Rh-based catalysts, processes for their preparation and use, and processes for the hydroformylation of olefins

Abstract

The application relates to the field of olefin catalysis, and discloses a Rh-based catalyst, a preparation method and application thereof, and an olefin hydroformylation method. The catalyst comprises a carrier, an active component and an additive. The active element in the active component is Rh, and the active element in the additive is Co. Rh in the active component is combined with CoO and is loaded on the surface of the carrier, and the CoO is formed by Co in the additive. The Rh-based catalyst has the characteristics of high catalytic activity and easy separation and recovery in a liquid phase, and has the potential for application and industrial production. Specifically, the Rh-based catalyst has excellent catalytic activity in the application of high-carbon olefin hydroformylation reaction.

Description

Technical Field

[0001] This invention relates to the field of olefin catalysis, specifically to Rh-based catalysts, their preparation methods and applications, and methods for the hydroformylation of olefins. Background Technology

[0002] The hydroformylation of olefins is one of the most widely used organic synthesis reactions in chemical production. This reaction refers to the conversion of olefin molecules into aldehyde molecules with one more carbon atom under the action of a catalyst. This process has good atom economy and is currently the most important technology for the production of aldehyde compounds, with a global production capacity of over 20 million tons per year.

[0003] Aldehydes can be further converted into compounds such as alcohols, acids, or amines through reactions such as hydrogenation, oxidation, and reductive amination. These chemicals can be widely used in plasticizers, fragrances, and pharmaceuticals, and have high economic value.

[0004] Currently, the main industrial method is the homogeneous reaction system, which uses metal complexes composed of organophosphorus ligands as catalysts to catalyze the hydroformylation of olefins.

[0005] While homogeneous systems can achieve high olefin conversion rates and product selectivity, homogeneous catalysts face challenges such as difficult catalyst separation, precious metal loss due to catalyst decomposition, and phosphorus pollution. Furthermore, the synthesis of organophosphorus ligands is cumbersome and requires stringent storage and usage conditions.

[0006] The aforementioned problems increase the production cost and energy consumption of homogeneous catalytic systems. In contrast, constructing heterogeneous catalysts by loading the active component onto a support surface allows for the simultaneous catalytic hydroformylation of olefins, while leveraging the advantages of separation and recovery inherent in heterogeneous catalysts to ensure efficient operation of the overall reaction process. Therefore, there is a strong demand for developing a heterogeneous hydroformylation catalyst that meets application requirements at the industrial level.

[0007] The team led by Zeng Jie at the Institute of Advanced Technology, University of Science and Technology of China, disclosed a Rh / CoO nanocatalyst, its preparation method, and its application in CN106362766A. The catalyst uses two-dimensional crystal structure CoO nanosheets as a support and Rh as the active component, and exhibits excellent activity in the hydroformylation reaction of propylene.

[0008] The team led by Zhang Tao at the Dalian Institute of Chemical Physics disclosed in CN107537481A a supported single-atom rhodium-based catalyst and its application in the hydroformylation of olefins. The catalyst uses ZnO nanorods as a support and Rh as the active component, and exhibits excellent activity in the hydroformylation of styrene. Its catalytic performance exceeds that of the classic Wilkinson catalyst RhCl(PPh3)3.

[0009] The team led by Ding Yunjie at the Dalian Institute of Chemical Physics disclosed a catalyst system for the hydroformylation of propylene to butyraldehyde and a method for using it in CN104667977A. The system uses an organic ligand polymer composed of organic ligand monomers containing phosphorus and vinyl groups as a support to support Rh, Ir, or Co, which has a high propylene conversion rate and butyraldehyde selectivity.

[0010] However, the preparation processes of heterogeneous hydroformylation catalysts currently reported in patent literature or papers are all quite complex, and most of them are for the hydroformylation of low-carbon olefins.

[0011] Therefore, developing a catalyst that is easy to prepare and has excellent catalytic performance for the hydroformylation of high-carbon olefins has become a major goal in this field. Summary of the Invention

[0012] The purpose of this invention is to provide a catalyst with excellent catalytic performance that can be used to catalyze the hydroformylation reaction of high-carbon olefins.

[0013] To achieve the above objectives, a first aspect of the present invention provides an Rh-based catalyst comprising a support, an active component, and an auxiliary agent, wherein the active element in the active component is Rh, and the active element in the auxiliary agent is Co; the Rh in the active component is combined with CoO and loaded on the surface of the support, wherein the CoO is formed by Co in the auxiliary agent.

[0014] A second aspect of the present invention provides a method for preparing a Rh-based catalyst, the method comprising:

[0015] (1) The raw material solution containing Rh salt and Co salt is mixed and contacted with the carrier to obtain the first material of solid-liquid mixture;

[0016] (2) The first material is subjected to aging and separation in sequence to obtain a solid second material;

[0017] (3) The second material is subjected to drying and reduction calcination treatment in sequence to obtain the Rh-based catalyst. The reduction calcination treatment is carried out in the presence of a reducing atmosphere.

[0018] A third aspect of the invention provides an Rh-based catalyst prepared by the method described in the second aspect.

[0019] A fourth aspect of the invention provides the use of the Rh-based catalysts described in the first and / or third aspects in hydroformylation reactions.

[0020] A fifth aspect of the present invention provides a method for hydroformylation of olefins, the method comprising: introducing an olefin feedstock into a liquid-solid batch reactor containing a catalyst in the presence of syngas to carry out a hydroformylation reaction;

[0021] The catalyst is the Rh-based catalyst described in the first aspect and / or the third aspect.

[0022] The catalyst provided in this invention can be used for the formylation reaction of high-carbon olefins.

[0023] The Rh-based catalyst of this invention features high catalytic activity and ease of separation and recovery in the liquid phase, making it a potential application in industrial production. Specifically, the Rh-based catalyst of this invention exhibits excellent catalytic activity in the hydroformylation reaction of high-carbon olefins.

[0024] The preparation method provided in this invention is simple, with mild and controllable conditions. The resulting product has high reactivity and high selectivity for carbonylation products (aldehydes and alcohols), making it easy to scale up for production and promising for industrial scale-up. It also features easy separation and recovery, which can greatly reduce reaction energy consumption and cost, making it suitable for industrial applications. Attached Figure Description

[0025] Figure 1 This is the wide-angle XRD pattern of the catalyst in Example 3. Detailed Implementation

[0026] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0027] As previously stated, a first aspect of the present invention provides an Rh-based catalyst comprising a support, an active component, and an auxiliary agent, wherein the active element in the active component is Rh, and the active element in the auxiliary agent is Co; the Rh in the active component is combined with CoO and loaded on the surface of the support, wherein the CoO is formed by Co in the auxiliary agent.

[0028] Preferably, the support is at least one of SiO2, Al2O3, hydroxyapatite, TiO2, and ZrO2.

[0029] In a particularly preferred embodiment, the support is hydrophilic fumed silica nanoparticles. More preferably, the support is hydrophilic fumed SiO2 nanoparticles (Hydrophilic-380).

[0030] In a preferred embodiment, the content of Rh element in the active component is 0.1-1 wt%, based on the mass of the carrier.

[0031] Preferably, based on the mass of the carrier, the content of Co element in the additive is 3-8 wt%.

[0032] Preferably, the molar ratio of Rh element to Co element is 1-10:100, more preferably 5-7:100.

[0033] As previously described, a second aspect of the present invention provides a method for preparing a Rh-based catalyst, the method comprising:

[0034] (1) The raw material solution containing Rh salt and Co salt is mixed and contacted with the carrier to obtain the first material of solid-liquid mixture;

[0035] (2) The first material is subjected to aging and separation in sequence to obtain a solid second material;

[0036] (3) The second material is subjected to drying and reduction calcination treatment in sequence to obtain the Rh-based catalyst. The reduction calcination treatment is carried out in the presence of a reducing atmosphere.

[0037] Preferably, in step (1), the mixing contact is performed in the presence of ultrasound.

[0038] Preferably, the conditions for ultrasound treatment include: a temperature of 20-40℃ and a treatment time of 0.5-2h.

[0039] In a preferred embodiment, in step (1), the molar ratio of Rh salt (calculated as Rh element) to Co salt (calculated as Co element) in the raw material solution is 0.1-10:100, more preferably 0.5-7:100.

[0040] Preferably, in step (1), the weight ratio of the raw material solution to the carrier is 4-8:1; more preferably, it is 4-6:1.

[0041] In a preferred embodiment, the mixing contact time in step (1) is 0.5-2 hours.

[0042] More preferably, in step (1), the temperature of the mixing contact is 20-40°C.

[0043] Preferably, the Rh salt is rhodium trichloride. More preferably, the Rh salt is RhCl3·3H2O.

[0044] Preferably, the Co salt is selected from at least one of cobalt nitrate, cobalt chloride, and cobalt acetate.

[0045] Preferably, the solvent in the raw material solution is selected from at least one of water, methanol, ethanol and acetone.

[0046] According to a preferred embodiment, in step (2), the aging treatment temperature is 10-40°C.

[0047] Preferably, in step (2), the aging treatment time is 0.5-12 hours.

[0048] In a preferred embodiment, in step (3), the drying temperature is 60-100°C, more preferably 60-80°C.

[0049] Preferably, in step (3), the temperature of the reduction roasting treatment is 400-700℃.

[0050] Preferably, in step (3), the reduction calcination treatment time is 2-6 hours, more preferably 3-6 hours.

[0051] Preferably, in step (3), the reducing atmosphere is hydrogen, a hydrogen-argon mixture, or a hydrogen-nitrogen mixture.

[0052] According to a particularly preferred embodiment, the preparation method of the Rh-based catalyst includes: dissolving Rh salt and Co salt in a solvent, stirring at room temperature to uniformly disperse the two to obtain a mixed solution; then adding the solution dropwise to a support, and at room temperature, using ultrasonic treatment to uniformly mix the metal precursor salt solution with the support; then allowing the resulting mixture to age at room temperature for 5-24 hours; next, drying the product to remove the solvent; and finally reducing the product at a first preset temperature in a hydrogen-containing atmosphere to obtain the Rh-based catalyst.

[0053] As previously stated, a third aspect of the present invention provides an Rh-based catalyst prepared by the method described in the second aspect.

[0054] As previously stated, the fourth aspect of the present invention provides the use of the Rh-based catalysts described in the first and / or third aspects in hydroformylation reactions.

[0055] The catalyst described in this invention has a good recovery effect after the reaction is completed. The separated catalyst can be recycled, reducing production costs and facilitating industrial production applications.

[0056] As mentioned above, a fifth aspect of the present invention provides a method for hydroformylation of olefins, the method comprising: introducing an olefin feedstock into a liquid-solid batch reactor containing a catalyst in the presence of syngas to carry out a hydroformylation reaction;

[0057] The catalyst is the Rh-based catalyst described in the first aspect and / or the third aspect.

[0058] Preferably, the olefin feedstock is C6-C. 12 olefins.

[0059] Preferably, the olefin feedstock contains diisobutylene. More preferably, the diisobutylene content in the olefin feedstock is not less than 85 wt%.

[0060] According to a preferred embodiment, the synthesis gas contains CO and H2.

[0061] Preferably, the molar ratio of CO to H2 in the synthesis gas is 1:0.6-1.5.

[0062] In a preferred embodiment, the hydroformylation reaction is carried out at a temperature of 100-180°C, more preferably 100-120°C.

[0063] Preferably, the reaction time for the hydroformylation reaction is 2-12 hours.

[0064] According to a particularly preferred embodiment, the method for olefin hydroformylation includes: loading an Rh-based catalyst into a high-pressure reactor, adding olefin feedstock and an organic solvent to the reactor, sealing it, and then introducing syngas (volume ratio: CO:H2 = 1:1) to a first preset pressure, followed by depressurization to displace air from the system; after three displacements, introducing syngas at a second preset pressure (volume ratio: CO:H2 = 1:1), and adjusting the temperature to 100-120°C to carry out the olefin hydroformylation reaction for 2-8 hours; further, the first preset pressure used to displace the reactor is 1-2 MPa; the second preset pressure is 3-6 MPa; and the mass ratio of the added Rh-based catalyst to the olefin feedstock is (0.05-0.2):1.

[0065] The present invention will be described in detail below through examples. In the following examples, all raw materials used were obtained through commercial means.

[0066] Unless otherwise specified, in this invention, the term "room temperature" refers to 25±1℃.

[0067] In the examples, the catalytic activity of the catalyst is expressed as the conversion rate of olefins and the selectivity of aldehydes and alcohols, and the calculation formula is as follows:

[0068] Olefin conversion rate = (1 - molar amount of olefin after reaction / initial molar amount of olefin) * 100%

[0069] Aldehyde selectivity = (Molar amount of aldehyde in the product) / (Initial molar amount of olefin - Molar amount of olefin after reaction) * 100%

[0070] Alcohol selectivity = (molar amount of alcohol in the product) / (molar amount of initial olefin - molar amount of olefin after reaction) * 100%

[0071] Example 1

[0072] The specific steps for preparing Rh-based catalysts and applying them to the hydroformylation of high-carbon olefins are as follows:

[0073] (1) Weigh 1.38 mg of RhCl3·3H2O and 246 mg of Co(NO3)2·6H2O and dissolve them in 5 mL of anhydrous ethanol to obtain a precursor salt solution of the active component.

[0074] (2) At room temperature, with the aid of a vortex oscillator, the precursor salt solution was added dropwise to 1.000 g of commercially available hydrophilic nano-silica carrier (Hydrophilic-380) for impregnation. Subsequently, the mixture was ultrasonically treated at room temperature to ensure that the carrier and the precursor solution were mixed evenly.

[0075] (3) The mixture was aged at room temperature for 12 hours and then completely dried in an oven at 80°C to obtain the catalyst precursor.

[0076] (4) The catalyst precursor was reduced in a hydrogen atmosphere at a preset temperature of 500℃ for 3 hours to obtain a supported Rh-based catalyst.

[0077] In this catalyst, based on the weight of the support, the mass percentage of Rh is 0.1 wt% and the mass percentage of Co is 5 wt%.

[0078] (5) Take 200 mg of the catalyst A prepared above and add it to a 100 mL high-pressure reactor. Add 10 mmol of the raw material 2,4,4-trimethyl-1-pentene and 10 mL of cyclohexane to the reactor. After sealing, purge with 2 MPa of syngas (CO:H2 = 1:1). Then depressurize and replace the gas in the reactor. Repeat this process three times. Then purge with 4 MPa of syngas (CO:H2 = 1:1). Then heat to 120 °C and react for 8 h. After stopping the reaction, cool to room temperature and depressurize. Add 300 μL of n-decane as an internal standard to the reaction solution and take a sample. Analyze the sample using an Agilent 6890N chromatograph equipped with a DB-WAX capillary column. The catalytic activity test results of the catalyst are shown in Table 1.

[0079] Example 2

[0080] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the only difference being:

[0081] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 4.14 mg.

[0082] In this catalyst, based on the weight of the support, the mass percentage of Rh is 0.3 wt% and the mass percentage of Co is 5 wt%.

[0083] Example 3

[0084] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the only difference being:

[0085] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 6.90 mg.

[0086] In this catalyst, based on the weight of the support, the mass percentage of Rh is 0.5 wt% and the mass percentage of Co is 5 wt%.

[0087] Example 4

[0088] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the only difference being:

[0089] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 9.66 mg.

[0090] In this catalyst, based on the weight of the support, the mass percentage of Rh is 0.7 wt% and the mass percentage of Co is 5.0 wt%.

[0091] Example 5

[0092] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the only difference being:

[0093] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 13.80 mg.

[0094] In this catalyst, based on the weight of the support, the mass percentage of Rh is 1.0 wt% and the mass percentage of Co is 5.0 wt%.

[0095] Example 6

[0096] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the difference being:

[0097] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 6.90 mg, and the carrier used in step (2) is 1.000 g of commercially available nano Al2O3.

[0098] In this catalyst, based on the weight of the support, the mass percentage of Rh is 0.5 wt% and the mass percentage of Co is 5 wt%.

[0099] Example 7

[0100] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the difference being:

[0101] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 6.90 mg, and the carrier used in step (2) is 1.000 g of commercially available nano hydroxyapatite.

[0102] In this catalyst, based on the weight of the support, the mass percentage of Rh is 0.5 wt% and the mass percentage of Co is 5 wt%.

[0103] Example 8

[0104] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the difference being:

[0105] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 6.90 mg, and the olefin raw material in the olefin hydroformylation activity test is 10 mmol of 1-hexene.

[0106] Example 9

[0107] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the difference being:

[0108] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 6.90 mg, and the olefin raw material in the olefin hydroformylation activity test is 10 mmol of 1-octene.

[0109] Example 10

[0110] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the difference being:

[0111] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 6.90 mg, and the olefin raw material in the olefin hydroformylation activity test is 10 mmol of 1-decene.

[0112] Example 11

[0113] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the difference being:

[0114] In this embodiment, the amount of RhCl3·3H2O used in step (1) is 6.90 mg, and the olefin raw material in the olefin hydroformylation activity test is 10 mmol of 1-dodecene.

[0115] Comparative Example 1

[0116] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the only difference being:

[0117] In this comparative example, the amount of RhCl3·3H2O used in step (1) was 0 mg.

[0118] Comparative Example 2

[0119] The catalyst was prepared and its activity in the olefin hydroformylation reaction was tested according to the steps in Example 1, with the only difference being:

[0120] In this comparative example, the amount of Co(NO3)2·6H2O used in step (1) was 0 mg.

[0121] Figure 1 The image shows the wide-angle XRD pattern of the catalyst in Example 3. As shown, characteristic diffraction peaks belonging to the (111) and (200) crystal planes of CoO can be observed at 2θ = 36.5° and 42.4°, respectively, indicating that the Co promoter forms CoO particles on the catalyst surface after calcination and reduction treatment. In addition, studies have shown that Co vacancies on the CoO surface can effectively bind with Rh and improve the catalytic activity of Rh sites.

[0122] The effects of Co and Rh content on catalyst performance in the catalysts of Examples 1 to 5 and Comparative Examples 1 to 2 are shown in Table 1 for specific test results.

[0123] Table 1

[0124]

[0125]

[0126] As shown in Table 1, the Rh-based catalyst prepared in this invention exhibits high olefin conversion and selectivity for carbonylation products (aldehydes and alcohols) in the catalytic hydroformylation of heterogeneous olefins, with Rh playing a crucial role. The catalyst performance gradually improves with increasing Rh content. Specifically, based on the mass of the SiO2 support, the optimal Rh mass fraction is 0.5-0.7 wt%, and further addition beyond this range does not significantly enhance performance.

[0127] Examples 3, 6, and 7 involve fixing the Co and Rh content in the catalyst and changing the support used to affect the catalyst performance. The specific test results are shown in Table 2.

[0128] Table 2

[0129] Mass ratio of Rh to Co Conversion rate (%) Aldehyde selectivity (%) Alcohol selectivity (%) Example 3 0.5:5 96.6 88.1 5.6 Example 6 0.5:5 97.2 85.9 7.9 Example 7 0.5:5 97.2 86.2 6.5

[0130] As can be seen from Table 2, the type of support has no significant effect on the performance of the catalyst. The preparation method provided by this invention can form CoO-modified Rh active species with excellent activity on the surface of different supports to catalyze the hydroformylation reaction of olefins.

[0131] The effect of olefin type on catalyst activity in the olefin hydroformylation activity tests of Examples 3, 8 to 11 is shown in Table 3.

[0132] Table 3

[0133] Example Mass ratio of Rh to Co olefin types Conversion rate, % Aldehyde selectivity, % Alcohol selectivity, % Example 3 0.5:5 2,4,4-Trimethyl-1-pentene 96.6 88.1 5.6 Example 8 0.5:5 1-Hexene 99.6 94.7 1.2 Example 9 0.5:5 1-Octenene 99.1 93.1 0.9 Example 10 0.5:5 1-Decanene 99.3 94.2 1.1 Example 11 0.5:5 1-Dodecene 99.5 95.3 1.0

[0134] As can be seen from Table 3, the Rh-based catalyst prepared in this invention has excellent substrate applicability for C6-C reactions. 12 It exhibits good catalytic activity in the hydroformylation of both straight-chain and branched-chain olefins.

[0135] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A Rh-based catalyst, characterized in that, The catalyst includes a support, an active component, and an auxiliary agent. The active element in the active component is Rh, and the active element in the auxiliary agent is Co. The Rh in the active component combines with CoO and is loaded on the surface of the support, and the CoO is formed by Co in the auxiliary agent.

2. The Rh-based catalyst according to claim 1, characterized in that, The carrier is at least one of SiO2, Al2O3, hydroxyapatite, TiO2, and ZrO2.

3. The Rh-based catalyst according to claim 1 or 2, characterized in that, Based on the mass of the carrier, the content of Rh element in the active component is 0.1-1 wt%.

4. The Rh-based catalyst according to any one of claims 1-3, characterized in that, Based on the mass of the carrier, the Co content in the additive is 3-8 wt%.

5. The Rh-based catalyst according to any one of claims 1-3, characterized in that, The molar ratio of Rh to Co is 1-10:100, preferably 5-7:

100.

6. A method for preparing Rh-based catalysts, characterized in that, The method includes: (1) The raw material solution containing Rh salt and Co salt is mixed and contacted with the carrier to obtain the first material of solid-liquid mixture; (2) The first material is subjected to aging and separation in sequence to obtain a solid second material; (3) The second material is subjected to drying and reduction calcination treatment in sequence to obtain the Rh-based catalyst. The reduction calcination treatment is carried out in the presence of a reducing atmosphere.

7. The method according to claim 6, characterized in that, In step (1), the mixing contact is performed in the presence of ultrasound; Preferably, the conditions for ultrasound treatment include: a temperature of 20-40℃ and a treatment time of 0.5-2h.

8. The method according to claim 6 or 7, characterized in that, In step (1), the molar ratio of Rh salt (calculated as Rh element) to Co salt (calculated as Co element) in the raw material solution is 0.1-10:100, preferably 0.5-7:100; Preferably, in step (1), the weight ratio of the raw material solution to the carrier is 4-6:

1.

9. The method according to any one of claims 6-8, characterized in that, In step (1), the temperature of the mixing contact is 20-40°C; Preferably, the Rh salt is rhodium trichloride; Preferably, the Co salt is selected from at least one of cobalt nitrate, cobalt chloride, and cobalt acetate; Preferably, the solvent in the raw material solution is selected from at least one of water, methanol, ethanol and acetone.

10. The method according to any one of claims 6-9, characterized in that, In step (2), the aging treatment temperature is 10-40℃; Preferably, in step (2), the aging treatment time is 0.5-12 hours.

11. The method according to any one of claims 6-10, characterized in that, In step (3), the drying temperature is 60-100℃.

12. The method according to any one of claims 6-11, characterized in that, In step (3), the temperature of the reduction calcination treatment is 400-700℃; Preferably, in step (3), the reduction calcination treatment takes 2-6 hours; Preferably, in step (3), the reducing atmosphere is hydrogen, a hydrogen-argon mixture, or a hydrogen-nitrogen mixture.

13. The Rh-based catalyst prepared by the method according to any one of claims 6-12.

14. The use of the Rh-based catalyst according to any one of claims 1-5, 13 in the hydroformylation reaction.

15. A method for hydroformylation of an olefin, characterized in that, The method includes: introducing an olefin feedstock into a liquid-solid batch reactor containing a catalyst for hydroformylation in the presence of syngas; The catalyst is the Rh-based catalyst according to any one of claims 1-5 and 13.

16. The method according to claim 15, characterized in that, The olefin feedstock is C6-C. 12 olefins; Preferably, the olefin feedstock contains diisobutylene; Preferably, the content of diisobutylene in the olefin feedstock is not less than 85 wt%.

17. The method according to claim 15 or 16, characterized in that, The synthesis gas contains CO and H2; Preferably, the molar ratio of CO to H2 in the synthesis gas is 1:0.6-1.

5.

18. The method according to any one of claims 15-17, characterized in that, The reaction temperature for the hydroformylation reaction is 100-180℃, preferably 100-120℃; Preferably, the reaction time for the hydroformylation reaction is 2-12 hours.

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