Molecular sieve supported composite material as well as preparation method and application thereof

Abstract

The invention provides a molecular sieve supported composite material as well as a preparation method and application thereof, and belongs to the technical field of catalysts. The molecular sieve supported composite material comprises a carrier and an active component supported on the carrier, the carrier comprises an AFI type AlPO4-5 molecular sieve, and the active component comprises a cluster formed by a noble metal simple substance or a cluster formed by a noble metal oxide. According to the invention, long-chain 1-dodecene is used as a raw material, a twelve-membered ring AFI type AlPO4-5 molecular sieve with a larger pore size is selected as a carrier, and high-activity metal clusters are loaded by using a straight pore structure with high specific surface, easy-to-modulate surface properties and confinement of the molecular sieve, so that the use of noble metals is reduced, and the catalytic activity of the catalyst is improved. The production cost is reduced; and meanwhile, the selective preparation of Guerbet alcohol precursors (2-methyltridecanal) and n-tridecanal is realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to a molecular sieve-supported composite material and a preparation method and application thereof. Background Art

[0002] Guerbet alcohols are saturated alcohols with 100% linear alkyl groups, and they offer superior performance compared to unsaturated alcohols of the same carbon chain length. At room temperature, Guerbet alcohols with carbon chain lengths ranging from C12 to C24 exist as low-volatility, transparent liquids with excellent thermal stability and biodegradability, making them a promising alternative to linear alcohols. Traditionally, Guerbet alcohols are typically prepared by condensing lower-carbon alcohols to produce higher-carbon alcohols, or by formylation of short-chain olefins with synthesis gas to produce aldehydes, which are then condensed and hydrogenated to produce higher-carbon alcohols.

[0003] The development of a hydroformylation route for long-chain olefins has significantly simplified the preparation of higher alcohols. While producing the primary straight-chain aldehyde, higher aldehydes with branches of varying lengths are also produced. These branched aldehydes can then be hydrogenated to directly produce Guerbet alcohols with varying branch lengths, regardless of the carbon number. Among these, 2-methyl branched aldehyde, the precursor of the shortest-branched Guerbet alcohol, produces the alcohols that exhibit the best performance among Guerbet alcohols with varying branch lengths and the same carbon number.

[0004] At present, the preparation of n-tridecanal by hydroformylation of 1-dodecene catalyzed by active metal Rh supported on a ten-membered ring hydrophobic MFI type zeolite has achieved a conversion rate of 23.7% (the total conversion rate of 1-dodecene into various isoolefins, various isoaldehydes and normal aldehydes), and the total selectivity of aldehydes (all isoaldehydes and normal aldehydes) has reached 91.8%, with a ratio of normal aldehyde to isoaldehyde of 155:1. The characteristics of the zeolite are mainly used to achieve the highly selective conversion of n-tridecanal, while greatly reducing the generation of other branched aldehydes.

[0005] However, there is no report on the preparation of 2-methyltridecanal in the prior art. Summary of the Invention

[0006] In view of this, the present invention aims to provide a molecular sieve-supported composite material, a preparation method thereof, and applications thereof. The molecular sieve-supported composite material obtained by the present invention is used as a catalyst in the hydroformylation reaction of 1-dodecene to produce a Guerbet alcohol precursor (2-methyltridecanal) and n-tridecanal with high selectivity.

[0007] In order to achieve the above object, the present invention provides the following solutions:

[0008] The present invention provides a molecular sieve-supported composite material, comprising a carrier and an active component supported on the carrier; the carrier comprises an AFI type AlPO4-5 molecular sieve, and the active component comprises clusters formed by a single noble metal or clusters formed by a noble metal oxide.

[0009] Preferably, the noble metal element or the noble metal in the noble metal oxide independently includes one or more of Pt, Pd, Ru and Rh.

[0010] The present invention provides a method for preparing the molecular sieve-supported composite material described in the above scheme, comprising the following steps:

[0011] The molecular sieve, the first soluble noble metal salt and the first water are first mixed, and the obtained slurry is dried and then subjected to a first calcination or a first calcination followed by a first reduction to obtain the molecular sieve-supported composite material; the molecular sieve includes an AFI type AlPO4-5 molecular sieve.

[0012] Preferably, the temperature of the first calcination is 300-500° C., and the time is 2-6 hours.

[0013] Preferably, the first reducing atmosphere comprises a mixed atmosphere of hydrogen and argon, wherein the volume ratio of hydrogen to argon is 1:9; the temperature of the first reducing is 300-500° C., and the time is 2-3 hours.

[0014] The present invention provides a method for preparing the molecular sieve-supported composite material described in the above scheme, comprising the following steps:

[0015] The template, the aluminum-containing compound, the phosphate-containing compound, the second water, the second soluble noble metal salt and the second noble metal complexing agent are mixed, crystallized, and subjected to solid-liquid separation to obtain a crystallized product;

[0016] The obtained crystallized product is subjected to a second calcination or a second calcination followed by a second reduction to obtain the molecular sieve supported composite material.

[0017] Preferably, the crystallization includes static crystallization or dynamic crystallization; the temperature of the static crystallization is 160-180° C., and the time is 3-5 days; the temperature of the dynamic crystallization is 160-180° C., and the time is 1-3 days.

[0018] Preferably, the atmosphere of the second calcination is an air atmosphere, the temperature is 500-600°C, and the time is 8-12 hours; the atmosphere of the second reduction includes a mixed atmosphere of hydrogen and argon, and the volume ratio of hydrogen to argon is 1:9; the temperature of the second reduction is 300-500°C, and the time is 2-3 hours.

[0019] The present invention provides the molecular sieve-supported composite material described in the above scheme, or the present invention provides the use of the molecular sieve-supported composite material prepared by the preparation method described in the above scheme as a catalyst in catalyzing the hydroformylation reaction of 1-dodecene.

[0020] Preferably, the method for catalyzing the hydroformylation of 1-dodecene comprises the following steps:

[0021] The molecular sieve-supported composite material, 1-dodecene, H2, CO and an organic solvent are mixed and subjected to a hydroformylation reaction to obtain a mixture containing 2-methyltridecanal and n-tridecanal.

[0022] The present invention provides a molecular sieve-supported composite material, comprising a carrier and an active component supported on the carrier; the carrier comprises an AFI-type AlPO4-5 molecular sieve, and the active component comprises clusters formed by a noble metal element or a noble metal oxide. The present invention uses long-chain 1-dodecene as a raw material and selects a twelve-membered ring straight-channel AFI-type AlPO4-5 molecular sieve with a larger pore size as a carrier. The molecular sieve's high specific surface area, easily modifiable surface properties, and confined straight-channel structure are utilized to support highly active metal clusters, thereby reducing the use of noble metals and production costs while achieving the selective preparation of Guerbet alcohol precursors (2-methyltridecanal) and tridecaldehyde.

[0023] The molecular sieve-supported composite material provided by the present invention is used as a catalyst to catalyze the hydroformylation reaction of 1-dodecene. The larger pore size (twelve-membered ring) enables the highly selective preparation of Guerbet alcohol precursors (2-methyltridecanal) and n-tridecanal. The hydrophilicity advantage is utilized to selectively adsorb the double bond end of 1-dodecene (more hydrophilic) and the desorption product (hydrophobic product), thereby promoting the forward shift of the equilibrium.

[0024] The present invention provides a method for preparing the molecular sieve-supported composite material described in the above scheme. The present invention introduces active components by in-situ encapsulation (claim 6) and impregnation (claim 9) of molecular sieves to prepare a highly dispersed confined catalyst, which effectively limits the catalyst deactivation caused by rapid sintering and agglomeration of the active components during the reaction process, thereby improving the catalytic activity of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0026] Figure 1The XRD patterns of the AlPO4-5 molecular sieve supported composite materials obtained in Example 1 and Example 2 are shown. DETAILED DESCRIPTION

[0027] The present invention provides a molecular sieve-supported composite material, comprising a carrier and an active component supported on the carrier; the carrier comprises an AFI type AlPO4-5 molecular sieve, and the active component comprises clusters formed by a single noble metal or clusters formed by a noble metal oxide.

[0028] In the present invention, the noble metal element or the noble metal oxide independently comprises one or more of Pt, Pd, Ru, and Rh. In the present invention, the loading amount of the active component in the molecular sieve-supported composite material is preferably 0.098 to 0.295%; the loading amount of the active component in the present invention is calculated based on the loading amount of the noble metal element in the molecular sieve-supported composite material.

[0029] The present invention uses long-chain 1-dodecene as a raw material and selects a twelve-membered ring straight-channel AFI-type AlPO4-5 molecular sieve with a larger pore size as a carrier. The molecular sieve has a high specific surface area, easily adjustable surface properties, and a confined straight-channel structure to load highly active metal clusters, thereby reducing the use of precious metals and production costs while achieving the selective preparation of Guerbet alcohol precursors (2-methyltridecanal) and n-tridecanal.

[0030] The molecular sieve-supported composite material provided by the present invention is used as a catalyst to catalyze the hydroformylation reaction of 1-dodecene. The larger pore size (twelve-membered ring) enables the highly selective preparation of Guerbet alcohol precursors (2-methyltridecanal) and n-tridecanal. The hydrophilicity advantage is utilized to selectively adsorb the double bond end of 1-dodecene (more hydrophilic) and the desorption product (hydrophobic product), thereby promoting the forward shift of the equilibrium.

[0031] The present invention provides a method for preparing the molecular sieve-supported composite material described in the above scheme, comprising the following steps:

[0032] The molecular sieve, the first soluble noble metal salt and the first water are first mixed, and the obtained slurry is dried and then subjected to a first calcination or a first calcination followed by a first reduction to obtain the molecular sieve-supported composite material; the molecular sieve includes an AFI type AlPO4-5 molecular sieve.

[0033] Unless otherwise specified, the raw materials and equipment used in the present invention are all commercially available products.

[0034] In the present invention, the preparation method of the AFI type AlPO4-5 molecular sieve preferably includes the following steps:

[0035] The template agent (referred to as the first template agent), the aluminum-containing compound (referred to as the first aluminum-containing compound), the phosphate-containing compound (referred to as the first phosphate-containing compound) and the third water are mixed to obtain a first gel;

[0036] crystallizing the first gel (referred to as the first crystallization) to obtain a crystallized product (referred to as the first crystallized product);

[0037] The first crystallized product is subjected to a third calcination to obtain the AFI type AlPO4-5 molecular sieve.

[0038] In the present invention, the first template preferably includes triethylamine; the first aluminum-containing compound preferably includes pseudo-boehmite; the first phosphate-containing compound preferably includes phosphoric acid; the phosphoric acid is preferably added in the form of a phosphoric acid aqueous solution, and the mass fraction of the phosphoric acid aqueous solution is preferably 85%. In the present invention, the molar ratio of the first template and the first aluminum-containing compound is preferably (0.8-1):1. In embodiments of the present invention, it can be specifically 1:1, 0.9:1 or 0.8:1. The molar ratio of the first aluminum-containing compound and the first phosphate-containing compound (the molar amount of the first phosphate-containing compound is preferably calculated based on the molar amount of the pure substance in the first phosphate-containing compound, that is, the molar amount of pure H3PO4 in the phosphoric acid aqueous solution) is preferably 1:(1.4-1.6). In embodiments of the present invention, it can be specifically 1:1.6, 1:1.4 or 1:1.5. The ratio of the molar amount of the first aluminum-containing compound to the total molar amount of the third water, the water in the first phosphate-containing compound and the water in the first aluminum-containing compound is preferably 1:(40-45). In embodiments of the present invention, it can be specifically 1:45, 1:44, 1:40 or 1:42. In the present invention, the molar amount of the first aluminum-containing compound is preferably calculated based on the molar amount of Al2O3 in pseudo-boehmite; the water in the first phosphate-containing compound is preferably water in a phosphoric acid aqueous solution; the water in the first aluminum-containing compound is preferably the crystallization water in the first aluminum-containing compound, that is, the crystallization water in pseudo-boehmite.

[0039] In the present invention, the third mixing time is preferably 2 to 4 hours, and in embodiments of the present invention, specifically 2 hours, 3 hours, or 4 hours; the temperature is preferably room temperature. In the present invention, the molar composition of the first gel includes Al2O3:TEA:0.8P2O5:45H2O.

[0040] In the present invention, the first crystallization preferably includes dynamic hydrothermal crystallization; the temperature of the first crystallization is preferably 170° C., and the time is preferably 24 hours.

[0041] Prior to the third calcination, the present invention preferably cools the resulting reaction solution, centrifuges it, and dries the resulting solid product. In the present invention, the number of centrifugations is preferably three, the speed of each centrifugation is preferably 5000 rpm, and the duration of each centrifugation is preferably 3 minutes. The drying temperature is preferably 80°C, and the drying time is preferably 12 hours. In the present invention, the temperature of the third calcination is preferably 550°C, the atmosphere is preferably air, and the drying time is preferably 10 hours.

[0042] In the molecular sieve synthesis process of the present invention, a first phosphate-containing compound (such as phosphoric acid) is used to hydrolyze a first aluminum-containing compound (such as pseudo-boehmite), and a template agent plays a guiding role, ultimately forming an AFI-type AlPO4-5 molecular sieve with a twelve-membered ring topology.

[0043] After obtaining the molecular sieve, the present invention first mixes the molecular sieve, a first soluble precious metal salt and a first water, and the obtained slurry is dried and then first calcined or first reduced after the first calcination to obtain the molecular sieve-supported composite material; the molecular sieve includes an AFI type AlPO4-5 molecular sieve.

[0044] In the present invention, the first mixing preferably includes mixing a first soluble precious metal salt and a first water to obtain a first soluble precious metal salt solution; and mixing the molecular sieve and the first soluble precious metal salt solution.

[0045] In the present invention, the concentration of the first soluble precious metal salt solution is preferably 0.0098 mol / L; the volume ratio of the first soluble precious metal salt solution to the mass ratio of the first aluminum-containing compound is preferably (7.59-22.77) mL:6.27 g. In an embodiment of the present invention, it can be specifically 7.59 mL:6.27 g, 10 mL:6.27 g or 22.77 mL:6.27 g. In the present invention, the first soluble precious metal salt preferably includes one or more of a first soluble precious metal chloride, a first soluble precious metal acetate and a first soluble precious metal nitrate; the first soluble precious metal chloride preferably includes one or more of palladium chloride, platinum chloride, ruthenium trichloride and rhodium trichloride.

[0046] Before the first calcination, the present invention also preferably grinds the dried material; the drying temperature is preferably 80° C., and the drying time is preferably 12 hours.

[0047] In the present invention, the temperature of the first calcination is preferably 500-600°C, and in embodiments of the present invention, it can be specifically 500°C, 550°C or 600°C; the atmosphere of the first calcination preferably includes an air atmosphere; the time of the first calcination is preferably 2-6h, and in embodiments of the present invention, it can be specifically 2h, 3h, 4h, 5h or 6h.

[0048] The present invention can solidify the precious metal particles through the first calcination and remove the anions (such as Cl - )

[0049] In the present invention, the first reducing atmosphere preferably includes a mixed atmosphere of hydrogen and argon, and the volume ratio of hydrogen to argon is preferably 1:9; the temperature of the first reducing is preferably 300-500°C, and in an embodiment of the present invention, it can be specifically 300°C, 400°C, 450°C or 500°C, and the time is preferably 2-3h, and in an embodiment of the present invention, it can be specifically 2h, 2.5h or 3h.

[0050] The present invention provides a method for preparing the molecular sieve-supported composite material described in the above scheme, comprising the following steps:

[0051] The template, the aluminum-containing compound, the phosphate-containing compound, the second water, the second soluble noble metal salt and the second noble metal complexing agent are mixed, crystallized, and subjected to solid-liquid separation to obtain a crystallized product;

[0052] The obtained crystallized product is subjected to a second calcination or a second calcination followed by a second reduction to obtain the molecular sieve supported composite material.

[0053] The present invention mixes a template (referred to as a second template), an aluminum-containing compound (referred to as a second aluminum-containing compound), a phosphate-containing compound (referred to as a second phosphate-containing compound), a second water, a second soluble precious metal salt and a precious metal complexing agent for a second time, performs crystallization (referred to as a second crystallization), and obtains a crystallized product (referred to as a second crystallization product) through solid-liquid separation.

[0054] In the present invention, the second mixing preferably includes:

[0055] mixing the second soluble noble metal salt and the fourth water to obtain a mixed solution;

[0056] mixing the mixed solution and a noble metal complexing agent to obtain a second soluble noble metal salt solution;

[0057] mixing a second template, a second aluminum-containing compound, a second phosphate-containing compound, and a fifth water to obtain a second gel;

[0058] The second gel and the second soluble precious metal salt solution are mixed.

[0059] In the present invention, the concentration of the mixed solution is preferably 0.0098 mol / L. In the present invention, the precious metal complexing agent preferably includes aqueous ammonia, and the mass fraction of the aqueous ammonia is preferably 28%. In the present invention, the volume ratio of the mixed solution to the precious metal complexing agent is preferably (7.59-22.77) mL: (0.23-0.68) g. In embodiments of the present invention, the ratio can be 7.59 mL: 0.23 g, 10 mL: 0.23 g, 22.77 mL: 0.23 g, 7.59 mL: 0.68 g, or 22.77 mL: 0.68 g.

[0060] In the present invention, the preparation method of the second gel is the same as the preparation method of the first gel described above, and will not be repeated here.

[0061] In the present invention, the mass ratio of the second aluminum-containing compound to the volume ratio of the mixed solution is 6.27g:(7.59-22.77)mL. In embodiments of the present invention, the ratio can be 6.27g:7.59mL, 6.27g:10mL, 6.27g:15mL or 6.27g:22.77mL. In the present invention, the second water preferably includes fourth water and fifth water.

[0062] In the present invention, the types of the second soluble noble metal salt, the second template, the second aluminum-containing compound and the second phosphate-containing compound are the same as those described above and will not be repeated here.

[0063] In the present invention, the noble metal complexing agent can prevent the noble metal from agglomerating.

[0064] In the present invention, the crystallization (i.e., the second crystallization) preferably includes static crystallization or dynamic crystallization; the temperature of the static crystallization is preferably 160-180°C, and in an embodiment of the present invention, it can be specifically 160°C, 170°C or 180°C; the time of the static crystallization is preferably 3-5 days, and in an embodiment of the present invention, it can be specifically 3 days, 4 days or 5 days; the temperature of the dynamic crystallization is preferably 160-180°C, and in an embodiment of the present invention, it can be specifically 160°C, 170°C or 180°C; the time of the dynamic crystallization is preferably 1-3 days, and in an embodiment of the present invention, it can be specifically 1 day, 2 days or 3 days.

[0065] In the present invention, the solid-liquid separation preferably includes centrifugation; the number of centrifugation is preferably 3 times, the speed of each centrifugation is preferably 5000 rpm, and the time of each centrifugation is preferably 3 minutes.

[0066] Before the second calcination, the present invention preferably dries the second crystallized product; the drying temperature is preferably 80-100°C, and in embodiments of the present invention, it can be 80°C, 90°C or 100°C, and the drying time is preferably 8-12h, and in embodiments of the present invention, it can be 8h, 9h, 10h, 11h or 12h.

[0067] In the present invention, the atmosphere of the second calcination is preferably an air atmosphere; the temperature of the second calcination is preferably 500-600°C, and in an embodiment of the present invention, it can be specifically 500°C, 550°C or 600°C; the time is 8-12h, and in an embodiment of the present invention, it can be specifically 8h, 9h, 10h, 11h or 12h; the present invention can remove the template through the second calcination.

[0068] In the present invention, the atmosphere of the second reduction preferably includes a mixed atmosphere of hydrogen and argon, and the volume ratio of the hydrogen to argon is preferably 1:9; in the present invention, the temperature of the second reduction is preferably 300-500°C, and in an embodiment of the present invention, it can be specifically 300°C, 400°C, 450°C or 500°C, and the time is preferably 2-3h, and in an embodiment of the present invention, it can be specifically 2h, 2.5h or 3h.

[0069] The present invention can reduce the calcined product noble metal oxide into a noble metal element through the second reduction or the first reduction.

[0070] The present invention uses an impregnation and in-situ encapsulation method to introduce the active component into a hydrophilic AFI-type AlPO4-5 molecular sieve without acidic sites (acidic sites can cause olefin isomerization, and isomerized olefins are byproducts). The molecular sieve is used as a carrier, so that the active component is highly dispersed in the carrier, and the carrier coats the active component, which reduces the agglomeration and deactivation of the metal sites during the reaction to a certain extent, and reduces the ratio of 1-dodecene isomerization. The hydrophilicity advantage is utilized to selectively adsorb the double bond end and desorption product of 1-dodecene, promoting equilibrium shift. At the same time, through the confinement effect of the molecular sieve, the terminal double bond and the molecular sieve pore form a key effect, performing CO selective insertion and hydrogenation reaction, so that the byproduct isomerized olefins generated during the reaction process cannot be further converted.

[0071] The present invention provides the use of the molecular sieve-supported composite material described in the above scheme or the molecular sieve-supported composite material prepared by the preparation method described in the above scheme as a catalyst in catalyzing the hydroformylation reaction of 1-dodecene.

[0072] In the present invention, the method for catalyzing the hydroformylation of 1-dodecene preferably comprises the following steps:

[0073] The molecular sieve-supported composite material, 1-dodecene, H2, CO and an organic solvent are mixed and subjected to a hydroformylation reaction to obtain a mixture containing 2-methyltridecanal and n-tridecanal.

[0074] In the present invention, the molecular sieve-supported composite material is a highly dispersed confined heterogeneous catalyst.

[0075] In the present invention, the organic solvent preferably includes one or more of methanol, ethanol, cyclohexane and toluene; the molar ratio of the mass of the molecular sieve-supported composite material to 1-dodecene is preferably 50 mg:0.7 mmol; the temperature of the hydroformylation reaction is preferably 50-100°C, and in an embodiment of the present invention, it can be specifically 50°C, 60°C, 70°C, 80°C, 90°C or 100°C; the time is preferably 1-12 h, and in an embodiment of the present invention, it can be specifically 1 h, 3 h, 5 h, 7 h, 10 h, 11 h or 12 h; the pressure is preferably 2-5 MPa, and in an embodiment of the present invention, it can be specifically 2 MPa, 3 MPa, 4 MPa or 5 MPa; the volume ratio of the molar amount of 1-dodecene to the organic solvent is preferably 0.7 mmol:10 mL; the volume ratio of H2 and CO is preferably 1:1.

[0076] To further illustrate the present invention, a molecular sieve-supported composite material, its preparation method and application provided by the present invention are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0077] Example 1

[0078] Synthesis of AlPO4-5 Molecular Sieve Precursor Solution

[0079] 4.09 g of triethylamine and 7.38 g of aqueous phosphoric acid solution (mass fraction 85%) were added sequentially to additional H2O (the total amount of water in the aqueous phosphoric acid solution, crystal water in pseudo-boehmite and additional H2O here was 32.48 g), and after stirring at 500 rpm until clarified, 6.27 g of pseudo-boehmite (composition: Al2O3·xH2O, Al2O3 mass fraction: 65%) was slowly added, and stirred at room temperature for 2 h to form a gel (i.e., AlPO4-5 molecular sieve precursor solution). The molar composition of the gel was Al2O3:TEA:0.8P2O5:45H2O.

[0080] The gel was added to a 100 mL high-pressure reactor and subjected to dynamic hydrothermal crystallization at 170° C. for 24 h. The sample was then taken out of the high-pressure reactor and cooled. After centrifugation (5000 rpm, 3 min) three times, the pH value of the supernatant was tested to be neutral. The obtained solid sample was dried at 80° C. for 12 h, ground, and calcined in a muffle furnace at 550° C. in an air atmosphere for 10 h to obtain AlPO4-5 molecular sieve solid powder.

[0081] Preparation of metal solution and synthesis of catalyst by impregnation method

[0082] Prepare a RhCl3 aqueous solution by adding water to 0.00049 mol of RhCl3·3H2O in a volumetric flask to 50 mL.

[0083] 7.59 mL of RhCl3 aqueous solution was added to a beaker, and the AlPO4-5 molecular sieve solid powder was added during stirring and stirred evenly. The stirred slurry was placed in an oven at 80°C and dried for 12 hours. After grinding, it was calcined in a muffle furnace at 550°C in an air atmosphere for 6 hours to obtain a product. The obtained product was reduced at 400°C for 2 hours in an atmosphere of 10% H2-90% Ar (volume ratio) to obtain a molecular sieve-supported composite material, which was used as a catalyst (denoted as catalyst #1) for activity testing.

[0084] Example 2

[0085] Synthesis of AlPO4-5 Molecular Sieve Precursor Solution

[0086] 4.09 g of triethylamine and 7.38 g of aqueous phosphoric acid solution (mass fraction 85%) were added sequentially to additional H2O (the total amount of water in the aqueous phosphoric acid solution, crystal water in pseudo-boehmite and additional H2O here was 32.48 g), and after stirring at 500 rpm until clarified, 6.27 g of pseudo-boehmite (composition: Al2O3·xH2O, Al2O3 mass fraction: 65%) was slowly added, and stirred at room temperature for 2 h to form a gel (i.e., AlPO4-5 molecular sieve precursor solution). The molar composition of the gel was Al2O3:TEA:0.8P2O5:45H2O.

[0087] Preparation of metal precursor solution and in-situ encapsulation synthesis of catalysts

[0088] 0.00049 mol of RhCl3h3H2O was added to a volumetric flask with water to make the volume 50 mL to prepare a RhCl3 aqueous solution; 7.59 mL of the RhCl3 aqueous solution was added to a beaker, and 0.23 g of ammonia water (ammonia mass fraction 28%) was added dropwise under stirring to mix well to obtain a Rh precursor solution;

[0089] The Rh precursor solution was added dropwise to the AlPO4-5 molecular sieve matrix solution, stirred and mixed at room temperature, and the resulting mixed solution was added to a 100 mL high-pressure reactor and subjected to dynamic hydrothermal crystallization at 170°C for 24 hours. The sample was then taken out of the high-pressure reactor, centrifuged three times (5000 rpm, 3 min), and the pH value of the supernatant was neutral. The resulting solid sample was dried at 80°C for 12 hours, and then calcined at 550°C in a muffle furnace in an air atmosphere for 10 hours to obtain a product. The resulting product was reduced at 400°C for 2 hours in an atmosphere of 10% H2-90% Ar (volume ratio) to obtain a molecular sieve-supported composite material, which was used as a catalyst (denoted as catalyst #2) for activity testing.

[0090] Example 3

[0091] The 7.59 mL of the prepared RhCl3 aqueous solution added dropwise to the AlPO4-5 molecular sieve precursor solution in Example 2 was replaced by 22.77 mL, and the mass of ammonia water was changed from 0.23 g to 0.68 g. Other conditions were the same as in Example 2. The catalyst was used for activity evaluation and was recorded as catalyst #3.

[0092] Example 4

[0093] The preparation method is the same as that of Example 2, except that the obtained product is not reduced, and a molecular sieve-supported composite material is obtained, which is used as a catalyst (denoted as catalyst #4) for activity testing.

[0094] Application Examples 1 to 6

[0095] The long-chain olefin hydroformylation reaction is carried out in a high-pressure reactor using catalysts #1, #2, #3, and #4.

[0096] Application Example 1 The reaction conditions are as follows: hydroformylation temperature 80°C, mixed gas pressure 4 MPa, reaction time 3 h, 50 mg of #1 catalyst, 0.7 mmol of 1-dodecene, 10 mL of toluene, H2, and CO (H2 and CO volume ratio of 1:1, total pressure 4 MPa) for reaction evaluation. The reaction results are shown in Table 1.

[0097] The reaction conditions of Application Example 2 are as follows: hydroformylation reaction temperature 80°C, pressure 4 MPa, time 3 h, 50 mg of catalyst #2, 0.7 mmol of 1-dodecene, 10 mL of toluene, H2, and CO (H2 and CO volume ratio of 1:1, total 4 MPa) were added for reaction evaluation. The reaction results are shown in Table 1.

[0098] The reaction conditions of Application Example 3 are as follows: hydroformylation temperature 80°C, pressure 4 MPa, time 1 h, 50 mg of catalyst #2, 0.7 mmol of 1-dodecene, 10 mL of toluene, H2, and CO (H2 and CO volume ratio of 1:1, total 4 MPa) were added for reaction evaluation. The reaction results are shown in Table 1.

[0099] The reaction conditions of Application Example 4 are as follows: hydroformylation temperature 80°C, pressure 4 MPa, time 3 h, 50 mg of catalyst #3, 0.7 mmol of 1-dodecene, 10 mL of toluene, H2, and CO (H2 and CO volume ratio of 1:1, total 4 MPa) were added for reaction evaluation. The reaction results are shown in Table 1.

[0100] The reaction conditions of Application Example 5 are as follows: hydroformylation temperature 80°C, pressure 4 MPa, time 1 h, 50 mg of catalyst #3, 0.7 mmol of 1-dodecene, 10 mL of toluene, H2, and CO (H2 and CO volume ratio of 1:1, total 4 MPa) were added for reaction evaluation. The reaction results are shown in Table 1.

[0101] The reaction conditions of Application Example 6 are as follows: hydroformylation reaction temperature 80°C, pressure 4 MPa, time 1 h, 50 mg of #4 catalyst, 0.7 mmol of 1-dodecene, 10 mL of toluene, H2, CO (H2 and CO volume ratio of 1:1, total 4 MPa) for reaction evaluation. The reaction results are shown in Table 1.

[0102] Table 1 Reaction conversion rate and product selectivity of application examples 1 to 6

[0103]

[0104] Note that the total conversion in Table 1 refers to the total conversion of all isomeric olefins, all isomeric aldehydes, and normal aldehydes; the total selectivity includes the percentage of the total conversion accounted for by all isomeric aldehydes and normal aldehydes.

[0105] As can be seen from Table 1, the catalyst prepared in the present invention can generate Guerbet alcohol precursor (2-methyltridecanal) and n-tridecanal with high selectivity.

[0106] Figure 1 The XRD patterns of the molecular sieve-supported composite materials obtained in Example 1 (black line) and Example 2 (red line) are shown in FIG. Figure 1 It can be seen that the present invention successfully prepared the molecular sieve-supported composite material.

[0107] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A molecular sieve-supported composite material, comprising a carrier and an active component supported on the carrier; the carrier comprises an AFI-type AlPO4-5 molecular sieve, and the active component comprises clusters formed by a single noble metal or a cluster formed by a noble metal oxide.

2. The molecular sieve-supported composite material according to claim 1, characterized in that The noble metal in the noble metal element or noble metal oxide independently includes one or more of Pt, Pd, Ru and Rh.

3. The method for preparing the molecular sieve-supported composite material according to claim 1 or 2, characterized in that: The following steps are involved: The molecular sieve, the first soluble noble metal salt and the first water are first mixed, and the obtained slurry is dried and then subjected to a first calcination or a first calcination followed by a first reduction to obtain the molecular sieve-supported composite material; the molecular sieve includes an AFI type AlPO4-5 molecular sieve.

4. The preparation method according to claim 3, characterized in that The temperature of the first calcination is 300-500° C., and the time is 2-6 hours.

5. The preparation method according to claim 3, characterized in that The first reduction atmosphere includes a mixed atmosphere of hydrogen and argon, and the volume ratio of hydrogen to argon is 1:9; the temperature of the first reduction is 300-500° C., and the time is 2-3 hours.

6. The method for preparing the molecular sieve-supported composite material according to claim 1 or 2, characterized in that: The following steps are involved: The template, the aluminum-containing compound, the phosphate-containing compound, the second water, the second soluble noble metal salt and the second noble metal complexing agent are mixed, crystallized, and subjected to solid-liquid separation to obtain a crystallized product; The obtained crystallized product is subjected to a second calcination or a second calcination followed by a second reduction to obtain the molecular sieve supported composite material.

7. The preparation method according to claim 6, characterized in that The crystallization includes static crystallization or dynamic crystallization; the temperature of the static crystallization is 160-180° C., and the time is 3-5 days; the temperature of the dynamic crystallization is 160-180° C., and the time is 1-3 days.

8. The preparation method according to claim 6, characterized in that The atmosphere of the second calcination is an air atmosphere, the temperature is 500-600°C, and the time is 8-12 hours; the atmosphere of the second reduction includes a mixed atmosphere of hydrogen and argon, and the volume ratio of hydrogen to argon is 1:9; the temperature of the second reduction is 300-500°C, and the time is 2-3 hours.

9. Use of the molecular sieve-supported composite material according to claim 1 or 2, or the molecular sieve-supported composite material prepared by the preparation method according to any one of claims 3 to 8, as a catalyst in catalyzing the hydroformylation of 1-dodecene.

10. The use according to claim 9, characterized in that The method for catalyzing the hydroformylation of 1-dodecene comprises the following steps: The molecular sieve-supported composite material, 1-dodecene, H2, CO and an organic solvent are mixed and subjected to a hydroformylation reaction to obtain a mixture containing 2-methyltridecanal and n-tridecanal.

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