Cobalt-rhodium-doped nitrided activated carbon supported composite catalyst and preparation method and application thereof

Abstract

The invention discloses a cobalt-rhodium-doped nitrided activated carbon supported composite catalyst and a preparation method thereof, and application of the catalyst in preparation of aldehyde by catalyzing olefin, especially application of diisobutylene in preparation of isononanal. In the composite catalyst, the content of Rh is 0.2-1.5 wt% in terms of Rh atoms, the content of Co is 0.1-0.8 wt% in terms of Co atoms, the mass ratio of Co to Rh is 10: 1-1: 1, preferably 2: 1, and Co and Rh exist in the form of nanoclusters or monatomic atoms and are connected to a carbon nitride skeleton structure in the form of covalent bonds. According to the composite catalyst, the structure mainly comprises micropores and is provided with a small number of mesopores and macropores, the adsorption capacity of the material is enhanced, meanwhile, the material belongs to a heterogeneous catalytic material, the technical problem that the material is difficult to recycle is solved, cyclic utilization is facilitated, and the use cost is reduced. 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 invention relates to the technical field of fine chemical industry, and in particular to a cobalt-rhodium doped nitrided activated carbon supported composite catalyst and a preparation method thereof, as well as use of the catalyst in catalyzing olefins to prepare aldehydes, in particular to use of diisobutylene in preparing isononanal. Background Art

[0002] Hydroformylation refers to the reaction process in which olefins react with synthesis gas under the catalysis of transition metal complexes to generate straight-chain aldehydes or branched-chain aldehydes. The reaction was first discovered and studied by German chemists in the process of studying the Fischer-Tropsch synthesis reaction. In industry, hydroformylation mainly uses homogeneous metal cobalt or rhodium complexes as catalysts, which makes it difficult to separate, recover and recycle the catalyst after the reaction. For example, in the hydroformylation reaction using the carbonyl complex of triphenylphosphine and rhodium as a catalyst, the catalyst needs to be separated from the product by distillation after the reaction. However, for high-carbon olefins (>C5), the product has a higher boiling point and must be distilled at high temperature to separate the catalyst, and high temperature will deactivate the homogeneous catalyst.

[0003] Therefore, heterogeneous catalysts are an important research direction in this field. In recent years, with the development and application of new carrier materials, heterogeneous hydroformylation catalysts have made great progress. Among them, representative new carrier materials include SiO2, metal oxide materials, etc. Professor Zeng Jie's team developed a CoO-loaded single-atom Rh catalyst and applied it to the preparation reaction of butyraldehyde, achieving good results, but the cost of the catalyst also limits the industrial application of such catalysts (Nature Communications 2016,7,14036). Professor Ma Xinbin's team used SiO2 as a carrier to load Rh single atoms and nanoclusters for the preparation of ethanolaldehyde, and obtained a higher TOF (183h-1), but the performance of such catalysts still cannot meet the large-scale production needs of long-chain olefins (Chem.Eng.J 2024,481,148529). In previous studies (Chinese patent, application number 202410745797.1), the inventors have developed a composite catalyst doped with Rh and Co using the metal organic framework ZIF-67 as a carrier, which can also achieve efficient olefin hydroformylation reaction, and the catalyst can be easily separated and recovered. However, the preparation process of the composite catalyst is relatively cumbersome, and it is necessary to synthesize ZIF-67 derived carbon materials first, and the cost is relatively high. Therefore, the development of high-performance, mass-producible heterogeneous hydroformylation catalysts is still a problem to be solved in this field. Summary of the invention

[0004] In view of the problems existing in the above-mentioned prior art, the present invention adds precious metal Rh and non-precious metal Co to a nitrided activated carbon material with strong adsorption function, forms a composite catalyst by roasting, and uses it in the diisobutylene hydroformylation reaction process. The catalyst has good stability, and the diisobutylene conversion rate and isononanal selectivity in the catalytic diisobutylene hydroformylation reaction are both ≥98%.

[0005] According to one aspect of the present invention, an object of the present invention is to provide a CoRh-doped nitrided activated carbon (CoRh-NAC) supported composite catalyst, wherein the Rh content is 0.2-1.5wt% based on Rh atoms, the Co content is 0.1-0.8wt% based on Co atoms, the mass ratio of Co to Rh is 10:1-1:1, preferably 2:1, and Co and Rh exist in the form of nanoclusters or single atoms and are connected to the carbon nitride skeleton structure in the form of covalent bonds, which makes the active centers more closely connected on the catalyst surface.

[0006] According to another aspect of the present invention, another object of the present invention is to provide a method for preparing the CoRh-NAC supported composite catalyst, the preparation method being carried out as follows:

[0007] 1) Mix the commercial activated carbon material and the nitrogen source in a certain mass ratio, and calcine at 400-800° C. for 1-4 hours under an inert atmosphere to form a nitrided activated carbon material NAC.

[0008] 2) dissolving the cobalt salt precursor and the rhodium salt precursor in a certain amount of solvent, adding an appropriate amount of NAC, mixing and stirring for 24-72 hours;

[0009] 3) The precipitate obtained in step 2) is centrifuged and washed three times with ethanol, the product is vacuum dried at 60-80° C., the obtained solid is ground and calcined at 300-850° C. for 2-4 hours under an inert atmosphere to obtain a CoRh-NAC supported composite catalyst.

[0010] Preferably, the nitrogen source in step 1) is selected from one or more of urea, alanine, glycine, melamine, EDTA, and chitosan;

[0011] Preferably, the calcination condition in step 1) is 600° C. and the reaction time is 4 hours;

[0012] Preferably, the cobalt salt in step 2) is selected from one or more of cobalt nitrate hexahydrate, cobalt sulfate heptahydrate, cobalt chloride hexahydrate, cobalt naphthenate, cobalt stearate, cobalt neodecanoate and cobalt boroacylate;

[0013] Preferably, the solvent in step 2) is selected from one or more of methanol, ethanol or propanol, preferably ethanol;

[0014] Preferably, the rhodium salt in step 2) is selected from one or more of rhodium trichloride trihydrate, sodium hexachlororhodate, rhodium acetate, and rhodium nitrate;

[0015] Preferably, the inert atmosphere in step 1) and step 3) is a nitrogen atmosphere or an argon atmosphere;

[0016] Preferably, the calcination temperature in step 3) is 600° C. and the calcination time is 2 hours.

[0017] According to another aspect of the present invention, another object of the present invention is to provide use of the CoRh-NAC supported composite catalyst 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 CoRh-NAC supported composite catalyst, the method being carried out as follows:

[0020] A certain amount of the CoRh-NAC supported composite catalyst according to the present invention, olefins, 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, and the reaction temperature is set at 80-200°C and the reaction time is 4-24 hours.

[0021] When the reaction conditions in the olefin hydroformylation reaction method according to the present invention, such as reaction temperature and reaction time, are within the above range, the optimal reaction efficiency can be achieved. For example, when the reaction conditions are lower than the range, the catalyst has a poor substrate conversion effect. When the reaction conditions are higher than the range, the amount of the byproduct isononanol in the system will increase, which is not conducive to the selectivity of the target product.

[0022] Preferably, after the olefin hydroformylation reaction method according to the present invention is completed, the catalyst can be directly separated by centrifugation from the system after the reaction is completed, and reused after being centrifuged and washed three times with ethyl acetate. After being reused ten times, its performance is not significantly reduced.

[0023] Preferably, the gas pressure of the olefin hydroformylation reaction is 0.5-10.0 MPa, the reaction temperature is 100° C., and the reaction time is 12 hours.

[0024] Preferably, the solvent is selected from one or more of toluene, tetrahydrofuran, acetonitrile, n-hexane, n-octane, dimethylformamide, n-heptane and cyclohexane.

[0025] 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 and the like.

[0026] Preferably, in the hydroformylation reaction method, the CoRh-NAC supported composite catalyst can be reused less than 50 times, preferably reused less than 30 times, and more preferably reused less than 10 times, while still maintaining a stable catalytic activity.

[0027] Beneficial Effects

[0028] According to the Rh-Co-C supported composite catalyst of the present invention, the structure is mainly micropores with a small amount of mesopores and macropores, which enhances the adsorption capacity of the material. At the same time, the material belongs to a heterogeneous catalytic material, which solves the technical problem that the material is difficult to recycle, is easy to recycle, and reduces the cost of use. The catalyst can realize the efficient hydroformylation of diisobutylene to prepare isononaldehyde, and can be recycled and reused, and has industrial application prospects in olefin hydroformylation. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 This is the XRD spectrum of the CoRh-NAC supported composite catalyst prepared in Example 1 of the present invention.

[0031] Figure 2 This is a SEM image of the CoRh-NAC supported composite catalyst prepared in Example 1 of the present invention.

[0032] Figure 3 This is a TEM image of the CoRh-NAC supported composite catalyst prepared in Example 1 of the present invention.

[0033] Figure 4 This is a diagram showing the effect of catalyst reuse in the hydroformylation reaction of diisobutylene catalyzed by the CoRh-NAC supported composite catalyst prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] Hereinafter, the preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the description, it should be understood that the terms used in the specification and the appended claims should not be interpreted as limited to the general and dictionary meanings, but should be interpreted based on the principle of allowing the inventor to appropriately define the terms for the best interpretation, based on the meaning and concept corresponding to the technical level of the present invention. Therefore, the description herein is only a preferred example for illustrative purposes, and is not intended to limit the scope of the present invention, so it should be understood that other equivalent implementations and modifications can be made without departing from the spirit and scope of the present invention.

[0035] In this document, the terms "include", "including", "have", "contain" or any other similar terms are open conjunctions, which are intended to cover non-exclusive inclusions. For example, a composition or product 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 product. In addition, unless otherwise explicitly stated, 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 A and B are both true (or exist). In addition, in this document, the interpretation of the terms "include", "including", "have", and "contain" should be considered to have been specifically disclosed and simultaneously cover closed or semi-closed conjunctions such as "consisting of" and "consisting essentially of".

[0036] In this article, all features or conditions defined in the form of numerical ranges or percentage ranges are only for brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be deemed to have covered and specifically disclosed all possible secondary ranges and individual values ​​within the range, especially integer values. For example, the range description of "1 to 8" should be deemed to have specifically disclosed all secondary ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., especially secondary ranges defined by all integer values, and should be deemed to have specifically disclosed individual values ​​such as 1, 2, 3, 4, 5, 6, 7, 8, etc. within the range. Unless otherwise specified, the above interpretation method applies to all contents of the entire present invention, regardless of whether the range is broad or not.

[0037] If the quantity or other numerical 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 the lower limit or preferred value of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, if 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, under the premise of achieving the purpose of the invention, numerical values ​​should be understood to have the accuracy of the number of significant digits of the numerical value. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0039] In addition, unless otherwise specified, the reagents and solvents disclosed below were purchased from Shanghai MacLean Biochemical Technology Co., Ltd., XRD was measured by using the D8 Advance series of Bruker, Germany, scanning electron microscopy was measured by using the S4800 series of Hitachi, Japan, and transmission electron microscopy was measured by using the H-7650 series of Hitachi, Japan.

[0040] The following examples are only listed as examples of embodiments of the present invention and do not constitute any limitation to the present invention. It can be understood by those skilled in the art that modifications within the scope of the essence and concept 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 all commercially available products.

[0041] Preparation Example 1: Preparation of Nitrided Activated Carbon (NAC)

[0042] 0.5g commercial activated carbon and 1.5g chitosan were ground and mixed evenly in a mortar, then placed in a tube furnace, heated to 600°C at a rate of 2 / min, and heated and calcined for 4 hours in a nitrogen atmosphere to obtain nitrided activated carbon NAC. Among them, the nitrogen content of nitrided activated carbon is 7.2wt%. 0.5g commercial activated carbon and 1.5g urea were ground and mixed evenly in a mortar, then placed in a tube furnace, heated to 600°C at a rate of 2 / min, and heated and calcined for 4 hours in a nitrogen atmosphere to obtain nitrided activated carbon NAC. Among them, the nitrogen content of nitrided activated carbon is 5.4wt%. 0.5g commercial activated carbon and 1.5g alanine were ground and mixed evenly in a mortar, then placed in a tube furnace, heated to 600°C at a rate of 2 / min, and heated and calcined for 4 hours in a nitrogen atmosphere to obtain nitrided activated carbon NAC. Among them, the nitrogen content of nitrided activated carbon is 6.2wt%. Considering the nitrogen content comprehensively, chitosan was selected as the nitrogen source.

[0043] Preparation Example 2: Preparation of Catalyst 1

[0044] 0.05g of cobalt nitrate hexahydrate, 0.004g of rhodium trichloride trihydrate, 0.2g of nitrided activated carbon NAC obtained in Preparation Example 1, and 25mL of ethanol were added to a beaker to fully dissolve to form a solution, and the mixed solution was stirred for 24 hours. The resulting precipitate was then centrifuged and washed three times with ethanol, and the product was dried overnight in a vacuum drying at 100°C. The obtained solid was placed in a tubular furnace, heated to 600°C at a rate of 2°C / min, and heated and calcined for 2 hours under a nitrogen atmosphere to obtain a CoRh-doped nitrided activated carbon supported composite catalyst. Wherein, based on the gross weight of the catalyst, the Rh content in the catalyst is 0.6wt%, and based on the Co atom, the Co content in the catalyst is 0.4wt%.

[0045] Preparation Example 3: Preparation of Catalyst 2

[0046] 0.025g of cobalt nitrate hexahydrate, 0.004g of rhodium trichloride trihydrate, 0.2g of nitrided activated carbon NAC obtained in Preparation Example 1, and 25mL of ethanol were added to a beaker to fully dissolve to form a solution, and the mixed solution was stirred for 24 hours. The resulting precipitate was then centrifuged and washed three times with ethanol, and the product was dried overnight in a vacuum drying at 100°C. The obtained solid was placed in a tubular furnace, heated to 600°C at a rate of 2°C / min, and heated and calcined for 2 hours under a nitrogen atmosphere to obtain a CoRh-doped nitrided activated carbon supported composite catalyst. Wherein, based on the gross weight of the catalyst, the Rh content in the catalyst is 0.6wt%, and based on the Co atom, the Co content in the catalyst is 0.2wt%.

[0047] Preparation Example 4: Preparation of Catalyst 3

[0048] 0.0125g of cobalt nitrate hexahydrate, 0.004g of rhodium trichloride trihydrate, 0.2g of nitrided activated carbon NAC obtained in Preparation Example 1, and 25mL of ethanol were added to a beaker to fully dissolve to form a solution, and the mixed solution was stirred for 24 hours. The resulting precipitate was then centrifuged and washed three times with ethanol, and the product was dried overnight in a vacuum drying at 100°C. The obtained solid was placed in a tubular furnace, heated to 600°C at a rate of 2°C / min, and heated and calcined for 2 hours under a nitrogen atmosphere to obtain a CoRh-doped nitrided activated carbon supported composite catalyst. Wherein, based on the gross weight of the catalyst, the Rh content in the catalyst is 0.6wt% in terms of Rh atoms, and the Co content in the catalyst is 0.1wt% in terms of Co atoms.

[0049] Preparation Example 5: Preparation of Catalyst 4

[0050] 0.0125g of cobalt nitrate hexahydrate, 0.004g of rhodium trichloride trihydrate, 0.2g of nitrided activated carbon NAC obtained in Preparation Example 1, and 25mL of ethanol were added to a beaker to fully dissolve to form a solution, and the mixed solution was stirred for 24 hours. The resulting precipitate was then centrifuged and washed three times with ethanol, and the product was dried overnight in a vacuum drying at 100°C. The obtained solid was placed in a tubular furnace, heated to 700°C at a rate of 2°C / min, and heated and calcined for 2 hours under a nitrogen atmosphere to obtain a CoRh-doped nitrided activated carbon supported composite catalyst. Wherein, based on the gross weight of the catalyst, the Rh content in the catalyst is 0.6wt%, and based on the Co atom, the Co content in the catalyst is 0.1wt%.

[0051] Preparation Example 6: Preparation of Catalyst 5

[0052] 0.0125g of cobalt nitrate hexahydrate, 0.004g of rhodium trichloride trihydrate, 0.2g of nitrided activated carbon NAC obtained in Preparation Example 1, and 25mL of ethanol were added to a beaker to fully dissolve to form a solution, and the mixed solution was stirred for 24 hours. The resulting precipitate was then centrifuged and washed three times with ethanol, and the product was dried overnight in a vacuum drying at 100°C. The obtained solid was placed in a tubular furnace, heated to 800°C at a rate of 2°C / min, and heated and calcined for 2 hours under a nitrogen atmosphere to obtain a CoRh-doped nitrided activated carbon supported composite catalyst. Wherein, based on the gross weight of the catalyst, the Rh content in the catalyst is 0.6wt%, and based on the Co atom, the Co content in the catalyst is 0.1wt%.

[0053] Test Example 1: Hydroformylation of olefins

[0054] 40 mg of the NAC intermediate material in Preparation Example 1, 1 mL of diisobutylene and 20 mL of tetrahydrofuran were added to a 50 mL high-pressure reactor, and charged with 3 MPa of CO / H2 mixed gas (V:V=1:1). The reaction was carried out at 100° C. for 12 hours. The conversion rate of diisobutylene was 0%, and the selectivity of aldehyde was 0%, as determined by gas chromatography.

[0055] Test Example 2: Hydroformylation of olefins

[0056] 40 mg of the CoRh-doped nitrided activated carbon-supported composite catalyst in Preparation Example 2, 1 mL of diisobutylene and 20 mL of tetrahydrofuran were added into a 50 mL high-pressure reactor, filled with 3 MPa of CO / H2 mixed gas (V:V=1:1), and reacted at 100°C for 12 hours. The conversion of diisobutylene was 98.32% when detected by gas chromatography, and the selectivity of aldehydes was 85.34%.

[0057] Test Example 3: Hydroformylation of olefins

[0058] 40 mg of the CoRh-doped nitrided activated carbon supported composite catalyst, 1 mL of diisobutylene and 20 mL of tetrahydrofuran in Preparation Example 3 were added to a 50 mL autoclave, and a 3 MPa CO / H2 mixed gas (V:V=1:1) was charged, and the reaction was carried out at 100° C. for 12 hours. The conversion rate of diisobutylene was 98.32%, and the selectivity of aldehyde was 95.85%. Comparing the data of Test Example 2 and Test Example 3, the increase of Co content in the catalyst may lead to a decrease in aldehyde selectivity.

[0059] Test Example 4: Hydroformylation of olefins

[0060] 40 mg of the CoRh-doped nitrided activated carbon-supported composite catalyst in Preparation Example 4, 1 mL of diisobutylene and 20 mL of tetrahydrofuran were added into a 50 mL high-pressure reactor, filled with 3 MPa of CO / H2 mixed gas (V:V=1:1), and reacted at 100°C for 12 hours. The conversion of diisobutylene was 98.32% when detected by gas chromatography, and the selectivity of aldehydes was 99.72%.

[0061] Test Example 5: Catalyst circulation experiment

[0062] The CoRh-doped nitrided activated carbon-supported composite catalyst in the product of Preparation Example 4 was filtered, washed and centrifuged, and then added to a 50mL high-pressure reactor with 1mL of diisobutylene and 20mL of tetrahydrofuran, and charged with 3MPa of CO / H2 mixed gas (V:V=1:1), and reacted at 100°C for 12 hours; gas chromatography analysis and detection showed that the catalyst was recycled 10 times, and the conversion rate of diisobutylene was higher than 98%, and the specific data are shown in Table 1. The selectivity of aldehydes was higher than 99%, and the Rh content was detected by ICP, and no Rh loss was observed. The specific data are shown in Table 1 below. It can be seen from the data in Table 1 that the CoRh-doped nitrided activated carbon-supported composite catalyst according to the present invention can still maintain good catalytic performance even if it is recycled 10 times.

[0063] Table 1: Comparison of CoRh-NAC cycle performance

[0064]

[0065]

[0066] Test Example 6: Hydroformylation of olefins

[0067] 40 mg of the catalyst prepared in Example 5, 1 mL of diisobutylene and 20 mL of tetrahydrofuran were added to a 50 mL high pressure reactor, and a 3 MPa CO / H2 mixed gas (V:V=1:1) was introduced. The mixture was reacted at 100° C. for 12 hours. The conversion of diisobutylene was 82.37% and the selectivity of aldehyde was 99.94% according to gas chromatography.

[0068] Test Example 7: Hydroformylation of olefins

[0069] 40 mg of the catalyst prepared in Example 6, 1 mL of diisobutylene and 20 mL of tetrahydrofuran were added to a 50 mL high-pressure reactor, and a 3 MPa CO / H2 mixed gas (V:V=1:1) was introduced. The mixture was reacted at 100° C. for 12 hours. The conversion of diisobutylene was 75.49% and the selectivity of aldehyde was 99.2%.

[0070] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A CoRh-doped nitrided activated carbon supported composite catalyst, wherein the Rh content is 0.2-1.5wt% based on Rh atoms, the Co content is 0.1-0.8wt% based on Co atoms, the mass ratio of Co to Rh is 10:1-1:1, preferably 2:1, and Co and Rh exist in the form of nanoclusters or single atoms and are connected to the carbon nitride skeleton structure in the form of covalent bonds.

2. The method for preparing the CoRh-doped nitrided activated carbon-supported composite catalyst according to claim 1, wherein the preparation method is carried out as follows: 1) Mixing the activated carbon material and the nitrogen source in a certain mass ratio, and calcining at 400-800° C. for 1-4 hours under an inert atmosphere to form a nitrided activated carbon material NAC; 2) dissolving the cobalt salt precursor and the rhodium salt precursor in a certain amount of solvent, adding an appropriate amount of NAC, mixing and stirring for 24-72 hours; 3) The precipitate obtained in step 2) is centrifuged and washed three times with ethanol, the product is vacuum dried at 60-80° C., the obtained solid is ground and calcined at 300-850° C. for 2-4 hours under an inert atmosphere to obtain a CoRh-doped nitrided activated carbon-supported composite catalyst.

3. The preparation method according to claim 2, It is characterized in that The nitrogen source in step 1) is selected from one or more of urea, alanine, glycine, melamine, EDTA, and chitosan; Preferably, the calcination condition in step 1) is 600° C. and the reaction time is 4 hours; Preferably, the cobalt salt in step 2) is selected from one or more of cobalt nitrate hexahydrate, cobalt sulfate heptahydrate, cobalt chloride hexahydrate, cobalt naphthenate, cobalt stearate, cobalt neodecanoate and cobalt boroacylate; Preferably, the solvent in step 2) is selected from one or more of methanol, ethanol or propanol, preferably ethanol; Preferably, the rhodium salt in step 2) is selected from one or more of rhodium trichloride trihydrate, sodium hexachlororhodate, rhodium acetate, and rhodium nitrate; Preferably, the inert atmosphere in step 1) and step 3) is a nitrogen atmosphere or an argon atmosphere; Preferably, the calcination temperature in step 3) is 600° C. and the calcination time is 2 hours.

4. Use of the CoRh-doped nitrided activated carbon supported composite catalyst according to claim 1 in the hydroformylation reaction of olefins.

5. The use according to claim 4, It is characterized in that The hydroformylation reaction of olefins is a reaction for preparing isononanal from diisobutylene.

6. A method for hydroformylation of olefins using the CoRh-doped nitrided activated carbon-supported composite catalyst according to claim 1, the method being carried out as follows: A certain amount of the CoRh-doped nitrided activated carbon-supported composite catalyst according to claim 1, olefins, and solvents were added to a high-pressure reactor, and a high-pressure mixture of CO and H in a volume ratio of 1:1 was charged into the reactor. 2 Mixed gas, set the reaction temperature to 80-200℃, and the reaction time to 4-24 hours.

7. The method according to claim 6, It is characterized in that The gas pressure of the olefin hydroformylation reaction is 0.5-10.0 MPa, the reaction temperature is 100° C., and the reaction time is 12 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, etc.; Preferably, in the hydroformylation reaction method, the CoRh-NAC supported composite catalyst is reused less than 50 times, preferably reused less than 30 times, and more preferably reused less than 10 times.

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