Catalyst for preparing isononanal through diisobutylene hydroformylation as well as preparation method and application of catalyst

Abstract

The invention discloses a nitrogen atom-doped silicon dioxide rhodium-loaded supported catalyst Rh (at) N-SiO2, based on the total weight of the catalyst, in terms of Rh atoms, the content of Rh is 0.2-0.5%, the balance is a nitrogen atom in-situ doped silicon dioxide carrier with a large specific surface area, based on the mass of the whole supported catalyst Rh (at) N-SiO2, the doping amount of nitrogen atoms is 0.5-10%, and the doping amount of rhodium is 0.5-10%. The invention also relates to a preparation method of the catalyst and application of the catalyst in catalyzing efficient hydroformylation of diisobutylene to prepare isononanal. The catalyst is good in long-term stability, and the diisobutylene conversion rate and the isononanal selectivity are both larger than or equal to 90% in the catalytic diisobutylene hydroformylation reaction. The structure of the catalyst mainly comprises micropores and contains a small amount of mesopores. The material belongs to a heterogeneous catalytic material, solves the technical problem that the material is difficult to recycle, is convenient to recycle, and reduces the use cost. The catalyst can realize high-efficiency hydroformylation of diisobutylene to prepare isononanal, can be recycled and has an industrial application prospect in the aspect of olefin hydroformylation.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemicals, and in particular to a nitrogen atom-doped silica-supported rhodium catalyst and a preparation method thereof, as well as use of the catalyst in catalyzing the preparation of isononanal from diisobutylene. Background Art

[0002] Hydroformylation involves the reaction of olefins with synthesis gas under transition metal catalysis to produce aldehydes with an additional carbon. This reaction boasts high atom economy, and the resulting aldehydes can be further processed through hydrogenation, reductive amination, and oxidation to produce high-value-added fine chemicals such as alcohols, amines, and acids. Approximately 23 million tons of oxygenates are produced annually through this process. The aldehydes and alcohols produced through hydroformylation are primarily used industrially to manufacture plasticizers, surfactants, and detergents. Among these, diisobutylene is hydroformylated to produce isononanal, which is further hydrogenated to produce isononanol, which is commonly used to produce plasticizers such as diisononyl phthalate (DINP), diisononyl adipate (DINA), and tris(hydroxymethyl)triisononanoate (TINTM). Plasticizers made with isononanol are primarily used in the PVC industry and can be found in automotive, wire and cable, and conductive applications. Therefore, research on diisobutylene hydroformylation is of great significance.

[0003] Rhodium is a well-known hydroformylation catalyst. Rh-based homogeneous catalysts have high activity and selectivity for linear aldehydes and are mainly used in industrial hydroformylation reaction processes. In particular, the Wilkinson catalyst based on [RhCl(PPh3)3] (Ph = phenyl) is widely used in commercial hydroformylation processes for the selective production of aldehydes. Although homogeneous catalysts have the advantages of controlling chemical selectivity, regioselectivity and enantioselectivity, in hydroformylation reactions, expensive Rh-based metal organic catalysts are still difficult to separate from raw materials and products, which greatly reduces process efficiency. In order to overcome this problem, many new heterogeneous catalysts have been developed. Among them, supported catalysts in heterogeneous systems have always attracted much attention. The catalytic performance depends on factors such as reaction conditions, catalyst composition, metal dispersion and the type of support used. Among them, the selection of a suitable support is crucial.

[0004] Xiao Fengshou's team developed a porous polymer-supported single-atom Rh catalyst and achieved good results (J.Am.Chem.Soc.2015,137,15,5204–5209), but the synthesis process of organic supports such as porous polymers is relatively complicated and their performance is easily affected by the environment. Therefore, in order to solve this problem, other inorganic supports such as activated carbon and metal oxides have also been proposed. Shi Feng's team prepared a CoFe bimetallic heterogeneous catalyst CoFe / NC supported on N-doped activated carbon. The catalyst CoFe / NC-800 treated at 800°C had the best catalytic activity. At a reaction pressure of 4 MPa and a reaction temperature of 130°C, the conversion rate of diisobutylene hydroformylation reached 92%, but the selectivity for isononanal was only 79.6%. (J.Phys.Chem.2022,126,273-281). Professor Ma Xinbin's team used SiO2 as a support to load Rh single atoms and nanoclusters for the preparation of ethanolaldehyde, and obtained a high TOF (183h -1 ), but the performance of such catalysts still cannot meet the large-scale production requirements of long-chain olefins (Chem. Eng. J 2024, 481, 148529).

[0005] Therefore, there is still a need to develop new Rh-based catalysts with long-term operational stability for industrial production. Summary of the Invention

[0006] To address the aforementioned issues with the existing technology, the present invention loads precious metal rhodium onto a nitrogen-doped, high-surface-area silica support, calcining it to form a Rh@N-SiO2 catalyst. This catalyst is then used in the diisobutylene hydroformylation reaction. This catalyst exhibits excellent long-term stability, achieving a diisobutylene conversion rate and isononanal selectivity of ≥90% in the diisobutylene hydroformylation reaction.

[0007] According to one aspect of the present invention, an object of the present invention is to provide a nitrogen-doped silica-supported rhodium supported catalyst Rh@N-SiO2, wherein the Rh content is 0.2-0.5% based on the total weight of the catalyst, calculated as Rh atoms, and the remainder is nitrogen atoms in situ doped with a silica support having a large specific surface area, wherein the nitrogen doping amount is 0.5% to 10%, preferably 0.5% to 5%, and more preferably 0.5% to 3%, based on the mass of the entire supported catalyst Rh@N-SiO2. This strengthens the interaction between the support and the rhodium active center, thereby regulating the electronic structure of the rhodium metal active center and anchoring the active site, thereby improving the activity and stability of the catalyst.

[0008] According to another aspect of the present invention, another object of the present invention is to provide a method for preparing the Rh@N-SiO2 catalyst, which is carried out as follows:

[0009] 1) Urea and 37% formaldehyde solution were added to a NaOH solution and stirred at room temperature for 30 minutes to prepare Solution A. A 0.2M HCl solution was placed in a polytetrafluoroethylene (PTFE) liner, and tetraethyl orthosilicate and Solution A were added sequentially with continuous stirring, wherein the molar ratio of urea:formaldehyde:tetraethyl orthosilicate was 1:5:1. The resulting mixture was heated to 30-60°C and stirred for 10 minutes. The liner was then sealed in a hydrothermal autoclave and maintained at 80-150°C for 24 hours. The resulting gel was filtered, washed with distilled water, and vacuum-dried at 60°C overnight. The mixture was then transferred to a tube furnace and heated to 200-600°C at a rate of 5°C / min. The mixture was calcined under an inert atmosphere for 2-12 hours to produce the nitrogen-doped silica support N-SiO2.

[0010] 2) dissolving the Rh salt in a solvent to obtain a Rh salt solution, adding the N-SiO2 prepared in step 1) to the Rh salt solution, stirring at room temperature for 4-24 hours, then removing the solvent and vacuum drying at 50-100°C for 2-12 hours, and finally transferring to a tube furnace, heating the temperature to 200-600°C at a rate of 2-5°C / min, and calcining under an inert atmosphere for 2-12 hours to obtain the catalyst Rh@N-SiO2.

[0011] Preferably, the calcination condition in step 1) is 400° C. and the calcination time is 3 hours.

[0012] Preferably, the calcination condition in step 2) is 300° C. and the calcination time is 2 hours.

[0013] Preferably, the rhodium salt in step 2) is selected from one or more of rhodium trichloride trihydrate, sodium hexachlororhodate, rhodium acetate, and rhodium nitrate.

[0014] Preferably, the solvent in step 2) is selected from one or more of water, methanol, ethanol, and isopropanol, and is preferably deionized water.

[0015] Preferably, the inert atmosphere in step 1) and step 2) is a nitrogen atmosphere or an argon atmosphere.

[0016] Preferably, in the catalyst Rh@N-SiO2 obtained in step 2), the Rh content is 0.2-0.5% in terms of Rh atoms based on the total weight of the catalyst, and the rest is nitrogen atoms doped into the silica support.

[0017] According to another aspect of the present invention, another object of the present invention is to provide use of the nitrogen atom-doped silica-supported rhodium catalyst Rh@N-SiO2 in the hydroformylation reaction of olefins.

[0018] Preferably, the hydroformylation reaction of olefins is a reaction of preparing isononanal from diisobutylene.

[0019] According to another aspect of the present invention, another object of the present invention is to provide a method for hydroformylation of olefins using the Rh@N-SiO2 catalyst, wherein the method is carried out as follows:

[0020] A certain amount of Rh@N-SiO2 catalyst according to the present invention, olefin, and solvent are added to a high-pressure reactor, and a high-pressure CO and H2 mixed gas with a volume ratio of 1:1 is filled into the reactor. The reaction temperature is set at 80-200°C and the reaction time is 4-24 hours.

[0021] Preferably, after the olefin hydroformylation reaction method according to the present invention is completed, the catalyst can be directly centrifuged and separated from the system after the reaction is completed, and reused after being centrifuged and washed three times with ethyl acetate. After being reused six times, its performance is not significantly reduced.

[0022] Preferably, the gas pressure of the olefin hydroformylation reaction is 0.5-10.0 MPa, the reaction temperature is 110° C., and the reaction time is 6 hours.

[0023] Preferably, the solvent is selected from one or more of toluene, tetrahydrofuran, acetonitrile, n-hexane, n-octane, dimethylformamide, n-heptane, and cyclohexane.

[0024] Preferably, the olefin is a C1-C12 olefin monomer containing at least one double bond, for example, selected from ethylene, propylene, n-butene, isobutylene, diisobutylene, and the like.

[0025] Preferably, in the hydroformylation reaction method, the Rh@N-SiO2 catalyst can be reused less than 50 times, preferably less than 30 times, and more preferably less than 6 times, while still maintaining stable catalytic activity.

[0026] Beneficial effects

[0027] The Rh@N-SiO2 catalyst described in the present invention has a predominantly microporous structure with a small amount of mesopores. Furthermore, this heterogeneous catalytic material overcomes the technical challenges of material recovery, facilitating recycling and reducing operational costs. This catalyst enables efficient hydroformylation of diisobutylene to produce isononanal and is recyclable, showing promising industrial applications in olefin hydroformylation. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are 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.

[0029] Figure 1 Schematic diagram of the process for preparing the Rh@N-SiO2 catalyst according to the present invention.

[0030] Figure 2 This is the BET diagram of the Rh@N-SiO2 catalyst in Example 1 of the present invention.

[0031] Figure 3 This is the SEM image of the Rh@N-SiO2 catalyst in Example 1 of the present invention.

[0032] Figure 4 This is the XPS graph of the Rh@N-SiO2 catalyst in Example 1 of the present invention.

[0033] Figure 5 This is a diagram showing the effect of catalyst reuse in the hydroformylation reaction of diisobutylene catalyzed by the Rh@N-SiO2 catalyst prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Prior to the description, it should be understood that the terms used in the specification and the appended claims are not to be construed as limited to their general and dictionary meanings, but rather should be interpreted based on the meanings and concepts corresponding to the technical aspects of the present invention, based on the principle that allows the inventor to appropriately define the terms for the best interpretation. Therefore, the description herein is merely a preferred example for illustrative purposes and is not intended to limit the scope of the present invention. It should be understood that other equivalent implementations and modifications may be made without departing from the spirit and scope of the present invention.

[0035] As used herein, the terms "comprises," "includes," "has," "contains" or any other similar terms are open conjunctions that are intended to cover non-exclusive inclusions. For example, a composition or article containing multiple elements is not limited to the elements listed herein, but may also include other elements that are not explicitly listed but are generally inherent to the composition or article. In addition, unless expressly stated to the contrary, the term "or" refers to an inclusive "or" rather than an exclusive "or." For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). In addition, as used herein, the terms "comprises," "includes," "has," and "contains" should be interpreted as specifically disclosed and simultaneously cover closed or semi-closed conjunctions such as "consisting of" and "consisting essentially of."

[0036] Throughout this document, all features or conditions defined as numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered to encompass and specifically disclose all possible subranges and individual values within those ranges, particularly integer values. For example, a description of a range "1 to 8" should be considered to specifically disclose all possible subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so forth, particularly those defined by all integer values, and should be considered to specifically disclose individual values within those ranges such as 1, 2, 3, 4, 5, 6, 7, and 8. Unless otherwise indicated, the foregoing interpretation applies to all of the present disclosure, regardless of whether the ranges are comprehensive or not.

[0037] If a quantity or other value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it should be understood that all ranges consisting of any upper limit or preferred value of the range and any lower limit or preferred value of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, when a numerical range is mentioned herein, unless otherwise specified, the range should include its endpoints and all integers and fractions within the range.

[0038] In this document, numerical values should be understood to have the accuracy of the number of significant digits of the numerical value, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0039] When the reaction conditions, such as reaction temperature and reaction time, in the olefin hydroformylation method according to the present invention are within the above ranges, optimal reaction efficiency can be achieved. For example, when the reaction conditions are below this range, the catalyst has a poor substrate conversion effect. When the reaction conditions are above this range, the production of the byproduct isononanol in the system will increase, which is not conducive to the selectivity of the target product.

[0040] In addition, unless otherwise specified, the reagents and solvents disclosed below were purchased from Shanghai MacLean Biochemical Technology Co., Ltd., BET was measured using Belsorp max x of Microtrac MRB from Microtrac Biotechnology, scanning electron microscopy was measured using S4800 series from Hitachi, Japan, and XPS was measured using Axis Supra+ from Shimadzu Kratos.

[0041] The following examples are merely examples of embodiments of the present invention and do not constitute any limitation thereto. Those skilled in the art will appreciate that modifications without departing from the spirit and scope of the present invention fall within the scope of protection of the present invention. Unless otherwise specified, the reagents and instruments used in the following examples are commercially available products.

[0042] Preparation Example 1: Preparation of Catalyst 1

[0043] Solution A was prepared by adding 1.5 g of urea and 10 mL of 37% formaldehyde solution to 10 mL of NaOH solution (pH 8) and stirring at room temperature for 30 minutes. At 30°C, 30 mL of distilled water and 5.0 mL of 0.2 M HCl solution were mixed in a polytetrafluoroethylene-lined container. 7 mL of tetraethyl orthosilicate and Solution A were added sequentially with continuous stirring. The mixture was heated to 30-60°C and stirred for 10 minutes. The container was then sealed and placed in a hydrothermal autoclave, where it was maintained at 80-150°C for 24 hours. The resulting gel was filtered, washed with distilled water, and vacuum-dried at 60°C overnight. Finally, the product was transferred to a tube furnace and heated to 400°C at a rate of 5°C / min. It was then calcined under a nitrogen atmosphere for 3 hours to produce the nitrogen-doped silica support, N-SiO2.

[0044] 8.2 mg of RhCl3·3H2O was dissolved in 50 mL of deionized water, and then 400 mg of the prepared N-SiO2 was added thereto. The mixture was immersed and stirred at room temperature for 12 hours, and then washed three times with deionized water. The mixture was dried at 60°C in a vacuum drying oven for 6 hours. Finally, the mixture was transferred to a tubular furnace and heated to 300°C at a rate of 5°C / min. The Rh@N-SiO2 supported catalyst 1 was obtained by calcining the mixture under a nitrogen atmosphere for 2 hours.

[0045] Figure 2 The BET characterization diagram of the Rh@N-SiO2 catalyst in this embodiment shows that its specific surface area is 447.0 m 2 / g, the catalyst is a large specific surface area supported catalyst containing a large number of micropores and a small amount of mesopores.

[0046] Figure 3This is the SEM characterization image of the Rh@N-SiO2 catalyst in this example. It can be seen from the figure that the catalyst has an irregular morphology and is an amorphous silica material.

[0047] Figure 4 This is the XPS characterization diagram of the Rh@N-SiO2 catalyst in this example. It can be seen from the figure that the doped nitrogen element exists in the form of pyridinic nitrogen and pyrrolic nitrogen.

[0048] Figure 5 This is a diagram showing the effect of catalyst reuse for the hydroformylation reaction of diisobutylene catalyzed by the Rh@N-SiO2 catalyst prepared in this example. The Rh@N-SiO2 catalyst can still maintain good catalytic performance even after being recycled 6 times, while the catalyst Rh-SiO2 not doped with nitrogen cannot be recycled multiple times. This further illustrates that the addition of nitrogen strengthens the interaction between the support and the rhodium active center, thereby regulating the electronic structure of the rhodium metal active center and anchoring the active site, thereby improving the activity and stability of the catalyst.

[0049] Preparation Example 2: Preparation of Catalyst 2

[0050] At 30°C, 30 mL of distilled water and 5.0 mL of 0.2 M HCl solution were mixed in a polytetrafluoroethylene (PTFE) liner. 7 mL of tetraethyl orthosilicate was added with continuous stirring. The mixture was heated to 30-60°C and stirred for 10 minutes. The liner was then sealed and placed in a hydrothermal autoclave, where it was maintained at 80-150°C for 24 hours. The resulting gel was filtered, washed with distilled water, and vacuum-dried at 60°C overnight. Finally, the gel was transferred to a tube furnace and heated to 400°C at a rate of 5°C / min. It was then calcined under a nitrogen atmosphere for 3 hours to produce the silica support SiO2.

[0051] 8.2 mg of RhCl3·3H2O was dissolved in 50 mL of deionized water, and then 400 mg of the prepared SiO2 was added thereto. The mixture was immersed and stirred at room temperature for 12 hours, and then washed three times with deionized water. The mixture was dried at 60°C in a vacuum drying oven for 6 hours. Finally, the mixture was transferred to a tubular furnace and heated to 300°C at a rate of 5°C / min. The mixture was calcined in a nitrogen atmosphere for 2 hours to obtain Rh-SiO2 solid-supported catalyst 2.

[0052] Test Example 1: Hydroformylation of olefins

[0053] 100 mg of the catalyst Rh@N-SiO2 prepared in Example 1, 1 mL of diisobutylene, and 10 mL of toluene were added to a 50 mL autoclave, and the mixture was charged with 5 MPa of CO / H2 (V:V=1:1). The reaction was carried out at 110°C for 6 hours. Gas chromatography analysis showed that the diisobutylene conversion was 90.9%, with an aldehyde selectivity of 93.1%.

[0054] Test Example 2: Hydroformylation of olefins

[0055] 100 mg of the catalyst Rh-SiO2 prepared in Example 2, 1 mL of diisobutylene, and 10 mL of toluene were added to a 50 mL autoclave, and charged with 5 MPa of CO / H2 mixed gas (V:V=1:1). The reaction was carried out at 110°C for 6 hours. Gas chromatography analysis showed that the diisobutylene conversion was 95.9%, with an aldehyde selectivity of 85.3%.

[0056] Test Example 3: Catalyst circulation experiment

[0057] The Rh@N-SiO2 catalysts and the Rh-SiO2 solid-supported composite catalyst prepared in Preparation Example 1 and Preparation Example 2, respectively, were filtered, washed, and centrifuged. They were then added to a 50 mL autoclave with 1 mL of diisobutylene and 10 mL of toluene. The mixture was then charged with a 5 MPa CO / H2 mixture (V:V = 1:1) and reacted at 110°C for 6 hours. Gas chromatography revealed that both catalysts were recycled six times. The Rh@N-SiO2 catalyst in Preparation Example 1 exhibited a diisobutylene conversion exceeding 85% and an aldehyde selectivity exceeding 91%. Specific data are shown in Table 1. As can be seen from the data in Table 1, the Rh@N-SiO2 solid-supported composite catalyst according to the present invention maintained good catalytic performance even after six cycles, while the undoped nitrogen-doped Rh-SiO2 catalyst could not be recycled multiple times.

[0058] Table 1: Comparison of cyclic performance between Rh@N-SiO2 and Rh-SiO2

[0059]

[0060] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A nitrogen-doped silica-supported rhodium supported catalyst Rh@N-SiO2, wherein the Rh content is 0.2-0.5% based on the total weight of the catalyst, calculated as Rh atoms, and the remainder is nitrogen atoms in situ doped on a silica support with a large specific surface area, wherein: Based on the mass of the entire supported catalyst Rh@N-SiO2, the doping amount of nitrogen atoms is 0.5% to 10%, preferably 0.5% to 5%, and more preferably 0.5% to 3%.

2. The preparation method of the Rh@N-SiO2 catalyst according to claim 1, wherein the preparation method is carried out as follows: 1) adding urea and 37% formaldehyde solution to a NaOH solution and stirring at room temperature for 30 minutes to prepare solution A; placing a 0.2M HCl solution in a polytetrafluoroethylene liner, and sequentially adding tetraethyl orthosilicate and solution A under continuous stirring, wherein the molar ratio of urea:formaldehyde:tetraethyl orthosilicate is 1:5:1; heating the resulting mixture to 30-60°C and stirring for 10 minutes, then sealing the liner in a hydrothermal autoclave and maintaining it at 80-150°C for 24 hours, finally filtering out the formed gel, washing with distilled water, vacuum drying at 60°C overnight, and finally transferring to a tube furnace, heating the temperature to 200-600°C at a rate of 5°C / min, and calcining under an inert atmosphere for 2-12 hours to prepare a nitrogen-doped silica support N-SiO2; 2) dissolving the Rh salt in a solvent to obtain a Rh salt solution, adding the N-SiO2 prepared in step 1) to the Rh salt solution, stirring at room temperature for 4-24 hours, then removing the solvent and vacuum drying at 50-100°C for 2-12 hours, and finally transferring to a tube furnace, heating the temperature to 200-600°C at a rate of 2-5°C / min, and calcining under an inert atmosphere for 2-12 hours to obtain the catalyst Rh@N-SiO2.

3. The method for preparing the Rh@N-SiO2 catalyst according to claim 2, characterized in that: The calcination condition in step 1) is 400° C. and the calcination time is 3 hours.

4. The method for preparing the Rh@N-SiO2 catalyst according to claim 2, wherein: The calcination condition in step 2) is 300° C. and the calcination time is 2 hours.

5. The method for preparing the Rh@N-SiO2 catalyst according to claim 2, wherein: The rhodium salt in step 2) is selected from one or more of rhodium trichloride trihydrate, sodium hexachlororhodate, rhodium acetate, and rhodium nitrate.

6. The method for preparing the Rh@N-SiO2 catalyst according to claim 2, wherein: The solvent in step 2) is selected from one or more of water, methanol, ethanol, and isopropanol, preferably deionized water.

7. The method for preparing the Rh@N-SiO2 catalyst according to claim 2, wherein: The inert atmosphere in step 1) and step 2) is a nitrogen atmosphere or an argon atmosphere.

8. The method for preparing the Rh@N-SiO2 catalyst according to claim 2, wherein: In the catalyst Rh@N-SiO2 obtained in step 2), the Rh content is 0.2-0.5% in terms of Rh atoms based on the total weight of the catalyst, and the rest is nitrogen atoms doped into the silica support.

9. Use of the Rh@N-SiO2 catalyst according to claim 1 in the hydroformylation reaction of olefins; Preferably, the hydroformylation reaction of olefins is a reaction of preparing isononanal from diisobutylene.

10. A method for hydroformylation of olefins using the Rh@N-SiO2 catalyst according to claim 1, wherein the method is carried out as follows: A certain amount of the Rh@N-SiO2 catalyst according to claim 1, an olefin, and a solvent are added to a high-pressure reactor, and a high-pressure CO and H2 mixed gas with a volume ratio of 1:1 is filled into the reactor. The reaction temperature is set at 80-200°C and the reaction time is 4-24 hours; Preferably, after the olefin hydroformylation reaction method is completed, the catalyst can be directly centrifuged from the system after the reaction is completed, and reused after being centrifuged and washed three times with ethyl acetate. After being reused six times, its performance is not significantly reduced; Preferably, the gas pressure of the olefin hydroformylation reaction is 0.5-10.0 MPa, the reaction temperature is 110° C., and the reaction time is 6 hours; Preferably, the solvent is selected from one or more of toluene, tetrahydrofuran, acetonitrile, n-hexane, n-octane, dimethylformamide, n-heptane, and cyclohexane; Preferably, the olefin is a C1-C12 olefin monomer containing at least one double bond, for example, it can be selected from ethylene, propylene, n-butene, isobutylene, diisobutylene; Preferably, in the hydroformylation reaction method, the Rh@N-SiO2 catalyst can be reused less than 50 times, preferably less than 30 times, and more preferably less than 6 times, while still maintaining stable catalytic activity.

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