Hydroformylation catalyst as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of metal-based catalysts, and discloses a hydroformylation catalyst as well as a preparation method and application thereof. According to the invention, cheap and easily available polystyrene is adopted as a reaction raw material, a novel hydroformylation catalyst is prepared through five steps of chemical reactions, and direct filtration can be carried out after the reaction is finished, so that the separation cost and difficulty of a catalytic system are greatly reduced; the catalyst prepared by the preparation method solves the problem that the reaction raw materials, the product and the catalyst are difficult to separate in the hydroformylation process; according to the method, the product can be obtained with high yield and high selectivity under relatively mild conditions, and meanwhile, the loss of a catalytic system can be reduced; and the activity of the catalytic system can still be maintained after repeated use, so that the production cost is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of metal-based catalysts, and in particular to a hydroformylation catalyst and a preparation method and application thereof. Background Art

[0002] Olefin hydroformylation refers to the reaction of preparing high-carbon linear aldehydes from α-olefins and synthesis gas. The aldehydes produced by this reaction are widely used in fragrances, surfactants, plasticizers and solvents. Among the many olefin hydroformylation reactions, the reaction of preparing isononanal by hydroformylation of isooctene has been widely studied; because isononanal is an important organic chemical raw material, it is widely used in plasticizers, surfactants, fragrances, detergents and organic synthesis, and isononanal can be used to synthesize many fine chemical products with high added value through subsequent conversion. It can be reduced to obtain isononanol and oxidized to obtain isononanoic acid. Due to the unique properties of high-branched isononanoic acid such as excellent wettability, permeability and emulsification, it also has important uses in lubricants, industrial detergents and other industries.

[0003] At present, the reaction of isooctene to prepare isononanal is still in the laboratory stage and has not yet entered industrial application. Although some related hydroformylation processes have been reported, the current research is mainly focused on homogeneous catalytic systems, water / oil two-phase catalytic systems, and multiphase solid-supported catalytic systems. In addition, the current isooctene hydroformylation reaction has the problem of difficult recovery of catalysts and ligands, and the phosphine-containing ligands used will pollute the natural environment.

[0004] In view of the problems existing in the reaction of preparing isononanal from isooctene, developing an olefin hydroformylation catalyst that can promote the conversion rate of isooctene and has a low production cost is the current research focus in this field. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a hydroformylation catalyst and a preparation method and application thereof. The catalyst is applied to the hydroformylation reaction to obtain isononanal with high yield and high selectivity under relatively mild conditions, while reducing the loss of the catalytic system.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a method for preparing a hydroformylation catalyst, the method comprising the following steps:

[0008] S1, using polystyrene as a raw material, reacting it with aluminum chloride and acetyl chloride to undergo FC acylation reaction to generate the catalyst intermediate A described in formula (1);

[0009] S2, subjecting the intermediate A described in step S1 to Baeyer-Villiger oxidation reaction in an acid catalyst and an oxidant to generate the catalyst intermediate B described in formula (2);

[0010] S3, subjecting the intermediate B described in step S2 to a reduction reaction with a reducing agent to generate a catalyst intermediate C described in formula (3);

[0011] S4, reacting the intermediate C described in step S3 with chlorophosphite under the action of an organic base to generate the catalyst intermediate D described in formula (4);

[0012] S5, immersing the catalyst intermediate D described in step S4 in a rhodium-containing compound solution, filtering and drying, to obtain a hydroformylation catalyst, wherein the chemical formula of the hydroformylation catalyst is Rh-(C 12 H 17 O3P) n ;

[0013]

[0014] The value of n is 100-1000.

[0015] In industry, hydroformylation catalysts have gone through four generations of catalysts; the first generation of hydroformylation catalysts are cobalt-based catalysts. Because cobalt has low reactivity, the reaction usually requires harsh reaction conditions, such as high reaction pressure and reaction temperature. The second generation of hydroformylation catalysts are rhodium-based catalytic systems; among them, rhodium-based catalysts modified with partial phosphine ligands are widely used and show extremely excellent reactivity and linear aldehyde selectivity. However, although this catalyst has excellent catalytic effect, it is troubled by the separation of catalyst and product and has a high cost. The third generation of hydroformylation catalysts mainly adopts a two-phase system, using water-soluble or ionic liquid solidified catalysts, so that it can be easily separated from organic products. The fourth generation of rhodium / phosphine water-soluble HRh(CO)(TPPTS)3 catalyst, because the boiling point of high carbon aldehydes / alcohols is very high, high carbon aldehydes / alcohols prepared from high carbon olefins must be separated from the catalyst by flash evaporation at high temperature; the activity of rhodium catalyst is 1000 times higher than that of cobalt catalyst, but the price of rhodium is 3500 times that of cobalt; in the hydroformylation reaction, the homogeneous rhodium phosphine catalytic system can show good conversion rate and selectivity, but the catalyst is difficult to separate from the product and reuse; and rhodium is a precious metal, and the loss of rhodium in industry greatly increases the cost of the process; in the current process flow, the reaction liquid after hydroformylation must be flashed and distilled to separate the catalytic system from the product and raw materials, and the heating of the catalyst system in this process will also reduce the life of the catalyst. In summary, the current reaction involving hydroformylation catalysts has the problem that the catalyst and ligand are difficult to recover, and the use of phosphine-containing ligands will cause pollution to the natural environment; and the selection of suitable ligands and catalysts is very important for the conversion rate of olefins and the production cost of products.

[0016] In view of the problems existing in the above-mentioned hydroformylation catalyst, the present invention adopts cheap and readily available polystyrene as a reaction raw material, performs acetylation at the para position of the polystyrene through FC acylation, and generates a catalyst intermediate containing an acetyl group at the para position; then performs Baeyer-Villiger oxidation to obtain a catalyst intermediate containing an ester group at the para position; then performs a reduction reaction, generates a phosphine-containing ligand with a chlorophosphite, and finally reacts with a rhodium-containing compound to obtain a hydroformylation catalyst.

[0017] The catalyst prepared by the method solves the problem that the reaction raw materials, products and catalysts are difficult to separate in the hydroformylation process; through the method, the product can be obtained with high yield and high selectivity under relatively mild conditions, and the loss of the catalyst system can be reduced; and the activity of the catalyst system can be maintained after repeated use, thereby reducing the production cost.

[0018] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in the step S1, the temperature when adding aluminum chloride is 0-3°C; the present invention adds aluminum chloride to polystyrene at a low temperature in order to prevent the reaction from being too violent and causing cross-linking of the polystyrene.

[0019] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, the step S1 further comprises an organic solvent carbon disulfide.

[0020] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in the step S1, the reaction temperature of the FC acylation reaction is 20-50° C., and the reaction time is 2-6 h.

[0021] As a more preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, the reaction temperature of the FC acylation reaction is 25° C. and the reaction time is 3 h.

[0022] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, during the FC acylation reaction, acetyl chloride is added dropwise, and the dropping speed of acetyl chloride should not be too fast, otherwise it will cause the temperature to rise too fast and the reaction to fail.

[0023] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in the step S1, the mass ratio of acetyl chloride to polystyrene is acetyl chloride:polystyrene=(1.1-2):1.

[0024] As a more preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, the mass ratio of acetyl chloride to polystyrene is acetyl chloride:polystyrene=1.75:1.

[0025] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in the step S1, after the FC acylation reaction, the reaction mixture is added to a large amount of crushed ice for quenching, and then concentrated hydrochloric acid is added dropwise for acidification; the concentrated hydrochloric acid cannot be added too quickly, otherwise liquid will spray out, causing a safety accident, and also affecting the yield of the reaction; after the acidification is completed, the polymer is separated from the organic layer, diluted with an appropriate amount of dichloroethane, and an excess of methanol is added to precipitate a white precipitate, the precipitate is redissolved in a small amount of THF, precipitated again in excess methanol, and dried under vacuum to obtain the catalyst intermediate A.

[0026] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in step S2, the acid catalyst is acetic anhydride and the oxidant is hydrogen peroxide.

[0027] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in step S2, the Baeyer-Villiger oxidation reaction time is 4 days to 8 days.

[0028] As a more preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, the time of the Baeyer-Villiger oxidation reaction is 6 days.

[0029] It should be noted that, in the Baeyer-Villiger oxidation reaction of the present invention, acetic anhydride and 30% hydrogen peroxide solution need to be added every 12 hours.

[0030] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in step S2, after the Baeyer-Villiger oxidation reaction is completed, the organic layer is separated by a separatory funnel, and a precipitate is precipitated in a large amount of methanol, the precipitated polymer is filtered, and dried under vacuum to obtain the catalyst intermediate B.

[0031] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in step S3, the reducing agent is hydrazine hydrate.

[0032] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in step S3, the temperature of the reduction reaction is 25°C-60°C, preferably 25°C ； The reaction time is 1d-3d, preferably 2 d .

[0033] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in the step S4, the reaction temperature is 25°C-50°C, preferably 25°C; the reaction time is 2h-10h, preferably 8h.

[0034] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in step S4, the reaction is carried out in an organic solvent, and the organic solvent is selected from cyclohexane, benzene, toluene, diethyl ether, tetrahydrofuran or chloroform.

[0035] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in the step S5, the rhodium-containing compound includes at least one of rhodium acetate, rhodium trifluoroacetate, tetrakis(triphenylphosphine)chlororhodium, and dicarbonyl acetylacetonate rhodium.

[0036] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in step S5, the concentration of the rhodium-containing compound solution is 0.5 mol / L-2 mol / L, preferably 1 mol / L.

[0037] As a preferred embodiment of the method for preparing the hydroformylation catalyst of the present invention, in step S5, the immersion temperature is 20°C-80°C, preferably 50°C; the immersion time is 1h-6h, preferably 2h, and after the reaction is completed, the mixture is filtered and dried at 90°C for 24 hours to obtain the catalyst.

[0038] The present invention also provides application of the hydroformylation catalyst in olefin hydroformylation reaction.

[0039] As a preferred embodiment of the application of the hydroformylation catalyst of the present invention in the olefin hydroformylation reaction, the method of the olefin hydroformylation reaction is: adding olefin, CO and H2, and the hydroformylation catalyst into a high-pressure reactor and stirring to carry out contact reaction. After the reaction is completed, the liquid product is extracted, treated and then detected by gas chromatography.

[0040] As a preferred embodiment of the use of the hydroformylation catalyst in the hydroformylation reaction of olefins according to the present invention, the mass percentage of the hydroformylation catalyst in the olefin is 0.1%-10%.

[0041] As a more preferred embodiment of the use of the hydroformylation catalyst in the hydroformylation reaction of olefins according to the present invention, the mass percentage of the hydroformylation catalyst in the olefin is 1%.

[0042] As a preferred embodiment of the application of the hydroformylation catalyst of the present invention in the olefin hydroformylation reaction, the reaction parameters of the olefin hydroformylation reaction are: reaction temperature is 50 ℃ -150℃, reaction time is 1h-24h, reaction pressure is 1MPa-10MPa.

[0043] As a more preferred embodiment of the application of the hydroformylation catalyst of the present invention in the olefin hydroformylation reaction, the reaction parameters of the olefin hydroformylation reaction are: reaction temperature of 100° C., reaction time of 12 h, and reaction pressure of 3 MPa.

[0044] As a preferred embodiment of the use of the hydroformylation catalyst of the present invention in the hydroformylation reaction of olefins, the olefin includes at least one of ethylene, propylene, butene, butadiene, pentene, cyclopentene, cyclopentadiene, hexene, cyclohexene, heptene, octene, cyclooctene, isooctene, nonene, and decene.

[0045] After the olefin hydroformylation reaction of the present invention is completed, the organic matter and the catalyst system can be separated by filtering, and the separated catalyst system can be continuously recycled.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] The invention adopts cheap and readily available polystyrene as a reaction raw material, and prepares a novel hydroformylation catalyst through five steps of chemical reaction. After the reaction is completed, the catalyst can be directly filtered, which greatly reduces the cost and difficulty of separating the catalytic system. The catalyst prepared by the preparation method of the invention solves the problem that the reaction raw materials, products and catalysts are difficult to separate in the hydroformylation process. Through the method, the product can be obtained with high yield and high selectivity under relatively mild conditions, and the loss of the catalytic system can be reduced. Moreover, the activity of the catalytic system can be maintained after repeated use, which reduces the production cost. DETAILED DESCRIPTION

[0048] To better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be understood by those skilled in the art that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0049] The reaction methods used in the examples are conventional methods unless otherwise specified; the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0050] Example 1

[0051] The preparation method of the hydroformylation catalyst described in this embodiment comprises the following steps:

[0052] S1. Take a 250mL double-mouthed round-bottom flask, add 5g polystyrene and 150mL carbon disulfide, introduce nitrogen to replace the gas in the reaction system, install a condenser tube on the round-bottom flask, put the whole system in an ice bath and stir vigorously; then add 14g aluminum chloride to the reaction solution, wait until the color of the solution in the flask turns orange-red, add 50mL carbon disulfide solution containing 6mL acetyl chloride dropwise, after the addition is complete, continue to react for 10-30min under ice bath, then warm to room temperature and continue to react for 2-5h, thereafter, add a large amount of crushed ice to quench the reaction mixture, then add concentrated hydrochloric acid dropwise to acidify; then separate the polymer from the organic layer, dilute with an appropriate amount of dichloroethane, add excess methanol to precipitate a white precipitate, which is the polymer. Redissolve it in a small amount of THF, precipitate it again in excess methanol, and dry it under vacuum to obtain 6.2-6.6g of catalyst intermediate A;

[0053] S2, take a 250mL round-bottom flask, add 10mL acetic anhydride, 10mL 30% H2O2 solution and 1-2 drops of concentrated H2SO4, then add 50mL chloroform solution containing 2g of intermediate A described in step S1, reflux and stir for 4-8 days, and add 5-10mL Ac2O and H2O2 to the system every 12 hours. The total volume of Ac2O and H2O2 is 120mL; then separate the organic layer with a separatory funnel, precipitate in a large amount of methanol, filter the precipitated polymer, and dry under vacuum to obtain 1.2-1.8g of catalyst intermediate B;

[0054] S3, dissolving 250 mg of the intermediate B described in step S2 in 15 ml of 1,4-dioxane and 2 mL of pure water, adding 0.1-0.3 mL of hydrazine hydrate to the solution under an ice bath, then raising the temperature to 25-60° C., the entire polymer material immediately aggregates and changes from colorless to dark blue, stirring continuously for 2-5 days, separating the product and drying it in an oven for 0.5-2 days, to obtain 128-165 mg of catalyst intermediate C;

[0055] S4, take 100 mg of the intermediate C described in step S3 and dissolve it in 10 mL of acetonitrile and 10 mL of chloroform, introduce nitrogen gas for replacement three times, add 100 μL of diisopropylethylamine and 100 μL of diethyl chlorophosphite under nitrogen atmosphere, and stir at 25-50°C for 2-10 hours. After the reaction is completed, add a large amount of methanol to precipitate, filter, and dry the polymer under vacuum to obtain 105-120 mg of catalyst intermediate D; characterized by P spectrum, 31 P NMR: 128 ppm;

[0056] S5. Take 100 mg of intermediate D and immerse it in 10 ml of toluene solution containing rhodium compound with a concentration of 0.5-2 mol / L. The immersion temperature is 25-50° C. and the immersion time is 2-5 hours. After the immersion, wash with an appropriate amount (20-50 mL) of methanol and dry at 90° C. for 24 hours to obtain 112 mg of hydroformylation catalyst.

[0057] The elemental analysis of the hydroformylation catalyst described in this example is: C, 63.58; H, 5.86; O, 19.57; P, 8.82, Rh, 2.17. 31 P NMR: 135 ppm.

[0058] The preparation process of the hydroformylation catalyst described in this embodiment is shown in the following formula:

[0059]

[0060] Example 2

[0061] In this example, the hydroformylation catalyst prepared in Example 1 was used to carry out olefin hydroformylation reaction. The specific steps were as follows: 20 g of isooctene was added to a 100 ml reactor, 200 mg of the hydroformylation catalyst described in Example 1 was added, the reactor was replaced with synthesis gas (H2:CO=1:1) three times, the synthesis gas was introduced and the pressure was increased to 3 MPa, the temperature was increased to 100°C and stirred to start the reaction; during the reaction, the synthesis gas was continuously introduced to keep the pressure stable, the reaction was continued for 12 hours, and then analyzed by gas chromatography.

[0062] In this example, the conversion rate of isooctene was 94%, and the selectivity of isononanal was 95%.

[0063] Example 3

[0064] In this example, the product after the reaction of Example 2 was separated by filtration, and the obtained product was subjected to steps S2-S5 of Example 1, and the olefin hydroformylation reaction of Example 2 was repeated 5 times. The isooctene conversion rate and the selectivity of isononanal are shown in Table 1 below:

[0065] Table 1

[0066] Number of applications Conversion rate (%) Selectivity (%) first 93.6 95.2 Second time 94.0 94.6 The third time 93.8 94.3 Fourth 91.2 95.2 Fifth 91.4 94.8

[0067] Example 4

[0068] The difference between this embodiment and embodiment 2 is that: in this embodiment, the hydroformylation catalyst prepared in embodiment 1 is used to carry out olefin hydroformylation reaction, and the specific steps are as follows: 12.5 g of 1-pentene and 200 mg of the hydroformylation catalyst described in embodiment 1 are added to a 100 ml reactor, the reactor is replaced with synthesis gas (H2:CO=1:1) three times, the synthesis gas is introduced to increase the pressure to 3 MPa, the temperature is increased to 100°C and stirred to start the reaction; during the reaction, the synthesis gas is continuously introduced to keep the pressure stable, the reaction is continued for 12 hours, and then analyzed by gas chromatography.

[0069] In this example, the conversion rate of 1-pentene is 97%, and the selectivity of hexanal is 96%.

[0070] Example 5

[0071] In this example, the product after the reaction of Example 4 was separated by filtration, and the obtained catalyst was used, that is, the olefin hydroformylation reaction of Example 4 was repeated 5 times. The conversion rate of 1-pentene and the selectivity of hexanal are shown in Table 2 below:

[0072] Table 2

[0073] Number of applications Conversion rate (%) Selectivity (%) first 96.9 96.2 Second time 98.5 94.8 The third time 96.3 96.2 Fourth 94.5 95.4 Fifth 95.7 94.8

[0074] Example 6

[0075] The difference between this embodiment and embodiment 2 is that: in this embodiment, the hydroformylation catalyst prepared in embodiment 1 is used to carry out olefin hydroformylation reaction, and the specific steps are as follows: 15 g of 1-hexene is added to a 100 ml reactor, 200 mg of the hydroformylation catalyst described in embodiment 1 is added, the reactor is replaced three times with synthesis gas (H2:CO=1:1), the synthesis gas is introduced to increase the pressure to 3 MPa, the temperature is increased to 100°C and stirred to start the reaction; during the reaction, the synthesis gas is continuously introduced to keep the pressure stable, the reaction is continued for 12 hours, and then analyzed by gas chromatography.

[0076] In this example, the conversion rate of 1-hexene was 97%, and the selectivity of heptanal was 98%.

[0077] Example 7

[0078] In this example, the product after the reaction of Example 6 was separated by filtration, and the obtained catalyst was used again, that is, the olefin hydroformylation reaction of Example 6 was repeated 5 times. The conversion rate of 1-hexene and the selectivity of heptanal are shown in Table 3 below:

[0079] Table 3

[0080] Number of applications Conversion rate (%) Selectivity (%) first 97.2 97.9 Second time 95.8 96.4 The third time 93.5 95.8 Fourth 94.2 96.1 Fifth 94.1 95.8

[0081] According to the results in Tables 1-3, the hydroformylation catalyst prepared by the present invention has a high conversion rate and selectivity in the reaction of preparing aldehydes by hydroformylation of olefins; the product and the catalyst system can be directly separated by filtration, which reduces the loss of the catalyst system and significantly improves the economic efficiency of the hydroformylation reaction; it can prepare isononanal with high selectivity and high yield, reducing production costs.

[0082] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing a hydroformylation catalyst, characterized in that: The method comprises the following steps: S1, using polystyrene as a raw material, reacting it with aluminum chloride and acetyl chloride to undergo FC acylation reaction to generate the catalyst intermediate A described in formula (1); S2, subjecting the intermediate A described in step S1 to Baeyer-Villiger oxidation reaction in an acid catalyst and an oxidant to generate the catalyst intermediate B described in formula (2); S3, subjecting the intermediate B described in step S2 to a reduction reaction with a reducing agent to generate a catalyst intermediate C described in formula (3); S4, reacting the intermediate C described in step S3 with chlorophosphite under the action of an organic base to generate the catalyst intermediate D described in formula (4); S5, immersing the catalyst intermediate D described in step S4 in a rhodium-containing compound solution, filtering and drying, to obtain a hydroformylation catalyst, wherein the chemical formula of the hydroformylation catalyst is Rh-(C 12 H 17 O3P) n ; The value of n is 100-1000.

2. The method for preparing a hydroformylation catalyst according to claim 1, characterized in that: In the step S1, the temperature when adding aluminum chloride is 0°C-3°C, the reaction temperature of the FC acylation reaction is 20°C-50°C, and the reaction time is 2h-6h.

3. The method for preparing a hydroformylation catalyst according to claim 1, characterized in that: In the step S1, the mass ratio of acetyl chloride to polystyrene is acetyl chloride:polystyrene=(1.1-2):

1.

4. The method for preparing a hydroformylation catalyst according to claim 1, characterized in that: In step S2, the acid catalyst is acetic anhydride, and the oxidant is hydrogen peroxide; and the Baeyer-Villiger oxidation reaction time is 4 days to 8 days.

5. The method for preparing a hydroformylation catalyst according to claim 1, characterized in that: In the step S3, the reducing agent is hydrazine hydrate; the temperature of the reduction reaction is 25° C.-60° C., and the time is 1 day-3 days.

6. The method for preparing a hydroformylation catalyst according to claim 1, characterized in that: In step S4, the reaction temperature is 25°C-50°C and the reaction time is 2h-10h.

7. The method for preparing a hydroformylation catalyst according to claim 1, characterized in that: In step S5, the rhodium-containing compound includes at least one of rhodium acetate, rhodium trifluoroacetate, tetrakis(triphenylphosphine)chlororhodium, and dicarbonyl acetylacetonate rhodium; the concentration of the rhodium-containing compound solution is 0.5 mol / L-2 mol / L; the immersion temperature is 20°C-80°C; and the immersion time is 1h-6h.

8. A hydroformylation catalyst, characterized in that The hydroformylation catalyst is prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the hydroformylation catalyst according to claim 8 in olefin hydroformylation reaction.

10. Use of the hydroformylation catalyst according to claim 9 in olefin hydroformylation reaction, characterized in that: The method for the olefin hydroformylation reaction is: adding olefin, CO and H2, and the hydroformylation catalyst into a high-pressure reactor and stirring to carry out contact reaction, and after the reaction is completed, extracting the liquid phase product and treating it and then conducting gas chromatography detection; The olefins include at least one of ethylene, propylene, butene, butadiene, pentene, cyclopentene, cyclopentadiene, hexene, cyclohexene, heptene, octene, cyclooctene, isooctene, nonene, and decene; The mass percentage of the hydroformylation catalyst in the olefin is 0.1%-10%; The reaction parameters of the olefin hydroformylation reaction are: reaction temperature of 50° C.-150° C., reaction time of 1 h-24 h, and reaction pressure of 1 MPa-10 MPa.

Images