Efficient and stable catalyst, and preparation method therefor and use thereof

Abstract

Disclosed in the present invention are an efficient and stable catalyst, and a preparation method therefor and a use thereof. The catalyst comprises a metal oxide support having a three-dimensional porous structure, and a polyoxometalate dispersed in a monomolecular state and attached to the metal oxide support, wherein the polyoxometalate is a proton-type polyoxometalate capable of providing hydrogen ions. Further, the catalyst also comprises an active metal component dispersed in a monatomic state and attached to one or both of the polyoxometalate and the metal oxide support. The present invention overcomes the problem in the prior art of inability to fully use the active sites of a polyoxometalate and a metal, has excellent catalytic activity and good stability, and is suitable for being used in reactions such as alkylation, esterification, hydrogenation, and amination.

Description

High-efficiency stable catalyst, preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, in particular to a high-efficiency stable catalyst, a preparation method and application thereof. BACKGROUND

[0002] Polyoxometalates (POMs) are formed by bridging of heteroatoms (such as P, Si, Fe, Co, etc.) and polyatomic (such as Mo, W, V, Nb, Ta, etc.) through oxygen atoms. Polyoxometalates not only have acidity, but also have redox properties, and are a new type of multifunctional catalyst. However, since polyoxometalates are a non-porous solid substance (specific surface area less than 10 m 2 / g), when polyoxometalates are directly used as catalysts, due to their small specific surface area, the number of exposed acid active sites is limited, and non-polar reactants cannot enter the bulk phase, resulting in insufficient catalytic activity, and homogeneous phase reaction catalysts are not easy to separate.

[0003] It is known that supporting polyoxometalates on a carrier helps to achieve homogeneous heterogeneous, makes the catalyst easy to recover, reduces corrosion, and increases the specific surface area, enhancing the mechanical strength of the catalyst. Alumina, as one of the commonly used catalyst carriers, has been reported in many documents to support polyoxometalates thereon. However, the catalytic activity of the reported metal oxide supported polyoxometalates is still not satisfactory, for example, it still needs to be carried out at a higher temperature or under pressure; in addition, it is still a challenge to make polyoxometalates stably exist on alumina and reduce the loss as much as possible.

[0004] Chinese patent document CN117138812A discloses a composite nano-catalyst and a preparation method thereof. The document introduces polyoxometalate in situ during the synthesis of the porous nano-alumina carrier, which can catalyze the hydrolysis of aluminum precursors and promote the generation of five-coordinated aluminum sites, so that the polyoxometalate can be anchored in situ during the generation of the five-coordinated aluminum sites, and then the polyoxometalate can stably exist on the porous nano-alumina carrier. However, the reaction catalyzed by the composite nano-catalyst, such as the selective oxidation reaction of 2-methylbutyraldehyde, still needs to be carried out at 80℃ and under pressure. In addition, according to the multiple schemes disclosed in the document, when the polyoxometalate used is in the form of a salt, such as ammonium phosphomolybdate and sodium phosphotungstate, the prepared catalyst has higher activity and selectivity than when the polyoxometalate is in the form of an acid, such as phosphomolybdic acid and phosphotungstic acid. Since the salt form of polyoxometalate generally has a higher cost than the acid form, it also means that pursuing higher activity and selectivity will have to pay a higher cost accordingly. SUMMARY

[0005] The technical problem solved by the present application is to overcome one or more deficiencies in the prior art and provide a novel catalyst with excellent performance.

[0006] The present application also provides a preparation method of the above catalyst.

[0007] The present application also provides application of the novel catalyst in an acid catalytic system or a selective catalytic reaction, in particular in esterification, oxidation reaction, dehydrogenation reaction and hydrogenation reaction, which has obviously better catalytic effect.

[0008] Based on this, one technical solution of the present application is a catalyst, which comprises a metal oxide carrier with a three-dimensional porous structure and a heteropoly acid dispersed in a monomolecular state and connected to the metal oxide carrier, the heteropoly acid being a proton-type heteropoly acid capable of providing hydrogen ions.

[0009] Another technical solution of the present application is a catalyst, which comprises a metal oxide carrier with a three-dimensional porous structure, a heteropoly acid dispersed in a monomolecular state and connected to the metal oxide carrier, and an active metal component dispersed in a monatomic state and connected to one or both of the heteropoly acid and the metal oxide carrier, the heteropoly acid being a proton-type heteropoly acid capable of providing hydrogen ions.

[0010] In some embodiments of the present application, in the proton-type heteropoly acid, heteroatoms and polyatomic atoms are bridged by oxygen atoms, the heteroatoms comprising at least one selected from P, Si, Fe and Co, and the polyatomic atoms comprising at least one selected from Mo, W, V, Nb and Ta.

[0011] Further, the proton-type heteropoly acid is connected to the metal oxide carrier at least by a covalent bond.

[0012] Still further, the covalent bond is formed between the polyatomic atoms in the proton-type heteropoly acid, the terminal oxygen in the proton-type heteropoly acid and the metal atoms in the metal oxide carrier.

[0013] According to some preferred aspects of the present application, the active metal component is connected to the proton-type heteropoly acid by a chemical bond, the chemical bond comprising a coordination bond, and the active metal component is also selectively adsorbed on the metal oxide carrier.

[0014] In some embodiments of the present application, the metal oxide carrier is a hollow structure.

[0015] In some embodiments of the present application, the hollow structure has a single hollow chamber or a hollow cavity combination formed by aggregation of a plurality of hollow chambers that are all or partially communicated.

[0016] In some embodiments of the present application, the average diameter of the hollow chamber or cavity combination is 1-90 nm.

[0017] In some embodiments of the present application, the ratio of the average diameter of the hollow chamber or cavity combination to the average particle size of the catalyst is 0.3-0.9:1.

[0018] In some embodiments of the present application, the catalyst comprises a hollow spherical porous alumina carrier self-assembled from two-dimensional nanosheets, and the proton-type heteropoly acid is dispersed in a monomolecular state in the framework, inside the pores and on the surface of the porous alumina carrier.

[0019] According to the present application, the proton-type heteropoly acid in a monomolecular state is distributed in the framework, inside the pores and on the surface of the metal oxide carrier.

[0020] In some embodiments of the present application, the active metal component is a combination of one or more selected from transition metals.

[0021] Further, the active metal component is a combination of one or more selected from Groups IB-II B and Groups VB-VIII B.

[0022] Still further, the active metal component is a combination of one or more selected from Pd, Pt, Ru, Au, Ag, Rh, Ni, Cu, Fe and Co.

[0023] In some embodiments of the present application, the mass content of the active metal component in the catalyst is 0.01%-15% by mass percentage.

[0024] Further, the mass content of the active metal component in the catalyst is 0.04%-15% by mass percentage.

[0025] In some embodiments of the present application, the proton-type heteropoly acid comprises a combination of one or more selected from phosphomolybdic acid, phosphotungstic acid, silicotungstic acid, silicomolybdic acid, phosphovanadic heteropoly acid, phosphoniobic heteropoly acid, phosphotantalum heteropoly acid, ferric molybdenum heteropoly acid, ferric tungsten heteropoly acid, ferric vanadic heteropoly acid, cobalt molybdenum heteropoly acid, cobalt tungsten heteropoly acid, cobalt vanadic heteropoly acid.

[0026] In some embodiments of the present application, the mass content of the proton-type heteropoly acid in the catalyst is 1%-68% by mass percentage.

[0027] Further, the mass content of the proton-type heteropoly acid in the catalyst is 7%-45% by mass percentage.

[0028] Further, the mass content of the protonic heteropoly acid in the catalyst is 7%-25% by mass.

[0029] In some embodiments of the present application, the average pore size of the catalyst is 2-30 nm, the average pore volume is 0.4-1.5 cc / g, and the average density is 0.5-4.0 g / cm 3 .

[0030] In some embodiments of the present application, the average particle size of the catalyst is 10-350 nm. Further, the average particle size of the catalyst is 80-250 nm.

[0031] In some embodiments of the present application, the specific surface area of the catalyst is greater than or equal to 200 m 2 / g as measured by the BET method.

[0032] Further, the specific surface area of the catalyst is less than or equal to 1000 m 2 / g as measured by the BET method.

[0033] Further, the specific surface area of the catalyst is 200-800 m 2 / g as measured by the BET method.

[0034] In some embodiments, the catalyst is in a spherical structure. The "spherical structure" refers to a standard spherical structure or a structure close to a spherical structure, i.e., including a substantially spherical manner.

[0035] In some embodiments of the present application, the metal oxide carrier includes a zinc oxide carrier, a magnesium oxide carrier, a copper oxide carrier, an aluminum oxide carrier, or a titanium oxide carrier.

[0036] In some embodiments of the present application, for a catalyst without an active metal component, the catalyst is prepared by a preparation method satisfying the following conditions:

[0037] (a) using a precursor of a metal oxide as a raw material, wherein the precursor of the metal oxide refers to a substance that can be converted into a metal oxide through one or more conversion processes, and the conversion processes at least include a process that generates a chemical reaction;

[0038] (b) performing the one or more conversion processes in the presence of the protonic heteropoly acid and water.

[0039] In some embodiments of the present application, for a catalyst with an active metal component, the catalyst is prepared by a preparation method satisfying the following conditions:

[0040] (a) using a metal oxide precursor, an active metal precursor, respectively, as raw material, the metal oxide precursor and the active metal precursor respectively refer to substances which can be converted into a metal oxide or an active metal component through one or more conversion processes, the conversion processes at least including a process of generating a chemical reaction;

[0041] (b) performing the one or more conversion processes in the presence of the protic heteropoly acid and water.

[0042] In the present application, the presence of the protic heteropoly acid can participate in the conversion process of the metal oxide precursor, and the two work together to not only promote the formation of the conversion of the three-dimensional porous metal oxide carrier, but also facilitate the dispersion of the protic heteropoly acid in a monomolecular state, and can also promote the connection between the protic heteropoly acid and the metal oxide carrier to be more stable, for example, it is conducive to the formation of a covalent bond between the polyatomic atoms in the protic heteropoly acid, the terminal oxygen in the protic heteropoly acid and the metal atoms in the metal oxide carrier, in addition, there can also be hydrogen bonding force and the like.

[0043] In some embodiments of the present application, the metal oxide precursor is selected from acidic, basic or neutral metal-containing and organic group-containing compounds.

[0044] In some embodiments of the present application, the metal-containing and organic group-containing compound is selected from C1-C12 metal alkoxide, C1-C12 hydrocarbon metal, metal organic complex or complex.

[0045] In some embodiments of the present application, the metal oxide precursor is a combination of one or more selected from an aluminum alcohol compound, a magnesium alcohol compound, a copper alcohol compound, a zinc alcohol compound, a titanium alcohol compound, an aluminum hydrocarbon compound, a titanium hydrocarbon compound, a zinc hydrocarbon compound, an organic aluminum salt, an organic titanium salt and an organic zinc salt.

[0046] In some embodiments of the present application, the active metal precursor is a salt of an active metal component and / or an acid of an active metal component, the salt of the active metal component includes a combination of one or more selected from metal nitrate, metal sulfate, metal halide, metal acetylacetone complex, metal sulfide, and the acid of the active metal component includes halogenated metal acid.

[0047] In some embodiments of the present application, the metal oxide precursor is a combination of one or more selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, aluminum isopropoxide, aluminum n-butylate, aluminum acetate, aluminum propionate, titanium acetylacetone, titanium acid tetraethyl ester, titanium acid tetraisopropyl ester, titanium acid tetrabutyl ester and zinc acetylacetone.

[0048] In some embodiments of the present application, the active metal precursor is a combination of one or more selected from the group consisting of palladium chloride, palladium nitrate, platinum acetylacetonate, gold chloride, silver nitrate, ruthenium chloride, ruthenium nitrate, rhodium chloride, rhodium nitrate, cobalt nitrate, nickel nitrate, iron chloride, iron sulfate, copper nitrate, copper sulfate, chloroplatinic acid, chloropalladic acid, chloroauric acid, and rhodium acetylacetonate.

[0049] In some embodiments of the present application, the precursor of the metal oxide is a substance that can be converted into the metal oxide carrier with a three-dimensional porous structure through a gelation treatment and a calcination treatment performed in sequence.

[0050] In some embodiments of the present application, the preparation method of the catalyst further satisfies the conditions that:

[0051] (c) the conversion treatment includes a gelation treatment, and the gelation treatment is performed in the presence of water, an organic solvent, and a surfactant.

[0052] For a catalyst without an active metal component, the present application provides another technical solution: a preparation method of the catalyst described above, the preparation method comprising:

[0053] gelation treatment: mixing and reacting the protolytic heteropoly acid and the precursor of the metal oxide in the presence of water, an organic solvent, and a surfactant, and inducing solvent evaporation to prepare a gel, wherein: the temperature of the mixing and reacting is controlled to be 20-50°C, and the reaction time is controlled to be no less than 12 hours;

[0054] calcination treatment: drying the gel and then performing calcination to obtain the catalyst.

[0055] For a catalyst with an active metal component, the present application provides another technical solution: a preparation method of the catalyst described above, the preparation method comprising:

[0056] gelation treatment: mixing and reacting the protolytic heteropoly acid and the precursor of the metal oxide in the presence of water, an organic solvent, and a surfactant, and inducing solvent evaporation to prepare a gel, wherein: the temperature of the mixing and reacting is controlled to be 20-50°C, and the reaction time is controlled to be no less than 12 hours;

[0057] calcination treatment: drying the gel and then performing calcination, and performing a reduction treatment in the presence of a reducing agent to obtain the catalyst;

[0058] In some embodiments of the present application, the preparation method further includes a step of adding an active metal precursor before the mixing and reacting, or a step of coating with a solution containing the active metal precursor after the calcination and before the reduction treatment, the coating including spraying, brushing, rolling, dipping, or scraping.

[0059] According to some preferred aspects of the present application, the mass ratio of the water to the precursor of the metal oxide is 0.001-15:1.

[0060] Further, the mass ratio of the water to the precursor of the metal oxide is 0.01-10:1.

[0061] Still further, the mass ratio of the water to the precursor of the metal oxide is 0.1-5:1.

[0062] In some embodiments of the present application, the mass ratio of the water to the precursor of the metal oxide is 0.01-6:1, for example, it can also be 0.01-3:1, or 0.02-3:1, or 0.04-1:1.

[0063] According to some preferred aspects of the present application, the volume ratio of the water to the organic solvent is 0.001-5:1. Further, the volume ratio of the water to the organic solvent is 0.01-2:1. Still further, the volume ratio of the water to the organic solvent is 0.005-1:1.

[0064] In some embodiments of the present application, the volume ratio of the water to the organic solvent is 0.001-1:1, for example, it can be 0.001-0.5:1, or 0.001-0.2:1. In some embodiments of the present application, the surfactant is a block copolymer nonionic surfactant and / or an ionic surfactant, the block copolymer nonionic surfactant comprises a combination of one or more selected from nonionic surfactant P123, nonionic surfactant F127, nonionic surfactant F108, and the ionic surfactant comprises a combination of one or more selected from cetyltrimethylammonium bromide, sodium oleate, sodium dodecylbenzenesulfonate, sodium stearate.

[0065] In some embodiments of the present application, the mass ratio of the surfactant to the protic heteropoly acid is 3-30:1.

[0066] In some embodiments of the present application, the organic solvent is a polar organic solvent, and the mass ratio of the protic heteropoly acid to the organic solvent is 1:80-1000.

[0067] In some embodiments of the present application, the organic solvent is a combination of one or more selected from methanol, ethanol, isopropanol, acetone, tetrahydrofuran, N,N-dimethylformamide.

[0068] In some embodiments of the present application, the time for the mixing reaction is controlled to be 12-15h, 15-18h, 18-21h, 21-24h, 24-27h, 27-30h or 30-48h.

[0069] In some embodiments of the present application, the solvent evaporation is controlled to be induced at a temperature of 40-120℃ for 1-72h.

[0070] Further, the solvent evaporation is controlled to be induced at a temperature of 60-75℃ for 10-60h.

[0071] In some embodiments of the present application, the calcination is performed at 200-700℃.

[0072] In some embodiments of the present application, the calcination is performed in a muffle furnace, and the calcination time is controlled to be 1-6h, and the heating rate is controlled to be 1-30℃ / min.

[0073] In some embodiments of the present application, the calcination is performed in an oxygen-containing environment, which includes an air atmosphere or a pure oxygen atmosphere formed by introducing pure oxygen gas with a purity of more than 99%.

[0074] In some preferred embodiments of the present application, when the preparation method employs impregnation or spraying with a solution containing the active metal precursor after the calcination and before the reduction treatment, the active metal precursor and the solid obtained by the calcination are dispersed in solvents respectively, mixed and stirred, separated, to obtain a solid loaded with the active metal precursor, and then the reduction treatment is performed.

[0075] Further, the solvent can be a ketone solvent, for example, acetone, etc.

[0076] Further, when the preparation method employs impregnation or spraying with a solution containing the active metal precursor after the calcination and before the reduction treatment, a solid loaded with the active metal precursor is obtained; further, in some specific cases, the active metal precursor can be dispersed in a ketone solvent, and then the solid obtained by the calcination is ultrasonically dispersed in the foregoing solution, continuously stirred, and heated until the ketone solvent is completely evaporated, to obtain a solid loaded with the active metal precursor.

[0077] According to some specific aspects of the present application, when the preparation method employs adding an active metal precursor before the mixing reaction, the embodiments of the gelation treatment include:

[0078] The protonic heteropoly acid, water and organic solvent are mixed and uniformly dispersed to obtain a first solution; then the surfactant, the precursor of aluminum oxide and the active metal precursor are added into the first solution for mixing and dispersion, reaction is carried out at room temperature, and a gel is prepared through solvent evaporation induction.

[0079] In some preferred embodiments of the present application, the reduction treatment comprises: performing a first roasting in an oxygen-containing environment, and then performing a second roasting in a reducing atmosphere.

[0080] Further, the roasting temperature of the first roasting is 200-400℃.

[0081] Further, the roasting temperature of the second roasting is 150-300℃.

[0082] In some preferred embodiments of the present application, the roasting temperature of the second roasting is less than the roasting temperature of the first roasting.

[0083] In some preferred embodiments of the present application, in the reduction treatment, the oxygen-containing environment comprises an air atmosphere or a pure oxygen atmosphere formed by introducing a pure oxygen gas with a purity greater than 99%, and the reducing atmosphere comprises a hydrogen atmosphere.

[0084] The present application provides still another technical solution: a catalyst composition comprising the above-mentioned catalyst and at least one other catalyst different from the catalyst, wherein the mass content of the catalyst is more than 50%.

[0085] In some embodiments of the present application, in the catalyst composition, the mass content of the above-mentioned catalyst is more than 55%, or more than 60%, or more than 65%, or more than 70%, or more than 75%, or more than 80%, or more than 85%, or more than 90%, or more than 95%, or more than 96%, or more than 97%, or more than 98%, or more than 99%.

[0086] The present application provides still another technical solution: the above-mentioned catalyst, or the catalyst prepared by the above-mentioned preparation method of catalyst, or the above-mentioned catalyst composition is applied in the following reactions: oxidation reaction of aromatic hydrocarbon, alcohol or aldehyde, esterification of olefin and acid or esterification of alcohol and acid, epoxidation reaction of olefin, alkylation reaction of aromatic compound, isomerization reaction, dehydration reaction of alcohol, etherification reaction, hydration reaction of olefin, aldol condensation reaction, hydrogenation reaction, amination reaction of alcohol, ketone or olefin.

[0087] In some embodiments of the present application, the oxidation reaction comprises: using an aromatic hydrocarbon, an alcohol or an aldehyde as a starting material, and allowing the starting material to undergo an oxidation reaction in the presence of the catalyst or the catalyst composition and an oxidant to generate a corresponding acid; wherein the oxidant is oxygen, and the oxidant is provided by introducing greater than 99% pure oxygen gas or air into the reaction system; and the catalyst or the catalyst composition is added in an amount of 0.01% to 3% of the amount of the starting material.

[0088] In some embodiments of the present application, the oxidation reaction comprises: allowing a C3-C10 aldehyde, a C3-C10 alcohol or a C6-C12 aromatic hydrocarbon to undergo an oxidation reaction in the presence of an oxidant and the catalyst or the catalyst composition to generate a C3-C10 acid; further, the oxidant can be oxygen or air, and the catalyst or the catalyst composition is added in an amount of 0.01wt.% to 2.0wt.% of the amount of the C3-C10 aldehyde. Still further, when the C3-C10 aldehyde is used as a substrate, the reaction is allowed to proceed at 30-55°C; when the C3-C10 alcohol is used as a substrate, the reaction is allowed to proceed at 70-100°C; and when the C6-C12 aromatic hydrocarbon is used as a substrate, the reaction is allowed to proceed at 120-160°C.

[0089] Further, the oxidation reaction comprises: allowing a phenyl C 1-6 alkyl alcohol to react with hydrogen peroxide in the presence of the catalyst or the catalyst composition to generate a phenyl C 1-6 alkyl aldehyde; further, the reaction is allowed to proceed at 40-70°C; the catalyst or the catalyst composition is added in an amount of 0.01wt.% to 3.0wt.% of the amount of the phenyl C 1-6 alkyl alcohol; and the phenyl C 1-6 alkyl alcohol can be benzyl alcohol, phenethyl alcohol, etc.

[0090] In some embodiments of the present application, the epoxidation reaction of an olefin comprises: allowing a C 3-20 alkene to undergo an epoxidation reaction in the presence of an oxidant and the catalyst or the catalyst composition in a solvent to generate a corresponding epoxide; wherein the oxidant comprises hydrogen peroxide, and the hydrogen peroxide is added in an amount of 5% to 50% of the amount of the C 3-20 alkene; the catalyst or the catalyst composition is added in an amount of 0.1% to 5% of the amount of the C 3-20 alkene.

[0091] Further, the epoxidation reaction of the olefin includes: reacting a-pinene with hydrogen peroxide in the presence of the catalyst or the catalyst composition to produce epoxy pinane, and the reaction is carried out at 50-80°C; or reacting limonene with hydrogen peroxide in the presence of the catalyst or the catalyst composition to produce epoxy limonene, and the reaction is carried out at 50-80°C.

[0092] In some embodiments of the present application, the esterification reaction includes: esterification of an alcohol or an olefin with an acid in the presence of the catalyst or the catalyst composition to produce an ester; wherein the alcohol includes a C 1-20 a hydrocarbyl alcohol, the acid includes a C 1-20 a hydrocarbyl carboxylic acid and / or a C 1-20 a hydrocarbyloxy C 1-20 a hydrocarbyl carboxylic acid, and the olefin includes a C 3-20 a cyclic olefin; and the catalyst or the catalyst composition is added in an amount of 0.01%-3% of the mass percentage of the alcohol and the acid.

[0093] In some embodiments of the present application, the esterification reaction includes: esterification of 2-methylbutyric acid with methanol, ethanol, isopropyl alcohol, n-butyl alcohol or n-hexyl alcohol, respectively; or the esterification reaction includes: esterification of salicylic acid with n-hexyl alcohol, n-pentyl alcohol, benzyl alcohol, leaf alcohol, cyclohexyl alcohol, isooctanol or isophorone, respectively; or the esterification reaction includes: esterification of allyl alcohol with acetic acid, hexanoic acid, heptanoic acid, phenylpropionic acid, phenoxyacetic acid or cyclohexyloxyacetic acid, respectively; or the esterification reaction includes: esterification of acetic acid with o-tert-butylcyclohexanol, p-tert-butylcyclohexanol, a-phenyl ethanol or β-phenyl ethanol, respectively; or the esterification reaction includes: esterification of dicyclopentadiene with acetic acid, propionic acid, n-butyric acid or isobutyric acid, respectively; or the esterification reaction includes: esterification of dodecanedioic acid with methanol.

[0094] Further, in the esterification reaction, the acid can be 2-methylbutyric acid, and the alcohol can be methanol, ethanol, isopropyl alcohol, n-butyl alcohol, n-hexyl alcohol, n-pentyl alcohol, n-hexyl alcohol, and the reaction is carried out at 40-80°C, and the catalyst or the catalyst composition is added in an amount of 0.01wt.%-2.0wt.% of the acid.

[0095] Further, in the esterification reaction, the acid can be salicylic acid, and the alcohol can be n-pentyl alcohol, n-hexyl alcohol, benzyl alcohol, leaf alcohol, cyclohexyl alcohol, isooctanol, isophorone, and the reaction is carried out at 60-100°C, 300-700mmHg, and the catalyst or the catalyst composition is added in an amount of 0.01wt.%-2.0wt.% of the acid.

[0096] Further, in the esterification reaction, the acid can be acetic acid, hexanoic acid, heptanoic acid, phenylpropionic acid, phenoxyacetic acid, cyclohexyloxyacetic acid, and the alcohol can be allyl alcohol, and the reaction is carried out at 60-100°C, and the catalyst or the catalyst composition is added in an amount of 0.01-2.0 wt.% based on the amount of the alcohol added.

[0097] Further, in the esterification reaction, the acid can be acetic acid, and the alcohol can be o-tert-butylcyclohexanol, p-tert-butylcyclohexanol, α-phenyl-ethanol, β-phenyl-ethanol, and the reaction is carried out at 60-100°C, 300-700 mmHg, and the catalyst or the catalyst composition is added in an amount of 0.01-2.0 wt.% based on the amount of the alcohol added.

[0098] Further, in the esterification reaction, the olefin can be dicyclopentadiene, and the acid can be acetic acid, propionic acid, n-butyric acid, isobutyric acid, and the reaction is carried out at 60-100°C, and the catalyst or the catalyst composition is added in an amount of 0.01-2.0 wt.% based on the amount of the olefin added.

[0099] In some embodiments of the present application, the alkylation reaction of the aromatic compound includes reacting an olefin with C 1-10 alkyl-substituted phenol, or an alkylation reaction of an alcohol with substituted or unsubstituted benzene in the presence of the catalyst or the catalyst composition; wherein the olefin is C 2-10 alkyl-substituted phenol, or an alkylation reaction of an alcohol with substituted or unsubstituted benzene in the presence of the catalyst or the catalyst composition; wherein the olefin is C 1-10 the alkyl-substituted phenol is a phenol substituted with one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, and the substitution position is meta, and the alcohol is C 1-6 alkyl-substituted phenol, or an alkylation reaction of an alcohol with substituted or unsubstituted benzene in the presence of the catalyst or the catalyst composition; wherein the olefin is C 1-6 alkyl-substituted phenol, or an alkylation reaction of an alcohol with substituted or unsubstituted benzene in the presence of the catalyst or the catalyst composition; wherein the olefin is C

[0100] Further, the alkylation reaction includes continuously alkylating propylene with m-cresol in the presence of the catalyst or the catalyst composition to prepare thymol, and further, the reaction is carried out at 200-240°C, 0.05-0.5 MPa.

[0101] In some embodiments of the present application, the isomerization reaction includes isomerizing o-cresol in the presence of the catalyst or the catalyst composition to prepare m-cresol and p-cresol, and further, the reaction is carried out at 240-300°C, 0.05-0.4 MPa.

[0102] In some embodiments of the present application, the dehydration reaction of the alcohol includes: dehydrating 2-(1-hydroxypentyl)-cyclopentanone in the presence of the catalyst or the catalyst composition to prepare 2-pentylidenecyclopentanone, or dehydrating hydroxycyclopentadecanolide to prepare habanolide; further, the reaction is carried out at 80-110℃ and 150-500mmHg, and the catalyst or the catalyst composition is added in an amount of 0.01%-3% of the added amount of the 2-(1-hydroxypentyl)-cyclopentanone or the hydroxycyclopentadecanolide.

[0103] In some embodiments of the present application, the hydration reaction of the olefin includes: hydrating C 2-20 The olefin is subjected to hydration reaction with water to prepare the corresponding alcohol; wherein the C 2-20 The olefin is ethylene, propylene, butylene, pentene, hexene, cyclopropene, cyclobutene, cyclopentene or cyclohexene.

[0104] Further, the hydration reaction includes: hydrating propylene in the presence of the catalyst or the catalyst composition to prepare isopropyl alcohol; further, the reaction is carried out at 100-160℃ and 1-8MPa.

[0105] In some embodiments of the present application, the hydrogenation reaction includes: reacting substituted or unsubstituted phenol with hydrogen in the presence of the catalyst or the catalyst composition to prepare the corresponding substituted or unsubstituted cyclohexanol, or reacting cyclopentybutyrolactone, alcohol with hydrogen to prepare the corresponding substituted or unsubstituted cyclohexyl propionate, or hydrogenating rose oxide to prepare phenylverdol, or hydrogenating habanolide to prepare cyclopentadecanolide; wherein the substituted or unsubstituted phenol includes C 1-6 alkyl-substituted phenol, the alcohol is C 1-6 alkyl alcohol.

[0106] Further, the hydrogenation reaction includes: hydrogenating p-tert-butyl phenol in the presence of the catalyst or the catalyst composition to prepare p-tert-butyl cyclohexanol; further, the reaction is carried out at a pressure of 1-5MPa and a temperature of 60-90℃.

[0107] In some embodiments of the present application, the hydrogenation reaction includes: hydrogenating o-tert-butyl phenol in the presence of the catalyst or the catalyst composition to prepare o-tert-butyl cyclohexanol; further, the reaction is carried out at a pressure of 1-3MPa and a temperature of 60-90℃.

[0108] In some embodiments of the present application, the hydrogenation reaction comprises: hydrogenating cyclopentyl butyrolactone in an alcohol-containing system in the presence of the catalyst or the catalyst composition to prepare cyclohexyl propionate. Further, the alcohol in the alcohol-containing system is selected from C 1-20 The hydrocarbon-based alcohol can be, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, allyl alcohol, etc.; the reaction is carried out at 1-4 MPa at 100-150°C.

[0109] In some embodiments of the present application, the hydrogenation reaction comprises: hydrogenating rose oxide in the presence of the catalyst or the catalyst composition to prepare phenyl allyl alcohol; further, the addition amount of the catalyst or the catalyst composition is 0.01wt.%-1.0wt.% of the addition amount of rose oxide; the reaction is carried out at 80-150°C at 1-3 MPa.

[0110] In some embodiments of the present application, the hydrogenation reaction comprises: hydrogenating habanolide in the presence of the catalyst or the catalyst composition to prepare cyclopentadecanolide; further, the reaction is carried out at 30-50°C, and the addition amount of the catalyst or the catalyst composition is 0.01wt.%-1.0wt.% of the addition amount of the habanolide.

[0111] In some embodiments of the present application, the isomerization reaction comprises: isomerizing 2-pentylidene cyclopentanone in the presence of the catalyst or the catalyst composition to prepare 2-pentyl cyclopentenone; further, the reaction is carried out at 20-60°C, and the addition amount of the catalyst or the catalyst composition is 0.01wt.%-1.0wt.% of the addition amount of 2-pentylidene cyclopentanone.

[0112] In some embodiments of the present application, the amination reaction comprises: mixing an alcohol, a ketone or an olefin in the presence of ammonia in the presence of the catalyst or the catalyst composition to generate a corresponding amine; the alcohol is C 1-10 The hydrocarbon-based alcohol, the ketone is C 3-10 The hydrocarbon-based ketone, the olefin is C 2-20 The olefin.

[0113] Further, the amination reaction comprises: hydrogenating C 2-6 The alkyl alcohol and ammonia gas in the presence of the catalyst or the catalyst composition to prepare C 2-6 The alkyl amine; further, the reaction is carried out at 100-150°C at a pressure of 0.1-0.6 MPa; C 2-6 The alkyl alcohol can be ethanol, propanol, etc.

[0114] In some embodiments of the present application, the amination reaction comprises: hydrogenating C 3-6Preparation of C 3-6 alkyl amine; further, the reaction is carried out at 100-150 ℃, 0.1-0.6 MPa. 3-6 The alkyl ketone can be acetone, butanone, etc.

[0115] In some embodiments of the present application, the amination reaction comprises: preparing C 2-10 Preparation of C 2-10 alkyl amine; further, the reaction is carried out at 120-180 ℃, 2-6 MPa. 2-10 The alkene can be isobutylene, ethylene, propylene, etc.

[0116] In some embodiments of the present application, the etherification reaction comprises: preparing trideca-oxa-bicyclo[10.4.0]hexadecene by self-etherification of 2-(3-hydroxypropyl)cyclododecanone in the presence of the catalyst or the catalyst composition; further, the reaction is carried out at 80-100 ℃, 150-500 mmHg, and the addition amount of the catalyst or the catalyst composition is 0.01 wt.%-2.0 wt.% of the addition amount of the 2-(3-hydroxypropyl)cyclododecanone.

[0117] In some embodiments of the present application, the aldol condensation reaction comprises: preparing 2-pentylidenecyclopentanone by aldol condensation reaction of cyclopentanone and n-pentanal in the presence of the catalyst or the catalyst composition. Further, the aldol condensation reaction is carried out at 80-150 ℃, 0.1-3 MPa, and more further at 80-130 ℃, 0.5-1.5 MPa.

[0118] The present application has the following advantages compared with the prior art due to the use of the above technical solutions:

[0119] The present application provides a novel catalyst structure, which takes a metal oxide carrier with a three-dimensional porous structure as a basis and loads a proton-type heteropoly acid capable of providing hydrogen ions, and in particular, the novel catalyst structure of the present application is based on a metal oxide carrier with a three-dimensional porous structure, which enables the proton-type heteropoly acid to be dispersed in a monomolecular state while also having a stable connection relationship between them, and further, the present application also provides a catalyst in which the proton-type heteropoly acid is dispersed in a monomolecular state and the active metal component is dispersed in a monatomic state on the basis of the metal oxide carrier with a three-dimensional porous structure, and the interaction between the components and structures of them achieves a significant synergistic effect; the catalyst of the present application has been proved to have higher catalytic activity and stability in multiple reaction systems. The preparation method of the present application is simple to operate and has low raw material cost. BRIEF DESCRIPTION OF DRAWINGS

[0120] Figure 1 is an XRD pattern of H3PMo / AS-20H prepared in Example 1;

[0121] Figure 2 is a TEM image of H3PMo / AS-20H prepared in Example 1;

[0122] Figure 3 is a STEM-HAADF image of H3PMo / AS-20H prepared in Example 1;

[0123] Figure 4 is a corresponding particle size distribution histogram of H3PMo / AS-20H prepared in Example 1;

[0124] Figure 5 is a nitrogen adsorption-desorption plot of H3PMo / AS-20H prepared in Example 1;

[0125] Figure 6 is a TEM image of H3PMo / TiO2-20H prepared in Example 12;

[0126] Figure 7 is a TEM image of H3PMo / ZnO-20H prepared in Example 13;

[0127] Figure 8 is an XRD pattern of Pd-H3PMo / AS-20H prepared in Example 14;

[0128] Figure 9 is a SEM image of Pd-H3PMo / AS-20H prepared in Example 14;

[0129] Figure 10 is a TEM image of Pd-H3PMo / AS-20H prepared in Example 14;

[0130] Figure 11 is a STEM-HAADF image of Pd-H3PMo / AS-20H prepared in Example 14;

[0131] Figure 12 is a corresponding particle size distribution histogram of Pd-H3PMo / AS-20H prepared in Example 14;

[0132] Figure 13 is a nitrogen adsorption-desorption plot of Pd-H3PMo / AS-20H prepared in Example 14;

[0133] Figure 14 is an XRD pattern of Pd-H3PW / AS-20H prepared in Example 15;

[0134] Figure 15 is a SEM image of Pd-H3PW / AS-20H prepared in Example 15;

[0135] Figure 16 is a TEM image of Pd-H3PW / AS-20H prepared in Example 15;

[0136] Figure 17 is a STEM-HAADF image of Pd-H3PW / AS-20H prepared in Example 15;

[0137] Figure 18 is a corresponding particle size distribution histogram of Pd-H3PW / AS-20H prepared in Example 15;

[0138] Figure 19 is a nitrogen adsorption-desorption plot of Pd-H3PW / AS-20H prepared in Example 15;

[0139] Figure 20 is an XRD plot of Pd-H4SiW / AS-20H prepared in Example 16;

[0140] Figure 21 is an SEM image of Pd-H4SiW / AS-20H prepared in Example 16;

[0141] Figure 22 is a TEM image of Pd-H4SiW / AS-20H prepared in Example 16;

[0142] Figure 23 is a nitrogen adsorption-desorption plot of Pd-H4SiW / AS-20H prepared in Example 16;

[0143] Figure 24 is an XRD plot of Pd-H4SiMo / AS-20H prepared in Example 17;

[0144] Figure 25 is an SEM image of Pd-H4SiMo / AS-20H prepared in Example 17;

[0145] Figure 26 is a TEM image of Pd-H4SiMo / AS-20H prepared in Example 17;

[0146] Figure 27 is a nitrogen adsorption-desorption plot of Pd-H4SiMo / AS-20H prepared in Example 17;

[0147] Figure 28 is a TEM image of Pd-H3PMo / AS-14H prepared in Example 18;

[0148] Figure 29 is a TEM image of Pd-H3PMo / AS-8H prepared in Example 19;

[0149] Figure 30 is a TEM image of Pd-H3PMo / AS-2H prepared in Example 20;

[0150] Figure 31 is a TEM image of Pd-H3PMo / AS-30H prepared in Example 21;

[0151] Figure 32 is a TEM image of Pd-H3PMo / AS-50H prepared in Example 22;

[0152] Figure 33 is a TEM image of Pd-H3PMo / AS-100H prepared in Example 23;

[0153] Figure 34 is an XRD pattern of Pt-H3PMo / AS-20H prepared in Example 24;

[0154] Figure 35 is a TEM image of Pt-H3PMo / AS-20H prepared in Example 24;

[0155] Figure 36 is an XRD pattern of Co-H3PMo / AS-20H prepared in Example 25;

[0156] Figure 37 is an XRD pattern of Ni-H3PMo / AS-20H prepared in Example 26;

[0157] Figure 38 is an XRD pattern of Pd@H3PMo / AS-20H prepared in Example 36;

[0158] Figure 39 is a TEM image of Pd@H3PMo / AS-20H prepared in Example 36;

[0159] Figure 40 is a TEM image of Pd-H3PMo / AS-20H-85 prepared in Example 37;

[0160] Figure 41 is a TEM image of Pd-H3PMo / AS-F-20H prepared in Example 40;

[0161] Figure 42 is a TEM image of Pd-H3PMo / AS-C-20H prepared in Example 41;

[0162] Figure 43 is an XRD pattern of catalyst H3PMo@AS prepared in Comparative Example 1;

[0163] Figure 44 is an XRD pattern of catalyst Pd-APMo / AS-20H prepared in Comparative Example 2;

[0164] Figure 45 is a TEM image of catalyst Pd-APMo / AS-20H prepared in Comparative Example 2;

[0165] Figure 46 is a TEM image of catalyst H3PMo / AS-ethanol prepared in Comparative Example 3. DETAILED DESCRIPTION

[0166] The present application is directed to the in-depth study of the catalyst loaded with heteropoly acid, and further studies the formation mechanism, and innovatively proposes a new type of catalyst of metal oxide carrier loaded with proton type heteropoly acid based on three-dimensional porous structure, which mainly has the following characteristics: (1) taking the proton type heteropoly acid capable of providing hydrogen ions as the loading component, (2) dispersing the proton type heteropoly acid in a monomolecular state, and (3) enabling the proton type heteropoly acid to be connected to the metal oxide carrier with three-dimensional porous structure, and realizing stable loading through stable connection. Compared with the metal oxide carrier loaded with heteropoly acid disclosed in the prior art, such as the composite nano catalyst (polyoxometalate is loaded on the five-coordinated aluminum sites of porous nano aluminum oxide) disclosed in Chinese patent document CN117138812A, the present application has obtained more excellent effects in terms of catalyst preparation cost and catalyst activity. When the proton type heteropoly acid is further dispersed in a monomolecular state and combined with the active metal component dispersed in a single-atom state, and the active metal component is connected to one or both of the heteropoly acid and the metal oxide carrier, a catalyst form of double monodispersion combined with three-dimensional porous metal oxide is formed, so that the catalyst of the present application can be applied to more application scenarios.

[0167] Further, in the catalyst structure of the present application, the proton type heteropoly acid is uniformly distributed in a monomolecular state, so that the active sites of the proton type heteropoly acid are fully exposed. At the same time, in the catalyst of double monodispersion combined with three-dimensional porous metal oxide, the monomolecular state promotes the active metal component to be dispersed in a single-atom form and always maintain a uniform dispersion state. The metal oxide carrier and the proton type heteropoly acid and / or the proton type heteropoly acid and the active metal component form stable and strong interactions and improve the microstructure, and a stable loading state is constructed. At the same time, a catalyst with three-dimensional porous structure can also be formed. Practice shows that the catalyst of the present application can obtain unexpectedly excellent stability, catalytic activity and selectivity in the catalytic process of acid catalytic reactions and selective catalytic reactions, such as the oxidation reaction of aromatic hydrocarbons, alcohols or aldehydes, the esterification reaction of olefins with acids or the esterification reaction of alcohols with acids, the epoxidation reaction of olefins, the alkylation reaction of aromatic compounds, the isomerization reaction, the dehydration reaction of alcohols, the etherification reaction, the hydration reaction of olefins, etc. The service life is long, the catalytic effect is good, and the conditions of some catalytic reactions can also be significantly improved to make the reaction more mild. In addition, the catalyst has relatively low cost and the preparation method is simple and controllable.

[0168] The above solutions will be further described in combination with specific examples. It should be understood that these examples are used to illustrate the basic principles, main features and advantages of the present application, and the present application is not limited in scope by the following examples. The implementation conditions used in the examples can be further adjusted according to specific requirements. The implementation conditions not mentioned are usually the conditions in conventional experiments.

[0169] The raw materials used in the following examples, unless otherwise specified, are commercially available or prepared by conventional methods in the art, wherein the surfactant: P123 is purchased from Sigma-Aldrich.

[0170] Example 1

[0171] This example provides a method for preparing a catalyst and the catalyst prepared thereby. Specifically, the method for preparing the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring and uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven to dry overnight. The solid obtained after drying is placed in a muffle furnace and calcined at 350°C under an air atmosphere for 3 h at a heating rate of 5°C / min, to obtain the catalyst, which is denoted as H3PMo / AS-20H.

[0172] The obtained catalyst H3PMo / AS-20H is structurally characterized. The actual loading of phosphomolybdic acid in the catalyst is about 21.8%.

[0173] FIG. 1 is an XRD pattern of H3PMo / AS-20H. It is observed that no characteristic diffraction peak of the heteropoly acid molecule appears on the XRD, indicating that the proton-type heteropoly acid-phosphomolybdic acid is uniformly dispersed on the porous alumina support.

[0174] FIG. 2 is a TEM pattern of H3PMo / AS-20H. It can be seen that the catalyst is a three-dimensional porous hollow structure assembled by two-dimensional sheets, with a diameter of about 180 nm and a hollow part with a diameter of about 80 nm.

[0175] FIG. 3 is a STEM-HAADF image of H3PMo / AS-20H, and FIG. 4 is a corresponding histogram of the particle size distribution of the heteropoly acid. It is observed that there are phosphomolybdic acid single clusters with a size of about 0.71 nm distributed on the catalyst, indicating that the phosphomolybdic acid is monomolecularly dispersed on the catalyst H3PMo / AS-20H.

[0176] FIG. 5 is a nitrogen adsorption-desorption pattern of H3PMo / AS-20H. It is observed that the nitrogen adsorption-desorption pattern of the catalyst exhibits a typical type IV adsorption-desorption curve with a type I hysteresis loop, indicating that there are a large number of mesoporous structures in the catalyst.

[0177] The H3PMo / AS-20H catalyst is spherical with a diameter of about 180 nm, a specific surface area of about 701 m 2 / g, an average pore size of about 6.5 nm, an average pore volume of about 1.4 cc / g, and an average density of about 3.0 g / cm 3 .

[0178] Example 2

[0179] This example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphotungstic acid, mixing with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70 °C, obtaining a gel after 48 h, then placing in an oven to dry overnight. The obtained solid after drying is placed in a muffle furnace, calcined at 350 °C under an air atmosphere for 3 h with a heating rate of 5 °C / min, to obtain the catalyst, which is recorded as H3PW / AS-20H.

[0180] Example 3

[0181] This example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphotungstic acid, mixing with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70 °C, obtaining a gel after 48 h, then placing in an oven to dry overnight. The obtained solid after drying is placed in a muffle furnace, calcined at 350 °C under an air atmosphere for 3 h with a heating rate of 5 °C / min, to obtain the catalyst, which is recorded as H3PW / AS-20H.

[0182] Example 4

[0183] This example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphotungstic acid, mixing with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70 °C, obtaining a gel after 48 h, then placing in an oven to dry overnight. The obtained solid after drying is placed in a muffle furnace, calcined at 350 °C under an air atmosphere for 3 h with a heating rate of 5 °C / min, to obtain the catalyst, which is recorded as H3PW / AS-20H.

[0184] Example 5

[0185] The example provides a preparation method of a catalyst and the catalyst prepared by the method, and specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 14 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 °C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 °C under an air atmosphere for 3 h at a heating rate of 5 °C / min, and the catalyst is obtained and recorded as H3PMo / AS-14H.

[0186] Example 6

[0187] The example provides a preparation method of a catalyst and the catalyst prepared by the method, and specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 8 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 °C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 °C under an air atmosphere for 3 h at a heating rate of 5 °C / min, and the catalyst is obtained and recorded as H3PMo / AS-8H.

[0188] Example 7

[0189] The example provides a preparation method of a catalyst and the catalyst prepared by the method, and specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 2 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 °C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 °C under an air atmosphere for 3 h at a heating rate of 5 °C / min, and the catalyst is obtained and recorded as H3PMo / AS-2H.

[0190] Example 8

[0191] The example provides a preparation method of a catalyst and the catalyst prepared by the method, and specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 30 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 °C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 °C under an air atmosphere for 3 h at a heating rate of 5 °C / min, and the catalyst is obtained and recorded as H3PMo / AS-30H.

[0192] Example 9

[0193] The example provides a preparation method of a catalyst and the catalyst prepared by the method, and specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 30 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 °C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 °C under an air atmosphere for 3 h at a heating rate of 5 °C / min, and the catalyst is obtained and recorded as H3PMo / AS-30H.

[0194] Example 10

[0195] The example provides a preparation method of a catalyst and the catalyst prepared by the method, and specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 30 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 °C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 °C under an air atmosphere for 3 h at a heating rate of 5 °C / min, and the catalyst is obtained and recorded as H3PMo / AS-30H.

[0196] Example 11

[0197] The example provides a preparation method of a catalyst and the catalyst prepared by the method. Specifically, the preparation method of the catalyst comprises the following steps: 0.8 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 DEG C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 DEG C under an air atmosphere for 3 h at a heating rate of 5 DEG C / min, and the catalyst is obtained and recorded as 7% H3PMo / AS-20H.

[0198] Example 12

[0199] The example provides a preparation method of a catalyst and the catalyst prepared by the method. Specifically, the preparation method of the catalyst comprises the following steps: 0.8 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 DEG C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 DEG C under an air atmosphere for 3 h at a heating rate of 5 DEG C / min, and the catalyst is obtained and recorded as 7% H3PMo / AS-20H.

[0200] FIG. 6 is a TEM diagram of H3PMo / TiO2-20H, and it can be seen that the catalyst is a three-dimensional porous structure assembled by two-dimensional sheets.

[0201] The H3PMo / TiO2-20H catalyst is spherical, with a diameter of about 50 nm, a specific surface area of about 468 m 2 / g, an average pore size of about 8.9 nm, an average pore volume of about 1.1 cc / g, and an average density of about 4.0 g / cm 3 .

[0202] Example 13

[0203] The example provides a preparation method of a catalyst and the catalyst prepared by the method. Specifically, the preparation method of the catalyst comprises the following steps: 0.8 g of phosphomolybdic acid is mixed with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of aluminum isopropoxide are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 DEG C, and a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350 DEG C under an air atmosphere for 3 h at a heating rate of 5 DEG C / min, and the catalyst is obtained and recorded as 7% H3PMo / AS-20H.

[0204] Figure 7 is a TEM image of H3PMo / ZnO-20H.

[0205] The H3PMo / ZnO-20H catalyst is spherical with a diameter of about 297 nm, a specific surface area of about 510 m2 / g, an average pore size of about 6.5 nm, an average pore volume of about 1.2 cc / g, and an average density of about 4.9 g / cm3. 2 3

[0206] Example 14

[0207] This example provides a method for preparing a catalyst and the catalyst prepared thereby. Specifically, the method for preparing the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing the phosphomolybdic acid with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring and uniformly dispersing, sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, and then placing the gel in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace and calcined at 350°C for 3 h under an air atmosphere at a heating rate of 5°C / min, to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. The obtained solid is then placed in a muffle furnace and calcined at 300°C under an air atmosphere at a heating rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, and the catalyst is obtained after natural cooling, which is denoted as Pd-H3PMo / AS-20H.

[0208] The Pd-H3PMo / AS-20H obtained is subjected to structural characterization. The actual loading of phosphomolybdic acid in the catalyst is 22%, and the actual loading of palladium is 0.6%.

[0209] Figure 8 is an XRD image of Pd-H3PMo / AS-20H. It is observed that there are no characteristic diffraction peaks of the heteropoly acid molecules or palladium, indicating that the heteropoly acid and palladium are uniformly dispersed on the porous alumina support.

[0210] Figure 9 is an SEM image of Pd-H3PMo / AS-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled from two-dimensional sheets.

[0211] ​​Figure 10 is a TEM image of Pd-H3PMo / AS-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled by two-dimensional sheets, with a diameter of about 181 nm and a hollow part with a diameter of about 80 nm. No palladium particles are observed, indicating that palladium is highly dispersed.

[0212] Figure 11 is a STEM-HAADF image of Pd-H3PMo / AS-20H, and Figure 12 is a corresponding particle size distribution histogram. It is observed that the catalyst is distributed with phosphomolybdate single clusters with a size of about 0.71 nm, indicating that phosphomolybdate is monomolecularly dispersed on the catalyst Pd-H3PMo / AS-20H.

[0213] Figure 13 is a nitrogen adsorption-desorption graph of Pd-H3PMo / AS-20H. It is observed that the nitrogen adsorption-desorption graph of the catalyst exhibits a typical type IV adsorption-desorption curve with a type I hysteresis loop, indicating that there is a large amount of mesoporous structure in the catalyst.

[0214] The catalyst is spherical with a diameter of about 181 nm, a specific surface area of about 697 m 2 / g, an average pore size of 6.6 nm, an average pore volume of 1.3 cc / g, and an average density of 2.6 g / cm 3 .

[0215] Example 15

[0216] This example provides a catalyst preparation method and a catalyst prepared thereby. Specifically, the catalyst preparation method comprises: weighing 2.9 g of phosphotungstic acid, mixing with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, and uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, and then placing in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace and calcined at 350°C under an air atmosphere for 3 h at a heating rate of 5°C / min, to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere at a heating rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a pure H2 atmosphere at 250°C for 2 h, and after natural cooling, a catalyst is obtained, which is recorded as Pd-H3PW / AS-20H.

[0217] The catalyst is structurally characterized, and the actual loading of phosphotungstic acid in the catalyst is 22%, and the actual loading of palladium is 0.6%.

[0218] Figure 14 is an XRD pattern of Pd-H3PW / AS-20H, and it is observed that no characteristic diffraction peaks of heteropoly acid molecules or palladium are present, indicating that the heteropoly acid and palladium are uniformly dispersed on the catalyst;

[0219] Figure 15 is an SEM image of Pd-H3PW / AS-20H, and it is observed that the catalyst is a three-dimensional porous hollow structure assembled from two-dimensional sheets;

[0220] Figure 16 is a TEM image of Pd-H3PW / AS-20H, and it is observed that the catalyst is a three-dimensional porous hollow structure assembled from two-dimensional sheets, and no palladium particles are observed, indicating that the palladium is highly dispersed;

[0221] Figure 17 is a STEM-HAADF image of Pd-H3PW / AS-20H, and Figure 18 is a corresponding particle size distribution histogram, and it is observed that the catalyst is distributed with phosphotungstic acid single clusters with a size of about 0.71 nm, indicating that the phosphotungstic acid is monomolecularly dispersed on the catalyst Pd-H3PW / AS-20H;

[0222] Figure 19 is a nitrogen adsorption-desorption graph of Pd-H3PW / AS-20H, and it is observed that the nitrogen adsorption-desorption graph of the catalyst exhibits a typical type IV adsorption-desorption curve and has a type I hysteresis loop, indicating that a large amount of mesoporous structures are present in the catalyst;

[0223] The catalyst is spherical with a diameter of about 178 nm, a specific surface area of about 650 m 2 / g, an average pore size of 5.9 nm, an average pore volume of 1.1 cc / g, and an average density of 2.8 g / cm 3 .

[0224] Example 16

[0225] The example provides a preparation method of a catalyst and the catalyst prepared by the method. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of silicotungstic acid, mixing the silicotungstic acid with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70℃, obtaining a gel after 48 h, and then placing the gel in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace and calcined at 350℃ for 3 h under an air atmosphere at a temperature rising rate of 5℃ / min, to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate is dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the solution. After continuous stirring for 6 h, the mixture is heated to 40℃ until the acetone is completely evaporated. Then, the obtained solid is placed in a muffle furnace and calcined at 300℃ under an air atmosphere at a temperature rising rate of 5℃ / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250℃ for 2 h, and the catalyst is obtained after natural cooling, which is recorded as Pd-H4SiW / AS-20H.

[0226] The catalyst is structurally characterized, and the actual loading of silicotungstic acid in the catalyst is 23%, and the actual loading of palladium is 0.6%;

[0227] FIG. 20 is an XRD pattern of Pd-H4SiW / AS-20H. It is observed that no characteristic diffraction peak of the heteropoly acid molecule or palladium appears, indicating that the heteropoly acid and palladium are uniformly dispersed on the catalyst;

[0228] FIG. 21 is an SEM pattern of Pd-H4SiW / AS-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled by two-dimensional sheets;

[0229] FIG. 22 is a TEM pattern of Pd-H4SiW / AS-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled by two-dimensional sheets, and no palladium particles are observed, indicating that the palladium is highly dispersed;

[0230] FIG. 23 is a nitrogen adsorption / desorption pattern of Pd-H4SiW / AS-20H. It is observed that the nitrogen adsorption / desorption pattern of the catalyst exhibits a typical type IV adsorption / desorption curve and has a type I hysteresis loop, indicating that a large amount of mesoporous structures exist in the catalyst;

[0231] The catalyst is spherical with a diameter of about 175 nm, a specific surface area of about 647 m 2 / g, an average pore size of 5.8 nm, an average pore volume of 0.9 cc / g, and an average density of 3.0 g / cm 3 .

[0232] Example 17

[0233] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of silicomolybdic acid, mixing with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace, calcined at 350°C under an air atmosphere for 3 h with a heating rate of 5°C / min, to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere with a heating rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, and the catalyst is obtained after natural cooling, which is recorded as Pd-H4SiMo / AS-20H.

[0234] The catalyst is structurally characterized. The actual loading of silicomolybdic acid in the catalyst is 22%, and the actual loading of palladium is 0.5%;

[0235] FIG. 24 is an XRD pattern of Pd-H4SiMo / AS-20H. It is observed that no characteristic diffraction peaks of the heteropoly acid molecules or palladium are present, indicating that the heteropoly acid and palladium are uniformly dispersed on the catalyst;

[0236] FIG. 25 is an SEM image of Pd-H4SiMo / AS-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled from two-dimensional sheets;

[0237] FIG. 26 is a TEM image of Pd-H4SiMo / AS-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled from two-dimensional sheets, and no palladium particles are observed, indicating that the palladium is highly dispersed;

[0238] FIG. 27 is a nitrogen adsorption-desorption graph of Pd-H4SiMo / AS-20H. It is observed that the nitrogen adsorption-desorption graph of the catalyst exhibits a typical type IV adsorption-desorption curve with a type I hysteresis loop, indicating that a large amount of mesoporous structures are present in the catalyst;

[0239] The catalyst is spherical with a diameter of about 177 nm, a specific surface area of about 682 m 2 / g, an average pore size of 6.4 nm, an average pore volume of 1.2 cc / g, and an average density of 2.8 g / cm3 .

[0240] Example 18

[0241] The present example provides a method for preparing a catalyst and the catalyst prepared thereby. Specifically, the method for preparing the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 14 mL of deionized water, fully stirring and uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven to dry overnight. The solid obtained after drying is placed in a muffle furnace and calcined at 350°C under an air atmosphere for 3 h at a heating rate of 5°C / min, to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. The obtained solid is then placed in a muffle furnace and calcined at 300°C under an air atmosphere at a heating rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, and after natural cooling, a catalyst is obtained, which is recorded as Pd-H3PMo / AS-14H.

[0242] The obtained catalyst is structurally characterized, and the actual loading of phosphomolybdic acid in the catalyst is 22%, and the actual loading of palladium is 0.7%;

[0243] FIG. 28 is a TEM image of Pd-H3PMo / AS-14H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled from two-dimensional sheets, and it can be seen that the degree of hollow of the catalyst is reduced when the amount of water is reduced, and no palladium particles are observed, indicating that the palladium is highly dispersed;

[0244] The catalyst is spherical with a diameter of about 157 nm, a specific surface area of about 619 m 2 / g, an average pore size of 6.3 nm, an average pore volume of 1.0 cc / g, and an average density of 3.1 g / cm 3 .

[0245] Example 19

[0246] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 8 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace, calcined at 350°C under an air atmosphere for 3 h with a temperature rising rate of 5°C / min, to obtain a metal oxide loaded heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide loaded heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere with a temperature rising rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, to obtain the catalyst, which is recorded as Pd-H3PMo / AS-8H.

[0247] The catalyst is structurally characterized. The actual loading amount of phosphomolybdic acid in the catalyst is 22%, and the actual loading amount of palladium is 0.6%.

[0248] FIG. 29 is a TEM image. It is observed that as the amount of water added is further reduced, the hollow structure is no longer obvious. And no palladium particles are observed, indicating that the palladium is highly dispersed.

[0249] The catalyst is spherical with a diameter of about 152 nm, a specific surface area of about 384 m 2 / g, an average pore size of about 6.6 nm, an average pore volume of about 0.7 cc / g, and an average density of about 3.3 g / cm 3 .

[0250] Example 20

[0251] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 2 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace, calcined at 350°C under an air atmosphere for 3 h with a temperature rising rate of 5°C / min, to obtain a metal oxide loaded heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide loaded heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere with a temperature rising rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, to obtain the catalyst, which is recorded as Pd-H3PMo / AS-2H.

[0252] The obtained catalyst is structurally characterized. The actual loading amount of phosphomolybdic acid in the catalyst is 23%, and the actual loading amount of palladium is 0.6%.

[0253] FIG. 30 is a TEM image. It is observed that when the water amount is reduced to 2 mL, the hollow degree is low, and no palladium particles are observed, indicating that the palladium is highly dispersed.

[0254] The catalyst is spherical with a diameter of about 141 nm, a specific surface area of about 573 m2 / g, an average pore size of about 5.5 nm, an average pore volume of about 0.8 cc / g, and an average density of about 2.9 g / cm3. 2 3 .

[0255] Example 21

[0256] ​The present example provides a catalyst preparation method and a catalyst prepared thereby. Specifically, the catalyst preparation method comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 30 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven to dry overnight. The obtained solid after drying is placed in a muffle furnace, calcined at 350°C under an air atmosphere for 3 h with a heating rate of 5°C / min, to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere with a heating rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, to obtain the catalyst, which is recorded as Pd-H3PMo / AS-30H.

[0257] The obtained catalyst is structurally characterized, and the actual loading of phosphomolybdic acid in the catalyst is 22%, and the actual loading of palladium is 0.6%.

[0258] FIG. 31 is a TEM image of Pd-H3PMo / AS-30H. It is observed that the catalyst has a three-dimensional porous structure, and no palladium particles are observed, indicating that palladium is highly dispersed.

[0259] The specific surface area of the catalyst is about 480 m 2 / g, the average pore size is 9.2 nm, the average pore volume is 1.1 cc / g, and the average density is 3.1 g / cm 3 .

[0260] Example 22

[0261] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 50 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace, calcined at 350°C under an air atmosphere for 3 h with a temperature rising rate of 5°C / min, to obtain a metal oxide loaded heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide loaded heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere with a temperature rising rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, to obtain the catalyst, which is recorded as Pd-H3PMo / AS-50H.

[0262] The obtained catalyst is structurally characterized. The actual loading amount of phosphomolybdic acid in the catalyst is 22%, and the actual loading amount of palladium is 0.5%.

[0263] FIG. 32 is a TEM image of Pd-H3PMo / AS-50H. It is observed that the catalyst has a three-dimensional porous structure, and no palladium particles are observed, indicating that palladium is highly dispersed.

[0264] The catalyst is in the form of nanosheets, the specific surface area is about 402 m 2 / g, the average pore size is about 8.6 nm, the average pore volume is about 1.0 cc / g, and the average density is about 3.3 g / cm 3 .

[0265] Example 23

[0266] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 100 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace, calcined at 350°C under an air atmosphere for 3 h with a heating rate of 5°C / min, to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere with a heating rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, to obtain the catalyst, which is recorded as Pd-H3PMo / AS-100H.

[0267] The obtained catalyst is structurally characterized. The actual loading of phosphomolybdic acid in the catalyst is 23%, and the actual loading of palladium is 0.6%.

[0268] FIG. 33 is a TEM image of Pd-H3PMo / AS-100H. It is observed that the catalyst has a three-dimensional porous structure, and no palladium particles are observed, indicating that palladium is highly dispersed.

[0269] The catalyst is in the form of nanosheets, the specific surface area is about 441 m 2 / g, the average pore size is about 11.7 nm, the average pore volume is about 1.29 cc / g, and the average density is about 3.2 g / cm 3 .

[0270] Example 24

[0271] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing in an oven for drying overnight. Placing the obtained solid after drying in a muffle furnace, calcining at 350°C under an air atmosphere for 3 h with a heating rate of 5°C / min, obtaining a metal oxide supported heteropoly acid. Adding 31.2 mL of a platinum acetylacetone solution (100 mg of platinum acetylacetone dissolved in 100 mL of acetone) into 150 mL of acetone, fully stirring. Then, ultrasonically dispersing 3 g of the metal oxide supported heteropoly acid in the above solution. After continuously stirring for 6 h, heating the mixture to 40°C until the acetone is completely evaporated. Then placing the obtained solid in a muffle furnace, calcining at 300°C under an air atmosphere with a heating rate of 5°C / min for 2 h. Next, reducing the obtained sample in a muffle furnace under a pure H2 atmosphere at 200°C for 2 h, obtaining the catalyst after natural cooling, which is recorded as Pt-H3PMo / AS-20H.

[0272] The obtained catalyst is structurally characterized. The actual loading of phosphomolybdic acid in the catalyst is 22%, and the actual loading of platinum is 0.6%.

[0273] FIG. 34 is an XRD pattern of Pt-H3PMo / AS-20H. It is observed that no characteristic diffraction peaks of heteropoly acid molecules or platinum are present, indicating that the heteropoly acid and platinum are uniformly dispersed on the catalyst.

[0274] FIG. 35 is a TEM image of Pt-H3PMo / AS-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled by two-dimensional sheets, and no palladium particles are observed, indicating that the platinum is highly dispersed.

[0275] The catalyst is spherical with a diameter of about 180 nm, a specific surface area of about 690 m 2 / g, an average pore size of about 6.7 nm, an average pore volume of about 1.3 cc / g, and an average density of about 2.7 g / cm 3 .

[0276] Example 25

[0277] The example provides a preparation method of a catalyst and the catalyst prepared by the method. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing the phosphomolybdic acid with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70 °C, obtaining a gel after 48 h, then placing the gel in an oven for drying overnight. Placing the obtained solid after drying in a muffle furnace, calcining at 350 °C under an air atmosphere for 3 h at a temperature rising rate of 5 °C / min, to obtain a metal oxide loaded heteropoly acid. Adding 31.2 mL of a cobalt nitrate solution (100 mg of cobalt nitrate is dissolved in 100 mL of acetone) into 150 mL of acetone and fully stirring. Then, 3 g of the metal oxide loaded heteropoly acid is ultrasonically dispersed in the solution. After continuous stirring for 6 h, the mixture is heated to 40 °C until the acetone is completely evaporated. Then, the obtained solid is placed in a muffle furnace and calcined at 300 °C under an air atmosphere at a temperature rising rate of 5 °C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250 °C for 2 h, to obtain the catalyst, which is recorded as Co-H3PMo / AS-20H.

[0278] The obtained catalyst is structurally characterized. The actual loading amount of the phosphomolybdic acid in the catalyst is 23%, and the actual loading amount of cobalt is 0.7%.

[0279] FIG. 36 is an XRD pattern of Co-H3PMo / AS-20H. It is observed that no characteristic diffraction peak of the heteropoly acid molecule or cobalt is observed, indicating that the heteropoly acid and cobalt are uniformly dispersed on the catalyst.

[0280] Example 26

[0281] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing the phosphomolybdic acid with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 48 h, then placing the gel in an oven for drying overnight. Placing the obtained solid after drying in a muffle furnace, calcining at 350°C under an air atmosphere for 3 h at a temperature increasing rate of 5°C / min, to obtain a metal oxide loaded heteropoly acid. Adding 31.2 mL of a nickel nitrate solution (100 mg of nickel nitrate dissolved in 100 mL of acetone) into 150 mL of acetone and fully stirring. Then, dispersing 3 g of the metal oxide loaded heteropoly acid in the solution by ultrasonic. After continuously stirring for 6 h, heating the mixture to 40°C until the acetone is completely evaporated. Then placing the obtained solid in a muffle furnace, calcining at 300°C under an air atmosphere at a temperature increasing rate of 5°C / min for 2 h. Next, reducing the obtained sample in a pure H2 atmosphere of a muffle furnace at 250°C for 2 h, to obtain the catalyst, which is recorded as Ni-H3PMo / AS-20H.

[0282] The obtained catalyst is subjected to structural characterization. The actual loading amount of the phosphomolybdic acid in the catalyst is 23%, and the actual loading amount of nickel is 0.5%.

[0283] FIG. 37 is an XRD pattern of the Ni-H3PMo / AS-20H, and it is observed that no characteristic diffraction peak of the heteropoly acid molecule or nickel is present, indicating that the heteropoly acid and nickel are uniformly dispersed on the catalyst.

[0284] Examples 27-35

[0285] The present examples provide a preparation method of a catalyst and the catalyst prepared thereby, which are basically the same as those of Example 14, and the only difference is that some raw materials or their amounts are different, which can be seen from Table 1.

[0286] Table 1

[0287] Example 36

[0288] The example provides a preparation method of a catalyst and the catalyst prepared by the method. Specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is weighed and mixed with 500 mL of anhydrous ethanol and 20 mL of deionized water, and then stirred sufficiently and uniformly dispersed; 20 g of P123, 31.2 mg of palladium nitrate and 50 g of aluminum isopropoxide are sequentially added; the mixture is sufficiently reacted at room temperature for 24 h; then solvent evaporation induction is performed at 70 °C for 48 h to obtain a gel; and then the gel is placed in an oven for drying overnight. The obtained solid after drying is calcined in a muffle furnace at 350 °C for 3 h under an air atmosphere, and the heating rate is 5 °C / min to obtain a metal oxide loaded heteropoly acid. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250 °C for 2 h, and the catalyst is obtained after natural cooling, which is recorded as Pd@H3PMo / AS-20H.

[0289] The obtained catalyst is structurally characterized. The actual loading amount of phosphomolybdic acid in the catalyst is 23%, and the actual loading amount of palladium is 0.7%.

[0290] FIG. 38 is an XRD pattern of Pd@H3PMo / AS-20H. It is observed that no characteristic diffraction peak of the heteropoly acid molecule or palladium appears, indicating that the heteropoly acid and palladium are uniformly dispersed on the catalyst.

[0291] FIG. 39 is a TEM pattern of Pd@H3PMo / AS-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled by two-dimensional sheets, and no palladium particles are observed, indicating that palladium is highly dispersed.

[0292] The catalyst is spherical, with a diameter of about 166 nm, a specific surface area of about 625 m 2 / g, an average pore size of about 6.7 nm, an average pore volume of about 1.1 cc / g, and an average density of about 3.1 g / cm 3 .

[0293] Example 37

[0294] The example provides a catalyst preparation method and a catalyst prepared thereby. Specifically, the catalyst preparation method comprises: weighing 2.9 g of phosphomolybdic acid, mixing the phosphomolybdic acid with 500 mL of anhydrous isopropyl alcohol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of P123 and 50 g of aluminum isopropyl alcohol, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 85°C, obtaining a gel after 48 h, and then placing the gel in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace, calcined at 350°C under an air atmosphere for 3 h at a temperature rising rate of 5°C / min, to obtain a metal oxide loaded heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide loaded heteropoly acid is ultrasonically dispersed in the solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then, the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere at a temperature rising rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, to obtain the catalyst, which is recorded as Pd-H3PMo / AS-20H-85.

[0295] The obtained catalyst is structurally characterized. The actual loading amount of phosphomolybdic acid in the catalyst is 23%, and the actual loading amount of palladium is 0.6%.

[0296] FIG. 40 is a TEM image of Pd-H3PMo / AS-20H-85. It is observed that the catalyst has a hollow porous spherical structure, and no palladium particles are observed, indicating that the palladium is highly dispersed.

[0297] Example 38

[0298] The example provides a preparation method of a catalyst and the catalyst prepared by the method, and specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is weighed, mixed with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of triisobutyl aluminum are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 °C, a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace, calcined at 350 °C under an air atmosphere for 3 h at a temperature rising rate of 5 °C / min, and a metal oxide supported heteropoly acid is obtained. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate is dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the solution. After continuous stirring for 6 h, the mixture is heated to 40 °C until the acetone is completely evaporated. Then, the obtained solid is placed in a muffle furnace and calcined at 300 °C under an air atmosphere at a temperature rising rate of 5 °C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250 °C for 2 h, and a catalyst is obtained after natural cooling, which is recorded as Pd-H3PMo / AS-20H-T.

[0299] Example 39

[0300] The example provides a preparation method of a catalyst and the catalyst prepared by the method, and specifically, the preparation method of the catalyst comprises the following steps: 2.9 g of phosphomolybdic acid is weighed, mixed with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirred, uniformly dispersed, 20 g of P123 and 50 g of triisobutyl aluminum are sequentially added, fully reacted at room temperature for 24 h, then solvent evaporation induction is performed at 70 °C, a gel is obtained after 48 h, and then the gel is placed in an oven for drying overnight. The obtained solid after drying is placed in a muffle furnace, calcined at 350 °C under an air atmosphere for 3 h at a temperature rising rate of 5 °C / min, and a metal oxide supported heteropoly acid is obtained. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate is dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the solution. After continuous stirring for 6 h, the mixture is heated to 40 °C until the acetone is completely evaporated. Then, the obtained solid is placed in a muffle furnace and calcined at 300 °C under an air atmosphere at a temperature rising rate of 5 °C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250 °C for 2 h, and a catalyst is obtained after natural cooling, which is recorded as Pd-H3PMo / AS-20H-T.

[0301] Example 40

[0302] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of F127 and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C, obtaining a gel after 72 h, then placing in an oven for drying overnight. The solid obtained after drying is placed in a muffle furnace, calcined at 350°C under an air atmosphere for 3 h with a heating rate of 5°C / min, to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere with a heating rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, to obtain the catalyst, which is recorded as Pd-H3PMo / AS-F-20H.

[0303] The obtained catalyst is structurally characterized. The actual loading of phosphomolybdic acid in the catalyst is 22%, and the actual loading of palladium is 0.6%.

[0304] FIG. 41 is a TEM image of Pd-H3PMo / AS-F-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled from two-dimensional sheets, and no palladium particles are observed, indicating that palladium is highly dispersed.

[0305] The catalyst is spherical with a diameter of about 174 nm, a specific surface area of about 630 m 2 / g, an average pore size of about 7.1 nm, an average pore volume of about 1.2 cc / g, and an average density of about 3.1 g / cm 3 .

[0306] Example 41

[0307] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation method of the catalyst comprises: weighing 2.9 g of phosphomolybdic acid, mixing the phosphomolybdic acid with 500 mL of anhydrous ethanol and 20 mL of deionized water, fully stirring, uniformly dispersing, then sequentially adding 20 g of hexadecyl trimethyl ammonium bromide (CTAB) and 50 g of aluminum isopropoxide, fully reacting at room temperature for 24 h, then performing solvent evaporation induction at 70°C for 10 h to obtain a gel, and then placing the gel in an oven for drying overnight. The solid obtained after drying is calcined in a muffle furnace at 350°C for 3 h under an air atmosphere at a heating rate of 5°C / min to obtain a metal oxide supported heteropoly acid. 31.2 mL of a palladium nitrate solution (100 mg of palladium nitrate dissolved in 100 mL of acetone) is added to 150 mL of acetone and fully stirred. Then, 3 g of the metal oxide supported heteropoly acid is ultrasonically dispersed in the above solution. After continuous stirring for 6 h, the mixture is heated to 40°C until the acetone is completely evaporated. Then, the obtained solid is placed in a muffle furnace and calcined at 300°C under an air atmosphere at a heating rate of 5°C / min for 2 h. Next, the obtained sample is reduced in a muffle furnace under a pure H2 atmosphere at 250°C for 2 h, and the catalyst is obtained after natural cooling, which is denoted as Pd-H3PMo / AS-C-20H.

[0308] The obtained catalyst is structurally characterized. The actual loading of phosphomolybdic acid in the catalyst is 23%, and the actual loading of palladium is 0.5%.

[0309] FIG. 42 is a TEM image of Pd-H3PMo / AS-C-20H. It is observed that the catalyst is a three-dimensional porous hollow structure assembled from two-dimensional sheets, and no palladium particles are observed, indicating that the palladium is highly dispersed.

[0310] The catalyst is spherical with a diameter of about 173 nm, a specific surface area of about 641 m 2 / g, an average pore size of about 6.9 nm, an average pore volume of about 1.2 cc / g, and an average density of about 3.2 g / cm 3 .

[0311] Comparative Example 1

[0312] The present example provides a preparation method of a catalyst and the catalyst prepared thereby. Specifically, the preparation steps comprise:

[0313] 20 g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) is placed in 400 mL of anhydrous ethanol, and 2.2 g of phosphomolybdic acid is dispersed in 80 mL of anhydrous ethanol and added dropwise to the ethanol solution of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer at a uniform speed, and stirred and mixed to obtain a first configuration.

[0314] The first configuration was stirred for 6 h to obtain a second configuration.

[0315] The second configuration was aged in an oven at 60°C for 48 h to obtain a solid mixture, and the solid mixture was calcined in an air furnace at a calcination temperature of 350°C, a temperature rising rate of 1°C / min, and a calcination time of 4 h to obtain the catalyst H3PMo@AS.

[0316] FIG. 43 is an XRD image of the H3PMo@AS prepared in this example. As can be seen from the figure, diffraction peaks of the heteropoly acid appear, indicating that the heteropoly acid is not dispersed in a monomolecular state on the catalyst.

[0317] Comparative Example 2

[0318] The preparation was basically the same as in Example 14, except that phosphomolybdic acid was replaced by the same mass of an aprotic heteropoly acid, ammonium phosphomolybdate. The obtained catalyst was recorded as Pd-APMo / AS-20H.

[0319] The obtained catalyst was subjected to structural characterization. The actual loading of ammonium phosphomolybdate in the catalyst was about 21%, and the actual loading of palladium was about 0.3%.

[0320] FIG. 44 is an XRD image of Pd-APMo / AS-20H. It was observed that the XRD spectrum of the composite sample had characteristic diffraction peaks of ammonium phosphomolybdate, indicating that the aprotic heteropoly acid-heteropoly acid salt form could not achieve monodispersion on the porous alumina carrier. This can be attributed to the lack of proton H + At this time, the interaction between the raw materials was insufficient, resulting in poor dispersion of the aprotic heteropoly acid-heteropoly salt salt form.

[0321] FIG. 45 is a TEM image of Pd-APMo / AS-20H. It was observed that the catalyst was basically a two-dimensional nanosheet structure.

[0322] Comparative Example 3

[0323] The preparation was basically the same as in Example 1, except that deionized water was replaced by the same volume of anhydrous ethanol. The obtained catalyst was recorded as H3PMo / AS-ethanol.

[0324] FIG. 46 is a TEM image of H3PMo / AS-ethanol. The results show that a solid structure can only be obtained without water, proving that water is a necessary condition for forming a hollow structure.

[0325] Application Example 1

[0326] The catalysts prepared in Examples 1-13 and Comparative Examples 1 and 3 were evaluated in a 2-methylbutyraldehyde selective oxidation reaction to prepare 2-methylbutyric acid in a reaction kettle, and the operation process was as follows:

[0327] The operation process is as follows: 4 g of the catalyst and 800 g of 2-methylbutyraldehyde are sequentially added into a 2 L reaction kettle, and after nitrogen replacement, oxygen is continuously introduced at a flow rate of 30 mL / min, and the temperature is increased to 45°C for reaction. After 8 hours of reaction, the reaction is stopped. The product is separated and analyzed by using a Shimadzu GC2014 gas chromatograph, wherein the chromatographic column is HP-INNOWax, and the detector is an FID detector. The conversion rate of 2-methylbutyraldehyde and the selectivity of 2-methylbutyric acid are calculated by using a normalization method, and the calculation results are shown in Table 2.

[0328] Table 2

[0329] Application Example 2

[0330] The catalytic performance of the catalysts prepared in Examples 1-13 and Comparative Examples 1 and 3 in the esterification reaction of lauric diacid and methanol to prepare lauric diacid dimethyl ester is evaluated by using a reaction kettle, and the operation process is as follows:

[0331] In a 100 mL high-pressure reaction kettle, 0.02 g of the catalyst, 10 g of lauric diacid, and 30 g of methanol are sequentially added, and the temperature is increased to 60°C for 12 h of reaction. The reaction product is separated and analyzed by using a Shimadzu GC2014 gas chromatograph, wherein the chromatographic column is HP-INNOWax, and the detector is an FID detector. The conversion rate of lauric diacid and the selectivity of lauric diacid dimethyl ester are calculated by using a normalization method. The specific results are shown in Table 3.

[0332] Table 3

[0333] Application Example 3

[0334] The performance of the catalysts prepared in Examples 1-14, Example 25, Example 26, and Comparative Examples 1-3 in the continuous alkylation of propylene and m-cresol to prepare thymol is evaluated: a stainless steel pipe is used as the reactor, wherein the outer diameter is 16 mm, the inner diameter is 12 mm, the length is 600 mm, and the catalyst loading is 10 g. The reaction conditions are as follows: the reaction temperature is 220°C, the reaction pressure is 0.2 MPa, the mass hourly space velocity of m-cresol is 2.5 h -1 , the molar ratio of propylene to m-cresol is 0.6:1, and the operation is performed for 200 h.

[0335] The specific results are shown in Table 4.

[0336] Table 4

[0337] Application Example 4 (ortho-tert-butyl phenol hydrogenation reaction)

[0338] (1) The performance of the catalysts prepared in Examples 14-23, Example 33, Examples 36-41 and Comparative Example 2 in the reaction of preparing o-tert-butylcyclohexanol by hydrogenating o-tert-butylphenol was evaluated, and the operation process was as follows: a stainless steel tube with an outer diameter of 16 mm, an inner diameter of 12 mm and a length of 600 mm was used as the reactor, and the catalyst loading was 10 g. The reaction pressure was 3 MPa, the reaction temperature was 80-85 °C, the mass liquid hourly space velocity (LHSV) of o-tert-butylphenol was 1 h -1 , hydrogen was used as the hydrogenation agent, and the molar ratio of hydrogen to o-tert-butylphenol was 5:1.

[0339] The specific results are shown in Table 5.

[0340] Table 5

[0341] Application Example 5 (hydrogenation reaction of cyclopentybutyrolactone)

[0342] (1) The performance of the catalysts prepared in Examples 14-23, Example 33, Examples 36-41 and Comparative Example 2 in the reaction of preparing o-tert-butylcyclohexanol by hydrogenating o-tert-butylphenol was evaluated, and the operation process was as follows: a stainless steel tube with an outer diameter of 16 mm, an inner diameter of 12 mm and a length of 600 mm was used as the reactor, and the catalyst loading was 10 g. The reaction pressure was 3 MPa, the reaction temperature was 80-85 °C, the mass liquid hourly space velocity (LHSV) of o-tert-butylphenol was 1 h -1 , hydrogen was used as the hydrogenation agent, and the molar ratio of hydrogen to o-tert-butylphenol was 5:1.

[0343] The reaction formula is:

[0344] The specific results are shown in Table 6-1.

[0345] Table 6-1

[0346] (2) Cycle stability test:

[0347] The catalytic reaction was carried out in a fixed bed reactor, the mass space velocity of cyclopentybutyrolactone was 0.5 h -1 , the molar ratio of methanol to cyclopentybutyrolactone was 5:1, the molar ratio of hydrogen to cyclopentybutyrolactone was 20:1, the catalyst loading was 8 g, the reaction temperature was 145 °C, and the reaction pressure was 4 MPa. The conversion and selectivity results of each running time stage are shown in Table 6-2.

[0348] Table 6-2

[0349] Application Example 6 (preparation of 2-pentylcyclopentenone by hydrogenation isomerization of 2-pentylidene cyclopentanone)

[0350] The reaction performance of the catalyst prepared in Example 14-23, Example 33, Example 36-41 and Comparative Example 2 in the preparation of 2-pentyl cyclopentenone by hydrogen isomerization of 2-pentylidene cyclopentanone was evaluated, and the operation process was as follows: 6 g of the catalyst, 1200 g of 2-pentylidene cyclopentanone, and nitrogen were sequentially added into a 2 L reaction kettle, hydrogen was continuously introduced after replacement of nitrogen, the hydrogen flow rate was 200 mL / min, then the temperature was increased to 40°C, and constant temperature reaction was performed for 12 h. After the product was separated, Agilent 7890 gas chromatograph was used for analysis, wherein the chromatographic column was HP-INNOWax, and the detector was FID detector.

[0351] The reaction formula was as follows:

[0352] The specific results are shown in Table 7.

[0353] Table 7

[0354] Application Example 7 (Preparation of phenylvalol by hydrogenation of rose oxide)

[0355] The reaction performance of the catalyst prepared in Example 24 in the preparation of phenylvalol by hydrogenation of rose oxide was evaluated, and the operation process was as follows: 0.1 g of the catalyst and 50 g of rose oxide were sequentially added into a 100 mL high-pressure reaction kettle, hydrogen was replaced after replacement of nitrogen, and then the pressure was increased to 3 MPa, then the temperature was increased to 140°C, and reaction was performed for 12 h. After the product was separated, Agilent 7890 gas chromatograph was used for analysis, wherein the chromatographic column was HP-INNOWax, and the detector was FID detector. The conversion rate and selectivity were calculated by normalization method.

[0356] The reaction formula was as follows:

[0357] The specific results are shown in Table 8.

[0358] Table 8

[0359] Application Example 8 (Preparation of ethylamine by hydrogenation of ethanol)

[0360] The performance of the catalyst prepared in Example 25 in the preparation of ethylamine by hydrogenation of ethanol was evaluated: a stainless steel tube was used as the reactor, the outer diameter was 16 mm, the inner diameter was 12 mm, the length was 600 mm, and the catalyst loading was 10 g. The reaction conditions were as follows: the reaction temperature was 140°C, the reaction pressure was 0.4 MPa, the mass liquid hourly space velocity of ethanol was 0.5 h -1 , and the molar ratio of ammonia to alcohol was 1:1. After the product was separated, Agilent 7890 gas chromatograph was used for analysis, wherein the chromatographic column was HP-INNOWax, and the detector was TCD detector.

[0361] The reaction formula was as follows:

[0362] The specific results are shown in Table 9.

[0363] Table 9

[0364] Note: The ethylamine selectivity refers to the total selectivity of monoethylamine + diethylamine + triethylamine.

[0365] Application Example 9 (Preparation of isopropylamine by ammination of acetone)

[0366] The performance of the catalyst prepared in Example 26 in the reaction of preparing isopropylamine by ammination of acetone was evaluated. A stainless steel tube was used as the reactor, with an outer diameter of 16 mm, an inner diameter of 12 mm, and a length of 600 mm, and the catalyst loading was 10 g. The reaction conditions were as follows: a reaction temperature of 90°C, a reaction pressure of 0.4 MPa, a mass hourly space velocity of acetone of 2 h -1 -1, a molar ratio of ammonia to acetone of 2:1, and a molar ratio of hydrogen to acetone of 1.5:1. After the product was separated, it was analyzed using an Agilent 7890 gas chromatograph, with an HP-INNOWax column and a TCD detector.

[0367] The reaction equation is as follows:

[0368] The specific results are shown in Table 10.

[0369] Table 10

[0370] Note: The isopropylamine selectivity refers to the total selectivity of monoisopropylamine and diisopropylamine.

[0371] Application Example 10 (Preparation of tert-butylamine by ammination of isobutylene)

[0372] The performance of the catalyst prepared in Example 26 in the reaction of preparing tert-butylamine by ammination of isobutylene was evaluated. A stainless steel tube was used as the reactor, with an outer diameter of 16 mm, an inner diameter of 12 mm, and a length of 600 mm, and the catalyst loading was 10 g. The reaction conditions were as follows: a reaction temperature of 170°C, a reaction pressure of 6 MPa, a mass hourly space velocity of isobutylene of 0.5 h -1 -1, and a molar ratio of ammonia to isobutylene of 1:1. After the product was separated, it was analyzed using an Agilent 7890 gas chromatograph, with an HP-INNOWax column and a TCD detector.

[0373] The reaction equation is as follows:

[0374] The specific results are shown in Table 11.

[0375] Table 11

[0376] Application Example 11

[0377] The performance of the catalysts prepared in Examples 1-4, 14-17 and Comparative Examples 1-3 was evaluated in the oxidation reaction of benzyl alcohol with hydrogen peroxide, and the operation process was as follows: 10 g of the catalyst, 600 g of benzyl alcohol, 620 mL of 30% by mass hydrogen peroxide and 1000 mL of acetonitrile were sequentially added into a 5 L round bottom flask, and the condensation reflux was performed, and the temperature was raised to 60°C for 10 h of reaction.

[0378] The reaction formula was as follows:

[0379] The specific results are shown in Table 12.

[0380] Table 12

[0381] Application Example 12 (selective oxidation reaction of C3-C10 aldehyde)

[0382] The performance of the catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 was evaluated in the reaction of selective oxidation of C3-C10 aldehyde to prepare the corresponding acid, and the operation process was as follows: 4 g of the catalyst and 800 g of the substrate were sequentially added into a 2 L reaction kettle, and after nitrogen replacement, oxygen was continuously introduced, the oxygen flow rate was 30 mL / min, the temperature was raised to 45°C for reaction, and the reaction was stopped after 8 h of reaction. After the product was separated, it was analyzed by Shimadzu GC2014 gas chromatograph, wherein the chromatographic column was HP-INNOWax, and the detector was FID detector.

[0383] The specific results are shown in Table 13.

[0384] Table 13

[0385] Application Example 13 (selective oxidation of alcohol to prepare acid)

[0386] The performance of the catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 was evaluated in the reaction of selective oxidation of alcohol to prepare acid, and the operation process was as follows: 4 g of the catalyst and 800 g of the substrate were sequentially added into a 2 L reaction kettle, and after nitrogen replacement, oxygen was continuously introduced, the pressure was raised to 0.5 MPa, the oxygen flow rate was 50 mL / min, the temperature was raised to 95°C for reaction, and the reaction was stopped after 8 h of reaction. After the product was separated, it was analyzed by Shimadzu GC2014 gas chromatograph, wherein the chromatographic column was HP-INNOWax, and the detector was FID detector. The conversion rate and selectivity were calculated by normalization method.

[0387] The specific results are shown in Table 14.

[0388] Table 14

[0389] Application Example 14 (Preparation of aromatic acid by selective oxidation of aromatic hydrocarbon)

[0390] The performance of the catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 in the reaction of preparing aromatic acid by selective oxidation of aromatic hydrocarbon was evaluated, and the operation process was as follows: 4 g of catalyst and 800 g of substrate were sequentially added into a 2 L reaction kettle, and after nitrogen replacement, oxygen was continuously introduced, the pressure was increased to 2 MPa, the oxygen flow rate was 50 mL / min, and the temperature was increased to 145°C for reaction. After 8 hours of reaction, the reaction was stopped. The product was separated and analyzed by Shimadzu GC2014 gas chromatograph, wherein the chromatographic column was HP-INNOWax, and the detector was FID detector. The conversion rate and selectivity were calculated by normalization method.

[0391] The specific results are shown in Table 15.

[0392] Table 15

[0393] Application Example 15 (Esterification reaction)

[0394] The performance of the catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 in the esterification reaction of 2-methylbutyric acid with methanol, ethanol, isopropanol, n-butanol and n-hexanol was evaluated, and the operation process was as follows: 0.1 g of catalyst and 20 g of 2-methylbutyric acid, and the corresponding alcohol (controlling the molar ratio of acid to alcohol to be 0.7:1) were sequentially added into a 100 mL high-pressure reaction kettle, and the temperature was increased to 65°C for 6 h of reaction. The product was separated and analyzed by Agilent 7890 gas chromatograph, wherein the chromatographic column was HP-INNOWax, and the detector was FID detector. The conversion rate and selectivity were calculated by normalization method.

[0395] The specific results are shown in Table 16 (the conversion rate is the conversion rate of 2-methylbutyric acid, and the selectivity is the selectivity of the corresponding ester prepared).

[0396] Table 16

[0397] Application Example 16 (Esterification reaction)

[0398] The catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 were evaluated for their performance in the esterification reaction of salicylic acid with n-pentanol, n-hexanol, benzyl alcohol, leaf alcohol, cyclohexanol, isooctanol, isophorone. The operation process was as follows: 4 g of catalyst and 800 g of salicylic acid, and the corresponding alcohol (controlling the molar ratio of acid to alcohol to be 0.95:1) were sequentially added into a 2 L reaction kettle, which was heated to 80°C, and the system pressure was controlled at 500 mmHg, and the generated water was removed through a water trap, and the oil phase was refluxed, and the reaction was carried out for 6 hours. After the product was separated, it was analyzed by Agilent 1260 liquid chromatograph. The conversion rate and selectivity were calculated by normalization method.

[0399] The specific results are shown in Table 17 (the conversion rate is the conversion rate of salicylic acid, and the selectivity is the selectivity of the corresponding ester prepared).

[0400] Table 17

[0401] Application Example 17 (esterification reaction)

[0402] The catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 were evaluated for their performance in the esterification reaction of salicylic acid with n-pentanol, n-hexanol, benzyl alcohol, leaf alcohol, cyclohexanol, isooctanol, isophorone. The operation process was as follows: 4 g of catalyst and 800 g of salicylic acid, and the corresponding alcohol (controlling the molar ratio of acid to alcohol to be 0.95:1) were sequentially added into a 2 L reaction kettle, which was heated to 80°C, and the system pressure was controlled at 500 mmHg, and the generated water was removed through a water trap, and the oil phase was refluxed, and the reaction was carried out for 6 hours. After the product was separated, it was analyzed by Agilent 1260 liquid chromatograph. The conversion rate and selectivity were calculated by normalization method.

[0403] The specific results are shown in Table 18.

[0404] Table 18

[0405] Application Example 18 (esterification reaction)

[0406] The catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 were evaluated for their performance in catalyzing the esterification of acetic acid with o-tert-butylcyclohexanol, p-tert-butylcyclohexanol, a-phenylethanol and β-phenylethanol. The operation process was as follows: 4 g of catalyst and 800 g of acetic acid and the corresponding alcohol (the molar ratio of acid to alcohol was controlled to be 1.2) were sequentially added into a 2 L reactor, which was heated to 80 °C, and the vacuum degree of the system was controlled to be 500 mmHg. The generated water was removed through a water trap, and the oil phase was refluxed. The reaction was carried out for 6 h. After the product was separated, Agilent 7890 gas chromatography was used for analysis, in which the chromatographic column was HP-INNOWax, and the detector was FID detector. The conversion rate and selectivity were calculated by normalization method.

[0407] The specific results are shown in Table 19.

[0408] Table 19

[0409] Application Example 19 (esterification reaction)

[0410] The catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 were evaluated for their performance in catalyzing the esterification of acetic acid, propionic acid, n-butyric acid, isobutyric acid and dicyclopentadiene. The operation process was as follows: 4 g of catalyst and 800 g of dicyclopentadiene and the corresponding acid (the molar ratio of acid to alkene was controlled to be 1.2:1) were sequentially added into a 2 L reactor, which was heated to 80 °C, and the reaction was carried out for 6 h. After the product was separated, Agilent 7890 gas chromatography was used for analysis, in which the chromatographic column was HP-INNOWax, and the detector was FID detector. The conversion rate and selectivity were calculated by normalization method.

[0411] The specific results are shown in Table 20.

[0412] Table 20

[0413] Application Example 20

[0414] (1) Preparation of epoxy pinane by reacting a-pinene with hydrogen peroxide

[0415] The catalysts prepared in Examples 14-26, Example 33, Examples 36-41 and Comparative Examples 1-3 were evaluated for their performance in preparing epoxy pinane by reacting a-pinene with hydrogen peroxide. The operation process was as follows: 4 g of catalyst, 600 g of toluene and 300 g of a-pinene were sequentially added into a 2 L reactor, which was heated to 70 °C, and 200 g of hydrogen peroxide (mass fraction 50%) was added dropwise for 12 h, and the reaction was carried out for 3 h at constant temperature. After the product was separated, Agilent 7890 gas chromatography was used for analysis, in which the chromatographic column was HP-INNOWax, and the detector was FID detector.

[0416] Reaction formula:

[0417] (2) Preparation of epoxy limonene by reaction of limonene with hydrogen peroxide

[0418] The reaction performance of the catalysts prepared in Examples 14-26, Example 33, Examples 36-41 and Comparative Examples 1-3 in the reaction of limonene with hydrogen peroxide to prepare epoxy limonene was evaluated, and the operation process was as follows: 4 g of the catalyst, 600 g of toluene and 300 g of limonene were sequentially added into a 2 L reaction kettle, and the temperature was raised to 70°C, 60 g of hydrogen peroxide (mass fraction 50%) was added dropwise for 8 hours, and the reaction was kept at constant temperature for 3 h. After the product was separated, it was analyzed by Agilent 7890 gas chromatograph, wherein the chromatographic column was HP-INNOWax, and the detector was FID detector.

[0419] Reaction formula:

[0420] The specific results are shown in Table 21.

[0421] Table 21

[0422] Application Example 22 (Preparation of m-cresol and p-cresol by isomerization of o-cresol)

[0423] The performance of the catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 in the preparation of m-cresol and p-cresol by isomerization of o-cresol was evaluated: a stainless steel tube was used as the reactor, with an outer diameter of 16 mm, an inner diameter of 12 mm, and a length of 600 mm, and the catalyst loading was 10 g. The reaction conditions were: reaction temperature 280°C, reaction pressure 0.15 MPa, mass hourly space velocity of o-cresol 0.8 h -1 , and the operation was carried out for 100 h. The conversion rate of o-cresol per pass, the selectivity of m-cresol and the selectivity of p-cresol were analyzed by chromatography.

[0424] The specific results are shown in Table 23.

[0425] Table 23

[0426] Application Example 23 (Preparation of 2-pentylidenecyclopentanone by dehydration of 2-(1-hydroxypentyl)-cyclopentanone)

[0427] The catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 were evaluated for their reaction performance in the dehydration of 2-(1-hydroxypentyl)-cyclopentanone to prepare 2-pentylidenecyclopentanone. The operation process was as follows: 6 g of the catalyst was added into a 2 L reactor, 1200 g of 2-(1-hydroxypentyl)-cyclopentanone was added, the system was heated to 90°C, the vacuum degree was controlled at about 350 mmHg, and the reaction was carried out for 12 h. The product was separated and analyzed by Agilent 7890 gas chromatograph, wherein the chromatographic column was HP-INNOWax and the detector was FID detector.

[0428] Reaction formula:

[0429] The specific results are shown in Table 24.

[0430] Table 24

[0431] Application Example 24 (Dehydration of hydroxycyclopentadecanolide to prepare habanolide)

[0432] The catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 were evaluated for their reaction performance in the dehydration of hydroxycyclopentadecanolide to prepare habanolide. The operation process was as follows: 6 g of the catalyst was added into a 2 L reactor, 1200 g of hydroxycyclopentadecanolide was added, the system was heated to 100°C, the vacuum degree was controlled at about 350 mmHg, and the reaction was carried out for 12 h. The product was separated and analyzed by Agilent 7890 gas chromatograph, wherein the chromatographic column was HP-INNOWax and the detector was FID detector.

[0433] Reaction formula:

[0434] The specific results are shown in Table 25.

[0435] Table 25

[0436] Application Example 25

[0437] The catalysts prepared in Examples 1-5, Example 14, Example 25, Example 26 and Comparative Examples 1-3 were evaluated for their reaction performance in the etherification of isopropanol to prepare isopropyl ether. The operation process was as follows: 3 g of the catalyst was added into a 2 L reactor, 600 g of isopropanol and 600 g of cyclohexane were added, the system was heated to 69°C, and the reaction was carried out for 12 h. The product was separated and analyzed by Agilent 7890 gas chromatograph, wherein the chromatographic column was HP-INNOWax and the detector was FID detector.

[0438] The specific results are shown in Table 26.

[0439] Table 26

[0440] Example 26 (Preparation of isopropyl alcohol by hydration of propylene)

[0441] The performance of the catalysts prepared in Examples 1-14, Example 25, Example 26 and Comparative Examples 1-3 in the preparation of isopropyl alcohol by hydration of propylene was evaluated. A stainless steel tube with an outer diameter of 16 mm, an inner diameter of 12 mm and a length of 600 mm was used as the reactor, and the catalyst loading was 10 g. The reaction conditions were as follows: a reaction temperature of 150°C, a reaction pressure of 7 MPa, a volume liquid hourly space velocity (LHSV) of propylene of 0.8 h -1 , and a molar ratio of water to propylene of 10:1. After the product was separated, it was analyzed using an Agilent 7890 gas chromatograph, in which the chromatographic column was an HP-INNOWax and the detector was an FID detector.

[0442] The specific results are shown in Table 27.

[0443] Table 27

[0444] Example 27 (Preparation of cyclopentadecanolide by hydrogenation of habanolide)

[0445] The performance of the catalyst prepared in Example 24 in the preparation of cyclopentadecanolide by hydrogenation of habanolide was evaluated. The operation process was as follows: 0.1 g of the catalyst, 50 g of habanolide, and hydrogen were sequentially added to a 100 mL high-pressure reaction kettle, the hydrogen was replaced after the pressure was charged to 0.5 MPa, and then the temperature was raised to 40°C for 12 h of reaction. After the product was separated, it was analyzed using an Agilent 7890 gas chromatograph, in which the chromatographic column was an HP-INNOWax and the detector was an FID detector. The conversion rate and selectivity were calculated using the normalization method.

[0446] The reaction formula was as follows:

[0447] The specific results are shown in Table 28.

[0448] Table 28

[0449] Example 28 (Preparation of p-tert-butylcyclohexanol by hydrogenation of p-tert-butylphenol)

[0450] The performance of the catalyst prepared in Example 25 in the hydrogenation reaction of p-tert-butylphenol was evaluated. A stainless steel tube with an outer diameter of 16 mm, an inner diameter of 12 mm and a length of 600 mm was used as the reactor, and the catalyst loading was 10 g. The reaction pressure was 3 MPa, the reaction temperature was 80-85°C, the mass LHSV of p-tert-butylphenol was 0.5 h -1 , and hydrogen was used as the hydrogenation agent, with a molar ratio of hydrogen to p-tert-butylphenol of 5:1.

[0451] The specific results are shown in Table 29.

[0452] Table 29

[0453] Application Example 29

[0454] The catalysts prepared in Examples 27-32, 34-35 were evaluated for their performance in the reaction of thymol hydrogenation to prepare menthol, and the operation process was as follows: a stainless steel tube was used as the reactor, with an outer diameter of 16 mm, an inner diameter of 12 mm, and a length of 600 mm, and the catalyst loading was 10 g. The reaction pressure was 4 MPa, the reaction temperature was 140-150°C, the mass liquid hourly space velocity of thymol was 0.5 h -1 , hydrogen was used as the hydrogenation agent, and the molar ratio of hydrogen to thymol was 10:1.

[0455] The specific results are shown in Table 30.

[0456] Table 30

[0457] Application Example 30 (aldol condensation reaction)

[0458] The catalysts prepared in Examples 1-14, Example 25, Example 26, and Comparative Examples 1-3 were evaluated for their performance in the aldol condensation reaction of cyclopentanone and n-pentanal to prepare 2-pentylidenecyclopentanone, and the operation process was as follows:

[0459] In a high-pressure reaction kettle, 168 g of cyclopentanone and 3.4 g of catalyst were added under a nitrogen atmosphere, the pressure was increased to 1 MPa, and then stirring was started and the temperature was increased to 130°C; then 68 g of n-pentanal was added dropwise (dropwise addition time: 6 h), and after the dropwise addition was completed, the temperature was kept constant for 2 h. The catalyst was separated from the reaction liquid by filtration, and quantitative analysis of the reaction liquid was performed on an Agilent 7890 gas chromatograph, using a chromatographic column HP-INNOWax and an FID detector for detection.

[0460] The specific results are shown in Table 31.

[0461] Table 31

[0462] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made in accordance with the spirit and essence of the present application should be covered within the protection scope of the present application.

[0463] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as exactly that endpoint point. Any of the endpoints of the ranges or the separate values should be understood as not solely the precision as disclosed for that endpoint but also values so close thereto as to be considered equivalent to the disclosed value for the range or separate value. For values whose endpoints contain the term "about", the exact value of the endpoint is also included in the disclosure.

Claims

1. A catalyst characterized by: The catalyst comprises a metal oxide carrier with a three-dimensional porous structure, a heteropoly acid dispersed in a monomolecular state and connected to the metal oxide carrier, and optionally, an active metal component dispersed in a monatomic state and connected to one or both of the heteropoly acid and the metal oxide carrier, the heteropoly acid being a proton type heteropoly acid capable of providing hydrogen ions.

2. The catalyst of claim 1, wherein: In the proton type heteropoly acid, heteroatoms and polyatomic atoms are bridged by oxygen atoms, the heteroatoms including at least one selected from P, Si, Fe, Co, and the polyatomic atoms including at least one selected from Mo, W, V, Nb, and Ta; and / or, The proton type heteropoly acid is connected to the metal oxide carrier at least by a covalent bond, the covalent bond being formed between the polyatomic atoms in the proton type heteropoly acid, the terminal oxygen in the proton type heteropoly acid, and the metal atoms in the metal oxide carrier.

3. The catalyst of claim 1, wherein: The metal oxide carrier is a hollow structure; the hollow structure has a single hollow chamber or a hollow cavity combination formed by aggregation of a plurality of hollow chambers that are all or partially communicated; optionally, the average diameter of the hollow chamber or the hollow cavity combination is 1-90 nm; optionally, the ratio of the average diameter of the hollow chamber or the hollow cavity combination to the average particle size of the catalyst is 0.3-0.9:

1.

4. The catalyst of claim 1, wherein: The catalyst comprises a hollow spherical porous alumina carrier self-assembled from two-dimensional nanosheets, the proton type heteropoly acid being dispersed in a monomolecular state in the framework, inside the pores, and on the surface of the porous alumina carrier; and / or, the proton type heteropoly acid in a monomolecular state being distributed in the framework, inside the pores, and on the surface of the metal oxide carrier.

5. The catalyst of claim 1, wherein: The proton type heteropoly acid comprises a combination of one or more selected from phosphomolybdic acid, phosphotungstic acid, silicotungstic acid, silicomolybdic acid, phosphovanadomolybdic acid, phosphoniobium heteropoly acid, phosphotantalum heteropoly acid, iron molybdenum heteropoly acid, iron tungsten heteropoly acid, iron vanadium heteropoly acid, cobalt molybdenum heteropoly acid, cobalt tungsten heteropoly acid, and cobalt vanadium heteropoly acid; and / or, the mass content of the proton type heteropoly acid in the catalyst is 1%-68% by mass percentage, preferably 7%-45%, and further preferably 7%-25%.

6. The catalyst of claim 1, wherein: The average pore diameter of the catalyst is 2-30 nm, the average pore volume is 0.4-1.5 cc / g, and the average density is 0.5-4.0 g / cm 3 ; and / or, the average particle size of the catalyst is 10-350 nm, preferably 80-250 nm; and / or, the specific surface area of the catalyst is greater than or equal to 200 m 2 / g, as determined by the BET method; preferably, the specific surface area of the catalyst is less than or equal to 1000 m 2 / g; further preferably, the specific surface area of the catalyst is 200-800 m 2 / g; and / or, the catalyst is in a spherical structure.

7. The catalyst of claim 1, wherein: The metal oxide carrier comprises a zinc oxide carrier, a magnesium oxide carrier, a copper oxide carrier, an aluminum oxide carrier, or a titanium oxide carrier.

8. The catalyst of claim 1, wherein: The catalyst is prepared by a preparation method satisfying the following conditions: (a) using a precursor of a metal oxide and optionally, a precursor of an active metal as raw materials, the precursor of a metal oxide and the precursor of an active metal each being a substance capable of being converted into a metal oxide or an active metal component through one or more conversion processes, the conversion processes at least including a process generating a chemical reaction; (b) performing the one or more conversion processes in the presence of the proton type heteropoly acid and water.

9. The catalyst of claim 8, wherein: The precursor of a metal oxide is a substance that can be converted into the metal oxide carrier with a three-dimensional porous structure through gelation and calcination processes performed in sequence; and / or, the preparation method of the catalyst further satisfies the condition: (c) the conversion treatment comprises a gelation treatment, and the gelation treatment is carried out in the presence of water, an organic solvent and a surfactant simultaneously.

10. The catalyst of claim 1, wherein: the active metal component is linked to the protic heteropoly acid by a chemical bond, the chemical bond comprises a coordination bond, the active metal component is also selectively adsorbed on the metal oxide carrier; and / or, the active metal component is a combination of one or more selected from transition metals, preferably, the active metal component is a combination of one or more selected from groups IB-ⅡB and groups VB-ⅧB, further preferably, the active metal component is a combination of one or more selected from Pd, Pt, Ru, Au, Ag, Rh, Ni, Cu, Fe and Co; and / or, the mass content of the active metal component in the catalyst is 0.01%-15% by mass content, preferably 0.04%-15% by mass content.

11. A process for the preparation of a catalyst as claimed in any one of claims 1 to 10, characterized in that: the preparation method comprises: gelation treatment: mixing and reacting the protic heteropoly acid and the precursor of the metal oxide in the presence of water, an organic solvent and a surfactant, and inducing by solvent evaporation to form a gel, wherein: the temperature of the mixing and reacting is controlled to be 20-50℃, and the reaction time is controlled to be no less than 12h; calcination treatment: drying the gel and then calcining to obtain the catalyst; optionally, the preparation method further comprises a step of connecting a monomolecular dispersed active metal component on one or both of the heteropoly acid and the metal oxide carrier, the step comprising: adding an active metal precursor before the mixing and reacting or coating with a solution containing the active metal precursor after the calcination; and, carrying out a reduction treatment after the calcination.

12. The method of claim 11, wherein: the precursor of the metal oxide is a compound containing metal and organic group selected from acidic, basic or neutral, preferably, the compound containing metal and organic group is selected from C1-C12 metal alkoxide, C1-C12 hydrocarbyl metal, metal organic complex or complex, further preferably, the precursor of the metal oxide is a combination of one or more selected from aluminum alcohol compound, magnesium alcohol compound, copper alcohol compound, zinc alcohol compound, titanium alcohol compound, hydrocarbyl aluminum compound, hydrocarbyl titanium compound, hydrocarbyl zinc compound, organic aluminum salt, organic titanium salt and organic zinc salt, more further preferably, the precursor of the metal oxide is a combination of one or more selected from trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, aluminum isopropyl alcohol, aluminum n-butyl alcohol, aluminum acetate, aluminum propionate, titanium acetylacetonate, titanium tetraethylate, titanium tetraisopropylate, titanium tetrabutylate and zinc acetylacetonate; and / or, The active metal precursor is a salt of an active metal component and / or an acid of an active metal component, the salt of an active metal component includes a combination of one or more selected from metal nitrate, metal sulfate, metal halide, metal acetylacetone complex, metal sulfide, the acid of an active metal component includes a halogenated metal acid; preferably, the active metal precursor is a combination of one or more selected from palladium chloride, palladium nitrate, platinum acetylacetone, gold chloride, silver nitrate, ruthenium chloride, ruthenium nitrate, rhodium chloride, rhodium nitrate, cobalt nitrate, nickel nitrate, iron chloride, iron sulfate, copper nitrate, copper sulfate, chloroplatinic acid, chloropalladic acid, chloroauric acid, rhodium acetylacetone.

13. The method of claim 11, wherein: The feeding mass ratio of the water to the precursor of the metal oxide is 0.001-15:1, preferably 0.01-10:1, more preferably 0.1-5:1, further preferably 0.01-6:1; and / or, the feeding volume ratio of the water to the organic solvent is 0.001-5:1, preferably 0.01-2:1, more preferably 0.005-1:

1.

14. The method of claim 11, wherein: The feeding mass ratio of the water to the precursor of the metal oxide is 0.01-3:1, preferably 0.02-3:1, further preferably 0.02-3:1; and / or, the feeding volume ratio of the water to the organic solvent is 0.001-1:1, preferably 0.001-0.5:1, further preferably 0.001-0.2:1 15. The method of claim 11, wherein: The surfactant is a block copolymer nonionic surfactant and / or an ionic surfactant, the block copolymer nonionic surfactant includes a combination of one or more selected from nonionic surfactant P123, nonionic surfactant F127, nonionic surfactant F108, the ionic surfactant includes a combination of one or more selected from cetyltrimethylammonium bromide, sodium oleate, sodium dodecylbenzenesulfonate, sodium stearate, preferably, the feeding mass ratio of the surfactant to the protic heteropoly acid is 3-30:1; and / or, the organic solvent is a polar organic solvent, the feeding mass ratio of the protic heteropoly acid to the organic solvent is 1:80-1000; preferably, the organic solvent is a combination of one or more selected from methanol, ethanol, isopropanol, acetone, tetrahydrofuran, N,N-dimethylformamide.

16. The method of claim 11, wherein: The time for controlling the mixing reaction is 12-15h, 15-18h, 18-21h, 21-24h, 24-27h, 27-30h or 30-48h; and / or, the solvent evaporation induction is controlled to be carried out at a temperature of 40-120℃ for 1-72h, preferably, the solvent evaporation induction is controlled to be carried out at a temperature of 60-75℃ for 10-60h.

17. The method of claim 11, wherein: the calcination is performed at 200-700℃; and / or, the calcination is performed in a muffle furnace, the calcination time is controlled to be 1-6h, and the heating rate is controlled to be 1-30℃ / min; and / or, the calcination is performed in an oxygen-containing environment, the oxygen-containing environment includes an air atmosphere or a pure oxygen atmosphere formed by introducing a pure oxygen gas with a purity greater than 99%.

18. The method of claim 11, wherein: For the catalyst containing an active metal component, the preparation method further comprises, after the calcination and before the reduction treatment, impregnating or spraying a solution containing the active metal precursor to obtain a solid loaded with the active metal precursor, and then performing the reduction treatment.

19. The method of claim 11, wherein: Embodiments of the gelation treatment include: mixing a protic heteropoly acid, water, and an organic solvent to obtain a first solution; then adding a surfactant, a precursor of aluminum oxide, and an active metal precursor into the first solution to mix and disperse, performing a reaction at room temperature, and inducing a gel by solvent evaporation; and / or, The reduction treatment includes: performing a first calcination in an oxygen-containing environment, and then performing a second calcination in a reducing atmosphere; preferably, the calcination temperature of the first calcination is 200-400℃, and the calcination temperature of the second calcination is 150-300℃; further preferably, the calcination temperature of the second calcination is lower than the calcination temperature of the first calcination.

20. A catalyst composition characterized by: The catalyst composition includes the catalyst as claimed in any one of claims 1-10 and at least one other catalyst different from the catalyst, wherein the mass content of the catalyst is more than 50%.

21. Use of the catalyst as claimed in any one of claims 1-10, or the catalyst composition as claimed in claim 20, in the following reactions: oxidation of an aromatic hydrocarbon, an alcohol, or an aldehyde; esterification of an olefin with an acid or esterification of an alcohol with an acid; epoxidation of an olefin; alkylation of an aromatic compound; isomerization; dehydration of an alcohol; etherification; hydration of an olefin. For the catalyst containing an active metal component, the catalyst is also used in the following reactions: aldol condensation; hydrogenation; amination of an alcohol, a ketone, or an olefin.

22. The use according to claim 21, characterized in that: The oxidation reaction includes: using an aromatic hydrocarbon, an alcohol, or an aldehyde as a starting material, and allowing the starting material to undergo an oxidation reaction in the presence of the catalyst or the catalyst composition, and an oxidizing agent to generate a corresponding acid; wherein the oxidizing agent is oxygen, the oxidizing agent is provided by introducing a pure oxygen gas with a purity greater than 99% or air into a reaction system; the addition amount of the catalyst or the catalyst composition is 0.01%-3% of the addition amount of the starting material in terms of mass percentage; and / or, The oxidation reaction includes: using an aromatic hydrocarbon, an alcohol, or an aldehyde as a starting material, and allowing the starting material to undergo an oxidation reaction in the presence of the catalyst or the catalyst composition, and an oxidizing agent to generate a corresponding acid; wherein the oxidizing agent is oxygen, the oxidizing agent is provided by introducing a pure oxygen gas with a purity greater than 99% or air into a reaction system; the addition amount of the catalyst or the catalyst composition is 0.01%-3% of the addition amount of the starting material in terms of mass percentage; and / or, The esterification reaction includes: esterifying an alcohol or an olefin with an acid in the presence of the catalyst or the catalyst composition to generate an ester; wherein the alcohol includes a C 1-20 a hydrocarbyl alcohol, the acid includes a C 1-20 a hydrocarbyl carboxylic acid and / or a C 1-20 a hydrocarbyloxy C 1-20 a hydrocarbyl carboxylic acid, the olefin includes a C 3-20 a cyclic olefin; the catalyst or the catalyst composition is added in an amount of 0.01% to 3% of the alcohol and the acid in mass percentage; and / or, The epoxidation reaction of the olefin includes: allowing C 3-20 The olefin is subjected to an epoxidation reaction in a solvent in the presence of an oxidant and the catalyst or the catalyst composition, to generate a corresponding epoxide; wherein the oxidant includes hydrogen peroxide, and the added amount of hydrogen peroxide in the hydrogen peroxide is 5%-50% of the added amount of the C 3-20 of the olefin; and the added amount of the catalyst or the catalyst composition is 0.1%-5% of the added amount of the C 3-20 of the olefin; and the added amount of the catalyst or the catalyst composition is 0.1%-5% of the added amount of the C 3-20 The olefin includes α-pinene and / or limonene; and / or, The alkylation reaction of the aromatic compound includes reacting an olefin with C 1-10 alkyl-substituted phenol, or an alkylation reaction of an alcohol with substituted or unsubstituted benzene in the presence of the catalyst or the catalyst composition; wherein the olefin is C 2-10 alkyl-substituted phenol, or an alkylation reaction of an alcohol with substituted or unsubstituted benzene in the presence of the catalyst or the catalyst composition; wherein the olefin is C 1-10 The alkyl-substituted phenol is a phenol substituted with one of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, an n-pentyl group, an iso-pentyl group, a neopentyl group, and the substitution position is meta, and the alcohol is C 1-6 alkyl-substituted phenol, or an alkylation reaction of an alcohol with substituted or unsubstituted benzene in the presence of the catalyst or the catalyst composition; wherein the olefin is C 1-6 alkyl-substituted phenol, or an alkylation reaction of an alcohol with substituted or unsubstituted benzene in the presence of the catalyst or the catalyst composition; wherein the olefin is C The isomerization reaction includes: isomerization of o-cresol in the presence of the catalyst or the catalyst composition to prepare m-cresol and p-cresol, preferably, the reaction is carried out at 240-300℃ under 0.05-0.4 MPa; or hydrogen isomerization of 2-pentylidene cyclopentanone to prepare 2-pentylidene cyclopentenone, preferably, the reaction is carried out at 20-60℃, and the addition amount of the catalyst or the catalyst composition is 0.01wt.%-1.0wt.% of the addition amount of 2-pentylidene cyclopentanone; and / or, The dehydration reaction of the alcohol includes: dehydration of 2-(1-hydroxypentyl)-cyclopentanone in the presence of the catalyst or the catalyst composition to prepare 2-pentylidene cyclopentanone, or dehydration of hydroxycyclopentadecanolide to prepare habanolide, preferably, the reaction is carried out at 80-110℃ under 150-500 mmHg, and the addition amount of the catalyst or the catalyst composition is 0.01%-3% of the addition amount of the 2-(1-hydroxypentyl)-cyclopentanone or the hydroxycyclopentadecanolide in terms of mass percentage; and / or, The etherification reaction includes: self-etherification of 2-(3-hydroxypropyl)cyclododecanone in the presence of the catalyst or the catalyst composition to prepare trideca-oxabicyclo[10.4.0]hexadecane, preferably, the reaction is carried out at 80-100℃ under 150-500 mmHg, and the addition amount of the catalyst or the catalyst composition is 0.01wt.%-2.0wt.% of the addition amount of the 2-(3-hydroxypropyl)cyclododecanone; and / or, The hydration reaction of the olefin includes: in the presence of the catalyst or the catalyst composition, making C 2-20 The olefin is hydrated with water to prepare a corresponding alcohol; wherein the C 2-20 The olefin is ethylene, propylene, butene, pentene, hexene, cyclopropene, cyclobutene, cyclopentene or cyclohexene.

23. The use according to claim 21, characterized in that: The oxidation reaction includes: oxidation of C3-C10 aldehyde, C3-C10 alcohol or C6-C12 aromatic hydrocarbon in the presence of an oxidant and the catalyst or the catalyst composition to prepare C3-C10 acid, preferably, the oxidant is oxygen or air, and the addition amount of the catalyst or the catalyst composition is 0.01wt.%-2.0wt.% of the addition amount of the C3-C10 aldehyde; more preferably, when the C3-C10 aldehyde is used as the substrate, the reaction is carried out at 30-55℃; when the C3-C10 alcohol is used as the substrate, the reaction is carried out at 70-100℃; and when the C6-C12 aromatic hydrocarbon is used as the substrate, the reaction is carried out at 120-160℃; and / or, The oxidation reaction comprises: reacting a phenyl C 1-6 alkyl alcohol with hydrogen peroxide in the presence of the catalyst or the catalyst composition to produce a phenyl C 1-6 alkyl aldehyde; preferably, the reaction is carried out at 40-70 °C; the catalyst or the catalyst composition is added in an amount of 0.01 wt.%-3.0 wt.% of the phenyl C 1-6 alkyl alcohol; more preferably, the phenyl C 1-6 alkyl alcohol is benzyl alcohol or phenethyl alcohol; and / or, The epoxidation reaction of the olefin includes: reaction of α-pinene with hydrogen peroxide in the presence of the catalyst or the catalyst composition to prepare epoxy pinane, and the reaction is carried out at 50-80℃; or reaction of limonene with hydrogen peroxide in the presence of the catalyst or the catalyst composition to prepare epoxy limonene, and the reaction is carried out at 50-80℃; and / or, The esterification reaction includes: esterification of 2-methyl butyric acid with methanol, ethanol, isopropyl alcohol, n-butyl alcohol or n-hexyl alcohol, respectively; or, the esterification reaction includes: esterification of salicylic acid with n-hexyl alcohol, n-pentyl alcohol, benzyl alcohol, leaf alcohol, cyclohexyl alcohol, isooctanol or isophorone, respectively; or, the esterification reaction includes: esterification of allyl alcohol with acetic acid, hexanoic acid, heptanoic acid, phenylpropionic acid, phenoxyacetic acid or cyclohexyloxyacetic acid, respectively; or, the esterification reaction includes: esterification of acetic acid with o-tert-butyl cyclohexanol, p-tert-butyl cyclohexanol, α-phenyl ethanol or β-phenyl ethanol, respectively; or, the esterification reaction includes: esterification of dicyclopentadiene with acetic acid, propionic acid, n-butyric acid or isobutyric acid, respectively; or, the esterification reaction includes: esterification of lauric acid with methanol; preferably, in the esterification reaction, the addition amount of the catalyst or the catalyst composition is 0.01wt.%-2.0wt.% of the addition amount of the alcohol; and / or, The alkylation reaction of the aromatic compound includes: continuously alkylating propylene with m-cresol in the presence of the catalyst or the catalyst composition to prepare thymol; preferably, the alkylation reaction is carried out at 200-240℃, 0.05-0.5MPa; and / or, The hydration reaction includes: hydrating propylene in the presence of the catalyst or the catalyst composition to prepare isopropyl alcohol; preferably, the hydration reaction is carried out at 100-160℃, 1-8MPa.

24. The use according to claim 21, characterized in that: The hydrogenation reaction includes: reacting substituted or unsubstituted phenol with hydrogen in the presence of the catalyst or the catalyst composition to produce corresponding substituted or unsubstituted cyclohexanol, or reacting cyclopentyl butyrolactone, alcohol with hydrogen to produce corresponding substituted or unsubstituted cyclohexyl propionate, or hydrogenating rose oxide to produce phenylwinalcohol, or hydrogenating habanolide to produce cyclopentadecanolide; wherein the substituted or unsubstituted phenol includes C 1-6 alkyl-substituted phenol, the alcohol is C 1-6 alkyl alcohol; and / or, The amination reaction includes mixing a reaction of an alcohol, a ketone or an olefin in the presence of ammonia in the presence of the catalyst or the catalyst composition to generate a corresponding amine; the alcohol is a C 1-10 hydrocarbyl alcohol, the ketone is a C 3-10 hydrocarbyl ketone, and the olefin is a C 2-20 hydrocarbyl olefin; and / or, The aldol condensation reaction includes: aldol condensation of cyclopentanone with n-pentanal in the presence of the catalyst or the catalyst composition to generate 2-pentylidene cyclopentanone; preferably, the aldol condensation reaction is carried out at 80-150℃, 0.1-3MPa, more preferably at 80-130℃, 0.5-1.5MPa.

25. The use according to claim 21, characterized in that: The hydrogenation reaction includes: hydrogenating p-tert-butyl phenol in the presence of the catalyst or the catalyst composition to prepare p-tert-butyl cyclohexanol; preferably, the hydrogenation reaction is carried out at a pressure of 1-5MPa, a temperature of 60-90℃; and / or, The hydrogenation reaction includes: hydrogenating o-tert-butyl phenol in the presence of the catalyst or the catalyst composition to prepare o-tert-butyl cyclohexanol; preferably, the hydrogenation reaction is carried out at a pressure of 1-3MPa, a reaction temperature of 60-90℃; and / or, The hydrogenation reaction comprises: hydrogenating cyclopentyl butyrolactone in an alcohol-containing system in the presence of the catalyst or the catalyst composition to produce cyclohexyl propionate; preferably, the alcohol in the alcohol-containing system is selected from C 1-20 hydrocarbon-based alcohol; the hydrogenation reaction is carried out at 1-4 MPa at 100-150 °C; and / or, The hydrogenation reaction includes: hydrogenating rose ether in the presence of the catalyst or the catalyst composition to prepare phenyl allyl alcohol; preferably, the addition amount of the catalyst or the catalyst composition is 0.01wt.%-1.0wt.% of the addition amount of rose ether; the hydrogenation reaction is carried out at 80-150℃, 1-3MPa; and / or, The hydrogenation reaction includes: hydrogenating habanolide in the presence of the catalyst or the catalyst composition to prepare cyclopentadecanolide; preferably, the hydrogenation reaction is carried out at 30-50℃, the addition amount of the catalyst or the catalyst composition is 0.01wt.%-1.0wt.% of the addition amount of the habanolide.

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