A hydroformylation catalyst and its use

Abstract

The application provides a hydroformylation catalyst and application thereof. The hydroformylation catalyst comprises a rhodium metal compound, a cobalt metal compound and a phosphine-containing ligand; the molar ratio of the rhodium metal compound to the phosphine-containing ligand is 1:(1-100) in terms of the amount of substance of rhodium or cobalt atoms in the rhodium metal compound and the cobalt metal compound, and the molar ratio of the rhodium metal compound to the cobalt metal compound is 1:(1-10); and the phosphine-containing ligand comprises at least one phosphine ligand shown in the following formula. The catalyst of the application has high catalytic activity and stability in a hydroformylation reaction, and is beneficial to obtaining a high normal / iso ratio product.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hydroformylation reaction, and particularly relates to a catalyst for hydroformylation reaction and application thereof. BACKGROUND

[0002] The hydroformylation reaction of olefins is a large-scale carbonylation reaction in industry, can synthesize aldehyde compounds with high added value with 100% atomic utilization rate, and the aldehyde compounds can be further converted into important fine chemicals such as alcohol, carboxylic acid, ester and fatty amine. During the hydroformylation reaction, normal aldehyde and isomerized aldehyde are generated, wherein the straight-chain alcohol is widely used as a raw material of solvent, additive, various plasticizer, synthetic lubricating oil, detergent and the like. The branched aldehyde as a reaction by-product is less valued in industry. Therefore, for the hydroformylation reaction of olefins, it is particularly important to improve the selectivity of normal aldehyde.

[0003] At present, for the hydroformylation reaction of olefins, the catalysts mainly used are various coordination complexes of Co and Rh metals. Since the activity of rhodium-based catalyst is higher than that of cobalt, the rhodium-based catalyst has gradually replaced cobalt to become the dominant catalyst for industrial hydroformylation reaction. However, since the price of metal rhodium is high, the production cost is high, the reaction activity and the regioselectivity need to be improved to the maximum extent; in addition, the hydroformylation catalysts disclosed in the prior art (such as CN106431869A and CN110981709A) have insufficient ability to regulate the normal-isomer ratio of products in the internal olefin hydroformylation reaction, the selectivity of normal products is low, the product performance is poor, and the like, and there is still a large improvement space. Therefore, it is of great significance to develop a hydroformylation catalyst with high regioselectivity and high stability for the hydroformylation reaction of olefins. SUMMARY

[0004] In order to make up for the deficiencies in the prior art, the application provides a catalyst for hydroformylation reaction and application thereof. The hydroformylation catalyst has high catalytic activity and regioselectivity, the conversion rate is as high as 99% or more, the selectivity of normal aldehyde product is as high as 95% or more, the regioselectivity can be effectively improved, and the generation of by-products can be effectively inhibited.

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

[0006] A hydroformylation catalyst, the catalyst comprising a rhodium metal compound, a cobalt metal compound and a phosphine-containing ligand; wherein the molar ratio of the rhodium metal compound to the phosphine-containing ligand is 1:(1-100) in terms of the amount of substance of rhodium, cobalt atoms in the rhodium, cobalt metal compound, for example 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, etc., preferably 1:(10-50); the molar ratio of the rhodium metal compound to the cobalt metal compound is 1:(1-10), for example 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., preferably 1:(2-5).

[0007] In a preferred embodiment, the hydroformylation catalyst is obtained by mixing components comprising a rhodium metal compound, a cobalt metal compound and a phosphine-containing ligand.

[0008] In the present application, the rhodium metal compound is selected from one or more of halides of rhodium, complexes of rhodium coordinated with acetyl compounds, and the rhodium metal compound is preferably one or more of rhodium chloride (RhCl3), acetylacetone dicarbonyl rhodium (Rh(CO)2acac), acetylacetone triphenylphosphine carbonyl rhodium (ROPAC).

[0009] In the present application, the cobalt metal compound is selected from one or more of CoCl2, Co(NO3)2·6H2O, Co2(CO)8.

[0010] The hydroformylation catalyst of the present application, by adding rhodium, cobalt metal compounds as the main active component, and mixed with the phosphine-containing ligand to obtain a stable coordination catalyst, using the multiple unsaturated sites formed by rhodium, cobalt metal, improving the complexing strength between the single molecule metal and the phosphine-containing ligand, can greatly change the catalytic activity and stability of the catalyst in the hydroformylation reaction; and under the coordination of the phosphine ligand with rhodium and cobalt metal, the internal olefin is more inclined to convert to terminal olefin, which can realize the regulation of the n-iso ratio of the product, and is more conducive to promoting the generation of n-alkanes.

[0011] In the present application, the phosphine-containing ligand comprises at least one bisphosphine ligand represented by formula I;

[0012]

[0013] wherein R1, R2, R3 are each independently selected from any one of hydrogen, methyl, isopropyl, phenyl, methoxy; Ts represents p-toluenesulfonyl.

[0014] The hydrogenation catalyst of the present application can enhance the coordination strength with the metal catalyst by introducing nitrogen atoms through the phosphine-containing ligand, and the catalyst system after coordination has better reaction activity and better stability, which can significantly improve the conversion rate and selectivity of the hydroformylation reaction, and the catalyst after coordination is conducive to the conversion of internal olefins to terminal olefins in the reaction substrate, promoting the generation of normal isomers, thereby realizing high normal isomer ratio.

[0015] The phosphine-containing ligand of formula I can be prepared by the method of the prior art without any limitation. The synthesis method can refer to the literature Org. Lett. 2021, 23, 15, 6004-6009 and J. Am. Chem. Soc. 2018, 140, 19, 6062-6066 and supporting documents thereof.

[0016] In the present application, as a feasible solution, a preparation method of the phosphine-containing ligand is exemplarily given, which specifically comprises the following steps:

[0017] (1) Dissolve 2,2'-diaminobiphenyl in dichloromethane, then slowly add pyridine solution at 0-5℃, after the addition is completed, slowly drop the p-toluenesulfonyl chloride solution, after the reaction for at least 2 hours, quench the reaction with ammonium chloride aqueous solution, separate and dry to obtain substance B;

[0018] (2) Under the atmosphere of nitrogen, substance B is added to a reaction bottle containing anhydrous and dried tetrahydrofuran; the reaction solution is placed in a low-temperature cold bath at minus 65-75℃, and n-butyllithium is added dropwise to the solution; after the dropwise addition is completed, react for at least 30 min, then add phosphorus trichloride, continue to react for 10-12 hours, slowly recover to room temperature, quench the reaction with ammonium chloride aqueous solution, then separate and dry to obtain substance C;

[0019] (3) The phenolic compound is added to the reaction kettle, heated and stirred, and after melting, substance C is slowly added dropwise under the condition of nitrogen atmosphere; the generated hydrogen chloride is introduced into an alkaline absorption bottle; after the reaction is completed, the unreacted phenolic compound is washed away, and the phosphine-containing ligand is purified.

[0020] In step (1), the 2,2'-diaminobiphenyl is dissolved in dichloromethane, the concentration of the 2,2'-diaminobiphenyl is 0.4-0.6 mol / L, for example 0.5 mol / L; the molar ratio of the 2,2'-diaminobiphenyl to pyridine is 1:(1.8-2.2), for example 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, etc.; the molar ratio of the 2,2'-diaminobiphenyl to p-toluenesulfonyl chloride is 1:(1.8-2.2), for example 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, etc.; the reaction is quenched with an aqueous ammonium chloride solution, wherein the concentration of the aqueous ammonium chloride solution is not particularly limited, for example 0.8-1.2 mol / L, and the amount of the aqueous ammonium chloride solution added is generally 1.0 mol / L.

[0021] In step (2), the concentration of the substance B in tetrahydrofuran is 0.5-0.7 mol / L, for example 0.6 mol / L, the molar ratio of the substance B to n-butyllithium is 1:(1.2-1.5), for example 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc.; the molar ratio of the substance B to phosphorus trichloride is 1:(1.0-1.2), for example 1:1.0, 1:1.1, 1:1.2, etc. In this step, the reaction is quenched with an aqueous ammonium chloride solution, wherein the concentration of the aqueous ammonium chloride solution is not particularly limited, for example 0.8-1.2 mol / L, and the amount of the aqueous ammonium chloride solution added is generally 1.0 mol / L.

[0022] In step (3), the phenolic compound has a structure as shown in Formula II:

[0023]

[0024] The R1, R2, R3 are each independently selected from any one of hydrogen, methyl, isopropyl, phenyl, methoxy, preferably R1, R2, R3 are selected from hydrogen, methyl. The phenolic compound is added in excess, and after the reaction is completed, the unreacted phenolic compound is washed away; wherein the temperature of heating and melting is the melting point temperature of the phenolic compound, and the temperature of warming and stirring is lower than the melting point.

[0025] In another aspect of the present application, there is provided a use of the hydroformylation catalyst as described above in a hydroformylation reaction, in particular, a hydroformylation reaction of a reaction substrate with synthesis gas in the presence of the hydroformylation catalyst, wherein the reaction substrate is one or more of olefins.

[0026] The number of carbon atoms of the olefin is 8 or less; preferably, the olefin is selected from one or more of linear olefins with a carbon number of 8 or less; more preferably, at least one of propylene, 1-butene, 2-butene, pentene, hexene.

[0027] Specifically, the hydroformylation reaction of the olefin includes the following steps:

[0028] The olefin and the hydroformylation catalyst and the solvent are added into a high-pressure reaction kettle, and the nitrogen is replaced for 2-4 times, and then the synthesis gas is replaced for 2-4 times; the synthesis gas with a pressure of 0.8-3 MPa is introduced into the high-pressure reaction kettle, and the reaction is heated to prepare the corresponding aldehyde.

[0029] For example, the application of the hydroformylation catalyst in the catalytic synthesis of pentanal is taken as an example, and the preparation method of the pentanal includes the following steps:

[0030] The butene and the hydroformylation catalyst and the solvent are added into a high-pressure reaction kettle, and the nitrogen is replaced for 2-4 times, and then the synthesis gas is replaced for 2-4 times; the synthesis gas with a pressure of 0.8-3 MPa is introduced into the high-pressure reaction kettle, and the reaction is heated to prepare the pentanal.

[0031] The mass ratio of the butene to the hydroformylation catalyst is (1000-2000):1, for example, 1000:1, 1100:1, 1200:1, 1300:1, 1400:1, 1500:1, 1600:1, 1700:1, 1800:1, 1900:1, 2000:1, etc.

[0032] In the hydroformylation reaction, the reaction temperature is 70-120°C, for example, 80°C, 90°C, 100°C, 110°C, etc., and the reaction time is 4-8 h, for example, 5 h, 6 h, 7 h, etc.

[0033] In the present application, the synthesis gas includes CO and H2, and the molar ratio of CO to H2 is (0.6-1.4):1, for example, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, etc. The amount of the synthesis gas introduced is to make the pressure in the reaction kettle reach 0.8-3 MPa, for example, 0.9 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, etc.

[0034] In the present application, the solvent is selected from at least one of C5-C 20 aliphatic alkanes, C 6- C 20 aromatic hydrocarbons, C6-C 10 alcohols, and preferably at least one of pentanal, toluene, n-hexane, m-xylene. The amount of the solvent is to make the concentration of the hydroformylation catalyst be 0.05-0.4 g / L, for example, 0.1 g / L, 0.15 g / L, 0.2 g / L, 0.25 g / L, 0.3 g / L, 0.35 g / L, 0.4 g / L, etc., and preferably 0.1-0.2 g / L.

[0035] The hydroformylation catalyst is used for the hydroformylation reaction, and the olefin can be prepared into corresponding aldehyde.

[0036] The technical solution provided by the present application has the following beneficial effects:

[0037] The catalyst for hydroformylation has high catalytic activity and stability, the conversion rate is as high as 99% or more, the selectivity of normal aldehyde product is as high as 95% or more, the regional selectivity can be effectively improved, the generation of by-products is effectively inhibited, the control of the normal and abnormal ratio of the product in the hydroformylation reaction is greatly improved, and the normal form of the hydroformylation product is more beneficial to be generated.

[0038] The preparation method of pentanal provided by the present application has the advantages of simple process, low catalyst cost, mild reaction conditions, and easy scaling up and industrial application. DETAILED DESCRIPTION

[0039] The present application will be further described below through specific examples, and the examples described in the present application are only used to illustrate the present application and do not limit the scope of the present application.

[0040] Unless otherwise specified, the raw materials used in the following specific embodiments of the present application are obtained through commercial channels.

[0041]

Preparation Example 1

[0042] The bisphosphine ligand is prepared, and the synthesis route is as follows:

[0043]

[0044] 1 mol of 2,2'-diaminobiphenyl is dissolved in dichloromethane, then pyridine solution is slowly added at 0℃, and after the addition is completed, p-toluenesulfonyl chloride solution is slowly added, wherein the amount of p-toluenesulfonyl chloride added is 2 mol, and after 2 hours of reaction, the reaction is quenched with an aqueous ammonium chloride solution, and then the substance B is separated and dried.

[0045] 0.9 mol of substance B is added to a Schlenk flask containing anhydrous and dried tetrahydrofuran, and stirred uniformly under nitrogen atmosphere, and the reaction system is placed in a low-temperature cold bath at-75℃, and 1.3 mol of n-butyllithium solution is added dropwise to the solution. After the dropwise addition is completed, the reaction is continued for 30 min, then 0.5 mol of phosphorus trichloride is added, and the reaction is continued for 12 hours, then slowly restored to room temperature, the reaction is quenched with an aqueous ammonium chloride solution, and then separated and dried to obtain substance C.

[0046] Then 1 mol of phenol was added into the reactor, and the mixture was heated and melted under stirring. After that, 0.8 mol of the substance C was slowly added dropwise under the condition of nitrogen atmosphere. The generated hydrogen chloride was introduced into the alkaline absorption bottle. After the reaction was completed, the unreacted phenol was washed away, and the phosphine ligand was purified.

[0047] Spectrum characterization

[0048]

[0049] 1 H NMR (500 MHz, DMSO-d6) δ 7.76 - 7.70 (m, 4H), 7.66 (td, J = 7.4, 1.9 Hz, 2H), 7.54 (dd, J = 7.5, 2.1 Hz, 2H), 7.49 (dd, J = 7.5, 2.0 Hz, 2H), 7.30 - 7.26 (m, 6H), 7.26 - 7.24 (m, 1H), 7.24 - 7.16 (m, 1H), 7.06 - 7.00 (m, 2H), 2.43 (t, J = 1.0 Hz, 6H).

[0050] 13 C NMR (125 MHz, Chloroform-d) δ 155.91, 139.76, 137.76, 135.59, 130.05, 129.09, 129.07, 125.50, 124.78, 124.20, 124.10, 117.42, 115.80, 21.68.

[0051] Preparation Example 2

[0052] The bisphosphine ligand was prepared, and the synthetic route was as follows:

[0053]

[0054] 1 mol of 2,2'-diaminobiphenyl was dissolved in dichloromethane, and then pyridine solution was slowly added at 0°C. After the addition was completed, p-toluenesulfonyl chloride solution was slowly added dropwise, wherein the amount of p-toluenesulfonyl chloride added was 2 mol. After the reaction for 2 hours, the reaction was quenched with an aqueous ammonium chloride solution, and then the substance B was separated and dried.

[0055] 0.9 mol of the substance B was added into a Schlenk bottle containing anhydrous and dry tetrahydrofuran, and stirred uniformly under the condition of nitrogen atmosphere. The reaction system was placed in a low-temperature cold bath at -75°C, and 1.3 mol of n-butyllithium solution was added dropwise into the solution. After the dropwise addition was completed, the reaction was continued for 30 min, and then 0.5 mol of phosphorus trichloride was added. After the reaction for 12 hours, the temperature was slowly recovered to room temperature, the reaction was quenched with an aqueous ammonium chloride solution, and then the substance C was separated and dried.

[0056] Then 1 mol of 3,4,5-trimethylphenol was added into the reactor, and after warming and stirring and heating and melting, 0.8 mol of substance C was slowly added dropwise under the condition of nitrogen atmosphere to react. The generated hydrogen chloride was introduced into the alkaline absorption bottle. After the reaction was completed, the unreacted phenol was washed away, and the phosphine ligand was purified.

[0057] Spectrum characterization

[0058] 1 H NMR (500 MHz, DMSO-d6) δ 7.76-7.69 (m, 4H), 7.63 (td, J = 7.4, 2.0 Hz, 2H), 7.54 (dd, J = 7.5, 2.0 Hz, 2H), 7.49 (dd, J = 7.4, 2.0 Hz, 2H), 7.33-7.21 (m, 6H), 7.14 (t, J = 0.8 Hz, 2H), 2.43 (t, J = 1.0 Hz, 6H), 2.30-2.22 (m, 9H).

[0059] 13 C NMR (125 MHz, Chloroform-d) δ 155.40, 139.76, 137.76, 137.72, 136.73, 135.59, 130.05, 129.09, 128.95, 124.55, 124.10, 123.85, 117.42, 110.97, 21.53, 20.66, 18.06.

[0060] Gas chromatography analysis: chromatograph model: Agilent 7890B; carrier gas: high-purity nitrogen; sample injection mode: manual high-pressure sampler; nitrogen flow rate: 68.1 ml / min; vaporization chamber temperature: 270°C; split injection, split ratio: 30:1; sample injection amount: 0.2 μl; column temperature: first-order programmed temperature, initial value 35°C, holding for 5 minutes, then increasing to 260°C at a rate of 15°C / min, holding for 15 minutes; total running time is 25 minutes; external standard method is used for quantification.

[0061] Example 1

[0062] Preparation of pentanal

[0063] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.2 g of Co2(CO)8, 3.0 g of the phosphine ligand prepared in Preparation Example 1 and 20 ml of toluene solution were sequentially added, and after being replaced with nitrogen three times, synthetic gas three times and then being evacuated, 150 g of cis-2-butene was added, and then 1 MPa of synthetic gas was introduced, and the temperature was increased to 80°C for reaction for 6 hours to obtain pentanal. The synthetic gas was CO and H2in a molar ratio of 1:1.

[0064] Example 2

[0065] Preparation of pentanal

[0066] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.2 g of Co2(CO)8, 3.0 g of the phosphine ligand prepared in Preparation Example 1 and 20 ml of toluene solution were sequentially added, replaced with nitrogen three times, replaced with synthesis gas three times, and then evacuated. After that, 150 g of trans-2-butene was added, and then 1 MPa of synthesis gas was introduced. The temperature was raised to 80°C, and the reaction was carried out for 8 hours to obtain pentanal. The synthesis gas was CO and H2in a molar ratio of 1:1.

[0067] [Example 3]

[0068] Preparation of pentanal

[0069] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.2 g of Co2(CO)8, 6.0 g of the phosphine ligand prepared in Preparation Example 1 and 20 ml of toluene solution were sequentially added, replaced with nitrogen three times, replaced with synthesis gas three times, and then evacuated. After that, 150 g of trans-2-butene was added, and then 1 MPa of synthesis gas was introduced. The temperature was raised to 80°C, and the reaction was carried out for 8 hours to obtain pentanal. The synthesis gas was CO and H2in a molar ratio of 1:1.

[0070] [Example 4]

[0071] Preparation of pentanal

[0072] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.3 g of Co2(CO)8, 3.0 g of the phosphine ligand prepared in Preparation Example 1 and 20 ml of toluene solution were sequentially added, replaced with nitrogen three times, replaced with synthesis gas three times, and then evacuated. After that, 150 g of trans-2-butene was added, and then 1 MPa of synthesis gas was introduced. The temperature was raised to 80°C, and the reaction was carried out for 8 hours to obtain pentanal. The synthesis gas was CO and H2in a molar ratio of 1:1.

[0073] [Example 5]

[0074] Preparation of pentanal

[0075] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.2 g of Co2(CO)8, 3.0 g of the phosphine ligand prepared in Preparation Example 2 and 20 ml of toluene solution were sequentially added, replaced with nitrogen three times, replaced with synthesis gas three times, and then evacuated. After that, 150 g of trans-2-butene was added, and then 1 MPa of synthesis gas was introduced. The temperature was raised to 80°C, and the reaction was carried out for 8 hours to obtain pentanal. The synthesis gas was CO and H2in a molar ratio of 1:1.

[0076] [Example 6]

[0077] Preparation of butanal

[0078] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.2 g of Co2(CO)8, 2.5 g of the phosphine ligand prepared in Preparation Example 1, and 20 ml of a toluene solution were sequentially added, replaced with nitrogen three times, replaced with synthesis gas three times, and then evacuated. Next, 150 g of propylene was added, 1 MPa of synthesis gas was introduced again, the temperature was raised to 80°C, and the reaction was performed for 8 hours to obtain pentanal. The synthesis gas was CO and H2in a molar ratio of 1:1.

[0079] [Comparative Example 1]

[0080] Preparation of pentanal

[0081] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.2 g of Co2(CO)8, and 20 ml of a toluene solution were sequentially added, replaced with nitrogen three times, replaced with synthesis gas three times, and then evacuated. Next, 150 g of cis-2-butene was added, 1 MPa of synthesis gas was introduced again, the temperature was raised to 80°C, and the reaction was performed for 6 hours to obtain pentanal. The synthesis gas was CO and H2in a molar ratio of 1:1.

[0082] [Comparative Example 2]

[0083] Preparation of pentanal

[0084] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.2 g of Co2(CO)8, and 20 ml of a toluene solution were sequentially added, replaced with nitrogen three times, replaced with synthesis gas three times, and then evacuated. Next, 150 g of trans-2-butene was added, 1 MPa of synthesis gas was introduced again, the temperature was raised to 80°C, and the reaction was performed for 8 hours to obtain pentanal. The synthesis gas was CO and H2in a molar ratio of 1:1.

[0085] [Comparative Example 3]

[0086] Preparation of pentanal

[0087] Into a high-pressure reactor, 0.1 g of Rh(CO)2acac, 0.2 g of Co2(CO)8, 3.0 g of the phosphine ligand in Example 1 of CN114931961A, and 20 ml of a toluene solution were sequentially added, replaced with nitrogen three times, replaced with synthesis gas three times, and then evacuated. Next, 200 g of cis-2-butene was added, 1 MPa of synthesis gas was introduced again, the temperature was raised to 80°C, and the reaction was performed for 6 hours to obtain pentanal. The synthesis gas was CO and H2in a molar ratio of 1:1.

[0088] [Comparative Example 4]

[0089] Preparation of pentanal

[0090] Into a high-pressure reactor, 0.2 g Co2(CO)8, 3.0 g phosphine ligand prepared in Preparation Example 1 and 20 ml toluene solution were sequentially added, and the reactor was replaced with nitrogen three times, synthetic gas three times and then evacuated. Then, 150 g cis-2-butene was added, and 1 MPa of synthetic gas was introduced. The temperature was raised to 80°C, and the reaction was carried out for 6 hours to obtain pentanal. The synthetic gas was CO and H2 in a molar ratio of 1:1.

[0091] The reaction selectivity, conversion rate and normal / iso ratio of the products in the above examples and comparative examples were tested, and the test results are shown in Table 1.

[0092] Table 1, performance test results

[0093] No. Conversion / % Normal aldehyde selectivity / % Normal / iso ratio Example 1 99.3 95.8 28.1 Example 2 99.1 95.2 25.8 Example 3 99.0 95.4 24.1 Example 4 99.2 94.9 24.6 Example 5 99.3 94.6 24.8 Example 6 99.8 97.8 51 Comparative Example 1 98.9 41.5 2.1 Comparative Example 2 99.0 38.2 1.7 Comparative Example 3 99.2 93.2 15.5 Comparative Example 4 13.2 50.2 9.4

[0094] In Table 1, the normal / iso ratio refers to the mass ratio of normal and iso forms in the hydroformylation product.

[0095] As can be seen from Table 1, the catalyst for hydroformylation prepared by the present application can efficiently catalyze the synthesis of pentanal from 2-butene, the raw material conversion rate can be as high as 99.3%, the selectivity of normal aldehyde product can be as high as 95.8%, and the normal / iso ratio of the product n-pentanal is high.

[0096] The above description is only the preferred embodiments of the present application, and it should be pointed out that, for those skilled in the art, without departing from the method of the present application, a number of improvements and supplements can also be made, and these improvements and supplements should also be considered as the protection scope of the present application.

Claims

1. A hydroformylation catalyst, characterized in that, The catalyst comprises a rhodium metal compound, a cobalt metal compound, and a phosphine-containing ligand; wherein, based on the amount of rhodium and cobalt atoms in the rhodium and cobalt metal compounds, the molar ratio of the rhodium metal compound to the phosphine-containing ligand is 1:(1-100); and the molar ratio of the rhodium metal compound to the cobalt metal compound is 1:(1-10). The phosphine-containing ligand has the structure shown in Formula I; R1, R2, and R3 are each independently selected from hydrogen, methyl, isopropyl, phenyl, and methoxy; Ts represents p-toluenesulfonyl.

2. The hydroformylation catalyst according to claim 1, characterized in that, The molar ratio of the rhodium metal compound to the phosphine-containing ligand is 1:(10-50); the molar ratio of the rhodium metal compound to the cobalt metal compound is 1:(2-5).

3. The hydroformylation catalyst according to claim 1, characterized in that, The rhodium metal compound is selected from one or more of rhodium halides and rhodium-acetyl compound coordination complexes.

4. The hydroformylation catalyst according to claim 3, characterized in that, The rhodium metal compound is selected from one or more of RhCl3, Rh(CO)2acac, and ROPAC.

5. The hydroformylation catalyst according to claim 1, characterized in that, The cobalt metal compound is selected from one or more of CoCl2, Co(NO3)2·6H2O, and Co2(CO)8.

6. The use of the hydroformylation catalyst according to any one of claims 1-5 in the hydroformylation reaction.

7. The application according to claim 6, characterized in that, In the presence of the hydroformylation catalyst according to any one of claims 1-5, the reaction substrate is subjected to a hydroformylation reaction with syngas, wherein the reaction substrate is one or more olefins.

8. The application according to claim 7, characterized in that, The olefin has 8 or fewer carbon atoms.

9. The application according to claim 8, characterized in that, The olefin is selected from one or more straight-chain olefins having 8 or fewer carbon atoms.

10. The application according to claim 9, characterized in that, The olefin is selected from at least one of propylene, 1-butene, 2-butene, pentene, and hexene.

11. The application according to any one of claims 7-10, characterized in that, The hydroformylation reaction of the olefin includes the following steps: An olefin, a hydroformylation catalyst, and a solvent are added to a high-pressure reactor. The reactor is purged with nitrogen 2-4 times, followed by purging with syngas 2-4 times. Syngas at 0.8-3 MPa is introduced into the high-pressure reactor, and the temperature is raised to react and the corresponding aldehyde is obtained.

12. The application according to claim 11, characterized in that, The weight ratio of the olefin to the hydroformylation catalyst is (1000-2000):

1.

13. The application according to claim 11, characterized in that, The reaction temperature is 70-120℃, and the reaction time is 4-8h.

14. The application according to claim 11, characterized in that, The synthesis gas comprises CO and H2, wherein the molar ratio of CO to H2 is (0.6-1.4):1.

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