A nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst and its application

Abstract

This invention discloses a nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst and its applications, belonging to the field of heterogeneous catalysis technology. The catalyst consists of a metal component and an organic nitrogen ligand polymer. The metal component is metallic Co, and the organic nitrogen ligand polymer is a polymer with a large specific surface area and hierarchical porous structure generated by solvothermal polymerization of vinyl-functionalized organic nitrogen ligands. The catalyst exhibits high reactivity, high selectivity for the target product aldehyde, and good reaction stability in the hydroformylation of high-carbon terminal and internal olefins. This type of heterogeneous catalyst is suitable for fixed-bed, slurry-bed, and batch reactors. Compared with traditional triphenylphosphine ligand polymer-supported Co-based catalysts for the hydroformylation of high-carbon olefins, it exhibits higher catalytic activity and aldehyde selectivity. Furthermore, the use of this novel Co-based heterogeneous catalyst reduces catalyst separation and recovery costs, making it more suitable for large-scale industrial production.

Description

Technical Field

[0001] This invention relates to the field of heterogeneous catalysis technology, and in particular to a nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst and its application. Background Technology

[0002] The design and synthesis of porous organic polymers (POPs) has gradually become a new hot topic in the field of porous materials research. These are porous materials primarily composed of small organic molecules linked by covalent bonds. Compared to traditional inorganic microporous materials and metal-organic frameworks (MOFs), the framework of POPs is composed of purely organic molecules connected by covalent bonds, exhibiting open channels and excellent pore properties. Compared to soluble polymers, POPs have advantages such as large specific surface area, well-developed pores, and easy separation. More importantly, the diversity of organic chemical synthesis methods provides rich synthetic routes and construction methods for organic molecular networks. Functionalized organic molecules can be introduced purposefully to impart specific properties to the material, and the pore properties can be controlled by adjusting the structure of organic molecules. Furthermore, in most cases, compared to molecular network systems formed by non-covalent bonds, covalently linked organic microporous polymers maintain the material's pore properties while exhibiting a more stable molecular network structure. In addition, porous organic polymers containing ligands can serve as both supports and ligands, allowing for the targeted introduction of catalytically active metal units into the porous organic polymer. This enables them to be highly dispersed in the porous organic polymer support in the form of single atoms, which not only helps stabilize the metal active sites and reduce the loss of metal active components, but also greatly improves the utilization efficiency of the metal.

[0003] Currently, the catalysts reported in the literature for the hydroformylation of olefins mainly include homogeneous catalysts composed of metals and alkylphosphine ligands, phosphite ligands, phosphineamide ligands, and nitrogen ligands, as well as two-phase catalysis and supported homogeneous catalysts. Commonly used supports for supported catalysts include heterogeneous catalysts composed of activated carbon, silica, molecular sieves, heteropolyacids, mesoporous materials, functional organic polymers, and metal-organic frameworks (Catal. Sci. Technol., 2022, 12, 4962-4982; Chem. Commun., 2023, 59, 2126; Front. Chem. Sci. Eng. 2018, 113–123). These homogeneous catalysts exhibit high activity and high selectivity for n-aldehydes, but separation from the product is difficult, the process is complex, and trace metal impurities can cause fatal defects in downstream products. On the other hand, these heterogeneous catalysts still suffer from poor activity and selectivity, easy loss of active components, and poor reusability.

[0004] In 2021, Beller et al. (ACS Sustainable Chem. Eng., 2021, 9, 5148-5154) reported the application of phosphine oxide ligand-modified Co-based catalysts in the hydroformylation of 1-octene. The reaction conditions were mild (60-80 °C, 4 MPa, 24 h), with high total aldehyde selectivity, low total alcohol content, and high linear selectivity for nonanal. However, this system is a homogeneous catalysis and still faces challenges such as the difficulty in separating and recovering the catalyst.

[0005] In 2019, Fang et al. (Chemistry Select, 2019, 4(35): 10447-10451) used molecular sieves A with different pore sizes as supports and employed an equal-volume impregnation method with NaBH4 as a reducing agent to prepare a series of supported Co-based catalysts. In the 1-hexene hydroformylation reaction, the olefin conversion rate reached 74.2%, and the product aldehyde-to-isorhodium ratio was 1.93. However, its activity still needs to be improved, its cycle stability is poor, and the active components are easily lost.

[0006] In 2020, BAUER et al. (Nat Commun, 2020, 11(1):1059) applied metal-organic frameworks (MOFs) to the hydroformylation reaction catalyzed by Co2(CO)8. Their study found that appropriate micropores in MOFs could increase the formation rate of branched aldehydes, thereby increasing their selectivity. However, MOFs exhibit poor hydrothermal stability, and the raw materials are expensive; no data on their stability during recycling has been provided.

[0007] In 2020, Lee et al. (Fuel, 2020, 269:117397) prepared single-crystal Co3O4 nanocatalysts with different morphologies using a hydrothermal synthesis method. In the hydroformylation of 1-heptene, the same metallic Co oxide, Co3O4, with different morphologies and exposed crystal faces, yielded vastly different reaction results. For example, under conditions of 170℃ and 4MPa for 12 h, the octahedral Co3O4 catalyst achieved a 1-heptene conversion of 88% and a C8 aldehyde selectivity of 75.2%. The positive-to-isotropic ratio of the aldehyde was not reported. However, the reaction conditions were still too harsh, and the reaction time was relatively long.

[0008] Vinyl-polymerized porous organic polymer materials possess characteristics such as high specific surface area, hierarchical pore structure, and ease of modification. As catalytic materials, their unique swelling properties allow for the extensive utilization of active centers within their pores. Vinyl-polymerized porous organic polymer materials have been widely used as supports and ligand-supported Rh-based catalysts in the hydroformylation of olefins, achieving excellent catalytic activity, selectivity, and stability (Journal of Catalysis, 368(2018)197-206. Applied Catalysis A:General, 551(2018)98-105. J. Catal., 353(2017)123-132.). However, the aforementioned heterogeneous catalytic systems all utilize the noble metal Rh as a catalyst, resulting in high costs. Summary of the Invention

[0009] The purpose of this invention is to provide a nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst and its application. A homogeneous ligand heterogeneous strategy is adopted, in which homogeneous nitrogen-containing ligands are introduced into vinyl groups. The homogeneous nitrogen-containing ligands are polymerized in an autoclave using a solvothermal polymerization method to form a nitrogen-containing porous organic polymer with a high specific surface area and a hierarchical pore structure. After self-supporting with metallic Co, a nitrogen-containing porous organic polymer-supported Co-based heterogeneous catalyst is obtained.

[0010] The present invention adopts the following technical solution:

[0011] According to a first aspect of this disclosure, the present invention provides a nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst, the catalyst comprising a metal component and an organic nitrogen ligand polymer; the metal component is metallic Co, and the organic nitrogen ligand polymer is generated by solvothermal polymerization of vinyl-functionalized organic nitrogen ligands; the vinyl-functionalized organic nitrogen ligands are any one or a combination of L1, L2, and L3.

[0012]

[0013] Furthermore, the organic nitrogen ligand polymer is prepared by self-polymerization of ligand L1, or by copolymerization of L1 with L2 or L3.

[0014] Furthermore, the organic nitrogen ligand polymer has a hierarchical porous structure with a specific surface area of ​​100–3000 m². 2 / g, containing micropores, mesopores and macropores, with a pore volume of 0.1–5 cm³. 3 / g, with a pore size distribution of 0.1–50 nm.

[0015] According to a second aspect of this disclosure, the present invention provides a method for preparing the above-described catalyst:

[0016] a) Under a N2 atmosphere at 273–473 K, a vinyl-functionalized nitrogen ligand is added to a solvent, with or without a crosslinking agent, and a free radical initiator is added. The mixture is then stirred to obtain a mixed solution.

[0017] b) Transfer the mixed solution obtained in step a) to a high-pressure reactor for synthesis. Under a N2 atmosphere of 323K to 473K, perform solvothermal polymerization and let it stand for 1 to 100 hours (preferably 20 to 80 hours) to carry out the polymerization reaction. After the reaction is completed, remove the solvent under vacuum to obtain the organic nitrogen ligand polymer.

[0018] c) The organic nitrogen ligand polymer is placed in a solvent containing the metal active component Co, and stirred for 0.5 to 100 h (preferably 5 to 50 h) under a N2 atmosphere at 323 K to 473 K. The solvent is then removed under vacuum to obtain a nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst.

[0019] Furthermore, the solvent mentioned in steps a) and c) above is one or more of benzene, toluene, methanol, ethanol, tetrahydrofuran, dichloromethane or trichloromethane.

[0020] Furthermore, the crosslinking agent in step a) above is one or more of styrene, ethylene, propylene, divinylbenzene or 1,3,5-triethynylbenzene.

[0021] Furthermore, the aforementioned free radical initiator is one or more of cyclohexanone peroxide, benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, or azobisisoheptanenitrile. The weight ratio of the free radical initiator to the organic nitrogen ligand monomer is 1:100 to 1:5.

[0022] Furthermore, the molar ratio of the vinyl-functionalized organic nitrogen ligands in step a) is 0.01:1100:1 (preferably 0.1:1 to 1:1), and when a crosslinking agent is added, the molar ratio of the organic nitrogen ligand to the crosslinking agent is 0.01:110:1 (preferably 0.1:1 to 1:1), and the molar ratio of the organic nitrogen ligand to the free radical initiator is 300:110:1 (preferably 50:1 to 10:1).

[0023] Furthermore, the precursor of the metal component Co is derived from one or more of Co(OAc)2, Co(acac)2, Co(acac)3, Co(NO3)2, and CoCl2, and the loading of metal Co is 1 to 50 wt%.

[0024] According to a third aspect of this disclosure, the present invention provides an application of the above-described catalyst, specifically the application of the nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst in the hydroformylation reaction of high-carbon olefins. In the presence of the Co-based heterogeneous catalyst, high-carbon terminal olefins and internal olefins (C5-C12) are subjected to a hydroformylation reaction with syngas (CO / H2) in a trickle bed, slurry bed, or batch reactor. The preferred reaction temperature is 323-523 K, the preferred reaction pressure is 0.5-15 MPa, and the preferred liquid hourly space velocity is 0.05-8.0 h⁻¹. -1 The preferred gas space velocity is 500–10000 h⁻¹ -1 .

[0025] The reaction principle of this invention is as follows: This invention employs a homogeneous ligand heterogeneity strategy, introducing homogeneous nitrogen-containing ligands into vinyl groups. In a high-pressure reactor, solvothermal polymerization is used to polymerize these ligands into a nitrogen-containing porous organic polymer with a high specific surface area and a hierarchical pore structure. After self-supporting with metallic Co, a nitrogen-containing porous organic polymer-supported Co-based heterogeneous catalyst is obtained. This fully integrates the advantages of the porous organic polymer support (high specific surface area, hierarchical pore structure) and the ligand (coordinating with Co, immobilizing metallic Co, preventing Co loss, and regulating the electronic and steric effects of Co). The porous organic polymer material can encapsulate and confine the reaction substrate within nanoscale pores, increasing the substrate concentration at the catalytic sites. The vinyl porous organic polymer synthesized through solvothermal polymerization exhibits good swelling characteristics. These characteristics result in a catalyst with extremely high activity, high aldehyde selectivity, and high stability.

[0026] The beneficial effects of this invention are as follows: This invention provides a Co-based heterogeneous catalyst supported on a nitrogen-containing porous organic ligand polymer. The coordination between the N atom in the nitrogen-containing ligand and the metal facilitates high dispersion of the active metal, improving metal utilization efficiency and reducing leaching. The polymer possesses a high specific surface area porous structure, exhibiting the dual functions of both support and ligand, significantly enhancing catalytic activity. This type of heterogeneous catalyst can significantly improve catalytic activity and aldehyde selectivity in the hydroformylation of high-carbon olefins, particularly in the hydroformylation of internal olefins. Using this novel Co-based heterogeneous catalyst can reduce catalyst separation and recovery costs, facilitating large-scale industrial applications. Attached Figure Description

[0027] Figure 1 This is a typical structure diagram of a nitrogen-containing monomer with vinyl functionalization in this application.

[0028] Figure 2 This is a schematic diagram of the synthesis route of the nitrogen-containing porous organic polymer-supported Co-based heterogeneous catalyst of this application.

[0029] Figure 3This is a structural diagram of the crosslinking agent used in the polymerization process of this application.

[0030] Figure 4 This is the 1H spectrum of the vinyl-functionalized triphenylnitrogen monomer of Example 1 of this application.

[0031] Figure 5 This is the 13C spectrum of tribenzyl nitrogen with vinyl functionalization in Example 1 of this application.

[0032] Figure 6 These are SEM images and EDS mapping images of POL-NPh3(ad) before cobalt loading in Example 1 of this application.

[0033] Figure 7 These are SEM images and EDS mapping images of the (eh)Co / POL-NPh3 catalyst supported on cobalt-based catalyst in Example 1 of this application.

[0034] Figure 8 These are the thermogravimetric curves of the catalyst in Example 1 of this application under N2 atmosphere: (a) POL-NPh3 and (b) Co / POL-NPh3.

[0035] Figure 9 These are the N2 adsorption-desorption isotherms of POL-NPh3 (1) and Co / POL-NPh3 catalyst (2) in Example 1 of this application.

[0036] Figure 10 This is a pore size distribution curve of POL-NPh3 (a) and Co / POL-NPh3 catalyst (b) in Example 1 of this application.

[0037] Figure 11 Please refer to the FT-IR image of POL-NPh3 in Example 1.

[0038] Figure 12 Please see the FT-IR spectrum of the Co / POL-NPh3 catalyst in Example 1. Detailed Implementation

[0039] The technical solution of the present invention will be described in detail below through specific embodiments, but the content of the present invention is not limited to the following embodiments. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods. Unless otherwise specified, the materials and reagents used in the following embodiments are commercially available.

[0040] Example 1

[0041] Under a protective atmosphere of 298 K and inert gas N2, 1.0 g of tris(4-vinylbenzene) nitrogen ligand was dissolved in 10 mL of tetrahydrofuran. 25 mg of azobisisobutyronitrile (AIB) free radical initiator was added to the solution, and the mixture was stirred for 30 min. The resulting mixture was transferred to an autoclave and polymerized at 373 K using a solvothermal polymerization method for 24 h. After the polymerized solution was cooled to room temperature, the solvent was removed under vacuum at 302 K to obtain a nitrogen-containing porous organic polymer (100% yield), named POL-NPh3. Characterization by nitrogen adsorption-desorption testing showed a specific surface area of ​​1120.8 m². 2 / g, total pore volume is 1.57cm³ 3 / g, the pore size distribution by NLDFT method is 0.2–80 nm.

[0042] Nitrogen-containing porous organic polymer-supported Co-based heterogeneous catalyst: Under a protective atmosphere of 298 K and inert gas N2, 0.3345 g of Co(OAc)2 was dissolved in 25 mL of anhydrous ethanol, and 1 g of the nitrogen-containing porous organic polymer prepared above was added. The mixture was stirred for 24 h, filtered, and washed three times with anhydrous ethanol. The resulting solid mixture was then vacuum-treated at 348 K to remove the solvent, yielding the nitrogen-containing porous organic polymer-supported Co-based heterogeneous catalyst, named Co / POL-NPh3. Characterized by nitrogen adsorption-desorption testing, its specific surface area was 1054.6 m². 2 / g, total pore volume is 2.33cm³ 3 / g, the pore size distribution by NLDFT is 0.2–80 nm. Thermogravimetric analysis (TGA) curves of the Co / POL-NPh3 catalyst and the POL-NPh3 support show that under a nitrogen atmosphere, the catalyst only exhibits a significant skeletal decomposition weight loss peak above 430 °C. FT-IR spectra of the Co / POL-NPh3 catalyst and the POL-NPh3 support show that Co interacts with N atoms in the ligands within the catalyst.

[0043] The Co-based heterogeneous catalyst prepared above was loaded into a high-pressure reactor, and then 1-hexene and toluene solvent were added. Hydroformylation was carried out at 423 K, 3.0 MPa, and a reaction time of 4 h. The reaction products were collected by centrifugation and analyzed on an Agilent 7890A gas chromatograph equipped with an HP-5 capillary flame ionization (FID) detector. The results were calculated using the internal standard method with n-propanol as the internal standard. The results are listed in Table 1.

[0044] Example 2

[0045] In Example 2, except that 0.8 g of tris(4-vinylphenyl) nitrogen ligand and 0.2 g of di(4-vinylphenyl) nitrogen ligand were weighed and dissolved in 10 mL of tetrahydrofuran, the other procedures were the same as in Example 1, and the reaction results are listed in Table 1.

[0046] Example 3

[0047] In Example 3, except that 0.6 g of tris(4-vinylphenyl) nitrogen ligand and 0.4 g of di(4-vinylphenyl) nitrogen ligand were weighed and dissolved in 10 mL of tetrahydrofuran, the other procedures were the same as in Example 1, and the reaction results are listed in Table 1.

[0048] Example 4

[0049] In Example 4, except that 0.8 g of tris(4-vinylphenyl) nitrogen ligand and 0.2 g of 1-(4-vinylphenyl) nitrogen ligand were weighed and dissolved in 10 mL of tetrahydrofuran, the other procedures were the same as in Example 1, and the reaction results are listed in Table 1.

[0050] Example 5

[0051] In Example 5, except that 0.6 g of tris(4-vinylphenyl) nitrogen ligand and 0.4 g of 1-(4-vinylphenyl) nitrogen ligand were weighed and dissolved in 10 mL of tetrahydrofuran, the other procedures were the same as in Example 1, and the reaction results are listed in Table 1.

[0052] Example 6

[0053] In Example 6, except that 2.5 mg of the free radical initiator azobisisobutyronitrile was added to replace 25 mg of the free radical initiator azobisisobutyronitrile, the other processes were the same as in Example 1, and the reaction results are listed in Table 1.

[0054] Example 7

[0055] In Example 7, except that 0.158g of Co(OAc)2 was weighed out instead of 0.3345g of Co(OAc)2, the other processes were the same as in Example 1, and the reaction results are listed in Table 1.

[0056] Example 8

[0057] In Example 8, except that 0.0305g of Co(OAc)2 was weighed out instead of 0.3345g of Co(OAc)2, the other processes were the same as in Example 1, and the reaction results are listed in Table 1.

[0058] Example 9

[0059] In Example 9, except that 0.5375g of Co(NO3)2 was weighed out instead of 0.3345g of Co(OAc)2, the other processes were the same as in Example 1, and the reaction results are listed in Table 1.

[0060] Example 10

[0061] In Example 10, the process was the same as in Example 1, except that 0.2475g of CoCl2 was used instead of 0.3345g of Co(OAc)2. The reaction results are listed in Table 1.

[0062] Example 11

[0063] In Example 11, the process was the same as in Example 1, except that 0.487g of Co(acac)2 was weighed in place of 0.3345g of Co(OAc)2. The reaction results are listed in Table 1.

[0064] Example 12

[0065] In Example 12, the process was the same as in Example 1, except that the hydroformylation reaction temperature of 373K was used instead of the hydroformylation evaluation reaction temperature of 423K. The reaction results are listed in Table 1.

[0066] Example 13

[0067] In Example 13, the process was the same as in Example 1, except that the hydroformylation reaction pressure of 2.0 MPa was used instead of the hydroformylation evaluation reaction pressure of 3 MPa. The reaction results are listed in Table 1.

[0068] Example 14

[0069] In Example 14, the process was the same as in Example 1, except that the hydroformylation reaction time was 24 h instead of the 4 h evaluation reaction time. The reaction results are listed in Table 1.

[0070] Example 15

[0071] In Example 15, the process was the same as in Example 1, except that 1-octene was substituted for 1-hexene in the hydroformylation reaction. The reaction results are listed in Table 1.

[0072] Example 16

[0073] In Example 16, the process was the same as in Example 1, except that 2-octene was substituted for 1-hexene in the hydroformylation reaction. The reaction results are listed in Table 1.

[0074] Comparative Example 1

[0075] In Comparative Example 1, except that SiO2 support was used instead of nitrogen-containing porous organic polymer POL-NPh3 for catalyst preparation and subsequent evaluation of heterogeneous hydroformylation reaction, the other processes were the same as in Example 1, and the reaction results are listed in Table 1.

[0076] Comparative Example 2

[0077] In Comparative Example 2, except that the phosphorus-containing porous organic polymer POL-PPh3 was used instead of the nitrogen-containing porous organic polymer POL-NPh3 for catalyst preparation and subsequent evaluation of the heterogeneous hydroformylation reaction, the other processes were the same as in Example 1, and the reaction results are listed in Table 1.

[0078] Comparative Example 3

[0079] In Comparative Example 3, except that Al2O3 support was used instead of nitrogen-containing porous organic polymer POL-NPh3 for catalyst preparation and subsequent evaluation of heterogeneous hydroformylation reaction, the other processes were the same as in Example 1, and the reaction results are listed in Table 1.

[0080] Table 1 Results of hydroformylation of high-carbon olefins using Co / POL-NPh3 heterogeneous catalyst

[0081]

[0082]

[0083] The reaction data from Examples 1-5 show that when nitrogen ligand L1 is selected for self-polymerization, the Co / POL-NPh3 heterogeneous catalyst exhibits the best olefin conversion and aldehyde selectivity in the hydroformylation of high-carbon olefins. Data from Examples 1 and 6 show that an appropriate amount of free radical initiator helps improve olefin conversion and aldehyde selectivity. Data from Examples 1, 7-8, and 9-11 show that the Co-based loading and precursor type affect the hydroformylation performance of high-carbon olefins; the Co / POL-NPh3 heterogeneous catalyst exhibits the best performance when the precursor is Co(OAc)2 and the Co loading is 10 wt%. Data from Examples 1, 12, and 13 show that high temperature and high pressure are beneficial for improving the hydroformylation performance of the Co / POL-NPh3 heterogeneous catalyst. Data from Examples 1 and 16 show that the Co / POL-NPh3 heterogeneous catalyst has excellent reaction performance in the hydroformylation of high-carbon olefins. Data from Examples 1 and Comparative Examples 1-3 show that the Co-based catalyst supported on POL-NPh3 exhibits optimal performance in the hydroformylation of high-carbon olefins. Based on the reaction data from Examples 1-16 and Comparative Examples 1-3, the Co-based heterogeneous catalyst provided by this invention, when applied to the hydroformylation of high-carbon terminal and internal olefins, demonstrates excellent reactivity and selectivity, along with good reaction stability, providing an economically viable and industrially feasible heterogeneous Co-based catalyst for the hydroformylation of high-carbon olefins.

[0084] The above embodiments are merely illustrative examples to clearly illustrate the present invention and are not intended to limit the implementation. Those skilled in the art will recognize that other variations can be made based on the above description. All obvious variations derived therefrom fall within the scope of protection of this invention. Finally, it should be noted that the terms "comprising," "including," or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

Claims

1. An application of a nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst for catalyzing the hydroformylation of high-carbon olefins, characterized in that, The catalyst is composed of a metal component and an organic nitrogen ligand polymer; the metal component is metallic Co, and the organic nitrogen ligand polymer is generated by solvothermal polymerization of vinyl-functionalized organic nitrogen ligands; the vinyl-functionalized organic nitrogen ligands are any one or a combination of L1, L2, and L3. ； The high carbon olefins include C5-C12 high carbon end olefins and internal olefins.

2. The application of the nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst according to claim 1 for catalyzing the hydroformylation reaction of high-carbon olefins, characterized in that, The organic nitrogen ligand polymer is prepared by self-polymerization of ligand L1, or by copolymerization of L1 with L2 or L3.

3. The application of the nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst according to claim 1 for catalyzing the hydroformylation reaction of high-carbon olefins, characterized in that, The organic nitrogen ligand polymer has a hierarchical porous structure and a specific surface area of ​​100~3000 m². 2 / g, containing micropores, mesopores and macropores, with a pore volume of 0.1~5cm³. 3 / g, with a pore size distribution of 0.1~50nm.

4. The application of the nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst according to claim 1 for catalyzing the hydroformylation reaction of high-carbon olefins, characterized in that, The catalyst is prepared by the following method: a) Under a N2 atmosphere at 273~473K, add a vinyl-functionalized organic nitrogen ligand to a solvent, with or without a crosslinking agent, and then add a free radical initiator, and mix and stir to obtain a mixed solution; b) Transfer the mixed solution obtained in step a) to a high-pressure reactor for synthesis. Under a N2 atmosphere at 323K~473K, perform a solvothermal polymerization reaction and let it stand for 1~100h. After the reaction is completed, remove the solvent under vacuum to obtain the organic nitrogen ligand polymer. c) The organic nitrogen ligand polymer is placed in a solvent containing the metal active component Co, and stirred for 0.5 to 100 h at 323 K to 473 K under a N2 atmosphere. The solvent is then removed under vacuum to obtain a nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst.

5. The application of the nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst according to claim 4 for catalyzing the hydroformylation reaction of high-carbon olefins, characterized in that, The solvents mentioned in steps a) and c) are one or more of benzene, toluene, methanol, ethanol, tetrahydrofuran, dichloromethane, or chloroform; the crosslinking agent in step a) is one or more of styrene, ethylene, propylene, divinylbenzene, or 1,3,5-triethynylbenzene; the free radical initiator is one or more of cyclohexanone peroxide, benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, or azobisisoheptanenitrile; and the weight ratio of the free radical initiator to the organic nitrogen ligand monomer is 1:100 to 1:

5.

6. The application of the nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst according to claim 4 for catalyzing the hydroformylation reaction of high-carbon olefins, characterized in that, in When a crosslinking agent is added, the molar ratio of vinyl-functionalized organic nitrogen ligand to crosslinking agent is 0.1:1 to 1:1, and the molar ratio of vinyl-functionalized organic nitrogen ligand to free radical initiator is 50:1 to 10:

1.

7. The application of the nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst according to claim 4 for catalyzing the hydroformylation reaction of high-carbon olefins, characterized in that, The precursor of the metal component Co is derived from one or more of Co(OAc)2, Co(acac)2, Co(acac)3, Co(NO3)2, and CoCl2, and the loading of metal Co is 1 to 50 wt%.

8. The application of the nitrogen-containing porous organic ligand polymer-supported Co-based heterogeneous catalyst according to claim 1 for catalyzing the hydroformylation reaction of high-carbon olefins, characterized in that, Hydroformylation of high-carbon terminal or internal olefins with syngas is carried out in a trickle bed, slurry bed, or batch reactor in the presence of a Co-based heterogeneous catalyst. The reaction temperature is 323–523 K, the reaction pressure is 0.5–15 MPa, and the liquid hourly space velocity is 0.05–8.0 h⁻¹. -1 The gas space velocity is 500~10000 h. -1 .

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