A method for hydroformylation of Co-based Fischer-Tropsch products olefins

Abstract

The present invention relates to a method for hydroformylation of Co-based Fischer-Tropsch product olefins, characterized in that the method comprises the step of subjecting the Co-based Fischer-Tropsch product olefins and synthesis gas to a hydroformylation reaction in a reactor in the presence of an efficient catalyst, wherein the efficient catalyst is composed of a metal component and an organic ligand polymer, the metal component is one or more of metals Rh, Co, Ir or Ru, and the organic ligand polymer is a porous polymer generated by solvent thermal polymerization of an organic P ligand containing a vinyl group. The method of the present invention can directly hydroformylate the olefins in the Co-based Fischer-Tropsch product without separation to efficiently generate high-value oxygen-containing chemicals mainly composed of straight-chain aldehydes, with an olefin conversion rate greater than 80% and a product aldehyde normal-to-iso ratio greater than 10. The method of the present invention can enable the Co-based Fischer-Tropsch product containing olefins to be subjected to a multiphase hydroformylation reaction to efficiently synthesize oxygen-containing high-value chemicals mainly composed of straight-chain aldehydes, and has important economic and industrial application prospects.

Description

Technical Field

[0001] The present invention relates to a method for hydroformylation of olefins in Co-based Fischer-Tropsch products, belonging to the technical field of heterogeneous catalysis. Background Art

[0002] Currently, the main product of coal indirect liquefaction (Fischer-Tropsch synthesis) is high-quality diesel mainly composed of straight-chain hydrocarbons. The Fischer-Tropsch synthesis products contain a relatively large amount of olefins. If this part of olefins can be converted into oxygen-containing high-value chemicals such as aldehydes, alcohols, acids or esters with high added value, the economic efficiency of the Fischer-Tropsch synthesis technology can be greatly improved.

[0003] The product distribution of Co-based Fischer-Tropsch synthesis has two characteristics: 1) The olefin content in Co-based Fischer-Tropsch synthesis products is about 15%-40%, which is relatively high compared with that in Fe-based Fischer-Tropsch synthesis products (the olefin content is 30-70%); (2) The oxygen-containing chemicals in Co-based Fischer-Tropsch synthesis products are basically normal products, while both normal and isomeric products exist in Fe-based Fischer-Tropsch synthesis products. In view of the above characteristics, the olefin hydroformylation catalyst for Co-based Fischer-Tropsch synthesis products needs to meet two requirements: 1) The Co-based Fischer-Tropsch synthesis products have a relatively low olefin content, and the products directly enter the hydroformylation reaction stage without separation, so a highly efficient hydroformylation catalyst is required; (2) The Co-based Fischer-Tropsch synthesis products are basically normal products, and normal oxygen-containing chemicals have higher economic value and application fields. At the same time, in order to reduce the subsequent separation process of normal and isomeric products, a hydroformylation catalyst with high regioselectivity (high normal / iso ratio) is required. In summary, it is necessary to develop a highly efficient catalyst with a high normal / iso ratio and apply it to the hydroformylation reaction of Co-based Fischer-Tropsch product olefins.

[0004] The hydroformylation reaction is a typical atom-economic reaction, and the research on its catalytic process and catalysts has a history of nearly 80 years. Currently, more than 22 million tons of aldehydes and alcohols are produced worldwide every year using olefin hydroformylation technology. This reaction can convert raw olefins into aldehydes under relatively mild conditions, and the resulting aldehydes can be further hydrogenated to form alcohols. The homogeneous catalytic system has high catalytic activity and selectivity for the target product under mild reaction conditions, but the separation problem between the catalyst and the reaction materials is difficult, which hinders the large-scale industrial application of the homogeneous catalytic system. The biggest advantage of heterogeneous catalysis compared with homogeneous catalysis is that the catalyst is easily separated from the reaction materials. The main problems are harsh reaction conditions and relatively low reaction activity. Currently, the main research focus of hydroformylation is on developing a new type of heterogeneous catalyst that has both the advantages of easy separation of the catalyst and the reaction materials in heterogeneous catalysis and the high reaction activity and mild reaction conditions of homogeneous catalysis.

[0005] Balue et al. (J. Mol. Catal. A, Chem, 1999, 137: 193 - 203) used cation exchange resin as a carrier to form a heterogeneous catalyst by immobilizing rhodium sulfide compounds. The recycling experiments of styrene hydroformylation showed that the stability of this heterogeneous catalyst was poor and the phenomenon of Rh loss was relatively serious. Zeelie et al. (Appl. Catal. A: Gen, 2005, 285: 96 - 109) modified styrene and p-styryldiphenylphosphine on polyethylene fibers, and then 2 anchored Rh(acac)(CO) on the modified polyethylene fibers. The results of ethylene hydroformylation showed that at 100 °C and 5 bar, the conversion rate of this catalyst was relatively high but the stability was not good. After reacting for 50 h, the reaction activity decreased sharply and the catalyst deactivation phenomenon was relatively serious.

[0006] Ricken et al. (J. Mol. Catal. A: Chem, 2006, 257: 78 - 88) carried out different functional group modifications on the ligand NIXANTPHOS. The modified ligand and Rh(acac)(CO) 2 were co-loaded on polyglycerol polymers. The experiments of 1-octene hydroformylation showed that at 80 °C and 20 bar, the conversion rate of this catalyst could reach about 90%. However, polymer carriers purchased commercially or prepared by conventional styrene radical polymerization were severely restricted in their industrial applications due to problems such as gel formation, polymer swelling, limited loading amount of phosphorus ligands in the polymer backbone, and loss of catalytically active components.

[0007] US4252678 discloses the preparation of a colloidal dispersion containing transition metals such as Rh. The transition metal component forms a catalyst system with a colloidal dispersion of 1.0 to 20.0 nm and a hydroxyl-terminated (styrene / butadiene) functionalized copolymer, and is applied to the hydroformylation reaction of 1-octene. The catalyst prepared by this method cannot be applied to fixed-bed and trickle-bed reactors, and it is difficult to separate the catalyst from the product.

[0008] CN102281948A reports a polymer-supported transition metal catalyst complex and its use method, and prepares a soluble polymer-supported Rh catalyst with a relatively narrow molecular weight distribution. However, the processes of catalyst preparation, catalytic reaction, and catalyst separation are all complex. Catalyst preparation requires first controlling functional monomers and styrene to synthesize soluble polymers, then introducing ligands, and finally loading the Rh catalyst. Compressed gas needs to be added during the catalytic reaction process. The catalyst is separated from the reaction mixture by nanofiltration and the reaction results are not ideal either.

[0009] In summary, the biggest bottleneck restricting the homogeneous immobilization of hydroformylation is the loss of homogeneous catalysts and the decrease in activity exhibited by homogeneous catalysts immobilized on supports. For the hydroformylation reaction of Co-based Fischer-Tropsch product olefins, heterogeneous hydroformylation catalysts with high efficiency and high n / i ratio need to be developed. Summary of the Invention

[0010] To solve the above problems, the object of the present invention is to provide a method for the hydroformylation of Co-based Fischer-Tropsch product olefins. By using an efficient heterogeneous catalyst, the olefins in the Co-based Fischer-Tropsch products can directly undergo hydroformylation reaction without separation to efficiently produce high-value oxygen-containing chemicals mainly composed of linear aldehydes, which has important economic significance and industrial application prospects.

[0011] For this purpose, the present invention provides a method for the hydroformylation of Co-based Fischer-Tropsch product olefins. In the presence of an efficient catalyst, the Co-based Fischer-Tropsch product olefins and syngas are subjected to hydroformylation reaction in a reactor, wherein the efficient catalyst is composed of a metal component and an organic ligand polymer. The metal component is one or more of metals Rh, Co, Ir, or Ru, and the organic ligand polymer is a porous polymer formed by the solvothermal polymerization of a mixture of vinyl-containing organic P ligands L1, L2, and L3.

[0012] The structures of L1, L2, and L3 are as follows respectively:

[0013]

[0014] In one embodiment, the mass ratio of the phosphine ligands L1, L2, and L3 is 1:0.01 - 1:0.01 - 1, preferably 1:0.03 - 0.8:0.03 - 0.8, more preferably 1:0.1 - 0.15:0.05 - 0.08.

[0015] In one embodiment, the reaction conditions for the hydroformylation reaction are: reaction temperature 293 - 573K, reaction pressure 0.1 - 20MPa, syngas volume space velocity 100 - 20000h -1 , and the molar ratio of olefins to syngas in the Co-based Fischer-Tropsch product raw material is 0.01 - 10.

[0016] In one embodiment, the Co-based Fischer-Tropsch product raw material is C 2 -C 30 hydrocarbons and oxygen-containing organic compounds, and the C 2 -C 30 hydrocarbons contain olefins, and the olefins account for 5% - 90% of the total weight of the Co-based Fischer-Tropsch product raw material; the Co-based Fischer-Tropsch product olefin raw material refers to the product formed by the Fischer-Tropsch synthesis reaction under the action of a Co-based catalyst. The Fischer-Tropsch products are not separated and directly used as the raw materials required for the method of the present invention.

[0017] In one embodiment, the syngas source is a process for producing syngas using one or more of natural gas, coal, associated gas, coalbed methane, or hydrocarbons as raw materials, and the main components of the syngas are H 2 and CO, and the volume contents of H 2 and CO are 20% - 100%, and the H 2 / CO volume ratio is 0.5 - 5.0.

[0018] In one embodiment, the metal component is one or more of the metals Rh, Co, Ir, or Ru; the metal component accounts for 0.05% - 20% of the total mass of the catalyst.

[0019] In one embodiment, the preparation process of the highly efficient catalyst includes:

[0020] a) At 273 - 473K, in a solvent containing a vinyl-functionalized P ligand, a radical initiator is added and stirred for 0.5 - 50 h;

[0021] b) At 273 - 473K, the mixed solution from step a) is allowed to stand for 0.5 - 100 h for a polymerization reaction. After the polymerization is completed, the solvent is removed to obtain an organophosphorus ligand polymer;

[0022] c) The polymer from step b) is placed in a solvent containing one or more soluble compounds of the metal active components Rh, Co, Ir, or Ru, and stirred at 273 - 473K for 0.5 - 100 h; after the solvent is removed, the highly efficient catalyst is obtained.

[0023] In one embodiment, the hydroformylation reaction of Co-based Fischer-Tropsch product olefins is carried out continuously or batchwise, and the reactor is a fixed-bed, trickle-bed, or stirred-tank reactor. When the reactor is a fixed-bed or trickle-bed reactor, the hydroformylation reaction of Co-based Fischer-Tropsch product olefins is continuously carried out on the highly efficient catalyst, and the generated liquid product continuously flows out of the reactor and is collected through a product collection tank; when the reactor is a stirred-tank reactor, the hydroformylation reaction of Co-based Fischer-Tropsch product olefins is carried out batchwise on the highly efficient catalyst, and the generated liquid product is separated from the catalyst by filtration. The above-obtained liquid product is further processed by distillation, flash evaporation, extraction, etc. to obtain a high-purity product.

[0024] The beneficial effects of the present invention include but are not limited to the following: 1) converting olefins in Co-based Fischer-Tropsch synthesis products into high-value oxygenated chemicals such as n-aldehydes through hydroformylation reaction, effectively improving the economy of Fischer-Tropsch synthesis technology; 2) the reaction process of this invention has high olefin conversion rate and high selectivity for n- and iso-aldehydes, providing feasibility for the industrial application of this method; 3) compared with the existing industrial hydroformylation reaction technology, due to the use of a new type of heterogeneous catalyst, the separation cost of the catalyst from reactants and products is reduced, which is suitable for actual industrial production. Using the method of the present invention, olefins in Co-based Fischer-Tropsch products can be used to prepare high-value oxygenated chemicals such as n-aldehydes through heterogeneous hydroformylation reaction, greatly improving the economy of coal indirect liquefaction technology, and having broad application prospects. Detailed implementation manners

[0025] To better illustrate the preparation method of the high-efficiency catalyst and its application in the hydroformylation reaction of Co-based Fischer-Tropsch product olefins, some examples of the preparation of catalyst samples and their application in the reaction process are given below, but the present invention is not limited to the listed examples. Unless otherwise specifically stated, the contents and percentages in this application are calculated by "mass".

[0026] Example 1

[0027] At room temperature, 10 g of L1 ligand, 1.2 g of L2 ligand and 0.6 g of L3 ligand are dissolved in tetrahydrofuran solvent. After stirring for 1 h, the above mixed solution is polymerized at 120 °C for 24 h. After polymerization, the solvent is removed by reduced pressure pumping to obtain a porous organic polymer containing phosphine ligand. At room temperature, 50.13 mg of Rh(acac)(CO) 2 and 2 g of the above-prepared polymer are added to 50 ml of ethanol solvent. After stirring for 24 h, the solvent is removed by reduced pressure pumping to obtain a high-efficiency catalyst.

[0028] 0.5 g of the high-efficiency catalyst is loaded into the middle of a tubular reactor, and quartz sand is filled at both ends. Feedstock Co-based Fischer-Tropsch product (C 5 -C 20 hydrocarbons and oxygen-containing compounds (C 5 -C 20 alcohols and / or aldehydes), with an olefin mass content of about 30%) and syngas (CO:H 2 =1:1) are introduced. The Co-based Fischer-Tropsch product is pumped into the reaction system by a high-pressure pump, and the syngas is directly fed in gas form. At 383 K, 2.0 MPa, with a liquid hourly space velocity of 1.5 h -1 for the Co-based Fischer-Tropsch product and a gas hourly space velocity of 1000 h -1 for the syngas, the hydroformylation reaction is carried out. The obtained liquid-phase product is analyzed by HP-7890N gas chromatography, and the normalization method is used for calculation. The reaction results are listed in Table 1.

[0029] Example 2

[0030] In Example 2, except that 10 g of L1 ligand, 0.3 g of L2 ligand and 0.3 g of L3 ligand were used to replace 10 g of L1 ligand, 1.2 g of L2 ligand and 0.6 g of L3 ligand and dissolved in tetrahydrofuran solvent, other procedures were the same as those in Example 1. The reaction results are listed in Table 1.

[0031] Example 3

[0032] In Example 3, except that 10 g of L1 ligand, 0.1 g of L2 ligand and 0.1 g of L3 ligand were used to replace 10 g of L1 ligand, 1.2 g of L2 ligand and 0.6 g of L3 ligand and dissolved in tetrahydrofuran solvent, other procedures were the same as those in Example 1. The reaction results are listed in Table 1.

[0033] Example 4

[0034] In Example 4, except that 75.20 mg of Rh(acac)(CO) 2 was used to replace 50.13 mg of Rh(acac)(CO) 2 and dissolved in ethanol solvent, other procedures were the same as those in Example 1. The reaction results are listed in Table 1.

[0035] Example 5

[0036] In Example 5, the catalyst preparation process was the same as that in Example 1. Except that Co-based Fischer-Tropsch products (C 5 -C 12 hydrocarbons and oxygenates, with an olefin content of about 45%) were used to replace Co-based Fischer-Tropsch products (C 5 -C 20 hydrocarbons and oxygenates, with an olefin content of about 30%) for the evaluation of the multiphase hydroformylation reaction, other procedures were the same as those in Example 1. The reaction results are listed in Table 1.

[0037] Example 6

[0038] In Example 6, the catalyst preparation process was the same as that in Example 1. Except that Co-based Fischer-Tropsch products (C 5 -C 20 hydrocarbons and oxygenates, with an olefin content of about 15%) were used to replace Co-based Fischer-Tropsch products (C 5 -C 20 hydrocarbons and oxygenates, with an olefin content of about 30%) for the evaluation of the multiphase hydroformylation reaction, other procedures were the same as those in Example 1. The reaction results are listed in Table 1.

[0039] Example 7

[0040] In Example 7, the catalyst preparation process was the same as that in Example 1. Except that Co-based Fischer-Tropsch products (C2 -C 4 Hydrocarbons (olefin content about 50%) were used to replace the Co-based Fischer-Tropsch product (C 5 -C 20 Hydrocarbons and oxygenates (olefin content about 30%) were used for the evaluation of the multiphase hydroformylation reaction. The Co-based Fischer-Tropsch product and syngas were directly fed in gaseous form. At 383 K, 2.0 MPa, the gas hourly space velocity of the Fischer-Tropsch product was 1000 h -1 , and the gas hourly space velocity of syngas was 1500 h -1 . The hydroformylation reaction was carried out under these conditions. The obtained liquid and gas products were analyzed by HP-7890N gas chromatography, and the results were calculated by the normalization method. The reaction results are listed in Table 1.

[0041] Example 8

[0042] In Example 8, the catalyst preparation process was the same as that in Example 1. Except that the reaction temperature was 403 K instead of 383 K, other processes were the same as those in Example 1. The reaction results are listed in Table 1.

[0043] Example 9

[0044] In Example 9, the catalyst preparation process was the same as that in Example 1. Except that the reaction pressure was 5.0 MPa instead of 2.0 MPa, other processes were the same as those in Example 1. The reaction results are listed in Table 1.

[0045] Example 10

[0046] In Example 10, the catalyst preparation process was the same as that in Example 1. Except that the liquid hourly space velocity of the Co-based Fischer-Tropsch product was 1.0 h -1 instead of the liquid hourly space velocity of the Co-based Fischer-Tropsch product of 1.5 h -1 , other processes were the same as those in Example 1. The reaction results are listed in Table 1.

[0047] Comparative Example 1

[0048] In Comparative Example 1, except that 10 g of L1 ligand replaced 10 g of L1 ligand, 1.2 g of L2 ligand and 0.6 g of L3 ligand were dissolved in tetrahydrofuran solvent, other processes were the same as those in Example 1. The reaction results are listed in Table 1.

[0049] Comparative Example 2

[0050] In Comparative Example 2, except that 10 g of L1 ligand and 1.2 g of L2 ligand replaced 10 g of L1 ligand, 1.2 g of L2 ligand and 0.6 g of L3 ligand were dissolved in tetrahydrofuran solvent, other processes were the same as those in Example 1. The reaction results are listed in Table 1.

[0051] Table 1 Reaction results of olefin hydroformylation of Co-based Fischer-Tropsch products

[0052]

[0053]

[0054] Examples 1-10 and Comparative Examples 1-2 give the results of the hydroformylation reaction of Co-based Fischer-Tropsch product olefins. The difference between the catalysts prepared in Example 1 and Comparative Examples 1-2 lies in the different ligand compositions in the catalyst, and the rest of the reaction condition parameters are the same. In Example 1, when the catalyst contains ligands L1, L2, and L3 and the mass ratio of the three is 1:0.12:0.06, the olefin conversion rate is 76.3%, the total aldehyde selectivity is 86.5%, and the aldehyde n / i ratio is 12.1; in Comparative Example 1, when the catalyst only contains ligand L1, the olefin conversion rate is 48.7%, the total aldehyde selectivity is 54.2%, and the aldehyde n / i ratio is 3.6; in Comparative Example 2, when the catalyst only contains ligands L1 and L2 and the mass ratio of the two is 1:0.12, the olefin conversion rate is 62.4%, the total aldehyde selectivity is 65.8%, and the aldehyde n / i ratio is 8.5. The experimental results of Example 1 and Comparative Examples 1-2 show that when all three ligands L1, L2, and L3 are included in the highly efficient catalyst, the catalyst has excellent reaction activity and target product selectivity.

[0055] The difference between the catalysts prepared in Examples 1-3 lies in the different ratios of the three ligands L1, L2, and L3, and the rest of the reaction condition parameters are the same. In Example 1, when the mass ratio of ligands L1, L2, and L3 is 1:0.12:0.06, the olefin conversion rate is 76.3%, the total aldehyde selectivity is 86.5%, and the aldehyde n / i ratio is 12.1; in Example 2, when the mass ratio of ligands L1, L2, and L3 is 1:0.03:0.03, the olefin conversion rate is 54.5%, the total aldehyde selectivity is 60.5%, and the aldehyde n / i ratio is 5.2; in Example 3, when the mass ratio of ligands L1, L2, and L3 is 1:0.01:0.01, the olefin conversion rate is 49.5%, the total aldehyde selectivity is 53.8%, and the aldehyde n / i ratio is 3.8. The experimental results of Examples 1-3 show that when the mass ratio of ligands L1, L2, and L3 is 1:0.12:0.06, the highly efficient catalyst has more excellent olefin conversion rate and product aldehyde (especially linear aldehyde) selectivity.

[0056] Combined with the above reaction results, it can be seen that the heterogeneous catalyst provided by the present invention for the hydroformylation reaction of Co-based Fischer-Tropsch product olefins has high reaction activity and n-aldehyde selectivity (high n / i ratio); due to the use of a heterogeneous hydroformylation catalyst, the separation cost of the catalyst from the reactants and products is reduced, which is suitable for large-scale industrial production. Using the catalyst of the present invention, high-value oxygen-containing chemicals such as n-aldehyde can be prepared by the hydroformylation reaction of Co-based Fischer-Tropsch product olefins, effectively improving the economy of indirect coal liquefaction.

[0057] The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. Those skilled in the art will understand that other changes and modifications can be made without departing from the scope of the present invention. The scope of the present invention is defined by the appended claims.

Claims

1. A method for hydroformylation of Co-based Fischer-Tropsch olefins, characterized in that: The Co-based Fischer-Tropsch product olefin and synthesis gas are subjected to a hydroformylation reaction in a reactor in the presence of a high-efficiency catalyst, wherein the high-efficiency catalyst is composed of a metal component and an organic ligand polymer, the metal component is one or more of metals Rh, Co, Ir or Ru, and the organic ligand polymer is a porous polymer generated by solvent thermal polymerization after mixing vinyl-containing organic phosphine ligands L1, L2 and L3; The structures of L1, L2 and L3 are as follows: ； The mass ratio of the phosphine ligands L1, L2 and L3 is 1:0.1-0.15:0.05-0.

08.

2. The method according to claim 1, characterized in that The reaction conditions of the hydroformylation reaction are: reaction temperature 293-573 K, reaction pressure 0.1-20 MPa, synthesis gas volume space velocity 100-20000 h -1 The molar ratio of olefins to synthesis gas in the Co-based Fischer-Tropsch product feedstock is 0.01-10.

3. The method according to claim 2, characterized in that The reaction conditions of the hydroformylation reaction are: reaction temperature 353-453 K, reaction pressure 0.5-10 MPa, synthesis gas volume space velocity 500-8000 h -1 The molar ratio of olefins to synthesis gas in the Co-based Fischer-Tropsch product feedstock is 0.1-4.

4. The method according to claim 1, characterized in that: The Co-based Fischer-Tropsch product raw material is C2-C 30 hydrocarbons and oxygen-containing organic matter, and C2-C 30 The hydrocarbons contain olefins, and olefins account for 5%-90% of the total weight of the Co-based Fischer-Tropsch product raw materials; the Co-based Fischer-Tropsch product olefin raw materials refer to the products generated by the Fischer-Tropsch synthesis reaction under the action of a Co-based catalyst, and the Fischer-Tropsch products are not separated and are directly used as the required raw materials.

5. The method according to claim 1, characterized in that: The synthesis gas comes from a synthesis gas production process using one or more of natural gas, coal, oilfield gas, coalbed methane or hydrocarbons as raw materials, and the main components of the synthesis gas are H2 and CO, the volume content of H2 and CO is 20%-100%, and the volume ratio of H2 / CO is 0.5-5.

0.

6. The method according to claim 5, characterized in that The volume content of H2 and CO is 80%-100%, and the volume ratio of H2 / CO is 0.8-3.

0.

7. The method according to claim 1, characterized in that The metal component is one or more of metals Rh, Co, Ir or Ru; the metal component accounts for 0.05%-20% of the total mass of the catalyst.

8. The method according to claim 7, characterized in that The metal component accounts for 0.1%-5% of the total mass of the catalyst.

9. According to the method of claim 1, the preparation process of the high-efficiency catalyst comprises: a) 273-473K, add a free radical initiator to a solvent containing a vinyl functionalized phosphine ligand and stir for 0.5-50h; b) allowing the mixed solution of step a) to stand for 0.5-100 h at 273-473 K to perform a polymerization reaction, and after the polymerization is completed, removing the solvent to obtain an organic phosphine ligand polymer; c) placing the polymer of step b) in a solvent containing one or more soluble compounds of metal active components Rh, Co, Ir or Ru, and stirring at 273-473K for 0.5-100 h; after removing the solvent, a high-efficiency catalyst is obtained.

10. The method according to claim 9, wherein the preparation process of the high-efficiency catalyst comprises: a) 293-423K, add a free radical initiator to a solvent containing a vinyl functionalized phosphine ligand and stir for 1-20h; b) allowing the mixed solution of step a) to stand for 5-50 h at 323-423 K to perform a polymerization reaction, and after the polymerization is completed, removing the solvent to obtain an organic phosphine ligand polymer; c) placing the polymer from step b) in a solvent containing one or more soluble compounds of metal active components Rh, Co, Ir or Ru, and stirring at 293-423K for 5-50 hours; after removing the solvent, a high-efficiency catalyst is obtained.

11. The method according to claim 1, characterized in that: The Co-based Fischer-Tropsch product olefin hydroformylation reaction is carried out in a continuous manner, and the reactor is a fixed bed or a trickle bed.

12. The method according to claim 11, characterized in that The hydroformylation reaction of the Co-based Fischer-Tropsch product olefin is continuously carried out on the high-efficiency catalyst, and the generated liquid product continuously flows out of the reactor and is collected through a product collection tank; The liquid product obtained above is further treated by distillation, flash evaporation or extraction to obtain a high-purity product.

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