A heterogeneous catalytic process for the preparation of tricyclodecane unsaturated aldehydes

Abstract

The application discloses a kind of preparation tricyclodecane unsaturated aldehyde heterogeneous catalytic method, using dicyclopentadiene under the action of heterogeneous catalyst, by hydroformylation reaction generates tricyclodecane unsaturated aldehyde.The heterogeneous catalyst in with one or both of corresponding precursors of metal Rh or Co is the metal component to be loaded, with phosphine-containing porous organic polymer with multi-level pore structure as carrier, phosphine-containing organic polymer is polymerized by vinyl functionalized phosphine ligand.The application is applicable to fixed bed, slurry bed, bubble bed and continuous reactor such as trickle bed.And catalyst has the advantages of high catalytic activity and high selectivity of target product, good stability, easy separation and recovery.

Description

Technical Field

[0001] This invention belongs to the technical field of heterogeneous catalytic methods for preparing tricyclodecane unsaturated aldehydes, and in particular relates to a heterogeneous catalytic method for preparing tricyclodecane unsaturated aldehydes from dicyclopentadiene via a heterogeneous hydroformylation reaction under a syngas atmosphere (CO:H2=1:1). Background Technology

[0002] Hydroformylation is one of the most important homogeneous catalytic reactions in industry, widely used in the synthesis of aldehydes. Traditional hydroformylation processes use noble metal catalysts (such as Rh and Co) and are carried out under homogeneous conditions, which suffers from problems such as difficult catalyst recovery and complex product separation. In recent years, heterogeneous catalytic hydroformylation technology has attracted widespread attention due to its advantages such as easy catalyst separation and continuous operation.

[0003] Dicyclopentadiene, as a chemical raw material, is mainly produced through the dimerization of cyclopentadiene generated during petroleum refining. Its hydroformylation products are divided into tricyclodecane unsaturated aldehydes containing one formyl group and tricyclodecane dicarboxaldehyde containing two formyl groups. Tricyclodecane unsaturated aldehydes, as products of the incomplete hydroformylation of dicyclopentadiene, can be directly applied in the fine chemical industry or used as a raw material to generate tricyclodecane dicarboxaldehyde through secondary hydroformylation for use in the polymer field. However, existing production technologies for tricyclodecane unsaturated aldehydes primarily employ homogeneous catalysis, which suffers from poor reaction continuity, easy catalyst deactivation, and difficulty in catalyst recovery. Traditional heterogeneous catalysis processes for producing tricyclodecane unsaturated aldehydes often face problems such as low catalyst activity, poor selectivity of the target product, and easy deactivation. Therefore, developing a highly efficient, stable, and selective heterogeneous catalytic system to achieve highly selective preparation of tricyclodecane unsaturated aldehydes from dicyclopentadiene has significant industrial application value.

[0004] Patent CN117402045A describes a method for preparing tricyclodecane unsaturated aldehydes by the hydroformylation of dicyclopentadiene using a complex catalyst composed of Pt or Ru and phosphine ligands. However, the catalyst activity is poor, and the reaction is homogeneous, making continuous production impossible. Patent CN102795978A reports a method for preparing tricyclodecane unsaturated aldehydes by the hydroformylation of dicyclopentadiene using a phosphine ligand-modified supported catalyst. However, this method suffers from low catalyst dispersion, reducing the utilization of precious metals, and insufficient selectivity for the target product, tricyclodecane unsaturated aldehydes. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a heterogeneous catalytic method for preparing tricyclodecane unsaturated aldehydes, achieving continuous catalytic reactions with high conversion rates, high selectivity, and high stability.

[0006] The objective of this invention is achieved through the following technical solution: This invention discloses a heterogeneous catalytic method for preparing tricyclodecane unsaturated aldehydes. Using dicyclopentadiene as a raw material, the target product, tricyclodecane unsaturated aldehyde, is generated through a hydroformylation reaction under the action of a heterogeneous catalyst. The heterogeneous catalyst is a supported catalyst, using one or two of rhodium (Rh) or cobalt (Co) as the active component. The total metal loading in the heterogeneous catalyst ranges from 0.1-5 wt%, preferably from 0.2-3.0 wt%. A phosphine-containing porous organic polymer is used as the support. The phosphine-containing organic polymer is polymerized from any one or more of the following vinylphosphine ligands L1-L9 in any proportion. .

[0007] Furthermore, the phosphine-containing porous organic polymer has a specific surface area of ​​100-1000 m². 2 / g, pore volume 0.1-1.0cm³ 3 / g.

[0008] Furthermore, the preparation process of the heterogeneous catalyst includes: The preparation of phosphine-containing porous organic polymers is carried out by solvothermal polymerization, initiating the polymerization reaction of olefin groups in the raw material molecules with a free radical initiator to generate a phosphine-containing porous organic polymer carrier. The precursor of the active component is stirred with a phosphine-containing porous organic polymer support in an organic solvent. The active component forms multiple coordination bonds with the exposed phosphine in the phosphine-containing porous organic polymer support. After removing the organic solvent, a heterogeneous catalyst is obtained.

[0009] Furthermore, if the active component contained in the heterogeneous catalyst is either Rh or Co, the preparation process of the heterogeneous catalyst includes: a1) At 20~50℃ under an inert atmosphere, vinylphosphine ligand and free radical initiator are added to an organic solvent in a mass ratio of 200:1~10:1; preferably 100:1~20:1; after mixing, the mixture is stirred for 0.1~10 hours, preferably 0.5~5 hours; to obtain a mixed solution; b1) Transfer the mixed solution obtained in step a1) to a hydrothermal synthesis reactor, and carry out a solvothermal polymerization reaction at a temperature of 80~200℃, preferably 100~160℃, under an inert atmosphere for 10~72 hours. The preferred solvothermal polymerization reaction time is 12~48 hours to obtain a phosphine-containing organic polymer. c1) At 20-50°C under an inert atmosphere, the phosphine-containing organic polymer obtained in step b) is added to an organic solvent containing the active component precursor. After stirring for 1-48 hours, preferably 12-24 hours, the organic solvent is removed under vacuum to obtain a heterogeneous catalyst containing either Rh or Co as the active component.

[0010] Furthermore, if the heterogeneous catalyst simultaneously contains active components Co and Rh, the preparation process includes: a2) Under an inert atmosphere, the Rh precursor and vinylphosphine ligand are dissolved separately in an organic solvent, with a molar ratio of 1:20 to 1:1, preferably 1:10 to 1:2. The organic solvent containing the vinylphosphine ligand is heated to 40 to 100°C, and then the organic solution containing the Rh precursor is added dropwise to the organic solvent containing the vinylphosphine ligand. After the addition is complete, the mixture is stirred for 0.1 to 10 hours, preferably 2 to 8 hours, to obtain the Rh-P complex precursor solution. b2) Under an inert atmosphere, the Co precursor and vinylphosphine ligand are mixed and dissolved in an organic solvent at a molar ratio of 1:50 to 1:1, preferably 1:30 to 1:3, and stirred for 0.1 to 20 hours, preferably 2 to 12 hours, to obtain a Co-P complex precursor solution. c2) The Rh-P complex precursor solution and Co-P complex precursor solution obtained in steps a2) and b2) respectively, along with the free radical initiator, are dissolved together in an organic solvent and stirred until homogeneous. The molar ratio of Co to Rh ranges from 10:1 to 1:10, preferably from 5:1 to 1:4, and the weight ratio of the free radical initiator to the total amount of vinylphosphine ligands in the solution ranges from 1:100 to 1:20. The stirring time is 0.1 to 10 hours, preferably 0.5 to 5 hours. The mixed solution is transferred to a hydrothermal reactor for synthesis and subjected to solvothermal polymerization at a temperature of 80-200℃, preferably 100-160℃, under an inert atmosphere for 10-72 hours to obtain an Rh-containing catalyst precursor. The preferred solvothermal polymerization reaction time is 12-48 hours. The organic solvent is then removed, yielding a heterogeneous catalyst containing both Rh and Co components.

[0011] Furthermore, the organic solvent is one or more of benzene, toluene, N,N-dimethylformamide, tetrahydrofuran, methanol, ethanol, dichloromethane or trichloromethane, and when there are two or more, they are mixed in any proportion; The free radical initiator is one or more of cyclohexanone peroxide, benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, or azobisisoheptanenitrile, and when there are two or more, they are mixed in any proportion.

[0012] Furthermore, in the preparation process of the heterogeneous catalyst, the concentration of the material in the organic solvent ranges from 10 to 1000 g / L, preferably from 30 to 300 g / L.

[0013] Furthermore, the precursors of the active component Rh are Rh(CH3COO)2, RhH(CO)(PPh3)3, and Rh(CO)2. ( One or more of acac) and RhCl3; the precursor of Co is one or more of Co(CH3COO)2, Co2(CO)8, Co(acac)2, and CoCl2.

[0014] Furthermore, the dicyclopentadiene has a mass purity of 10% to 100%, preferably 30% to 80%, and the remaining components are one or more of benzene, toluene, n-hexane, cyclohexane, heptane, octane, tricyclodecane unsaturated aldehyde, and tricyclodecane dicarboxaldehyde.

[0015] Furthermore, when the hydroformylation reaction is carried out using the aforementioned heterogeneous catalyst, it is conducted in a fixed-bed, slurry-bed, bubble-bed, or trickle-bed reactor at a reaction temperature of 60–160°C, preferably 80–130°C, and a pressure of 1–8 MPa, preferably 2–6 MPa. A reaction mixture with an H2:CO volume ratio of 1:5–5:1, preferably 1:3–3:1, is introduced, along with a dicyclopentadiene liquid with a purity of 10%–100%. The space velocity of the reaction mixture is in the range of 300–2000 h⁻¹. -1 The liquid space velocity range for dicyclopentadiene is 0.1–5.0 h⁻¹. -1 .

[0016] The beneficial effects of this invention are as follows: 1. The heterogeneous catalyst of this invention contains a large number of exposed P sites and well-developed pores. Active metal atoms or ions form multiple coordination bonds with the exposed P sites on the polymer, preventing the active components from easily leaching. The active metal components may be highly dispersed in single-atom form within or on the surface of the porous organic polymer support, improving the utilization efficiency of the metal components. Simultaneously, the well-developed pores facilitate the diffusion of reactants and products, thereby endowing this type of catalyst with excellent catalytic performance and high-efficiency separation characteristics.

[0017] 2. The heterogeneous catalyst involved in this invention is suitable for continuous reactors such as fixed beds, slurry beds, bubble beds, and trickle beds, and has significant technical advantages in terms of reaction continuity, catalytic activity, stability, and yield of tricyclic decane unsaturated aldehydes. Detailed Implementation

[0018] The present invention will now be described in detail with reference to the embodiments.

[0019] Example 1: A heterogeneous catalytic method for preparing tricyclodecane unsaturated aldehydes according to the present invention uses dicyclopentadiene as a raw material, and generates the target product tricyclodecane unsaturated aldehydes through a hydroformylation reaction under the action of a heterogeneous catalyst; the heterogeneous catalyst is a supported catalyst, using one or two of rhodium (Rh) or cobalt (Co) as active components, and the total metal loading in the heterogeneous catalyst ranges from 0.1-5 wt%; a phosphine-containing porous organic polymer is used as a support, and the phosphine-containing organic polymer is polymerized from any one or two or more of the following vinylphosphine ligands L1-L9 in any proportion; .

[0020] The preparation methods of the ligands L1-L9 are referenced in patents CN112892602B and CN116174050B.

[0021] This example uses the L1 ligand, and the specific heterogeneous catalytic method for preparing tricyclic decane unsaturated aldehydes is as follows: Preparation of phosphorus-containing porous organic polymers: Under a protective atmosphere of inert argon, 10.0 g of L1 ligand was dissolved in 50 mL of tetrahydrofuran. 0.2 g of azobisisobutyronitrile (AIBN) was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was then transferred to an autoclave and polymerized at 100 °C under an inert argon atmosphere using a solvothermal polymerization method for 24 h. After the polymerized solution was cooled to room temperature, the tetrahydrofuran solvent was removed under vacuum at room temperature, yielding an organophosphorus self-polymerized support derived from the L1 monomer.

[0022] Preparation of heterogeneous catalysts: 12.6 mg of rhodium dicarbonyl acetylacetone was dissolved in 100.0 mL of tetrahydrofuran solvent, and 1.0 g of organic polymer support obtained by self-polymerization of L1 monomer was added. The mixture was stirred for 24 hours at room temperature under an inert argon atmosphere. Then, the tetrahydrofuran solvent was removed under vacuum at room temperature to obtain a heterogeneous catalyst with an Rh loading of 0.50% for the hydroformylation of dicyclopentadiene.

[0023] Preparation of tricyclodecane unsaturated aldehydes: 0.2 g (approximately 1 mL) of heterogeneous catalyst was packed into a fixed-bed reactor. The reaction temperature was raised to 100 °C and the pressure to 4 MPa under a syngas atmosphere (CO / H2 = 1:1). Then, liquid feedstock (70% dicyclopentadiene, the remainder cyclohexane) was introduced at a syngas space velocity of 1000 h⁻¹. -1 The liquid space velocity is 4.0 h⁻¹. -1 The reaction solution was collected in a collection tank to obtain tricyclic decane unsaturated aldehydes. Samples were taken and analyzed multiple times at fixed time intervals, and the average value was used to calculate the catalyst's time-of-flight (TOF) and the selectivity of the tricyclic decane unsaturated aldehydes.

[0024] Example 2: This example differs from Example 1 in that, in the preparation of the heterogeneous catalyst, 1.0 g of the free radical initiator azobisisobutyronitrile was weighed to replace 0.2 g of the free radical initiator azobisisobutyronitrile, and the rest of the preparation method is the same as in Example 1.

[0025] Example 3: This example differs from Example 1 in that 50.0 ml of tetrahydrofuran solvent is used instead of 100.0 ml of tetrahydrofuran solvent in the preparation of the heterogeneous catalyst. The rest of the preparation method is the same as in Example 1.

[0026] Example 4: This example differs from Example 1 in that 100.0 ml of dichloromethane solvent is used instead of 100.0 ml of tetrahydrofuran solvent in the preparation of the heterogeneous catalyst. The rest of the preparation method is the same as in Example 1.

[0027] Example 5: This example differs from Example 1 in that a polymerization temperature of 120°C is used instead of 100°C in the preparation of the phosphine-containing porous organic polymer; the rest of the preparation method is the same as in Example 1.

[0028] Example 6: This example differs from Example 1 in that a 12-hour polymerization time is used instead of a 24-hour polymerization time in the preparation of the phosphine-containing porous organic polymer; the rest of the preparation method is the same as in Example 1.

[0029] Example 7: This example differs from Example 1 in that L2 ligand is used instead of L1 ligand in the preparation of the phosphine-containing porous organic polymer; the rest of the preparation method is the same as in Example 1.

[0030] Example 8: This example differs from Example 1 in that L3 ligand is used instead of L1 ligand in the preparation of the phosphine-containing porous organic polymer; the rest of the preparation method is the same as in Example 1.

[0031] Example 9: This example differs from Example 1 in that, in the preparation of the phosphine-containing porous organic polymer, 10.0 g of L1 is replaced with 9.5 g of L1 and 0.5 g of L7, while the rest of the preparation method is the same as in Example 1.

[0032] Example 10: This example differs from Example 1 in that, in the preparation of the heterogeneous catalyst, 14.5 mg of cobalt carbonyl was weighed to replace rhodium dicarbonyl acetylacetone and dissolved in 10.0 ml of tetrahydrofuran solvent. The rest of the preparation method is the same as in Example 1.

[0033] Example 11: This example differs from Example 1 in that, in the preparation of the heterogeneous catalyst, 6.3 mg of rhodium dicarbonyl acetylacetone was weighed to replace rhodium dicarbonyl acetylacetone and dissolved in 10.0 ml of tetrahydrofuran solvent. The rest of the preparation method is the same as in Example 1.

[0034] Example 12: This example differs from Example 1 in that, in the preparation of the heterogeneous catalyst, 25.2 mg of rhodium dicarbonyl acetylacetone was weighed to replace rhodium dicarbonyl acetylacetone and dissolved in 10.0 ml of tetrahydrofuran solvent. The rest of the preparation method is the same as in Example 1.

[0035] Example 13: This example differs from Example 1 in that the content of dicyclopentadiene in the liquid material is adjusted to 50% and the remainder is cyclohexane in the preparation of tricyclodecane unsaturated aldehyde; the rest of the preparation method is the same as in Example 1.

[0036] Example 14: This example differs from Example 1 in that, in the preparation of tricyclodecane unsaturated aldehyde, the cyclohexane in the liquid is replaced with an equal amount of tricyclodecane unsaturated aldehyde, while the rest of the preparation method is the same as in Example 1.

[0037] Example 15: This example differs from Example 1 in that the reaction pressure in the preparation of tricyclodecane unsaturated aldehyde is 6 MPa, while the rest of the preparation method is the same as in Example 1.

[0038] Example 16: The difference between this example and Example 1 is that in the preparation of tricyclodecane unsaturated aldehyde, the composition of the synthesis gas is changed to (CO:H2=2:1), while the rest of the preparation method is the same as in Example 1.

[0039] Example 17: This example differs from Example 1 in that the heterogeneous catalyst in this example contains both Co and Rh active components, with a Co to Rh molar ratio of 1:1 and an Rh loading of 0.50%. The rest of the preparation method is the same as in Example 1.

[0040] Example 18: This example differs from Example 17 in that the heterogeneous catalyst in this example contains both Co and Rh active components, wherein the molar ratio of Co to Rh is 1:1, the loading of Rh is 0.25%, and the rest of the preparation method is the same as in Example 17.

[0041] Example 19: This example differs from Example 17 in that the heterogeneous catalyst in this example contains both Co and Rh active components, wherein the molar ratio of Co to Rh is 2:1, the loading of Rh is 0.50%, and the rest of the preparation method is the same as in Example 17.

[0042] Example 20: This example differs from Example 17 in that the heterogeneous catalyst in this example contains both Co and Rh active components, with a Co to Rh molar ratio of 4:1 and an Rh loading of 0.50%. The rest of the preparation method is the same as in Example 17.

[0043] Example 21: This example differs from Example 17 in that the heterogeneous catalyst in this example contains both Co and Rh active components, wherein the molar ratio of Co to Rh is 1:2, the loading of Rh is 0.50%, and the rest of the preparation method is the same as in Example 17.

[0044] Example 22: This example differs from Example 17 in that the fixed bed reactor is replaced with a trickle bed reactor, while the rest of the preparation method is the same as in Example 17.

[0045] Example 23: This example differs from Example 17 in that the synthesis gas space velocity is adjusted to 2000 h⁻¹. -1 The remaining preparation methods are the same as in Example 17.

[0046] Example 24: This example differs from Example 17 in that the liquid space velocity is adjusted to 3.0 h. -1 The remaining preparation methods are the same as in Example 17.

[0047] Example 25: This example differs from Example 17 in that L4 ligand is used instead of L1 ligand in the preparation of the phosphine-containing porous organic polymer, while the rest of the preparation method is the same as in Example 17.

[0048] Example 26: This example differs from Example 17 in that L5 ligand is used instead of L1 ligand in the preparation of the phosphine-containing porous organic polymer, while the rest of the preparation method is the same as in Example 17.

[0049] Example 27: This example differs from Example 17 in that L6 ligand is used instead of L1 ligand in the preparation of the phosphine-containing porous organic polymer, while the rest of the preparation method is the same as in Example 17.

[0050] Example 28: This example differs from Example 17 in that, in the preparation of the phosphine-containing porous organic polymer, L4 and L8 ligands are mixed to replace L1 ligand, with a molar ratio of L4:L8 of 10:1. The rest of the preparation method is the same as in Example 17.

[0051] Example 29: This example differs from Example 17 in that, in the preparation of the phosphine-containing porous organic polymer, the L4+L9 ligand (L4:L9 molar ratio 10:1) is used to replace the L1 ligand, while the rest of the preparation method is the same as in Example 17.

[0052] Example 30: This example differs from Example 17 in that, in the preparation of the phosphine-containing porous organic polymer, the L4+L9 ligand (L4:L9 molar ratio 1:1) is used to replace the L1 ligand, while the rest of the preparation method is the same as in Example 17.

[0053] Example 31: This example differs from Example 17 in that, in the preparation of the phosphine-containing porous organic polymer, the L1 ligand is replaced by the L1+L4+L7 ligand (L1:L4:L7 molar ratio 10:5:1), while the rest of the preparation method is the same as in Example 17.

[0054] Example 32: This example differs from Example 17 in that, in the preparation of the phosphine-containing porous organic polymer, the L1 ligand is replaced by the L1+L4+L7 ligand (L1:L4:L7 molar ratio 10:5:1), while the rest of the preparation method is the same as in Example 17.

[0055] Example 33: This example differs from Example 1 in that 2.5 mg of rhodium acetylacetone dicarbonyl is weighed out to replace 12.6 mg of rhodium acetylacetone dicarbonyl, while the rest of the preparation method is the same as in Example 1.

[0056] Example 34: This example differs from Example 1 in that 126 mg of rhodium dicarbonyl acetylacetone was weighed out to replace 12.6 mg of rhodium dicarbonyl acetylacetone, while the rest of the preparation method is the same as in Example 1.

[0057] Example 35: This example differs from Example 17 in that the heterogeneous catalyst in this example contains both Co and Rh active components, with a Co to Rh molar ratio of 10:1 and an Rh loading of 0.25%. The remaining preparation methods are the same as in Example 17.

[0058] Example 36: This example differs from Example 17 in that the heterogeneous catalyst in this example contains both Co and Rh active components, with a Co to Rh molar ratio of 1:10 and an Rh loading of 0.25%. The remaining preparation methods are the same as in Example 17.

[0059] Example 37: This example differs from Example 1 in that 0.2 g of azobisisobutyronitrile was replaced with 0.05 g in the preparation of the polymer support and catalyst, the material concentration in the solvent was 10 g / L, the stirring time was changed to 0.1 hours, the polymerization temperature was changed to 80 degrees Celsius, the polymerization time was changed to 10 hours, and the catalyst impregnation stirring time was changed to 1 hour. The rest of the preparation methods are the same as in Example 1.

[0060] Example 38: This example differs from Example 1 in that 0.2 g of azobisisobutyronitrile was replaced with 1 g in the preparation of the polymer support and catalyst, the material concentration in the solvent was 1000 g / L, the stirring time was changed to 10 hours, the polymerization temperature was changed to 200 degrees Celsius, the polymerization time was changed to 72 hours, and the catalyst impregnation stirring time was changed to 48 hours. The rest of the preparation method is the same as in Example 1.

[0061] Example 39: This example differs from Example 1 in that, during the preparation of the polymer carrier, 0.2 g of azobisisobutyronitrile was replaced with a combination of 0.1 g of cyclohexanone peroxide and 0.1 g of azobisisobutyronitrile, while the rest of the preparation method was the same as in Example 1.

[0062] Example 40: This example differs from Example 1 in that the organic solvent is replaced with an equal volume mixture of tetrahydrofuran and methanol during the preparation of the polymer support and catalyst. The rest of the preparation method is the same as in Example 1.

[0063] Example 41: This example differs from Example 1 in that, during the catalyst preparation process, rhodium dicarbonyl acetylacetone is replaced with an equimolar amount of rhodium triphenylphosphine carbonyl hydride, while the rest of the preparation method is the same as in Example 1.

[0064] Example 42: This example differs from Example 1 in that, during the catalyst preparation process, rhodium dicarbonyl acetylacetone is replaced with a combination of rhodium triphenylphosphine carbonyl hydride and rhodium trichloride (molar ratio of the two is 1:1, and the total molar amount is equal to that of rhodium dicarbonyl acetylacetone in Example 1). The rest of the preparation method is the same as in Example 1.

[0065] Example 43: This example differs from Example 1 in that, during the catalyst preparation process, rhodium dicarbonyl acetylacetone is replaced with an equimolar amount of cobalt acetylacetone, while the rest of the preparation method is the same as in Example 1.

[0066] Example 44: This example differs from Example 17 in that, during the catalyst preparation process, acetylacetone dicarbonyl methyl ether is replaced with an equimolar amount of triphenylphosphine carbonyl rhodium hydride, and cobalt carbonyl is replaced with an equimolar amount of cobalt acetylacetone. The rest of the preparation method is the same as in Example 17.

[0067] Example 45: This example differs from Example 17 in that, during the catalyst preparation process, rhodium diacetylacetone is replaced with a combination of rhodium triphenylphosphine carbonyl hydride and rhodium trichloride (molar ratio of the two is 2:1, and the total molar amount is equal to that of rhodium diacetylacetone in Example 17), and cobalt carbonyl is replaced with an equimolar combination of cobalt acetylacetone and cobalt chloride (molar ratio of the two is 1:1, and the total molar amount is equal to that of cobalt carbonyl in Example 17). The rest of the preparation method is the same as in Example 17.

[0068] Example 46: This example differs from Example 17 in that, during the catalyst preparation process, the molar ratio of Rh to vinylphosphine ligand in the Rh-P complex solution is 1:20, the molar ratio of Co to vinylphosphine ligand in the Co-P complex solution is 1:1, and the molar ratio of Co:Rh is 10:1. The rest is the same as in Example 17.

[0069] Example 47: This example differs from Example 17 in that the molar ratio of Rh to vinylphosphine ligand in the Rh-P complex solution is 1:1, the molar ratio of Co to vinylphosphine ligand in the Co-P complex solution is 1:50, and the molar ratio of Co:Rh is 1:10. The rest is the same as in Example 17.

[0070] Example 48: This example differs from Example 17 in that the liquid composition is 10% dicyclopentadiene, with the remainder being an equal mixture of tricyclodecane unsaturated aldehyde and tricyclodecane dicarboxaldehyde, and the rest is the same as in Example 17.

[0071] Example 49: This example differs from Example 17 in that the liquid composition is pure dicyclopentadiene (content 100%), and the rest is the same as in Example 17.

[0072] Example 50: This example differs from Example 17 in that the reaction temperature is 60°C, the preferred pressure is 1 MPa, the volume ratio of H2:CO in the reaction mixture is 1:5, and the reaction mixture contains 10% dicyclopentadiene liquid. The space velocity of the reaction mixture is 300 h⁻¹. -1 The liquid space velocity of dicyclopentadiene is 0.1 h⁻¹. -1 The rest is the same as in Example 17.

[0073] Example 51: This example differs from Example 17 in that the catalytic reaction temperature is 160°C, the pressure is 8 MPa, the volume ratio of H2:CO in the reaction mixture is 5:1, and the reaction mixture contains 100% pure dicyclopentadiene liquid. The space velocity of the reaction mixture is 2000 h⁻¹. -1 The liquid space velocity of dicyclopentadiene is 5.0 h⁻¹. -1 The rest is the same as in Example 17.

[0074] Example 52: This example differs from Example 17 in that the hydroformylation reaction of the catalyst is changed from a fixed bed to a bubbling bed, otherwise it is the same as Example 17.

[0075] Example 53: This example differs from Example 17 in that the hydroformylation reaction of the catalyst is changed from a fixed bed to a slurry bed, otherwise it is the same as Example 17.

[0076] Comparative Example 1: In Comparative Example 1, the heterogeneous catalyst was replaced with Rh / SiO2 with the same Rh content, and the rest of the preparation method was the same as in Example 1.

[0077] Comparative Example 2: In Comparative Example 2, the heterogeneous catalyst was replaced with Rh / C with the same Rh content, and the rest of the preparation method was the same as in Example 1.

[0078] Comparative Example 3: In Comparative Example 3, the heterogeneous catalyst was replaced with homogeneous Rh-PPh3, the reactor was replaced with an autoclave reactor, and the rest of the preparation method was the same as in Example 1.

[0079] Comparative Example 4: In Comparative Example 4, the heterogeneous catalyst was replaced with Rh(acac)(CO)2, the reactor was replaced with a high-pressure reactor, and the rest of the preparation method was the same as in Example 1.

[0080] Comparative Example 5: In Comparative Example 5, the heterogeneous catalyst contains both Co and Rh bimetallic active components. The Co and Rh precursor components are dissolved in tetrahydrofuran and directly impregnated with a P-containing porous organic polymer support. The molar ratio of Co to Rh is 1:1, and the loading of Rh is 0.50%. The rest of the preparation method is the same as in Example 1.

[0081] Comparative Example 6: In Comparative Example 6, the heterogeneous catalyst was replaced with a combination of Rh and commercially available Xantphos ligands, and the reactor was replaced with an autoclave reactor. The rest of the preparation method was the same as in Example 1.

[0082] Comparative Example 7: In Comparative Example 7, the heterogeneous catalyst was replaced with commercially available Wilkinson catalyst Rh(PPh3)3Cl, the reactor was replaced with an autoclave reactor, and the rest of the preparation method was the same as in Example 1.

[0083] The reactions in each embodiment and comparative example were collected in a collection vessel. The obtained products were analyzed by gas chromatography using an Agilent-7890B equipped with a DB-WAX capillary column and an FID detector, with n-butanol as an internal standard. The reaction tail gas was analyzed online using an Agilent-7890B gas chromatograph equipped with a Porapak-QS column and a TCD detector. The reaction results are listed in Table 1.

[0084] As can be seen from the results in Table 1, the heterogeneous catalytic method provided by this invention exhibits good substrate conversion, catalytic activity and target product selectivity in the reaction of dicyclopentadiene to prepare tricyclodecane unsaturated aldehydes, and has obvious technical advantages.

[0085] Table 1: Example 1 760 0.59 0.50 - 28 488 92.8 Example 2 580 0.63 0.50 - 29 493 92.8 Example 3 780 0.67 0.50 - 26 464 92.3 Example 4 910 0.91 0.50 - 27 486 94.5 Example 5 599 0.60 0.50 - 23 397 91.4 Example 6 677 0.59 0.50 - 19 331 91.6 Example 7 762 0.71 0.50 - 27 442 87.7 Example 8 555 0.46 0.50 - 30 501 89.3 Example 9 612 0.49 0.5 - 50 760 80.6 Example 10 732 0.56 0.50 (Co content) - 4 57 69.8 Example 11 643 0.51 0.25 - 16 536 91.1 Example 12 636 0.54 1.00 - 22 383 89.7 <![CDATA[Example 13 a > 675 0.60 0.50 - 24 311 93.7 Example 14 599 0.46 0.50 - 23 459 92.3 Example 15 647 0.60 0.50 - 29 543 96.9 Example 16 587 0.51 0.50 - 26 407 82.2 Example 17 576 0.50 0.50 1:1 37 637 90.4 Example 18 559 0.44 0.25 1:1 21 722 90.6 Example 19 672 0.51 0.50 2:1 45 792 92.3 Example 20 665 0.52 0.50 4:1 63 1142 94.7 Example 21 697 0.67 0.50 1:2 32 548 89.1 Example 22 699 0.63 0.50 1:1 36 610 90.2 Example 23 655 0.62 0.50 1:1 40 691 91.1 Example 24 692 0.66 0.50 1:1 33 615 90.3 Example 25 579 0.53 0.50 1:1 52 971 90.1 Example 26 681 0.61 0.50 1:1 58 1002 89.9 Example 27 188 0.15 0.50 1:1 37 718 95.1 Example 28 762 0.58 0.50 1:1 41 724 90.3 Example 29 773 0.59 0.50 1:1 43 771 93.2 Example 30 100 0.10 0.50 1:1 26 487 93.4 Example 31 812 0.67 0.50 1:1 50 912 94.2 Example 32 511 0.48 0.50 1:1 52 922 90.3 Example 33 1000 1.00 0.10 - 7 588 87.4 Example 34 873 0.47 5.00 - 88 154 92.1 Example 35 912 0.87 0.25 10:1 31 941 81.2 Example 36 901 0.84 0.25 1:10 18 631 91.7 Example 37 312 0.26 0.50 - 21 367 91.4 Example 38 981 0.88 0.50 - 31 544 92.3 Example 39 916 0.83 0.50 - 28 481 92.1 Example 40 933 0.81 0.50 - 27 472 91.9 Example 41 771 0.64 0.50 - 30 495 92.1 Example 42 752 0.63 0.50 - 21 309 78.4 <![CDATA[Example 43 a > 738 0.64 0.50 (Co content) - 4 51 67.2 Example 44 531 0.52 0.50 1:1 37 611 90.0 Example 45 602 0.58 0.50 1:1 33 539 85.1 Example 46 589 0.59 0.94 10:1 62 511 83.1 Example 47 517 0.49 4.80 1:10 97 189 93.4 Example 48 576 0.50 0.50 1:1 60 140 85.5 Example 49 576 0.50 0.50 1:1 35 811 91.9 Example 50 576 0.50 0.50 1:1 99 242 96.8 Example 51 576 0.50 0.50 1:1 41 989 88.1 Example 52 576 0.50 0.50 1:1 38 671 91.2 Example 53 576 0.50 0.50 1:1 35 666 91.8 Comparative Example 1 108 0.15 0.50 - 23 271 61.7 Comparative Example 2 273 0.21 0.50 - 30 348 60.2 Comparative Example 3 - - 0.50 - 89 517 69.9 Comparative Example 4 - - Same Rh content - 67 112 20.1 Comparative Example 5 677 0.46 0.50 1:1 30 509 88.4 Comparative Example 6 - - 0.50 - 59 407 82.3 Comparative Example 7 - - Same Rh content - 70 487 83.6 In the examples above: the catalyst is loaded into the reactor, and the product composition is: monocarbonylation product tricyclodecane unsaturated aldehyde, dicarbonylation product tricyclodecane diformaldehyde, dicyclopentadiene hydrogenation product, and etherification product. The reaction selectivity is the same as that of tricyclodecane unsaturated aldehyde. When the catalyst contains only Rh or Co, all metals are considered active sites in the TOF calculation; when the catalyst contains both Rh and Co, Rh is considered the active site in the TOF calculation. The density of the dicyclopentadiene liquid feed (70% dicyclopentadiene, the remainder being cyclohexane) is 0.87 g / cm³.3 Comparative Examples 3, 4, 6, and 7 used homogeneous catalysts, and the reactions were carried out in a high-pressure reactor with the same reaction temperature, pressure, and Rh content in the catalyst. The S / C (molar ratio of dicyclopentadiene to Rh) was 10000, toluene was used as the solvent, and the reaction time was 12 hours.

Claims

1. A heterogeneous catalytic method for preparing tricyclodecane unsaturated aldehydes, characterized in that: Using dicyclopentadiene as a raw material, a hydroformylation reaction is carried out under the action of a heterogeneous catalyst to generate the target product, tricyclodecane unsaturated aldehyde. The heterogeneous catalyst is a supported catalyst, with one or two of rhodium (Rh) or cobalt (Co) as the active component. The total metal loading in the heterogeneous catalyst ranges from 0.1 to 5 wt%, preferably from 0.2 to 3.0 wt%. A phosphine-containing porous organic polymer is used as a carrier. The phosphine-containing organic polymer is polymerized from any one or more of the following vinylphosphine ligands L1-L9 in any proportion. 。 2. The method according to claim 1, characterized in that: The aforementioned phosphine-containing porous organic polymer has a specific surface area of ​​100-1000 m². 2 / g, pore volume 0.1-1.0cm³ 3 / g.

3. The method according to claim 1, characterized in that: The preparation process of the heterogeneous catalyst includes: The preparation of phosphine-containing porous organic polymers is carried out by solvothermal polymerization, initiating the polymerization reaction of olefin groups in the raw material molecules with a free radical initiator to generate a phosphine-containing porous organic polymer carrier. The precursor of the active component is stirred with a phosphine-containing porous organic polymer support in an organic solvent. The active component forms multiple coordination bonds with the exposed phosphine in the phosphine-containing porous organic polymer support. After removing the organic solvent, a heterogeneous catalyst is obtained.

4. The method according to claim 3, characterized in that: If the active component in the heterogeneous catalyst is either Rh or Co, the preparation process of the heterogeneous catalyst includes: a1) At 20~50℃ under an inert atmosphere, vinylphosphine ligand and free radical initiator are added to an organic solvent in a mass ratio of 200:1~10:1; preferably 100:1~20:1; after mixing, the mixture is stirred for 0.1~10 hours, preferably 0.5~5 hours; to obtain a mixed solution; b1) Transfer the mixed solution obtained in step a1) to a hydrothermal synthesis reactor, and carry out a solvothermal polymerization reaction at a temperature of 80~200℃, preferably 100~160℃, under an inert atmosphere for 10~72 hours. The preferred solvothermal polymerization reaction time is 12~48 hours to obtain a phosphine-containing organic polymer. c1) At 20-50°C under an inert atmosphere, the phosphine-containing organic polymer obtained in step b) is added to an organic solvent containing the active component precursor. After stirring for 1-48 hours, preferably 12-24 hours, the organic solvent is removed under vacuum to obtain a heterogeneous catalyst containing either Rh or Co as the active component.

5. The method according to claim 3, characterized in that: If the heterogeneous catalyst contains both active components Co and Rh, the preparation process includes: a2) Under an inert atmosphere, the Rh precursor and vinylphosphine ligand are dissolved separately in an organic solvent, with a molar ratio of 1:20 to 1:1, preferably 1:10 to 1:

2. The organic solvent containing the vinylphosphine ligand is heated to 40 to 100°C, and then the organic solution containing the Rh precursor is added dropwise to the organic solvent containing the vinylphosphine ligand. After the addition is complete, the mixture is stirred for 0.1 to 10 hours, preferably 2 to 8 hours, to obtain the Rh-P complex precursor solution. b2) Under an inert atmosphere, the Co precursor and vinylphosphine ligand are mixed and dissolved in an organic solvent at a molar ratio of 1:50 to 1:1, preferably 1:30 to 1:3, and stirred for 0.1 to 20 hours, preferably 2 to 12 hours, to obtain a Co-P complex precursor solution. c2) The Rh-P complex precursor solution and Co-P complex precursor solution obtained in steps a2) and b2) respectively, along with the free radical initiator, are dissolved together in an organic solvent and stirred until homogeneous. The molar ratio of Co to Rh ranges from 10:1 to 1:10, preferably from 5:1 to 1:4, and the weight ratio of the free radical initiator to the total amount of vinylphosphine ligands in the solution ranges from 1:100 to 1:

20. The stirring time is 0.1 to 10 hours, preferably 0.5 to 5 hours. The mixed solution is transferred to a hydrothermal reactor for synthesis and subjected to solvothermal polymerization at a temperature of 80-200℃, preferably 100-160℃, under an inert atmosphere for 10-72 hours to obtain an Rh-containing catalyst precursor. The preferred solvothermal polymerization reaction time is 12-48 hours. The organic solvent is then removed, yielding a heterogeneous catalyst containing both Rh and Co components.

6. The method according to any one of claims 3-5, characterized in that: The organic solvent is one or more of benzene, toluene, N,N-dimethylformamide, tetrahydrofuran, methanol, ethanol, dichloromethane or trichloromethane, and when there are two or more, they are mixed in any proportion; The free radical initiator is one or more of cyclohexanone peroxide, benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, or azobisisoheptanenitrile, and when there are two or more, they are mixed in any proportion.

7. The method according to any one of claims 3-5, characterized in that: In the preparation process of the heterogeneous catalyst, the concentration of the material in the organic solvent ranges from 10 to 1000 g / L, preferably from 30 to 300 g / L.

8. The method according to any one of claims 4-5, characterized in that: The precursors of the active component Rh are Rh(CH3COO)2, RhH(CO)(PPh3)3, and Rh(CO). 2( One or more of acac) and RhCl3; the precursor of Co is one or more of Co(CH3COO)2, Co2(CO)8, Co(acac)2, and CoCl2.

9. The method according to claim 1, characterized in that: The dicyclopentadiene has a purity of 10% to 100%, preferably 30% to 80%, and the remaining components are one or more of benzene, toluene, n-hexane, cyclohexane, heptane, octane, tricyclodecane unsaturated aldehyde, and tricyclodecane dicarboxaldehyde.

10. The method according to claim 1, characterized in that: When the hydroformylation reaction is carried out using the aforementioned heterogeneous catalyst, it is conducted in a fixed-bed, slurry-bed, bubble-bed, or trickle-bed reactor. The reaction temperature is 60–160°C, preferably 80–130°C, and the pressure is 1–8 MPa, preferably 2–6 MPa. The volume ratio of the reaction mixture H2:CO is 1:5–5:1, preferably 1:3–3:1, along with a dicyclopentadiene liquid with a purity of 10%–100%. The space velocity of the reaction mixture is in the range of 300–2000 h⁻¹. -1 The liquid space velocity range for dicyclopentadiene is 0.1–5.0 h⁻¹. -1 .

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