Method for catalyzing olefin hydroformylation by molecular sieve confinement monatomic catalyst
By limiting the rhodium single atom catalyst in the molecular sieve framework, the problems of low catalyst activity and insufficient selectivity in the hydroformylation reaction of olefins in the prior art are solved, and the hydroformylation effect of efficient and type-selective catalysts is achieved, which is suitable for petrochemical industry.
Patent Information
- Application Number
- CN202410109873.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-01-26
- Publication Date
- 2025-07-29
AI Technical Summary
In the prior art, homogeneous catalysts have problems such as expensive phosphine ligands, high temperatures of catalysts and easy loss of rhodium metals in the olefin hydroformylation reaction. The heterogeneous supported catalysts have low catalytic activity and insufficient chemical selectivity, making it difficult to achieve selective catalysis of olefin molecules of specific sizes.
Using Rh1@zeolite molecular sieve limited domain single atom catalyst, a catalytic hydrogen formylation of olefin molecules smaller than the pore size of the molecular sieve is achieved by using molecular sieve limited domain rhodium single atoms in the molecular sieve framework structure and using molecular sieve such as ZSM-5 as a support.
It improves catalytic activity and selectivity, achieves high conversion and selectivity, has high catalytic efficiency, and is easy to separate and recycle the catalyst, which is suitable for hydroformylation reaction of small molecule olefins.
Smart Images
Figure CN120383522A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the application of a zeolite-confined single-atom catalyst in the hydroformylation technical field, belonging to the petrochemical technology field. Background Art
[0002] Hydroformylation is an important homogeneous reaction process for synthesizing aldehydes and their derivatives using olefins and syngas, with an annual output exceeding 24 million tons. Olefins, as reactants, mainly come from production processes such as naphtha cracking, ethylene oligomerization, paraffin cracking, and Fischer-Tropsch synthesis, with an annual output exceeding 300 million tons. In the traditional olefin preparation process, distillation technology is mainly used to purify the mixed olefins with similar physical properties generated during the production process. The energy consumption of this purification process is 1.0 MJ / year and the carbon dioxide emissions increase by 88 million tons / year, accounting for more than 30% of the total energy consumption in olefin production. By designing and synthesizing a catalyst with a shape-selective effect on the reactants, olefin molecules with specific sizes can be selected to achieve hydroformylation to produce the corresponding aldehyde products. This process can not only simplify the process from olefin production to conversion into aldehydes, but also conform to the principles of energy conservation, emission reduction, and consumption reduction. However, currently, the hydroformylation reaction in industry mainly relies on rhodium-based complexes with phosphine ligands - homogeneous catalysts. Such catalysts have high catalytic activity and selectivity, but there are problems such as expensive phosphine ligands, easy deactivation of the catalyst at high temperatures, and easy loss of rhodium metal. In addition, the characteristics of homogeneous catalysis also lead to difficulties in aspects such as catalyst separation and selective catalysis of olefin molecules. Heterogeneous supported catalysts have the advantages of excellent thermal stability and easy separation, recovery, and reuse, and at the same time allow the use of porous supports with specific pore structures to achieve shape-selective catalysis of substrate molecules. However, heterogeneous supported catalysts have the disadvantages of low catalytic activity and insufficient chemoselectivity. Therefore, developing new heterogeneous catalysts to effectively improve their activity, stability, and shape-selective catalysis in the olefin hydroformylation reaction is of great significance. Summary of the Invention
[0003] The present application discloses the application of a Rh1@zeolite zeolite-confined single-atom rhodium-based material, which can be used for catalyzing the hydroformylation of olefins, especially for shape-selectively catalyzing olefin molecules with a hydroformylation molecular size smaller than the zeolite pore size.
[0004] The Rh1@zeolite is Rh1@ZSM-5, and the olefin is selected from styrene.
[0005] The present invention also discloses a method for the hydroformylation reaction of olefins. The method includes performing hydroformylation on an olefin having the structure of R1R2C=CH2 and syngas CO / H2 at 80°C to 120°C to obtain the product R1R2CH-CH2CHO or R1R2CH(CHO)-CH3, characterized in that Rh1@zeolite is used as the catalyst.
[0006] Rh1@zeolite is a zeolite-confined single-atom rhodium-based catalyst.
[0007] Among them, R1 and R2 are independently selected from H, C 1-8 alkane, C 5-20 cycloalkane, C 6-12 arene, C with ring heteroatoms N, O, S 3-12 heteroarene, and the alkane, cycloalkane, arene or heteroarene is further substituted by C 1-6 alkane, halogen, NO3.
[0008] The syngas is a CO / H2 mixed gas with a ratio of 1:1.
[0009] The preferred product is R1R2CHCH2CHO.
[0010] The preferred catalytic reaction temperature is 100°C to 120°C, and the catalytic reaction time is 6h to 12h.
[0011] The olefin is C 2-12 olefin, aromatic ring-substituted olefin, and the olefin is a single olefin or a mixed olefin.
[0012] Preferably, the olefin is styrene.
[0013] The zeolite-confined single-atom rhodium Rh1@zeolite is prepared by the following method, including:
[0014] Step S1. Prepare an aqueous solution of a metal Rh complex by mixing a metal Rh salt with a ligand compound to form the aqueous solution. The ligand compound is selected from N-containing compounds, such as NH3, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
[0015] Step S2. Drop the aqueous solution of the metal Rh complex obtained in Step S1 into the silica-alumina sol precursor solution and stir at room temperature;
[0016] Step S3. Add zeolite seeds to the metal silica-alumina sol solution in Step S2, stir at room temperature for 1-2h, then transfer the mixed solution to a reaction kettle, carry out static crystallization at 120°C - 180°C for 12h - 72h, cool to room temperature, wash with water, and dry;
[0017] Step S4. Calcinate the sample powder obtained in Step S3 at 300°C - 500°C to obtain the sample.
[0018] Among them, Rh is in a single-atom site state and is in-situ confined in the zeolite framework structure.
[0019] The Rh salt is selected from inorganic salts, such as rhodium chloride, rhodium nitrate.
[0020] The type of the selected molecular sieve is not limited, and any molecular sieve that can use crystal seeds instead of it as a structure - directing agent to assist in synthesis can be used in the method of the present invention. During the synthesis process of the molecular sieve, it is not necessary to add a traditional organic template agent. The molecular sieve is selected from MFI - type molecular sieves, BEA* - type molecular sieves, FAU - type molecular sieves, RTH - type molecular sieves, MTW - type molecular sieves, LEV - type molecular sieves, FER - type molecular sieves, and MEL - type molecular sieves. The preferred molecular sieves are MFI - type molecular sieves or BEA* - type molecular sieves. The aforementioned "molecular sieve that can use crystal seeds instead of it as a structure - directing agent to assist in synthesis" and the specific synthesis scheme can be referred to Microporous and mesoporous materials, 2014, 189, 22 - 30.
[0021] The silica - alumina sol precursor solution is a commonly used precursor solution for preparing molecular sieves in the art. The silica - alumina sol precursor is generally a mixture of materials such as a silicon source, an aluminum source, an alkali source, a template agent, and water. Common silicon sources are tetraethyl orthosilicate, silica sol, and sodium silicate. The aluminum source is aluminum isopropoxide, aluminum nitrate, and sodium meta - aluminate, the alkali source is sodium hydroxide and potassium hydroxide, and the template agent is a structure - directing agent. Different molecular sieves correspond to different structure - directing agents. For example, for MFI, the template agent is tetrapropylammonium hydroxide, and for BEA* molecular sieve, it is tetraethylammonium hydroxide. In the silica - alumina sol precursor of the present invention (except for the preparation of crystal seeds), it does not contain a template agent, and crystal seeds are added to play the role of structure - directing.
[0022] Preferably, the N - containing compound in step S1 is ethylenediamine.
[0023] Preferably, the stirring time in step S2 is 4 - 5 h.
[0024] Preferably, the static crystallization time in step S3 is 24 h - 72 h.
[0025] In step S4, the calcination temperature is 350 °C - 450 °C, and the time is 2 h - 3 h.
[0026] The molecular sieve crystal seeds can be commercially purchased or prepared by the commonly used methods for preparing molecular sieves in the art. The specific synthesis scheme can be referred to Microporous and mesoporous materials, 2014, 189, 22 - 30.
[0027] As an example, the present invention discloses a method for preparing MFI - type molecular sieve crystal seeds, and the specific operation is as follows:
[0028] (1) Preparation: silicon source, tetraethyl orthosilicate or 40% aqueous silica solution, organic structure - directing agent, tetrapropylammonium hydroxide;
[0029] (2) Prepare the zeolite seed silica precursor solution. Add the required silicon source, water, and organic template agent in the ratio of TEOS / TPAOH / H2O = 1.0:0.28:9.6 to a plastic beaker and stir at room temperature. The resulting solution is the seed silica precursor solution.
[0030] (3) After stirring for 6 h - 12 h, transfer the resulting silica solution to a reaction kettle and carry out static crystallization at 120 °C - 140 °C for 12 h - 72 h. After cooling to room temperature, wash the obtained precipitate powder sample with water and dry it overnight at 60 °C - 80 °C or freeze-dry it overnight. Remove the organic structure-directing agent through high-temperature calcination at 500 °C - 600 °C for 6 h - 10 h. The resulting powder is the MFI-type zeolite seed.
[0031] The present invention selects to use zeolite molecular sieve seeds instead of traditional organic structure-directing agents to in-situ confine the preparation of single-atom molecular sieve catalysts (M1@zeolite). Using the seed method to in-situ confine the preparation of single-atom molecular sieve catalysts can accelerate the crystallization rate of molecular sieves, shorten the catalyst preparation cycle, and at the same time, there is no need for the process of high-temperature calcination to remove organic structure-directing agents, and this method has universality. This preparation method has been described in another patent application of the applicant.
[0032] The inventors unexpectedly found that the rhodium-based single-atom molecular sieve catalyst (Rh1@zeolite) prepared according to this method has high activity in catalyzing the hydroformylation of olefins such as styrene. The inventors also found and proved that the catalyst used in the present invention can achieve shape-selective catalysis of hydroformylation, that is, the catalyst selectively catalyzes olefin molecules with a size smaller than the molecular sieve pore window. As in the examples of the present invention, ZSM-5 molecular sieve (the molecular sieve pore is ) is used as the carrier. The examples of the present invention prove that this catalyst can only catalyze the hydroformylation reaction of olefins with a molecular size less than or equal to .
[0033] Term description
[0034] Confined effect: It refers to the phenomenon that when a substance is in a confined space, its physical and chemical properties change significantly due to the restriction of its movement. The molecular sieve-confined single-atom rhodium-based material refers to confining rhodium single atoms in the framework structure of the molecular sieve in this application.
[0035] Shape-selective catalysis: It refers to a unique catalytic property of a class of molecular sieves. When the catalytic active center is restricted inside the pore structure of this type of molecular sieve, the reaction occurs in Molecular sieve the internal pore channels of the crystal; only specific molecules with sizes and shapes matching the molecular sieve pore channels and capable of diffusing into the pore channels can react with the catalytic active center to form products.
[0036] In the present invention, the molecular size of the olefin molecule is smaller than the pore size of the molecular sieve, which means that any two of the three-dimensional dimensions of the olefin molecule are smaller than the pore size of the molecular sieve, so that the olefin molecule can enter or partially enter the molecular sieve pore and contact the active center. For example, if any two of the length, width or height of the olefin molecule are smaller than it can enter the pores of zeolite ZSM-5 to complete the hydroformylation reaction.
[0037] Beneficial effects
[0038] In the hydroformylation method of the present invention, since the molecular sieve-confined single-atom rhodium catalyst is used, the following effects are achieved in the method of the present invention:
[0039] 1. High conversion rate and selectivity. For example, the conversion rate of styrene hydroformylation is 99%, and the selectivity of phenylpropanal is 99%.
[0040] 2. High catalytic efficiency. For example, the TOF value of styrene hydroformylation is as high as 6006 mol Rh / mol C＝C / h, and the TON value is 36000 mol Rh / mol C＝C .
[0041] 3. Shape-selective catalysis. For example, in the olefin substrate expansion experiment, the molecular sieve-confined rhodium-based catalyst has the characteristic of selectively catalyzing the hydroformylation of olefin molecules smaller than the pore size of the molecular sieve, that is, the molecular size is smaller than It has the characteristic of selectively catalyzing hydroformylation.
[0042] 4. Shape-selective catalysis of olefin mixtures. For example, in the C8 mixed olefin reactants, it only selectively catalyzes the hydroformylation of α-olefins smaller than size. Description of the drawings
[0043] Figure 1 is a transmission electron microscope picture of MFI-type zeolite seeds.
[0044] Figure 2 is a spherical aberration electron microscope picture of Rh1@ZSM-5. Detailed implementation manners
[0045] Here, specific implementation cases will be described in detail. The specific operation steps in the following implementation cases do not represent all implementation manners consistent with the present invention, but they are only the most representative examples in the present invention. These implementation cases can better highlight the actual application effects of the present invention.
[0046] The technical solutions of the present invention will be described in detail below with specific implementation cases.
[0047] Example 1
[0048] Step 1. Preparation of MFI-type zeolite seeds: 16 g of tetrapropylammonium hydroxide (25%, aqueous solution) and 14.4 g of tetraethyl orthosilicate were added to a 50 mL plastic flask and stirred at room temperature for 12 h. Subsequently, the mixed solution was transferred to a reaction kettle with a 100 mL polytetrafluoroethylene liner and statically crystallized at 120 °C for 12 h. After the reaction, when the reaction kettle cooled to room temperature, the upper liquid was removed by centrifugation and washed 3 - 4 times with distilled water, and then freeze-dried overnight to obtain a white powder sample. The white powder sample was calcined at 550 °C for 6 h to obtain MFI-type zeolite seeds with a particle size of about 50 nm - 100 nm( Figure 1 ).
[0049] Step 2. Preparation of 0.09 M [Rh(NH2CH2CH2NH2)3]Cl3 aqueous solution: 0.19 g of rhodium trichloride was dissolved in 2 mL of aqueous solution, and then 1 mL of excess ethylenediamine solution was added and stirred at room temperature for 10 minutes. Subsequently, the [Rh(NH2CH2CH2NH2)3]Cl3 aqueous solution was transferred to a 10 mL volumetric flask and made up to 10 mL with distilled water.
[0050] Step 3. Preparation of single-atom zeolite silica precursor solution: 0.216 g of sodium aluminate and 0.382 g of sodium hydroxide were dissolved in 22.84 mL of distilled water. 0.25 mL of the [Rh(NH2CH2CH2NH2)3]Cl3 solution prepared in Step 2 was added to the above mixed solution, and after stirring at room temperature for 10 minutes, 5.765 g of silica sol (40%, aqueous solution) was added and stirring was continued at room temperature for 5 h.
[0051] Step 4. The seeds prepared in Step 1 were added to the silica sol solution prepared in Step 3. After stirring at room temperature for 1 h, the mixed solution was transferred to a 100 mL reaction kettle and statically crystallized at 180 °C for 24 h. After cooling to room temperature, it was centrifuged and washed with water, and the sample was dried overnight at 80 °C.
[0052] Step 5. Removal of metal protecting group ethylenediamine. The sample powder obtained in Step 4 was calcined in air at 400 °C for 2 h to remove the ethylenediamine ligand, and the obtained sample was Rh1@ZSM-5. Its pore properties are characterized in Table 1, and the aberration-corrected electron microscopy image is Figure 2 .
[0053] Through the above steps, the white powder rhodium-based single-atom zeolite catalyst (Rh1@ZSM-5) of the present invention was obtained.
[0054] Table 1. Characterization of the pore properties of Rh1@ZSM-5
[0055]
[0056] Comparative Example 1
[0057] Take the commercially available homogeneous catalyst rhodium(III) chloride triphenylphosphine, from Henan Bauhinia Co., with the product number 14694-95-2.
[0058] Application test experiments and data
[0059] The test experiment is to verify the shape-selective catalytic hydroformylation performance of the Rh1@ZSM-5 material in Example 1. The specific operations and results are as follows.
[0060] 1. Application test of single olefin hydroformylation.
[0061] Dissolve 2.5 mmol of monomers (styrene, 4-methylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 2,4,6-trimethylstyrene, 1,1-diphenylethylene, trans-1,2-diphenylethylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 2-methyl-1-heptene, 2-ethyl-1-hexene, 2,4,4-trimethyl-1-pentene) and 20 μL of n-dodecane internal standard molecules in 5 mL of toluene solution. Then add the catalyst to the above mixed solution and disperse it evenly.
[0062] Using a synthesis gas CO / H2 ratio of 1:1, replace the air in the reaction kettle 3 times, keep the pressure at 2 MPa, and stir at 100 °C for 6 h. After the reaction, the resulting solution is centrifuged, and the chemical components in it are analyzed by gas chromatography-mass spectrometry. After calculation, the conversion rate of olefins and the selectivity of aldehyde formation are obtained, and the results are shown in Tables 2 and 3. According to the conversion rate and aldehyde selectivity, the catalytic efficiency, TOF value, and TON value of different catalysts for styrene are calculated, and the results are shown in Table 2.
[0063] Among them, the first 2 rows in Table 2 are for verifying the conversion rate of styrene and the selectivity of phenylpropanal by the catalyst. In Example 1, the Rh content in Rh1@ZSM-5 is 0.07 wt%, and 10 mg is added, that is, 6.8×10 -5 mmol, and the usage amount of RhCl(PPh3)3 in Comparative Example 1 is 6.8×10 -5 mmol. The last 2 rows in Table 2 are for verifying the catalytic activity of the catalyst. To calculate the TOF and TON values, it is necessary to ensure that the conversion rate of styrene catalysis is greater than 80%. In Example 1, the addition amount of Rh1@ZSM-5 is also 6.8×10 -5 mmol, while the usage amount of RhCl(PPh3)3 in Comparative Example 1 is 2.7×10 -4 mmol.
[0064] Table 3 shows the verification of the shape-selective catalytic performance of the catalyst, that is, the hydroformylation catalytic performance for olefin substrates of different sizes. On the basis of ensuring that the conversion rate of small-molecule olefins (styrene and 1-octene) reaches more than 95%, the shape-selective catalytic performance was compared. The usage amount of Rh1@ZSM-5 in Example 1 was 6.8×10 -5 mmol, and the usage amount of RhCl(PPh3)3 in Comparative Example 1 was 2.04×10 -3 mmol.
[0065] 2. Hydroformylation test of mixed olefins.
[0066] Dissolve 2.5 mmol of C8 olefin mixture 1-octene, 2-ethyl-1-hexene, 2,4,4-trimethyl-1-pentene, with a ratio of 10:1:1 and 20 μL of n-dodecane internal standard molecule into 5 mL of toluene solution. Subsequently, add the catalyst to the above mixed solution and disperse it evenly. Among them, the contents of Example 1 and Comparative Example 1 are consistent with the usage amounts of the catalysts for catalyzing different-sized substrates above, that is, to ensure that the conversion rate of 1-octene reaches more than 95%, the usage amount of Rh1@ZSM-5 is 6.8×10 -5 mmol, and the usage amount of Comparative Example 1 is 2.04×10 -3 mmol.
[0067] Using a synthesis gas CO / H2 ratio of 1:1, after displacing the air in the reaction kettle 3 times, the pressure was maintained at 2 MPa, and stirred at 100 °C for 6 h. After the reaction solution was centrifuged to remove the catalyst solid, the chemical components in the solution were analyzed by gas chromatography-mass spectrometry. After calculation, the conversion rate of olefins and the selectivity of the generated aldehyde were obtained. According to the aldehyde yield, the selectivity of the olefin shape-selective catalysis of the catalyst was calculated, and the results are shown in Table 4.
[0068] Evaluation results:
[0069] Table 2. Comparison of styrene hydroformylation performance.
[0070] Catalyst of Example 1 Catalyst of Comparative Example 1 Conversion rate of styrene (%) 99 31 Selectivity of phenylpropionaldehyde (%) 99 95 <![CDATA[TOF value (mol C＝C / mol Rh / h)]]> 6006 1111 <![CDATA[TON value (mol C＝C / mol Rh )]]> 36000 6667
[0071] Table 3. Comparison of hydroformylation performance of olefin molecules of different sizes.
[0072]
[0073] Table 4. Shape-selective catalytic hydroformylation performance of Rh1@ZSM-5 and RhCl(PPh3)3 for mixed C8 isomers.
[0074]
[0075] Conclusion:
[0076] Compared with traditional homogeneous catalysts, the present invention shows that the rhodium-based single-atom molecular sieve catalyst has better catalytic performance with a low noble metal usage, has a shape-selective catalytic effect on olefin molecules smaller than the pore window of the molecular sieve, and has high stability, is easy to separate from the products, can be recycled, and has great industrial application prospects. It has a shape-selective catalytic effect on olefin molecules smaller than the pore window of the molecular sieve, has high stability, is easy to separate from the products, can be recycled, and has great industrial application prospects.
Claims
1. Application of a Rh1@zeolite molecular sieve-confined single-atom rhodium-based material, which is used for catalyzing the hydroformylation of olefins, especially for selectively catalyzing the hydroformylation of olefin molecules with molecular sizes smaller than the pore size of the molecular sieve.
2. The application according to claim 1, wherein the Rh1@zeolite is Rh1@ZSM-5, and the olefin is selected from styrene.
3. A method for the hydroformylation of olefins, comprising subjecting an olefin having the structure of R1R2C=CH2 to hydroformylation with syngas CO / H2 at 80°C to 120°C to obtain the product R1R2CH-CH2CHO or R1R2CH(CHO)-CH3, characterized in that Using Rh1@zeolite as a catalyst; wherein, R1 and R2 are independently selected from H, C 1-8 alkane, C 5-20 cycloalkane, C 6-12 aromatic hydrocarbon, C with ring heteroatoms N, O, S 3-12 heteroaromatic hydrocarbon, and the alkane, cycloalkane, aromatic hydrocarbon or heteroaromatic hydrocarbon is further substituted by C 1-6 alkane, halogen, NO3. The syngas is a CO / H2 mixed gas with a ratio of (0.8 - 1):(0.8 - 1).
4. The method according to claim 3, wherein, Rh1@zeolite is Rh1@ZSM-5, and the product is R1R2CHCH2CHO.
5. The method according to claim 3 or 4, wherein The catalytic reaction temperature is 100°C to 120°C, and the catalytic reaction time is 6h to 12h.
6. The method according to any one of claims 3 to 5, wherein: The olefin is C 2-12 olefin, aromatic ring-substituted olefin, and the olefin is a single olefin or a mixed olefin; preferably, the olefin is styrene.
7. The method according to any one of claims 3-6, wherein, The Rh1@zeolite is prepared by the following method, including: S1. Prepare an aqueous solution of a metal Rh complex by mixing a metal Rh salt and a ligand compound to form the aqueous solution. The ligand compound is selected from N-containing compounds. Preferably, the N-containing compound is selected from NH3, ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine, and more preferably ethylenediamine; S2. Drop the aqueous solution of the metal Rh complex obtained in step S1 into the silica-alumina sol precursor solution, and stir at room temperature for 4 - 5h; S3. Add molecular sieve seeds to the metal silica-alumina sol solution in step S2. After stirring at room temperature for 1 - 2h, transfer the mixed solution to a reaction kettle, and carry out static crystallization at 120°C - 180°C for 12h - 72h, preferably 24h - 72h. After cooling to room temperature, wash with water and dry; S4. Calcinate the sample powder obtained in step S3 at 300°C - 500°C, preferably at a calcination temperature of 350°C - 450°C for 2h - 3h to obtain the sample; Among them, Rh is in a single-atom site state and is in-situ confined in the molecular sieve framework structure; The Rh salt is selected from rhodium inorganic salts, preferably rhodium chloride or rhodium nitrate; The selected molecular sieve is not limited in type, and any molecular sieve that can use seeds to replace it as a structure-directing agent to assist in synthesis can be used; The silica-alumina sol precursor is generally a mixture of a silicon source, an aluminum source, an alkali source, a template agent, and water.
8. The method according to claim 7, wherein, The molecular sieve is selected from MFI-type molecular sieves, BEA* -type molecular sieves, FAU-type molecular sieves, RTH-type molecular sieves, MTW-type molecular sieves, LEV-type molecular sieves, FER-type molecular sieves, or MEL-type molecular sieves; preferably, the molecular sieve is an MFI-type molecular sieve or a BEA* -type molecular sieve.
9. The method according to claim 7 or 8, wherein The silicon source is selected from tetraethyl orthosilicate, silica sol, or sodium silicate; the aluminum source is aluminum isopropoxide, aluminum nitrate, or sodium metaaluminate; the alkali source is sodium hydroxide or potassium hydroxide; the template agent is tetrapropylammonium hydroxide or tetraethylammonium hydroxide.
10. The method according to any one of claims 3 to 9, wherein: The catalyst selectively catalyzes hydroformylation.