A metal rhodium-based catalyst, a supported catalyst thereof, a preparation method and application thereof

Abstract

The application belongs to the technical field of metal-based catalysts, and discloses a metal Rh-based catalyst, a supported catalyst thereof, a preparation method and application. The metal Rh-based catalyst is formed by coordination of a metal Rh central atom with a butanedione oxime ligand and a triphenylphosphine and substituted derivative ligand, and has a structure shown in formula (1). The supported metal Rh-based catalyst is formed by loading the metal Rh-based catalyst on a porous carrier. The metal Rh-based catalyst and the supported catalyst thereof prepared by the application can realize efficient hydroformylation of isooctene to form iso-nonyl aldehyde, and show high isooctene conversion rate and iso-nonyl aldehyde selectivity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal-based catalysts, in particular to a metal Rh-based catalyst, a supported catalyst thereof, a preparation method and application. BACKGROUND

[0002] The rapid development of hydroformylation technology is mainly driven by petroleum and coal chemical industry, in which the production of olefins by petroleum cracking and the production of olefin raw materials by Fischer-Tropsch reaction process provide an important material basis for the development of hydroformylation. Among them, the aldehyde prepared by hydroformylation reaction as a chemical intermediate can synthesize esters, carboxylic acids and fatty amines, etc., and its hydrogenation product alcohol can be widely used in fine chemical industry as a surfactant, plasticizer, etc., and has very broad application value.

[0003] Isoneral as an important organic chemical raw material is widely used in plasticizer, surfactant, perfume, cleaning agent and organic synthesis industries, and many fine chemical products with high added value can be synthesized from isoneral. At present, the industrial production technology of isoneral prepared by hydroformylation reaction of isooctene at home is still basically in the laboratory stage, and the related hydroformylation process is mainly concentrated in homogeneous catalytic system, water / oil two-phase catalytic system and heterogeneous solid catalytic system. Among them, the activity and selectivity of homogeneous catalyst are relatively high, however, the homogeneous catalyst still has the shortcomings of complex molecular structure, difficult synthesis, poor thermal stability, large loss, difficult recovery and separation, etc., which limits its industrial application; the selectivity and activity of heterogeneous catalyst are lower than those of homogeneous catalyst, but the heterogeneous catalyst has the advantages of convenient preparation process and easy separation from solvent, etc. The advantages of homogeneous catalyst and heterogeneous catalyst can be combined by loading homogeneous catalyst on a suitable carrier to form a heterogeneous supported catalyst. The activity of hydroformylation reaction depends largely on the selected catalyst, and the ligand of the olefin hydroformylation catalyst is mainly phosphine ligand, but the electronic and steric effects of phosphine ligand will lead to low activity and poor selectivity in the process of olefin hydroformylation reaction, so other ligands need to be added to improve the catalyst. SUMMARY

[0004] The purpose of the present application is to overcome the shortcomings of the prior art and provide a metal Rh-based catalyst, a supported catalyst thereof, a preparation method and application.

[0005] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] In a first aspect, the present application provides a metal Rh-based catalyst, the structural formula of which is shown as formula (1):

[0007]

[0008] In the formula, the dotted line is a coordination bond; the R group is selected from at least one of a hydrogen atom, a straight-chain alkyl group, a branched alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a substituted aryl group, and derivatives thereof.

[0009] The metal Rh-based catalyst of the present invention comprises a metal Rh central atom coordinated with a dimethylglyoxime ligand and triphenylphosphine and its substituted derivative ligands to form a structure shown in formula (1). The catalyst can be used for the hydroformylation reaction of isooctene to prepare isononanal, and exhibits high isooctene conversion rate and selectivity for producing isononanal.

[0010] As a preferred embodiment of the metal Rh-based catalyst of the present invention, the R group is selected from hydrogen atoms, C1-C 14 The R group is selected from at least one of a C3-C6 alkyl group, an alkoxy group, a cycloalkyl group of C3-C6, a phenyl group, a C1-C4 alkyl group or an alkoxy-substituted aryl group; preferably, the R group is selected from at least one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a methoxy group, an ethoxy group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-isopropylphenyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, a 2,6-di-tert-butylphenyl group, a 2,4,6-trimethylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group and a 4-methoxyphenyl group.

[0011] In a second aspect, the present invention provides a method for preparing the metal Rh-based catalyst, comprising the following steps:

[0012] Under an inert atmosphere, dimethylglyoxime ligand, triphenylphosphine and its substituted derivative ligand and carbonyl rhodium compound are reacted to obtain the metal Rh-based catalyst.

[0013] As a preferred embodiment of the preparation method of the present invention, the molar ratio of the dimethylglyoxime ligand to the carbonyl rhodium compound is (0.8-1.2):1, calculated as metal Rh; the molar ratio of the triphenylphosphine and its substituted derivative ligand to the carbonyl rhodium compound is (0.8-1.2):1; the carbonyl rhodium compound is selected from at least one of [Rh(CO)2Cl]2, ([Rh(CO)2(acac)]2 and dicarbonyl (pentamethylcyclopentadienyl) rhodium;

[0014] The reaction is carried out in an organic solvent, which is at least one of cyclohexane, benzene, ether, toluene, and tetrahydrofuran; the reaction temperature is 20° C. to 160° C., and the reaction time is 2 h to 20 h.

[0015] In a third aspect, the present invention provides a supported metal Rh-based catalyst, comprising a porous carrier and the metal Rh-based catalyst.

[0016] The metal Rh-based catalyst of the present application is formed by adding a butanedione oxime ligand to modify the phosphine ligand coordination, and the supported metal Rh-based catalyst is formed by loading the metal Rh-based catalyst onto a porous carrier to form a supported catalyst, and the metal Rh-based catalyst and the supported catalyst thereof prepared by the present application can realize the efficient hydroformylation of isooctene to prepare iso-nonyl aldehyde, and exhibit high isooctene conversion rate and iso-nonyl aldehyde selectivity.

[0017] As a preferred embodiment of the supported metal Rh-based catalyst of the present application, the porous carrier is selected from at least one of silica, alumina, diatomite, titanium oxide, zirconium oxide, cerium oxide, molybdenum oxide, tungsten oxide, magnesium oxide, zinc oxide, vanadium oxide, activated carbon, montmorillonite, molecular sieve, activated clay, covalent organic framework, metal organic framework, cyclodextrin, polyethylene, polystyrene, polyvinyl alcohol and mesoporous silica gel fiber.

[0018] In a fourth aspect, the present application provides a preparation method of the supported metal Rh-based catalyst, comprising the following steps:

[0019] Under an inert atmosphere, the porous carrier and the metal Rh-based catalyst are dispersed in an organic solvent for reaction, and the supported metal Rh-based catalyst is obtained.

[0020] As a preferred embodiment of the preparation method of the present application, the porous carrier is subjected to calcination treatment before use, the calcination temperature is 100-600℃, and the time is 0.5-12h; the mass ratio of the porous carrier to the metal Rh-based catalyst is (1000-10):1, more preferably (200-50):1, calculated by the amount of metal Rh; the organic solvent is at least one of cyclohexane, benzene, diethyl ether, toluene and tetrahydrofuran; the reaction temperature is 20-160℃, and the time is 2-20h.

[0021] In a fifth aspect, the present application provides the application of the metal Rh-based catalyst and the supported metal Rh-based catalyst in the preparation of iso-nonyl aldehyde by isooctene hydroformylation reaction.

[0022] As a preferred embodiment of the application of the present application, the method of the isooctene hydroformylation reaction is: iso-octene, CO and H2, the metal Rh-based catalyst and / or the supported metal Rh-based catalyst are added into a high-pressure reaction kettle for stirring and contact reaction, after the reaction is completed, the liquid product is extracted and treated for gas chromatography detection;

[0023] The isooctene is selected from at least one of branched octene; preferably, the isooctene is selected from at least one of C4 olefin polymerization product;

[0024] The reaction is carried out in an organic solvent; the organic solvent is selected from at least one of cyclohexane, benzene, toluene, ether, tetrahydrofuran, and isononanal;

[0025] Calculated as metal Rh, the amount of the metal Rh-based catalyst and / or the supported metal Rh-based catalyst is 0.01 mmol L -1 ~100mmol L -1 , preferably 0.5 mmol L -1 ~50mmol L -1 ; The molar ratio of added CO and H2 is 1:(1~1.1); the reaction temperature is 20℃~200℃, more preferably 60℃~120℃; the pressure is 0.2MPa~10MPa, more preferably 0.5MPa~6MPa; the time is 0.1h~36h, more preferably 3h~20h; the stirring rate is 200rpm~1000rpm, more preferably 500rpm~800rpm.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The invention adopts dimethylglyoxime ligand and triphenylphosphine and its substituted derivative ligand to coordinate with metal Rh to form a metal Rh catalyst. The supported metal Rh-based catalyst is formed by immobilizing the metal Rh-based catalyst on a porous carrier. Finally, the metal Rh-based catalyst and the supported catalyst are used for isooctene hydroformylation reaction to prepare isononanal.

[0028] The metal Rh-based catalyst prepared by the present invention is formed by adding a dimethylglyoxime ligand to coordinate with a modified phosphine ligand. The supported metal Rh-based catalyst is formed by loading the metal Rh-based catalyst onto a porous carrier. The metal Rh-based catalyst prepared by the present invention and its supported catalyst can achieve efficient hydroformylation of isooctene to produce isononaldehyde, demonstrating high isooctene conversion and selectivity for producing isononaldehyde. Furthermore, the metal Rh-based catalyst and its supported catalyst proposed by the present invention have a simple preparation process, reducing the use of costly and polluting phosphorus ligands. Furthermore, the active components in the supported catalyst are not easily deactivated, allowing for simple and effective separation and reuse of the supported catalyst after the reaction is completed. DETAILED DESCRIPTION

[0029] 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. Those skilled in the art should understand that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0030] Unless otherwise specified, the reaction methods used in the examples are conventional methods. The materials and reagents used are commercially available unless otherwise specified. The inert atmosphere can be at least one of nitrogen, argon, and helium. Argon was used as the inert atmosphere in the following examples.

[0031] Example 1

[0032] Under an inert atmosphere, equimolar amounts of dimethylglyoxime ligand, triphenylphosphine ligand, and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as Rh metal) were dispersed in toluene solvent in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to obtain the Rh metal catalyst, designated Rh-A.

[0033] The prepared metal Rh-based catalyst Rh-A was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst Rh-A (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctenal hydroformylation reaction to produce isononanal are shown in Table 1.

[0034] Example 2

[0035] Under an inert atmosphere, equimolar amounts of dimethylglyoxime ligand, tri(4-methylphenyl)phosphine ligand, and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as Rh metal) were dispersed in toluene solvent in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to obtain a Rh metal catalyst, designated Rh-B.

[0036] The prepared metal Rh-based catalyst Rh-B was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst Rh-B (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctene hydroformylation reaction to produce isononanal are shown in Table 1.

[0037] Example 3

[0038] Under an inert atmosphere, equimolar amounts of dimethylglyoxime ligand, tri(4-ethylphenyl)phosphine ligand, and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as Rh metal) were dispersed in toluene solvent in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to obtain the Rh metal catalyst, designated Rh-C.

[0039] The prepared metal Rh-based catalyst Rh-C was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst Rh-C (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctenal hydroformylation reaction to produce isononanal are shown in Table 1.

[0040] Example 4

[0041] Under an inert atmosphere, equimolar amounts of dimethylglyoxime ligand, tris(4-isopropylphenyl)phosphine ligand, and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as Rh metal) were dispersed in toluene solvent in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to obtain the Rh metal catalyst, designated Rh-D.

[0042] The prepared metal Rh-based catalyst Rh-D was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst Rh-D (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctene hydroformylation reaction to produce isononanal are shown in Table 1.

[0043] Example 5

[0044] Under an inert atmosphere, equimolar amounts of dimethylglyoxime ligand, tri(4-tert-butylphenyl)phosphine ligand, and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as Rh metal) were dispersed in toluene solvent in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to obtain the Rh metal catalyst, designated Rh-E.

[0045] The prepared metal Rh-based catalyst Rh-E was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst Rh-E (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctene hydroformylation reaction to produce isononanal are shown in Table 1.

[0046] Example 6

[0047] Under an inert atmosphere, equimolar amounts of dimethylglyoxime ligand, tris(3,5-dimethylphenyl)phosphine ligand, and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as Rh metal) were dispersed in toluene solvent in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to obtain the Rh metal catalyst, designated Rh-F.

[0048] The prepared metal Rh-based catalyst Rh-F was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst Rh-F (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctenal hydroformylation reaction to produce isononanal are shown in Table 1.

[0049] Example 7

[0050] Under inert atmosphere, equimolar amount of butanedione oxime ligand, tris(2,4,6-trimethylphenyl)phosphine ligand and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as metal Rh) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at 60 °C oil bath for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure to obtain the metal Rh-based catalyst, which was recorded as Rh-G.

[0051] The prepared metal Rh-based catalyst Rh-G was used for the hydroformylation reaction of isooctene to prepare isononyl aldehyde. A 500 mL high-pressure reactor was selected, after nitrogen washing, the prepared metal Rh-based catalyst Rh-G (2 mmol, calculated as metal Rh), toluene solvent (100 mL), isooctene (800 mmol) were sequentially added, the sampling valve was closed, the ratio of CO and H2 was 1:1, the system pressure was 4.0 MPa, the reaction temperature was 100 °C, and the stirring rate was 800 rpm. After the reaction was completed, the reactor was cooled to room temperature, the pressure was released, and the reaction liquid was extracted and treated for gas chromatography analysis. The conversion rate and selectivity of the isooctene hydroformylation reaction to prepare isononyl aldehyde were shown in Table 1.

[0052] Example 8

[0053] Under inert atmosphere, equimolar amount of butanedione oxime ligand, tris(2,4,6-trimethylphenyl)phosphine ligand and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as metal Rh) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at 60 °C oil bath for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure to obtain the metal Rh-based catalyst, which was recorded as Rh-G.

[0054] The prepared metal Rh-based catalyst Rh-H was used for the hydroformylation reaction of isooctene to prepare isononyl aldehyde. A 500 mL high-pressure reactor was selected, after nitrogen washing, the prepared metal Rh-based catalyst Rh-H (2 mmol, calculated as metal Rh), toluene solvent (100 mL), isooctene (800 mmol) were sequentially added, the sampling valve was closed, the ratio of CO and H2 was 1:1, the system pressure was 4.0 MPa, the reaction temperature was 100 °C, and the stirring rate was 800 rpm. After the reaction was completed, the reactor was cooled to room temperature, the pressure was released, and the reaction liquid was extracted and treated for gas chromatography analysis. The conversion rate and selectivity of the isooctene hydroformylation reaction to prepare isononyl aldehyde were shown in Table 1.

[0055] Example 9

[0056] Under an inert atmosphere, equimolar amounts of dimethylglyoxime ligand, tris(4-ethoxyphenyl)phosphine ligand, and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as Rh metal) were dispersed in toluene solvent in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to obtain the Rh metal catalyst, designated Rh-I.

[0057] The prepared metal Rh-based catalyst Rh-I was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst Rh-I (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctene hydroformylation reaction to produce isononanal are shown in Table 1.

[0058] Comparative Example 1

[0059] Under an inert atmosphere, equimolar amounts of dimethylglyoxime ligand and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as metallic Rh) were dispersed in toluene solvent in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to obtain the metallic Rh-based catalyst, designated A.

[0060] The prepared metal Rh-based catalyst A was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst A (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctene hydroformylation reaction to produce isononanal are shown in Table 1.

[0061] Comparative Example 2

[0062] Under an inert atmosphere, equimolar amounts of triphenylphosphine ligand and rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as metallic Rh) were dispersed in toluene in a Schlenk flask. The solution was stirred in an oil bath at 60°C for 10 hours. After the reaction, the toluene solvent was removed under reduced pressure to yield a metallic Rh-based catalyst, designated B.

[0063] The prepared metal Rh-based catalyst B was used in the hydroformylation of isooctene to produce isononanal. A 500 mL autoclave was purged with nitrogen and then charged with the prepared metal Rh-based catalyst B (2 mmol, calculated as metal Rh), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed, and a 1:1 ratio of CO and H₂ was introduced. The system pressure was maintained at 4.0 MPa, the reaction temperature was 100°C, and the reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctene hydroformylation reaction to produce isononanal are shown in Table 1.

[0064] Comparative Example 3

[0065] The carbonyl rhodium compound [Rh(CO)2Cl]2 was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with [Rh(CO)2Cl]2 (1 mmol), toluene solvent (100 mL), and isooctene (800 mmol). The injection valve was closed and a 1:1 ratio of CO and H2 was introduced. The system pressure was maintained at 4.0 MPa and the reaction temperature was 100°C. The reaction was stirred at 800 rpm for 8 hours. After the reaction was completed, the autoclave was cooled to room temperature, the pressure was released, the reaction liquid was extracted, and gas chromatography analysis was performed. The conversion and selectivity of the isooctenal hydroformylation reaction to produce isononanal are shown in Table 1.

[0066] Example 10

[0067] Under an inert atmosphere, activated carbon calcined at 150°C for 1 hour in a muffle furnace and the Rh-based metal catalyst Rh-A prepared in Example 1 were dispersed in toluene solvent in a Schlenk flask. The mass ratio of activated carbon to active ingredient Rh-based metal catalyst (calculated as Rh metal) was 100:1. The solution was stirred in a 60°C oil bath for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to obtain a supported Rh-based metal catalyst, designated S-Rh-A.

[0068] The prepared supported metal Rh-based catalyst S-Rh-A was used in the hydroformylation reaction of isooctene to produce nonanal. A 500 mL high-pressure reactor was selected, and after nitrogen washing, 2 mmol (calculated by metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-A, 100 mL of toluene solvent, and 800 mmol of isooctene were sequentially added. The ratio of CO and H2 was 1:1, the system pressure was 3.5 MPa, the reaction temperature was 100°C, the stirring rate was 800 rpm, the reaction time was 10 h, and after the reactor was cooled, it was depressurized and opened. The reaction liquid was extracted and treated, and gas chromatography analysis was performed. The performance results of the hydroformylation reaction of isooctene to produce nonanal are shown in Table 2.

[0069] Example 11

[0070] Under an inert atmosphere, activated carbon and the metal Rh-based catalyst Rh-B prepared in Example 2 were dispersed in toluene in a Schlenk flask after being calcined at 150°C in a muffle furnace for 1 h, ensuring that the mass ratio of activated carbon to active metal Rh-based catalyst (calculated by metal Rh) was 100:1. The above solution was stirred at 60°C in an oil bath for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure to obtain a supported metal Rh-based catalyst, which was denoted as S-Rh-B.

[0071] The prepared supported metal Rh-based catalyst S-Rh-B was used in the hydroformylation reaction of isooctene to produce nonanal. A 500 mL high-pressure reactor was selected, and after nitrogen washing, 2 mmol (calculated by metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-B, 100 mL of toluene solvent, and 800 mmol of isooctene were sequentially added. The ratio of CO and H2 was 1:1, the system pressure was 3.5 MPa, the reaction temperature was 100°C, the stirring rate was 800 rpm, the reaction time was 10 h, and after the reactor was cooled, it was depressurized and opened. The reaction liquid was extracted and treated, and gas chromatography analysis was performed. The performance results of the hydroformylation reaction of isooctene to produce nonanal are shown in Table 2.

[0072] Example 12

[0073] Under an inert atmosphere, activated carbon and the metal Rh-based catalyst Rh-C prepared in Example 3 were dispersed in toluene in a Schlenk flask after being calcined at 150°C in a muffle furnace for 1 h, ensuring that the mass ratio of activated carbon to active metal Rh-based catalyst (calculated by metal Rh) was 100:1. The above solution was stirred at 60°C in an oil bath for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure to obtain a supported metal Rh-based catalyst, which was denoted as S-Rh-C.

[0074] The prepared supported metal Rh-based catalyst S-Rh-C was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on the metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-C, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0075] Example 13

[0076] Under an inert atmosphere, activated carbon calcined in a muffle furnace at 150°C for 1 hour and the Rh-based metal catalyst Rh-D prepared in Example 4 were dispersed in toluene in a Schlenk flask. The mass ratio of activated carbon to active Rh-based metal catalyst (calculated as Rh metal) was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based metal catalyst, designated S-Rh-D.

[0077] The prepared supported metal Rh-based catalyst S-Rh-D was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on the metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-D, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0078] Example 14

[0079] Under an inert atmosphere, activated carbon calcined in a muffle furnace at 150°C for 1 hour and the Rh-based metal catalyst Rh-E prepared in Example 5 were dispersed in toluene in a Schlenk flask. The mass ratio of activated carbon to active Rh-based metal catalyst (calculated as Rh metal) was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based metal catalyst, designated S-Rh-E.

[0080] The prepared supported metal Rh-based catalyst S-Rh-E was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on the metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-E, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0081] Example 15

[0082] Under an inert atmosphere, activated carbon calcined in a muffle furnace at 150°C for 1 hour and the Rh-based metal catalyst Rh-F prepared in Example 6 were dispersed in toluene solvent in a Schlenk flask. The mass ratio of activated carbon to active ingredient Rh-based metal catalyst (calculated as Rh metal) was 100:1. The solution was stirred in a 60°C oil bath for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to obtain a supported Rh-based metal catalyst, designated S-Rh-F.

[0083] The prepared supported metal Rh-based catalyst S-Rh-F was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on the metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-F, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0084] Example 16

[0085] Under an inert atmosphere, activated carbon calcined in a muffle furnace at 150°C for 1 hour and the Rh-based metal catalyst Rh-G prepared in Example 7 were dispersed in toluene in a Schlenk flask. The mass ratio of activated carbon to active Rh-based metal catalyst (calculated as Rh metal) was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based metal catalyst, designated S-Rh-G.

[0086] The prepared supported metal Rh-based catalyst S-Rh-G was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-G, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0087] Example 17

[0088] Under an inert atmosphere, silica calcined at 150°C for 1 hour in a muffle furnace and the Rh-H metal catalyst prepared in Example 8 were dispersed in toluene solvent in a Schlenk flask. The mass ratio of silica to active Rh-based catalyst (calculated as Rh metal) was 100:1. The solution was stirred in a 60°C oil bath for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based metal catalyst, designated S-Rh-H.

[0089] The prepared supported metal Rh-based catalyst S-Rh-H was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on the metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-H, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0090] Example 18

[0091] Under an inert atmosphere, alumina calcined in a muffle furnace at 150°C for 1 hour and the Rh-based metal catalyst Rh-I prepared in Example 9 were dispersed in toluene in a Schlenk flask. The mass ratio of alumina to active Rh-based metal catalyst (calculated as Rh metal) was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based metal catalyst, designated S-Rh-I.

[0092] The prepared supported metal Rh-based catalyst S-Rh-I was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on the metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-I, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0093] Example 19

[0094] Under an inert atmosphere, magnesium oxide calcined in a muffle furnace at 150°C for 1 hour and the Rh-A metal catalyst prepared in Example 1 were dispersed in toluene in a Schlenk flask. The mass ratio of activated carbon to active Rh-based catalyst (calculated as Rh metal) was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based catalyst, designated S-Rh-J.

[0095] The prepared supported metal Rh-based catalyst S-Rh-J was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-J, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0096] Example 20

[0097] Under an inert atmosphere, molecular sieve MCM-41, calcined in a muffle furnace at 150°C for 1 hour, and the Rh-A metal catalyst prepared in Example 1 were dispersed in toluene solvent in a Schlenk flask. The mass ratio of molecular sieve MCM-41 to active Rh-based catalyst (calculated as Rh metal) was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based catalyst, designated S-Rh-K.

[0098] The prepared supported metal Rh-based catalyst S-Rh-K was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on the metal Rh) of the prepared supported metal Rh-based catalyst S-Rh-K, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0099] Comparative Example 4

[0100] Under an inert atmosphere, activated carbon calcined at 150°C for 1 hour in a muffle furnace and the Rh-based catalyst A prepared in Comparative Example 1 were dispersed in toluene in a Schlenk flask. The mass ratio of activated carbon to Rh-based catalyst (calculated as Rh metal) was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based catalyst, designated X.

[0101] The prepared supported metal Rh-based catalyst X was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (based on metal Rh) of the prepared supported metal Rh-based catalyst X, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H₂ was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, processed, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0102] Comparative Example 5

[0103] Under an inert atmosphere, activated carbon calcined in a muffle furnace at 150°C for 1 hour and the Rh-based catalyst B prepared in Comparative Example 2 were dispersed in toluene in a Schlenk flask. The mass ratio of activated carbon to Rh-based catalyst (calculated as Rh metal) was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported Rh-based catalyst, designated Y.

[0104] The prepared supported metal Rh-based catalyst Y was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (calculated as metal Rh) of the prepared supported metal Rh-based catalyst Y, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0105] Comparative Example 6

[0106] Under an inert atmosphere, activated carbon calcined in a muffle furnace at 150°C for 1 hour and a rhodium carbonyl compound [Rh(CO)2Cl]2 were dispersed in a toluene solvent in a Schlenk flask. The mass ratio of activated carbon to the active ingredient, rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as metallic Rh), was 100:1. The solution was stirred in an oil bath at 60°C for 10 hours. After completion of the reaction, the toluene solvent was removed under reduced pressure to yield a supported metallic Rh-based catalyst, designated Z.

[0107] The prepared supported metal Rh-based catalyst Z was used in the hydroformylation of isooctene to produce isononanal. A 500mL autoclave was purged with nitrogen and then charged with 2mmol (calculated as metal Rh) of the prepared supported metal Rh-based catalyst Z, 100mL of toluene solvent, and 800mmol of isooctene. A 1:1 ratio of CO and H2 was introduced, the system pressure was 3.5MPa, the reaction temperature was 100°C, the stirring rate was 800rpm, and the reaction time was 10h. After the reactor cooled, the pressure was released and the reaction liquid was extracted, treated, and analyzed by gas chromatography. The performance results of the isooctene hydroformylation reaction to produce isononanal are shown in Table 2.

[0108] Table 1 Performance of different metal Rh-based catalysts for the hydroformylation of isooctene to produce isononanal

[0109] sample catalyst Isooctene conversion rate (%) Isononanal selectivity (%) Example 1 Rh-A 91.8 93.6 Example 2 Rh-B 94.4 92.2 Example 3 Rh-C 92.3 93.1 Example 4 Rh-D 93.1 94.4 Example 5 Rh-E 92.7 93.5 Example 6 Rh-F 95.2 95.6 Example 7 Rh-G 93.2 91.8 Example 8 Rh-H 91.6 90.7 Example 9 Rh-I 90.5 92.3 Comparative Example 1 A 76.2 82.5 Comparative Example 2 B 82.1 84.4 Comparative Example 3 C 61.7 68.3

[0110] According to the performance of different metal Rh-based catalysts used in the isooctene hydroformylation reaction to produce isononanal in Table 1, it can be found that when the metal Rh-based catalysts prepared in Examples 1 to 9 were used in the isooctene hydroformylation reaction to produce isononanal, the isooctene conversion rate reached over 90%, and the selectivity for aldehyde products also reached over 90%. Among them, the metal Rh-based catalyst Rh-F prepared in Example 6, when used in the isooctene hydroformylation reaction to produce isononanal, achieved an isooctene conversion rate of 95.2% and an isononanal selectivity of 95.6%. By comparing the performance test results of the metal Rh-based catalysts in Comparative Examples 1 to 3, it can be found that the coordination of the dimethylglyoxime ligand and triphenylphosphine and its substituted derivative ligands with the metal Rh central atom significantly facilitates the isooctene hydroformylation reaction. The above test results demonstrate that the Rh catalysts prepared in the present invention have high conversion and selectivity when used in the isooctene hydroformylation reaction to produce isononanal.

[0111] Table 2 Performance of different supported metal Rh-based catalysts for isooctene hydroformylation to isononanal

[0112] sample Supported catalyst Isooctene conversion rate (%) Isononanal selectivity (%) Example 10 S-Rh-A 93.2 92.7 Example 11 S-Rh-B 93.5 92.4 Example 12 S-Rh-C 92.7 94.6 Example 13 S-Rh-D 92.4 93.1 Example 14 S-Rh-E 96.3 95.7 Example 15 S-Rh-F 95.1 92.8 Example 16 S-Rh-G 93.6 91.9 Example 17 S-Rh-H 91.8 92.5 Example 18 S-Rh-I 91.1 92.3 Example 19 S-Rh-J 89.5 92.6 Comparative Example 20 S-Rh-K 90.8 91.4 Comparative Example 4 X 72.8 85.3 Comparative Example 5 Y 83.3 82.7 Comparative Example 6 Z 60.3 70.1

[0113] By analyzing the performance test results of different supported metal Rh-based catalysts for the hydroformylation of isooctene to produce isononaldehyde in Table 2, it can be found that the supported metal Rh-based catalysts prepared in Examples 10 to 16 can achieve a conversion rate and selectivity of over 90% for the hydroformylation of isooctene to produce isononaldehyde. Among them, the supported metal Rh-based catalyst S-Rh-E prepared in Example 14 achieved an olefin conversion rate of 96.3% and a selectivity of 95.7% for the product aldehyde in the hydroformylation of isooctene to produce isononaldehyde. In addition, the test performance of the supported metal Rh-based catalysts prepared in Examples 17 to 20 shows that this active ingredient metal Rh-based catalyst can also be loaded on a variety of other porous supports to achieve efficient hydroformylation of isooctene to produce isononaldehyde. Analysis of the performance test results of the supported metal Rh-based catalysts prepared in Comparative Examples 4 to 6 for the hydroformylation of isooctene to produce isononanal further demonstrates that the coordination of the dimethylglyoxime ligand, as well as triphenylphosphine and its substituted derivatives, with the metal Rh central atom facilitates the isooctene hydroformylation reaction. Based on the above analysis, it can be concluded that the supported metal Rh-based catalysts prepared in the present invention can achieve efficient hydroformylation of isooctene to produce isononanal, demonstrating high isooctene conversion and selectivity for isononanal.

[0114] The present invention proposes using dimethylglyoxime ligands and triphenylphosphine and its substituted derivative ligands to coordinate with a metal Rh central atom to form a metal Rh-based catalyst. The preparation process is simple and the use of phosphorus ligands, which are expensive and easily polluting, is reduced. In addition, the active component metal Rh-based catalyst can be supported on various porous supports to form a supported metal Rh-based catalyst, which can achieve simple separation and reuse of the catalyst after the reaction is completed. More importantly, the metal Rh-based catalyst and its supported catalyst designed and synthesized by the present invention exhibit excellent performance in the hydroformylation of isooctene to prepare isononaldehyde, which provides a concept for the design and synthesis of catalysts for efficient olefin hydroformylation reactions.

[0115] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A metal Rh-based catalyst, characterized in that Its structural formula is shown in formula (1): Formula (1) In the formula, the dotted line is a coordination bond; the R group is selected from at least one of a hydrogen atom, a straight-chain alkyl group, a branched alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a substituted aryl group, and derivatives thereof.

2. The metal Rh-based catalyst according to claim 1, characterized in that The R group is selected from hydrogen atoms, C1-C 14 At least one of an alkyl group, an alkoxy group, a C3-C6 cycloalkyl group, a phenyl group, a C1-C4 alkyl group or an alkoxy-substituted aryl group.

3. A method for preparing the metal Rh-based catalyst according to claim 1 or 2, characterized in that: The following steps are involved: Under an inert atmosphere, dimethylglyoxime ligand, triphenylphosphine and its substituted derivative ligand and carbonyl rhodium compound are reacted to obtain the metal Rh-based catalyst.

4. The preparation method according to claim 3, characterized in that The molar ratio of the dimethylglyoxime ligand to the carbonyl rhodium compound is (0.8-1.2):1, calculated on the basis of metal Rh; the molar ratio of the triphenylphosphine and its substituted derivative ligand to the carbonyl rhodium compound is (0.8-1.2):1; the carbonyl rhodium compound is selected from at least one of [Rh(CO)2Cl]2, ([Rh(CO)2(acac)]2 and dicarbonyl (pentamethylcyclopentadienyl) rhodium; The reaction is carried out in an organic solvent, which is at least one of cyclohexane, benzene, ether, toluene, and tetrahydrofuran; the reaction temperature is 20° C. to 160° C., and the reaction time is 2 h to 20 h.

5. A supported metal Rh-based catalyst, characterized in that: The invention comprises a porous support and the metal Rh-based catalyst according to claim 1 or 2.

6. The supported metal Rh-based catalyst according to claim 5, characterized in that The porous carrier is selected from at least one of silicon oxide, aluminum oxide, diatomaceous earth, titanium oxide, zirconium oxide, cerium oxide, molybdenum oxide, tungsten oxide, magnesium oxide, zinc oxide, vanadium oxide, activated carbon, montmorillonite, molecular sieve, activated clay, covalent organic framework, metal organic framework, cyclodextrin, polyethylene, polystyrene, polyvinyl alcohol and mesoporous silica fiber.

7. A method for preparing a supported metal Rh-based catalyst according to claim 5 or 6, characterized in that: The following steps are involved: Under an inert atmosphere, the porous support and the metal Rh-based catalyst are dispersed in an organic solvent and reacted to obtain the product.

8. The preparation method according to claim 7, characterized in that The porous support is calcined before use, the calcination temperature is 100°C to 600°C, and the time is 0.5h to 12h; the mass ratio of the porous support to the metal Rh-based catalyst is (1000-10):1, calculated as metal Rh; the organic solvent is at least one of cyclohexane, benzene, ether, toluene, and tetrahydrofuran; the reaction temperature is 20°C to 160°C, and the time is 2h to 20h.

9. Use of the metal Rh-based catalyst according to claim 1 or 2, or the supported metal Rh-based catalyst according to claim 5 or 6, in the preparation of isononanal by hydroformylation of isooctene.

10. The use according to claim 9, characterized in that The isooctene hydroformylation reaction method comprises: adding isooctene, CO and H2, the metal Rh-based catalyst and / or the supported metal Rh-based catalyst into a high-pressure reactor, stirring and performing a contact reaction; after the reaction is completed, extracting a liquid phase product, treating it, and then performing gas chromatography detection; The isooctene is selected from at least one of branched octenes; The reaction is carried out in an organic solvent; the organic solvent is selected from at least one of cyclohexane, benzene, toluene, ether, tetrahydrofuran, and isononanal; Calculated as metal Rh, the amount of the metal Rh-based catalyst and / or the supported metal Rh-based catalyst is 0.01 mmol / L -1 ~100 mmol L -1 The molar ratio of added CO and H2 is 1: (1 to 1.1); the reaction temperature is 20°C to 200°C, the pressure is 0.2 MPa to 10 MPa, and the time is 0.1 h to 36 h; the stirring rate is 200 rpm to 1000 rpm.

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