulfate, hydrated sulfate and nitrate of metal M; the organic metal compound is an organic ligand compound of metal M; preferably the metal M precursor is a water-soluble inorganic salt of metal M.

[0054] The metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold.

[0055] Preferably, the molar ratio of metal M element to water in the aqueous solution of the metal M precursor used is 1:(50-500).

[0056] Optionally, in step S1, the general formula of the silylating agent is R5Si(R6)(R7)R8, wherein R5, R6, R7 and R8 are each independently halogen, alkyl, alkoxy, aromatic group, thiol or amine group, and at least one of R5, R6, R7 and R8 is alkyl, alkoxy, aromatic group, thiol or amine group; the number of carbon atoms of the alkyl, alkoxy, thiol and amine group is each independently 1-18, and the number of carbon atoms of the aromatic group is 6-18.

[0057] Preferably, the silylating agent is selected from one or more of dimethyldichlorosilane, N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, 1,7-dichlorooctylmethyltetrasiloxane, hexadecyltrimethoxysilane, octyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; further preferably at least one of N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.

[0058] Optionally, in step S1, the peroxide is one or more of hydrogen peroxide and organic peroxide; the organic peroxide includes cumene hydroperoxide, ethylbenzene hydroperoxide and tert-butyl hydroperoxide.

[0059] Optionally, the hydrothermal crystallization treatment in step S2 is performed under autogenous pressure, and the hydrothermal crystallization time is 0.5-10 days, and the hydrothermal crystallization temperature is 110-200°C; preferably, the hydrothermal crystallization time is 0.5-5 days, and the hydrothermal crystallization temperature is 150-200°C.

[0060] Optionally, the calcination treatment is performed at a calcination temperature of 400-900°C for 1-16 hours; preferably, the calcination temperature is 400-800°C, and the calcination time is 2-8 hours.

[0061] By means of the above technical solution, the present disclosure provides a method for selective oxidation of sulfides, and the present disclosure uses a metal-containing hierarchical pore molecular sieve composite catalytic material as a catalyst for preparing sulfoxide and / or sulfone compounds by selective oxidation of sulfides. The molecular sieve of the composite catalytic material has a large specific surface area, pore volume and reactivity for macromolecular substrates, and the metal oxide nanoparticles have a uniform particle size and are uniformly dispersed in the mesoporous channels of the hierarchical pore molecular sieve, thereby having a high dispersion degree. The selective oxidation reaction process is controllable, and high conversion rate and sulfoxide or sulfone selectivity can be obtained under relatively mild conditions.

[0062] Other features and advantages of the present disclosure will be described in detail in the following specific embodiments section. BRIEF DESCRIPTION OF DRAWINGS

[0063] The accompanying drawings are included to provide a further understanding of the present disclosure and constitute a part of the specification, and together with the specific embodiments below, serve to explain the present disclosure but do not constitute a limitation thereof. In the drawings:

[0064] Figure 1 FIG. 1 is an H2-TPR spectrum of CAT-1 prepared in Example 1 of the present disclosure. DETAILED DESCRIPTION

[0065] The specific embodiments of the present disclosure are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, and do not limit the present disclosure.

[0066] The first aspect of the present disclosure provides a method for selective oxidation of sulfides, which comprises the following steps:

[0067] contacting a mixture of raw materials containing sulfide compounds, aldehyde compounds and alcohol compounds with a catalyst in the presence of oxygen to perform an oxidation reaction;

[0068] The catalyst is a composite catalytic material, and the composite catalytic material comprises a full-silica molecular sieve and a metal element M dispersed in the intracrystalline of the full-silica molecular sieve; the metal element M is a metal element capable of forming an oxide aggregate.

[0069] The inventors of the present disclosure surprisingly found that using metal nanoparticle-molecular sieve composite catalytic material as catalyst in the oxidation reaction of sulfide compounds can effectively improve the oxidation reaction rate, shorten the reaction time, and achieve high conversion of sulfides and high selectivity of sulfoxide or sulfone under relatively mild conditions.

[0070] The inventors of the present disclosure surprisingly found that, in the process of synthesizing molecular sieve crystals, metal precursors are introduced, and then silanization reagents and peroxides are continuously introduced. After hydrothermal crystallization, washing, and calcination of the obtained mixture, a composite catalytic material including all-silicon molecular sieve and metal M oxide nanoparticle is obtained. The composite catalytic material not only has large specific surface area and pore volume performance, but also has uniform metal oxide nanoparticle size and uniform dispersion in the molecular sieve pores. When the value of T0 (i.e., T1-T2) in the composite catalytic material is 350°C or higher (T1 represents the reduction peak temperature of the composite catalytic material in H2-TPR test, and T2 represents the reduction peak temperature of the oxide aggregate in H2-TPR test), the composite catalytic material has good catalytic activity.

[0071] In a preferred embodiment, the composite catalytic material has the following H2-TPR characteristics:

[0072] The reduction peak temperature of the composite catalytic material in H2-TPR test is T1,

[0073] The reduction peak temperature of the oxide aggregate in H2-TPR test is T2,

[0074] T0 defined by the following formula (1) is any value between 350°C and 600°C:

[0075] T0 = T1-T2 Formula (1);

[0076] The present disclosure provides a metal oxide nanoparticle-molecular sieve composite catalytic material. The molecular sieve of the composite catalytic material has large specific surface area, pore volume, and macromolecular substrate reactivity. The metal oxide nanoparticle has uniform particle size and is uniformly dispersed in the mesoporous channels of the hierarchical pore molecular sieve. The composite catalytic material has high catalytic activity.

[0077] In the present disclosure, H2-TPR test refers to hydrogen temperature programmed reduction characterization method. During the temperature programmed reduction process, the composite catalytic material is reduced, which can provide information about the interaction between metal oxides or between metal oxides and the carrier during the reduction process of the supported metal catalyst. In the present disclosure, H2-TPR test is performed on AutoChem II 2920, and the test conditions include: 10% (Vol.) H2-90% (Vol.) Ar, 50 ml / min, reduction from 60°C to 900°C.

[0078] In a preferred embodiment, the value of T0 is any value between 350℃ and 550℃. When the T0 of the composite catalytic material is within this range, the catalytic activity is higher, and the conversion rate of sulfide and the selectivity of sulfoxide / sulfone are higher.

[0079] In a preferred embodiment, the sulfide compound is selected from one or more of alkyl sulfide, benzene ring sulfide and derivatives thereof.

[0080] The aldehyde compound is selected from one or more of alkyl aldehyde with carbon atom number of 4-10 or aryl aldehyde with carbon atom number of 7-12.

[0081] The alcohol compound is selected from one or more of alkyl alcohol with carbon atom number of 4-10 or aryl alcohol with carbon atom number of 7-12.

[0082] The molar ratio of the sulfide compound to the aldehyde compound and the alcohol compound is 1:(1-6):(0.001-2); preferably 1:(1-5):(0.001-2).

[0083] In an embodiment, the conditions of the oxidation reaction include: the reaction temperature is 40-100℃, preferably 60-80℃; the time is 1-48h, preferably 2-24h; the oxygen pressure is 0.1-0.5MPa, preferably 0.1-0.3MPa; the weight ratio of the catalyst to the sulfide compound is 1:(1-20); preferably 1:(1-10); in this preferred case, the oxidation reaction can be further promoted, the oxidation reaction rate can be effectively improved, and the conversion rate of sulfide can be increased.

[0084] In an embodiment, the reactor for the oxidation reaction includes any one of a tank reactor, a fixed bed reactor, a moving bed reactor, a suspended bed reactor and a slurry bed reactor.

[0085] In one embodiment, the all-silica molecular sieve in the composite catalytic material is one or more of MFI structure molecular sieve (such as S-1), MEL structure molecular sieve (such as S-2), BEA structure molecular sieve (such as Beta), MWW structure molecular sieve (such as MCM-22), two-dimensional hexagonal structure molecular sieve (such as MCM-41, SBA-15), MOR structure molecular sieve (such as MOR), TUN structure molecular sieve (such as TUN), and other structure silica molecular sieve (such as ZSM-48, MCM-48); preferably one or more of MFI structure molecular sieve, MEL structure molecular sieve, BEA structure molecular sieve, MCM structure molecular sieve, and SBA structure molecular sieve; further preferably one or more of MFI structure molecular sieve, MEL structure molecular sieve, and BEA structure molecular sieve, such as one of S-1, S-2, and Beta; further preferably MFI structure molecular sieve, such as S-1.

[0086] The metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper, and gold.

[0087] In the present disclosure, the metal M oxide aggregate refers to the conventional oxide species obtained from the metal M precursor (such as nitrate, chloride, etc.) known in the art after the calcination treatment during the synthesis of the molecular sieve; in one alternative embodiment, when the metal M is Co, the oxide aggregate is Co3O4aggregate;

[0088] In one alternative embodiment, when the metal M is Mn, the oxide aggregate is MnO2aggregate;

[0089] In one alternative embodiment, when the metal M is Fe, the oxide aggregate is Fe2O3aggregate;

[0090] In one alternative embodiment, when the metal M is Ni, the oxide aggregate is NiO aggregate;

[0091] In one alternative embodiment, when the metal M is Pd, the oxide aggregate is PdO aggregate;

[0092] In one alternative embodiment, when the metal M is Pt, the oxide aggregate is PtO2aggregate;

[0093] In one alternative embodiment, when the metal M is Cu, the oxide aggregate is CuO aggregate.

[0094] In one embodiment, the molar ratio of the metal M element to the silicon element in the composite catalytic material is (0.001-0.22): 1, preferably (0.001-0.15): 1.

[0095] In an embodiment, the BET specific surface area of the composite catalytic material is 400-800 m 2 / g; the total pore volume is 0.3-0.65 mL / g; the micropore volume is 0.1-0.19 mL / g; the mesopore volume is 0.2-0.46 mL / g; the metal element M exists in the form of metal nanoparticles, and the average particle size of the metal nanoparticles is 0.5-10 nm. The composite catalytic material in the present disclosure also has a hierarchical pore structure, which is beneficial to catalyzing reaction substrates of different sizes.

[0096] In an embodiment, the catalyst is prepared by a preparation method comprising the following steps:

[0097] S1, mixing a template agent, a silicon source, water, a metal M precursor, a silylating agent, and a peroxide to obtain a reaction mixture, wherein the silylating agent comprises at least one coordination group complexed with metal M ions;

[0098] S2, performing hydrothermal crystallization treatment and calcination treatment on the reaction mixture.

[0099] The present disclosure introduces a metal precursor, a silylating agent, and a peroxide into the raw materials for synthesizing a molecular sieve, which can achieve the effects of dispersing highly dispersed metal oxide nanoparticles and expanding the pores of the molecular sieve support layer, and prepare a hierarchical pore molecular sieve composite catalytic material with highly dispersed metal oxide nanoparticles.

[0100] In the present disclosure, the peroxide can complex the metal to achieve the effects of dispersing and stabilizing the metal; the silylating agent with one or more coordination groups (for example, at least one of an amine group, a mercapto group, and an oxygen-containing coordination group) is also added to the reaction mixture, and the coordination group can also complex the metal to achieve the effects of fixing and dispersing the metal, and the support layer effect of the alkyl chain can achieve the pore expansion effect; thereby preparing a hierarchical pore all-silica molecular sieve with highly dispersed metal oxide nanoparticles of metal M. In addition, the highly dispersed metal M oxide nanoparticles formed by the metal M introduced in the process of synthesizing the molecular sieve enter the crystal of the molecular sieve, and part of the metal oxide nanoparticles can also be formed on the surface of the pore of the molecular sieve.

[0101] In one embodiment, in step S1, the molar ratio of the silicon source: the template agent: water: the metal element M: the silylating agent is 1: (0.001-1): (5-100): (0.001-0.22): (0.025-0.4), preferably 1: (0.001-1): (5-50): (0.001-0.15): (0.025-0.3), wherein the silicon source is calculated as SiO2; and the molar ratio of the peroxide to the metal element M is (0.5-5): 1, preferably (0.5-3): 1. Specifically, the water used in step S1 can be the water commonly used in the synthesis of molecular sieves, and preferably is deionized water in order to avoid the introduction of heteroatoms.

[0102] In one preferred embodiment, step S1 comprises:

[0103] a. mixing the template agent, the silicon source and the water to obtain a hydrolysis solution of silicon;

[0104] b. adding the peroxide to the aqueous solution of the metal M precursor to obtain a first mixture; and mixing the first mixture with the hydrolysis solution of silicon to obtain a second mixture;

[0105] c. adding the silylating agent to the second mixture to obtain the reaction mixture; preferably, the mixing in step c. comprises stirring at 20-80°C for 0.5-2 hours.

[0106] In one embodiment, in step S1, the silicon source is selected from at least one of organosilicone grease, solid silica gel, white carbon black and silica sol; preferably, is selected from at least one of organosilicone grease, solid silica gel and white carbon black; and further preferably is organosilicone grease, the general formula of which is shown in the following formula (A):

[0107]

[0108] wherein R a , R b , R c , R d each independently is selected from an alkyl group having 1-6 carbon atoms, which is a branched or straight chain alkyl group; preferably, R a , R b , R c , R d each independently is selected from a straight chain alkyl group having 1-4 carbon atoms or a branched alkyl group having 3-4 carbon atoms. For example, R a , R b , R c , R d each independently is at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl; and further preferably Ra R1, R2, R3and R4are each independently selected from methyl and ethyl. b R1, R2, R3and R4are each independently selected from methyl and ethyl. c R1, R2, R3and R4are each independently selected from methyl and ethyl. d R1, R2, R3and R4are each independently selected from methyl and ethyl.

[0109] In a preferred embodiment, the organosilicon grease is selected from one or more of tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate, dimethyldiethyl silicate.

[0110] According to the present disclosure, in step S1, the template agent is an organic base, preferably at least one selected from quaternary ammonium base, aliphatic amine and aliphatic alcohol amine. Among them, the quaternary ammonium base can be an organic quaternary ammonium base; the aliphatic amine can be a compound formed by replacing at least one hydrogen in NH3 with an aliphatic hydrocarbon group (such as an alkyl group); the aliphatic alcohol amine can be a compound formed by replacing at least one hydrogen in various NH3 with a hydroxyl-containing aliphatic group (such as an alkyl group).

[0111] Further preferably, the general formula of the template agent is at least one selected from the following formula (B) shown structure quaternary ammonium base:

[0112] R1, R2, R3and R4are each independently selected from methyl and ethyl.

[0113] The template agent is preferably at least one selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (including various isomers of tetrapropylammonium hydroxide, such as tetra-n-propylammonium hydroxide and tetra-isopropylammonium hydroxide) and tetrabutylammonium hydroxide (including various isomers of tetrabutylammonium hydroxide, such as tetra-n-butylammonium hydroxide and tetra-isobutylammonium hydroxide).

[0114] In a preferred embodiment, the molecular sieve in the composite catalytic material is an MFI type molecular sieve, the template agent is tetrapropylammonium hydroxide or a mixture of tetrapropylammonium hydroxide and one or more selected from tetrapropylammonium chloride and tetrapropylammonium bromide; or

[0115] The molecular sieve in the composite catalytic material is an MEL type molecular sieve, the template agent is tetrabutylammonium hydroxide or a mixture of tetrabutylammonium hydroxide and one or more selected from tetrabutylammonium chloride and tetrabutylammonium bromide; or

[0116] The molecular sieve in the composite catalytic material is a Beta-type molecular sieve, and the template agent is tetraethylammonium hydroxide or a mixture of tetraethylammonium hydroxide and one or more selected from tetraethylammonium chloride and tetraethylammonium bromide. The present disclosure can prepare molecular sieves with different structures by selecting different template agents.

[0117] In one embodiment, in step a, the silicon source is an organosilicon grease, and after mixing the template agent, the organosilicon grease and water, a hydrolytic alcohol-removing treatment is further included to obtain the silicon hydrolysis solution;

[0118] The conditions of the hydrolytic alcohol-removing treatment include stirring and hydrolyzing at 0-95℃ for 2-10 hours, and preferably stirring and hydrolyzing at 50-95℃ for 2-8 hours. Preferably, the hydrolytic alcohol-removing treatment makes the mass content of alcohol generated by the hydrolysis of the organosilicon grease in the silicon hydrolysis solution be less than or equal to 10 ppm.

[0119] According to the present disclosure, the optional range of the type of metal precursor is wide, and any substance containing the metal (for example, a compound containing a metal element and / or a metal element) can achieve the purpose of the present disclosure.

[0120] In one embodiment, in step S1, the metal M precursor is one or more of an inorganic metal compound and an organic metal compound; the organic metal compound is an organic ligand compound of the metal M; and preferably, the metal M precursor is a water-soluble inorganic salt of the metal M.

[0121] The metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold.

[0122] Preferably, the metal M precursor is a water solution of the metal M precursor, and the molar ratio of the metal M element to water in the water solution of the metal M precursor is 1:(50-500).

[0123] In one embodiment, in step S1, the general formula of the silylating agent is R5Si(R6)(R7)R8, wherein R5, R6, R7 and R8 are each independently halogen, alkyl, alkoxy, aryl, thiol or amine, and at least one of R5, R6, R7 and R8 is alkyl, alkoxy, aryl, thiol or amine; the number of carbon atoms of the alkyl, alkoxy, thiol and amine is each independently 1-18, and preferably 1-12; and the number of carbon atoms of the aryl can be 6-18, and preferably 6-12.

[0124] Preferably, the silanization agent is selected from one or more of dimethyldichlorosilane, N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, 1,7-dichlorooctylmethyltetrasiloxane, hexadecyltrimethoxysilane, octyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; further preferably at least one of N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

[0125] In one embodiment, in step S1, the peroxide is one or more of hydrogen peroxide or organic peroxide; the organic peroxide includes cumene hydroperoxide (CHP), ethylbenzene hydroperoxide (EBHP), and tert-butyl hydroperoxide (TBHP).

[0126] In one embodiment, in step S2, the hydrothermal crystallization treatment is performed under autogenous pressure, and the hydrothermal crystallization time is 0.5-10 days, and the hydrothermal crystallization temperature is 110-200°C; preferably, the hydrothermal crystallization time is 0.5-5 days, and the hydrothermal crystallization temperature is 150-200°C.

[0127] In one embodiment, in step S2, the calcination treatment is performed at a calcination temperature of 400-900°C for a calcination time of 1-16 hours; preferably, the calcination temperature is 400-800°C, and the calcination time is 2-8 hours.

[0128] The present disclosure is further described in detail by the following examples.

[0129] The total specific surface area and total pore volume of the sample were determined on a Micromeritics ASAP 2450 static nitrogen adsorption instrument according to the standard method of ASTM D4222-98. The adsorption isotherm and desorption isotherm of the sample were determined by low-temperature nitrogen adsorption according to the standard method of ASTM D4222-98.

[0130] The H2-TPR experiment was performed on an AutoChem II 2920, and the experimental conditions were: 10% H2-90% Ar, 50 mL / min, reduction at 60-900°C.

[0131] Preparation Example 1

[0132] (1) 1.6 g of tetrapropylammonium hydroxide (TPAOH) aqueous solution with a concentration of 25.05% by weight, 20.8 g of tetraethyl silicate, and 52.8 g of water were sequentially added into a 500 mL beaker, mixed uniformly on a magnetic stirrer with heating and stirring functions, and stirred at 50°C for 2 hours, with water evaporation being replenished in a timely manner, to obtain a colorless and transparent silica gel solution;

[0133] (2) 0.03 g of cobalt nitrate hexahydrate and 0.18 g of water were stirred uniformly, 0.05 mmol of H2O2 was added, and the cobalt aqueous solution was mixed with the hydrolysis solution of silica obtained in step (1);

[0134] (3) 0.64 g of N-phenyl-3-aminopropyltrimethoxysilane (PHAPTMS) was added to the mixture of step (2), and stirred for 0.5 hours;

[0135] (4) The mixture obtained in step (3) was transferred into a stainless steel sealed autoclave, and crystallized at 175°C for 24 hours to obtain a sample, which was filtered, washed, dried at 110°C for 6 hours, and then calcined at 600°C in a muffle furnace for 6 hours, to obtain the metal nanoparticle and molecular sieve composite catalytic material product of the present application, which is recorded as CAT-1; the BET surface area, total pore volume, micropore volume, and mesopore volume of the obtained product are shown in Table 2, and the average particle size of the metal nanoparticles contained in CAT-1 is also listed in Table 2. The H2-TPR test of sample CAT-1 is shown in Table 3. Figure 1

[0136] Preparation Examples 2-9

[0137] The corresponding products were prepared according to the method of Example 1, the proportions and synthesis conditions and results are shown in Table 1, and the obtained products are recorded as CAT-2 to CAT-9.

[0138] Preparation Example 10

[0139] In this example, cobalt-containing hierarchical pore β molecular sieve was prepared according to the method of Example 1, the proportions and template agents were changed, and the obtained product is recorded as CAT-10, the template agent used is tetraethylammonium hydroxide (TEAOH), and the proportions and synthesis conditions and results are shown in Table 1.

[0140] Preparation Example 11

[0141] In this example, cobalt-containing hierarchical pore MEL molecular sieve was prepared according to the method of Example 1, the proportions and template agents were changed, and the obtained product is recorded as CAT-11, the template agent used is tetrabutylammonium hydroxide (TBAOH), and the proportions and synthesis conditions and results are shown in Table 1.

[0142] Preparation Example 12

[0143] ​The corresponding product was prepared according to the method of Example 1, and the ratio and synthesis conditions, results are listed in Table 1, other conditions and operations refer to the preparation of Example 1. Among them, the hydrothermal crystallization temperature is 120℃, the time is 6 days, the calcination temperature is 850℃, and the calcination time is 10 hours.

[0144] Preparation of Comparative Example 1

[0145] This comparative example was prepared according to the method of Example 1, except that no silanization reagent was added, and the product obtained was denoted as DCAT-1.

[0146] Preparation of Comparative Example 2

[0147] 0.03 g of cobalt nitrate hexahydrate and 0.18 g of water were stirred uniformly to obtain an aqueous solution of cobalt. Then 10.2 g of alumina carrier was added, stirred for 4 h, and the solvent was evaporated. The solid was collected and dried at 110℃ for 6 hours, and then calcined at 550℃ in a muffle furnace for 6 hours, and the product obtained was denoted as DCAT-2.

[0148] Preparation of Comparative Example 3

[0149] 0.03 g of cobalt nitrate hexahydrate and 0.18 g of water were stirred uniformly to obtain an aqueous solution of cobalt. Then 10.2 g of alumina carrier was added, stirred for 4 h, and the solvent was evaporated. The solid was collected and dried at 110℃ for 6 hours, and then calcined at 550℃ in a muffle furnace for 6 hours, and the product obtained was denoted as DCAT-2.

[0150] Table 1

[0151]

[0152]

[0153] In Table 1, TPAOH is tetrapropylammonium hydroxide, TPABr is tetrapropylammonium bromide, TBAOH is tetrabutylammonium hydroxide, TEAOH is tetraethylammonium hydroxide; PHAPTMS is N-phenyl-3-aminopropyltrimethoxysilane, APTES is 3-aminopropyltriethoxysilane, KH792 is silane coupling agent kh792 (diamino functional silane, N-aminoethyl-γ-aminopropyltrimethoxysilane); CHP is cumene hydroperoxide, TBHP is tert-butyl hydroperoxide. The reagents used in the present disclosure can be obtained through conventional purchase channels.

[0154] Table 2

[0155]

[0156] wherein pores having a diameter of less than 2 nm are micropores; and pores having a diameter of between 2 and 50 nm are mesopores.

[0157] According to Table 2, compared with Comparative Example 1 (no silanization reagent is added), the products obtained by adding the silanization reagent in the preparation process of Examples 1 to 12 have higher mesopore volumes, which indicates that the method provided by the present disclosure can effectively expand the pores of the molecular sieve.

[0158] Reaction Example 1

[0159] This test example is used to illustrate the reaction effect of the selective oxidation of sulfides provided by the present disclosure.

[0160] The samples prepared in the above preparation examples and comparative examples are used to catalyze the selective oxidation of sulfides, 1 mmol of sulfide is mixed with isobutyraldehyde and isobutanol (the molar amount of isobutyraldehyde and isobutanol is listed in Table 3), and then is contacted with 50 mg of catalyst in a slurry bed reactor, the reactor is connected with an oxygen balloon with a pressure of 0.1 MPa, the contact temperature is 60°C, and the contact time is 12 h, and the results are shown in the following table 2.

[0161] wherein the product distribution is determined on an Agilent 6890N chromatograph using an HP-5 capillary column (30 m x 0.25 mm).

[0162] The sulfide conversion rate (%) and the sulfoxide or sulfone selectivity (%) are calculated according to the following formula:

[0163] The sulfide conversion rate (%) = the number of moles of sulfide participating in the reaction / the number of moles of sulfide added x 100%;

[0164] The sulfoxide selectivity (%) = the number of moles of sulfoxide / the number of moles of sulfide participating in the reaction x 100%;

[0165] The sulfone selectivity (%) = the number of moles of sulfone / the number of moles of sulfide participating in the reaction x 100%;

[0166] wherein the number of moles of sulfide participating in the reaction = the number of moles of sulfide fed-in - the number of moles of sulfide remaining in the obtained reaction mixture.

[0167] Table 3

[0168]

[0169] In the embodiments, the T2 value of the oxide aggregate Co3O4 of the metal element cobalt is 350℃; the T2 value of the oxide aggregate MnO2 of the metal element manganese is 300℃; the T2 value of the oxide aggregate Fe2O3 of the metal element iron is 560℃; the T2 value of the oxide aggregate ZnO of the metal element zinc is 390℃, and the T2 value of the oxide aggregate CuO of the metal element copper is 300℃.

[0170] According to the data in Table 3, compared with Comparative Examples 1-3, the metal oxide nanoparticle and molecular sieve composite catalytic material T0 prepared in the embodiments 1-12 has a higher catalytic activity, and the thioether conversion rate and the sulfoxide / sulfone selectivity are higher in the range of 350-600℃. Under the relatively mild reaction conditions (60℃), the thioether conversion rate of more than 95% and the sulfoxide or sulfone selectivity of more than 90% can be obtained.

[0171] Comparing the embodiments 1-11 with the embodiment 12, the composite catalytic material T0 prepared in the embodiments 1-11 has a value in the range of 350-550℃, and the embodiments 1-11 have better catalytic effect and higher thioether conversion rate and sulfoxide / sulfone selectivity.

[0172] Reaction Example 2

[0173] The reaction effect under different reaction conditions is illustrated. CAT-9 is selected as the catalyst, and methyl p-tolyl sulfide is selected as the thioether raw material, and the catalyst amount is 50mg.

[0174] Referring to the operation process of Reaction Example 1, the reaction conditions are changed, and the specific reaction conditions and reaction results are shown in Table 4 below.

[0175] Table 4

[0176]

[0177] According to Table 3 and Table 4, comparing the catalytic effect of CAT-9 obtained in Reaction Example 2 and Reaction Example 1, it can be known that the oxidation reaction effect is better, and the thioether conversion rate and sulfoxide / sulfone selectivity are higher when the reaction temperature is in the range of 60-80℃ in Reaction Example 1.

[0178] The above describes the preferred embodiments of the present disclosure in detail, but the present disclosure is not limited to the specific details in the above embodiments, and various simple modifications can be made to the technical solutions of the present disclosure within the technical concept of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0179] It should also be noted that various technical features described in the above detailed description are capable of being combined in any suitable manner unless otherwise explicitly stated. To avoid unnecessary repetition, various possible combinations of features are not all explicitly described in the present disclosure.

[0180] Furthermore, various embodiments of the present disclosure can be combined in any suitable manner, as long as it does not contradict the idea of the present disclosure, and it should be considered as disclosed in the present disclosure.

Claims

1. A method for the selective oxidation of thioethers, characterized in that, The method includes the following steps: In the presence of oxygen, a mixed feedstock containing sulfide compounds, aldehyde compounds and alcohol compounds is brought into contact with a catalyst to carry out an oxidation reaction; The catalyst is a composite catalytic material, comprising an all-silica molecular sieve and a metal element M dispersed within the crystals of the all-silica molecular sieve; the metal element M is a metal element capable of forming oxide aggregates; the all-silica molecular sieve in the composite catalytic material is at least one of MFI structure molecular sieve, MEL structure molecular sieve, BEA structure molecular sieve, MWW structure molecular sieve, two-dimensional hexagonal structure molecular sieve, MOR structure molecular sieve, TUN structure molecular sieve, and other structures of silica molecular sieve; the metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper, and gold; When the metal M is Co, the oxide aggregate is a Co3O4 aggregate; When the metal M is Mn, the oxide aggregate is a MnO2 aggregate; When the metal M is Fe, the oxide aggregate is a Fe2O3 aggregate; When the metal M is Ni, the oxide aggregate is a NiO aggregate; When the metal M is Pd, the oxide aggregate is a PdO aggregate; When the metal M is Pt, the oxide aggregate is a PtO2 aggregate; or, When the metal M is Cu, the oxide aggregate is a CuO aggregate; The catalyst is prepared by a method comprising the following steps: Step S1 includes: a) mixing a template agent, a silicon source, and water to obtain a silicon hydrolysis solution; b) adding a peroxide to an aqueous solution of a metal M precursor and mixing to obtain a first mixture; mixing the first mixture with the silicon hydrolysis solution to obtain a second mixture; c) adding a silanizing agent to the second mixture and mixing to obtain a reaction mixture, wherein the silanizing agent contains at least one coordinating group that complexes with metal M ions; S2. The reaction mixture is subjected to hydrothermal crystallization and calcination.

2. The method according to claim 1, characterized in that, The composite catalytic material has the following H2-TPR characteristics: The reduction peak temperature of the composite catalytic material in the H2-TPR test is T1. The reduction peak temperature of the oxide aggregate in the H2-TPR test is T2. As defined in equation (1), T0 is any value between 350℃ and 600℃; T0 = ​​T1 - T2 (Equation 1) 3. The method according to claim 2, characterized in that, The value of T0 is any value between 350℃ and 550℃.

4. The method according to claim 1, characterized in that, The thioether compounds are selected from one or more of alkyl thioethers, thioethers with benzene rings and their derivatives; The aldehyde compounds are selected from one or more of alkyl aldehydes having 4 to 10 carbon atoms or aryl aldehydes having 7 to 12 carbon atoms. The alcohols are selected from one or more of alkyl alcohols having 4 to 10 carbon atoms or aryl alcohols having 7 to 12 carbon atoms. The molar ratio of the thioether compounds: aldehyde compounds: alcohol compounds is 1:(1-6):(0.001-2).

5. The method according to claim 4, characterized in that, The molar ratio of the thioether compounds: aldehyde compounds: alcohol compounds is 1:(1-5):(0.001-2).

6. The method according to claim 1, characterized in that, The conditions for the oxidation reaction include: a reaction temperature of 40-100℃; a reaction time of 1-48 hours; and an oxygen pressure of 0.1-0.5 MPa. The weight ratio of the catalyst to the thioether compound is 1:(1-20).

7. The method according to claim 1, characterized in that, The reactor for the oxidation reaction includes any one of the following: a batch reactor, a fixed-bed reactor, a moving-bed reactor, a suspended-bed reactor, and a slurry-bed reactor.

8. The method according to claim 6, characterized in that, The conditions for the oxidation reaction include: a reaction temperature of 60-80℃; a reaction time of 2-24 hours; and an oxygen pressure of 0.1-0.3 MPa. The weight ratio of the catalyst to the thioether compound is 1:(1-10).

9. The method according to claim 1, characterized in that, The all-silicon molecular sieve is selected from one or more of the following: MFI structured molecular sieve, MEL structured molecular sieve, BEA structured molecular sieve, MCM structured molecular sieve, and SBA structured molecular sieve.

10. The method according to claim 9, characterized in that, The all-silica molecular sieve is one or more of the following: MFI structure molecular sieve, MEL structure molecular sieve, and BEA structure molecular sieve.

11. The method according to claim 10, characterized in that, The all-silica molecular sieve is an MFI structure molecular sieve.

12. The method according to claim 1, characterized in that, In the composite catalytic material, the molar ratio of metal M to silicon is (0.001~0.22):

1.

13. The method according to claim 12, characterized in that, In the composite catalytic material, the molar ratio of metal M to silicon is (0.001–0.15):

1.

14. The method according to claim 1, characterized in that, The composite catalytic material has a BET specific surface area of ​​400~800 m². 2 / g, with a total pore volume of 0.3~0.65mL / g, a micropore volume of 0.1~0.19mL / g, and a mesopore volume of 0.2~0.46mL / g, wherein the metal element M exists in the form of metal nanoparticles, and the average particle size of the metal nanoparticles is 0.5~10nm.

15. The method according to claim 1, characterized in that, In step S1, the molar ratio of silicon source: template agent: water: metal element M: silanizing reagent is 1: (0.001~1): (5~100): (0.001~0.22): (0.025~0.4), where the silicon source is SiO2; the molar ratio of peroxide to metal element M is (0.5-5):

1.

16. The method according to claim 15, characterized in that, In step S1, the molar ratio of silicon source: template agent: water: metal element M: silanizing reagent is 1: (0.001~1): (5~50): (0.001~0.15): (0.025~0.3), where the silicon source is SiO2; the molar ratio of peroxide to metal element M is (0.5-3):

1.

17. The method according to claim 1, characterized in that, The mixing conditions in step c include stirring at 20~80℃ for 0.5~2 hours.

18. The method according to claim 1, characterized in that, In step S1, the silicon source is selected from at least one of organosilicon grease, solid silica gel, fumed silica, and silica sol.

19. The method according to claim 18, characterized in that, The silicon source is selected from at least one of organosilicone grease, solid silica gel, and fumed silica.

20. The method according to claim 19, characterized in that, The silicon source is an organosilicone grease, and the organosilicone grease has the general formula shown in formula (A): （A）； Where R a R b R c R d Each is independently selected from alkyl groups having 1 to 6 carbon atoms, wherein the alkyl group is a branched or straight-chain alkyl group.

21. The method according to claim 20, characterized in that, R a R b R c R d Each is independently selected from straight-chain alkyl groups having 1 to 4 carbon atoms or branched alkyl groups having 3 to 4 carbon atoms.

22. The method according to claim 21, characterized in that, The R a R b R c R d Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.

23. The method according to claim 20, characterized in that, The silicone grease is selected from one or more of tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate, and dimethyl diethyl silicone grease.

24. The method according to claim 1, characterized in that, In step S1, the template agent is an organic base.

25. The method according to claim 24, characterized in that, The template agent is selected from at least one of quaternary ammonium bases, aliphatic amines, and aliphatic alcoholic amines.

26. The method according to claim 25, characterized in that, The template agent has a general formula of at least one quaternary ammonium base selected from the structure shown in formula (B) below: (B); R1, R2, R3 and R4 are each selected from alkyl groups having 1 to 4 carbon atoms.

27. The method according to claim 26, characterized in that, R1, R2, R3 and R4 are each selected from straight-chain alkyl groups having 1 to 4 carbon atoms and branched alkyl groups having 3 to 4 carbon atoms.

28. The method according to claim 27, characterized in that, R1, R2, R3 and R4 are each selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

29. The method according to claim 1, characterized in that, The molecular sieve in the composite catalytic material is an MFI type molecular sieve, and the template agent is tetrapropylammonium hydroxide or a mixture of tetrapropylammonium hydroxide and one or more selected from tetrapropylammonium chloride and tetrapropylammonium bromide; or The molecular sieve in the composite catalytic material is a MEL-type molecular sieve, and the template agent is tetrabutylammonium hydroxide or a mixture of tetrabutylammonium hydroxide and one or more selected from tetrabutylammonium chloride and tetrabutylammonium bromide; or The molecular sieve in the composite catalytic material is a Beta-type molecular sieve, and the template agent is tetraethylammonium hydroxide or a mixture of tetraethylammonium hydroxide and one or more selected from tetraethylammonium chloride and tetraethylammonium bromide.

30. The method according to claim 1, characterized in that, In step a, the silicon source is silicone grease. After mixing the template agent, silicone grease and water, the process further includes hydrolysis and alcohol removal to obtain a hydrolyzed solution of the silicon. The conditions for the hydrolysis and alcohol removal treatment include: stirring and hydrolyzing at 0~95℃ for 2~10 hours.

31. The method according to claim 30, characterized in that, The conditions for the hydrolysis and alcohol removal treatment include: stirring and hydrolyzing at 50–95°C for 2–8 hours.

32. The method according to claim 1, characterized in that, In step S1, the precursor of metal M is one or more of inorganic metal compounds and organometallic compounds; the inorganic metal compound is a water-soluble inorganic salt of metal M; the water-soluble inorganic salt of metal M is selected from one or more of chloride, hydrated chloride, sulfate, hydrated sulfate and nitrate of metal M; the organometallic compound is an organic ligand compound of metal M. The metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper, and gold.

33. The method according to claim 32, characterized in that, The precursor of metal M is a water-soluble inorganic salt of metal M; The molar ratio of metal M to water in the aqueous solution of the metal M precursor is 1:(50~500).

34. The method according to claim 1, characterized in that, In step S1, the silanizing agent has the general formula R5Si(R6)(R7)R8, wherein R5, R6, R7, and R8 are each independently a halogen, alkyl, alkoxy, aromatic, mercapto, or amino group, and at least one of R5, R6, R7, and R8 is an alkyl, alkoxy, aromatic, mercapto, or amino group; the number of carbon atoms of the alkyl, alkoxy, mercapto, and amino groups is each independently 1 to 18, and the number of carbon atoms of the aromatic group is 6 to 18.

35. The method according to claim 34, characterized in that, The silanizing agent is selected from one or more of dimethyldichlorosilane, N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, 1,7-dichlorooctylmethyltetrasiloxane, hexadecyltrimethoxysilane, octyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

36. The method according to claim 35, characterized in that, The silanizing agent is at least one of N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

37. The method according to claim 1, characterized in that, In step S1, the peroxide is one or more of hydrogen peroxide or organic peroxides; the organic peroxide includes one or more of cumene hydroperoxide, ethylbenzene hydroperoxide, and tert-butyl hydroperoxide.

38. The method according to claim 1, characterized in that, In step S2, the conditions for the hydrothermal crystallization treatment include: under autogenous pressure, the hydrothermal crystallization time is 0.5 to 10 days, and the hydrothermal crystallization temperature is 110 to 200°C. The conditions for the calcination treatment include: a calcination temperature of 400~900℃ and a calcination time of 1~16 hours.

39. The method according to claim 38, characterized in that, In step S2, the conditions for the hydrothermal crystallization treatment include: under autogenous pressure, the hydrothermal crystallization time is 0.5 to 5 days, and the hydrothermal crystallization temperature is 150 to 200°C. The conditions for the roasting treatment include: a roasting temperature of 400~800℃ and a roasting time of 2~8 hours.

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