A method for producing high carbon aldehydes using multi-ligand composite catalyst

Abstract

The present invention provides a method for producing high carbon aldehydes by a multi-ligand composite catalyst, comprising the following steps: firstly, dissolving a composition comprising a rhodium catalyst precursor, a monodentate phosphine ligand, a bidentate phosphine ligand, a bisphosphite ligand and a phosphite ligand to obtain a catalyst system; reacting high carbon number olefins, carbon monoxide and hydrogen under the action of the catalyst system to obtain high carbon aldehydes. A method for producing high carbon aldehydes of the present invention obtains a catalyst system with a suitable active center concentration by reasonably proportioning a rhodium catalyst precursor, a monodentate phosphine ligand, a bidentate phosphine ligand, a bisphosphite ligand and a phosphite ligand, and prepares high carbon aldehydes by a hydroformylation reaction under the conditions of carbon monoxide and hydrogen, significantly improving the selectivity of the hydroformylation reaction of high carbon number olefins, reducing the isomerization side reaction of high carbon number olefins, significantly improving the positive-to-isomer ratio of high carbon aldehydes in the product, and improving the high carbon aldehyde yield, especially the linear high carbon aldehyde yield.

Description

Technical Field

[0001] The invention relates to a method for producing high carbon aldehydes by using a multi-ligand composite catalyst. Background Art

[0002] Hydroformylation is an important way to produce aldehydes or alcohols. Since it was discovered by German scientist Roelen in 1938, it has been popular for more than 70 years and is still one of the most important organic chemical production processes today. At present, there are more than ten hydroformylation processes (also known as carbonyl synthesis processes) used in industrial production, and most industrial devices use aldehydes and alcohols as the main products.

[0003] The preparation of high-carbon aldehydes and alcohols by hydroformylation of high-carbon olefins is an industrial production technology with high comprehensive economic indicators. However, the aldehyde and alcohol production technology mastered by my country is still concentrated on products such as C4 alcohols and C8 alcohols. The high-carbon alcohol products with increasing demand year by year are still in the initial stage in my country, and there is no high-carbon olefin hydroformylation technology with independent intellectual property rights. At present, the global production of isononyl alcohol is mainly controlled by a few manufacturers, including Exxon Mobil, Oxeno, BASF, Japan Kyowa Yuka Company and Taiwan Nan Ya Plastics Company. Among them, Exxon Mobil and Oxeno's production capacity accounts for 34.6% and 28.4% of the global total production capacity respectively, using the traditional hydroformylation process with cobalt as the catalyst.

[0004] Cobalt catalysis still plays an important role in the current hydroformylation of high carbon number olefins. However, due to its harsh reaction conditions, poor selectivity, many side reactions, high energy consumption and complex cobalt recovery process, its comprehensive economic and technical indicators are far inferior to rhodium catalysis. Therefore, the research on the hydroformylation of high carbon number olefins using rhodium catalysts has been continuous, mainly from two aspects: on the one hand, starting from the homogeneous catalytic system, developing new rhodium catalysts with phosphine ligands to make them more active and stable; on the other hand, starting from the two-phase catalytic system to solve the water solubility problem of high carbon number olefins and develop new two-phase catalytic systems. The reaction activity of the two-phase catalytic system is not as good as that of the homogeneous catalytic system, especially for high carbon number olefins with low water solubility. The limitation of mass transfer makes hydroformylation difficult, making the reaction activity of the two-phase catalytic system even lower. Therefore, for the hydroformylation of high carbon number olefins, the homogeneous catalytic system is still the focus of everyone's attention.

[0005] The homogeneous catalysis of high carbon number olefin hydroformylation technology mainly focuses on the development of catalysts, with an emphasis on various ligands, such as monophosphites, monoalkylphosphites, bisphosphites, bisalkylphosphites, bisphosphoramidites and ionic ligands. Due to the low reaction rate and severe isomerization of high carbon number olefins, there is a common problem that the conversion rate and selectivity cannot reach a high level at the same time. Summary of the invention

[0006] The technical problem to be solved by the present invention is that the high carbon number olefins in the prior art have a low reaction rate and severe isomerization, which leads to the common problem that the conversion rate and selectivity cannot reach a high level at the same time. The method of the present invention can reduce the degree of olefin isomerization during the hydrogenation reaction of high carbon number olefins and improve the yield of high carbon aldehydes.

[0007] To achieve the object of the present invention, the present invention provides a method for producing high carbon aldehydes, comprising the following steps:

[0008] S101: firstly dissolving a composition including a rhodium catalyst precursor, a monodentate phosphine ligand, a bidentate phosphine ligand, a bisphosphite ligand and a phosphite ligand to obtain a catalyst system;

[0009] S102: reacting high carbon number olefins, carbon monoxide and hydrogen under the action of the catalyst system to obtain high carbon aldehydes.

[0010] The invention discloses a method for producing high-carbon aldehydes. The method obtains a catalyst system with a suitable active center concentration by reasonably proportioning a rhodium catalyst precursor, a monodentate phosphine ligand, a bidentate phosphine ligand, a bisphosphite ligand and a phosphite ligand. The high-carbon aldehydes are prepared by a hydroformylation reaction under the conditions of carbon monoxide and hydrogen. The selectivity of the hydroformylation reaction of high-carbon olefins is significantly improved, the isomerization side reaction of the high-carbon olefins is reduced, the normal-to-isomer ratio of the high-carbon aldehydes in the product is significantly improved, and the yield of the high-carbon aldehydes, especially the yield of the linear high-carbon aldehydes, is improved.

[0011] The high carbon number olefin in the present invention refers to an olefin having no less than 6 carbon atoms, and the high carbon aldehyde refers to an aldehyde having no less than 6 carbon atoms.

[0012] As a specific embodiment of the present invention, the molar ratio of the sum of the bisphosphite ligand and the monodentate phosphine ligand to the rhodium catalyst precursor is 1-200:1, such as 30-170:1, 50-150:1, 80-120:1, 1:1, 50:1, 100:1, 150:1, 200:1 and any combination thereof. The present invention does not specifically limit the ratio of the bidentate phosphine ligand, the phosphite ligand and the phosphite ligand, as long as the present invention can be achieved, it is within the protection scope of the present invention.

[0013] Preferably, the molar concentration of the rhodium catalyst precursor is in the range of 0.01 mmol / L-5 mmol / L, for example, 1 mmol / L-4 mmol / L, 2 mmol / L-3 mmol / L, 1 mmol / L, 2 mmol / L, 3 mmol / L, 4 mmol / L, 5 mmol / L and any combination thereof.

[0014] As a specific embodiment of the present invention, the high carbon number olefin has a structure of formula (V):

[0015]

[0016] Wherein, R4 and R5 are independently selected from hydrogen, an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, and the aryl group having 6-20 carbon atoms has 0-5 substituents, and the sum of the carbon atoms of R4 and R5 is not less than 4.

[0017] Preferably, the aromatic substituent is at least one selected from nitro, halogen or an alkyl group having 1 to 4 carbon atoms, such as fluorine, bromine, chlorine, methyl, ethyl, propyl, butyl and the like.

[0018] The inventors have found that by controlling appropriate reaction conditions and raw material ratios, the isomerization side reaction of high-carbon olefins can be reduced, the normal-to-iso ratio of high-carbon aldehydes in the product can be significantly increased, and the yield of high-carbon aldehydes, especially the yield of linear high-carbon aldehydes, can be increased.

[0019] As a specific embodiment of the present invention, in the step S102, the reaction temperature is 50°C-150°C, for example, in the range of 70°C-130°C, 90°C-110°C, 50°C, 100°C, 150°C and any combination thereof; the reaction pressure is 0.5MPa-3MPa, for example, in the range of 1MPa-2MPa, 1MPa, 2MPa, 3MPa and any combination thereof.

[0020] As a specific embodiment of the present invention, the molar ratio of the hydrogen (H2) to the carbon monoxide (CO) is 1-4:1, for example, 2-3:1, 1:1, 2:1, 3:1, 4:1 and any combination thereof.

[0021] As a specific embodiment of the present invention, the bisphosphite ligand has a structure of formula (I):

[0022]

[0023] Wherein, X is selected from a C6-C28 organic divalent bridged arylene group; Y1, Y2, Z1, and Z2 are independently selected from one of hydrogen, tert-butyl or methoxy.

[0024] Preferably, X is at least one selected from 1,1'-biphenyl-2,2'-diyl, 3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl, 3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl, 1,4-phenylene, 1,3-phenylene, 1,5-naphthylene or 2,7,9,9-tetramethyl-9H-(xanthene)-4,5-diyl;

[0025] Q is a single bond and / or a blank bond connecting two adjacent benzene rings, that is, in the structure shown in formula (I), the two adjacent benzene rings may be connected by a single bond or a blank bond, that is, the two adjacent benzene rings may not be connected by a single bond.

[0026] For example, in the present invention, the bisphosphite ligand may have the structure of formula (I') or (I"):

[0027]

[0028] As a specific embodiment of the present invention, the monodentate phosphine ligand has a structure of formula (II):

[0029]

[0030] Wherein, R1, R2 and R3 are independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl or cycloalkenyl group having 5 to 20 carbon atoms and an aryl group having 6 to 36 carbon atoms.

[0031] As a specific embodiment of the present invention, the bidentate phosphine ligand has a structure of formula (III):

[0032]

[0033] Wherein, X is selected from a C6-C28 organic divalent bridged arylene group.

[0034] Preferably, X is selected from one of 1,1'-biphenyl-2,2'-diyl, 3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl, 3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl, 1,4-phenylene, 1,3-phenylene, 1,5-naphthylene or 2,7,9,9-tetramethyl-9H-(xanthene)-4,5-diyl.

[0035] R1, R2, R3 and R4 are each independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or cycloalkenyl group having 5 to 20 carbon atoms and an aryl group having 6 to 36 carbon atoms.

[0036] For example, the bidentate phosphine ligand may be of formula (III'):

[0037]

[0038] As a specific embodiment of the present invention, the phosphoramidite ligand has a structure of formula (IV):

[0039]

[0040] Among them, R1 is at least one selected from phenyl, N-indolyl or N-carbazolyl, and R2 is at least one selected from hydrogen, methyl ester, ethyl ester, cyano, halogen, n-butyl, methyl, methoxy, ethyl, ethoxy or trifluoromethyl.

[0041] For example, the phosphoramidite ligand may be of formula (IV'):

[0042]

[0043] The present invention does not specifically limit the selection of the rhodium catalyst precursor, as long as the rhodium catalyst precursor is applicable to the present invention and can increase the yield of high carbon aldehydes, it is within the protection scope of the present invention. As a specific embodiment of the present invention, the rhodium catalyst precursor is at least one selected from tris(triphenylphosphine) carbonyl rhodium hydride, tris(triphenylphosphine) rhodium chloride and acetylacetonato dicarbonyl rhodium; preferably, the rhodium catalyst precursor is tris(triphenylphosphine) carbonyl rhodium hydride.

[0044] As a specific embodiment of the present invention, the solvent selected in step S101 needs to be able to dissolve the rhodium catalyst precursor, the bisphosphite, the monodentate phosphine ligand, the bidentate phosphine ligand, the phosphite and the high carbon number olefin well. Specifically, in step S101, the solvent for dissolving the catalyst system is at least selected from one of toluene, xylene, nonanal and decane.

[0045] The invention discloses a method for producing high-carbon aldehydes. The method obtains a catalyst system with a suitable active center concentration by reasonably proportioning a rhodium catalyst precursor, a monodentate phosphine ligand, a bidentate phosphine ligand, a bisphosphite ligand and a phosphite ligand. The high-carbon aldehydes are prepared by a hydroformylation reaction under the conditions of carbon monoxide and hydrogen. The selectivity of the hydroformylation reaction of high-carbon olefins is significantly improved, the isomerization side reaction of the high-carbon olefins is reduced, the normal-to-isomer ratio of the high-carbon aldehydes in the product is significantly improved, and the yield of the high-carbon aldehydes, especially the yield of the linear high-carbon aldehydes, is improved. DETAILED DESCRIPTION

[0046] The present invention will be further described below in conjunction with specific embodiments, but they do not constitute any limitation to the present invention.

[0047] The sources of materials in the following examples are as follows:

[0048] 1. The phosphoramidite ligand having the structure of formula (IV') was purchased from J&K, cas: 247130-62-7;

[0049] 2. The bisphosphite ligand with the structure of formula (I") was purchased from J&K, cas: 121627-17-6;

[0050] 3. The bidentate phosphine ligand having the structure of formula (III') was purchased from J&K, cas: 111982-81-1;

[0051] 4. The bisphosphite ligand having the structure of formula (I') was prepared in the laboratory by the following method:

[0052] Step 1: Oxidative coupling of 2,4-di-tert-butylphenol

[0053]

[0054] Add solid NaOH, sodium dodecyl sulfate, deionized water, and di-tert-butylphenol to a three-necked flask and heat to 80 degrees Celsius. Slowly drop 30% hydrogen peroxide into the above solution and react at 90 degrees Celsius for 1 hour. Wash the filter cake with acetonitrile and filter again, repeat three times. The white solid product is the target product.

[0055] Step 2: Phosphinate

[0056]

[0057] Add biphenol and phosphorus trichloride to a three-necked flask and react for 1 hour. Then add tetrahydrofuran and heat to 60 degrees Celsius. Dissolve the product prepared in step 1 in 2-methyltetrahydrofuran and add it to the above solution and react for 1 hour. Wash the crude product with acetonitrile and filter it, repeat three times, and then wash it with methanol twice to obtain a white solid target product.

[0058] Example 1

[0059] A toluene solution containing 50 mmol / L triphenylphosphine and 0.5 mmol / L acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction liquid was detected by gas chromatography, and the conversion rate of 1-octene was 48.5%, the yield of total nonanal was 39%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 3.4, the selectivity of total nonanal was 80.41%, the selectivity of normal nonanal was 62.14%, and the yield of 2-octene was 2.6%.

[0060] Example 2

[0061] A toluene solution containing 3 mmol / L of a bisphosphite ligand having the structure of formula (III') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high-pressure reactor with stirring and stirred for complexation for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction liquid was detected by gas chromatography, and the conversion rate of 1-octene was 46%, the yield of total nonanal was 30.2%, the normal aldehyde / isomerized aldehyde (normal-iso ratio) was 95.1, the selectivity of total nonanal was 48.21%, the selectivity of normal nonanal was 46.97%, and the yield of 2-octene was 6.3%.

[0062] Example 3

[0063] A toluene solution containing 3 mmol / L of a bisphosphite ligand having the structure of formula (I') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 97.08%, the yield of total nonanal was 6.6%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 16, the selectivity of total nonanal was 6.8%, the selectivity of normal nonanal was 6.4%, and the yield of 2-octene was 66%.

[0064] Example 4

[0065] A toluene solution containing 3 mmol / L of a bisphosphite ligand having the structure of formula (IV') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction liquid was detected by gas chromatography, and the conversion rate of 1-octene was 97.37%, the yield of total nonanal was 20.78%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 133, the selectivity of total nonanal was 21.34%, the selectivity of normal nonanal was 21.18%, and the yield of 2-octene was 44.54%.

[0066] Example 5

[0067] A toluene solution containing 3 mmol / L of a bisphosphite ligand having the structure of formula (I") and 0.5 mmol / L of acetylacetonadicarbonylrhodium was added to a 100 mL high-pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction liquid was detected by gas chromatography, and the conversion rate of 1-octene was 91.8%, the yield of total nonanal was 31.4%, the normal aldehyde / isomerized aldehyde (normal-iso ratio) was 2.82, the selectivity of total nonanal was 34.2%, the selectivity of normal nonanal was 25.25%, and the yield of 2-octene was 39.7%.

[0068] Example 6

[0069] A toluene solution containing 3 mmol / L of a bisphosphite ligand having the structure of formula (IV'), 3 mmol / L of triphenylphosphine and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction liquid was detected by gas chromatography, and the conversion rate of 1-octene was 78.4%, the total nonanal yield was 37.8%, all of which were n-nonanal, the total nonanal selectivity was 48.21%, the n-nonanal selectivity was 48.21%, and the 2-octene yield was 17.8%.

[0070] Example 7

[0071] A toluene solution containing 3 mmol / L of a bisphosphite ligand having the structure of formula (I'), 3 mmol / L of triphenylphosphine and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 55%, the yield of total nonanal was 35%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 115, the selectivity of total nonanal was 63.64%, the selectivity of normal nonanal was 63.09%, and the yield of 2-octene was 10.8%.

[0072] Embodiment 1-7 compares the reaction effect of different ligands. When using rhodium / monodentate phosphine ligand as catalyst, the conversion rate of olefin is low, the total selectivity of high carbon aldehyde is high, the positive iso ratio is low, and olefin isomerization is rare. In the high carbon olefin hydroformylation reaction, when using rhodium / bisphosphite ligand or rhodium / phosphoramidite ligand as catalyst, olefin is almost completely converted, the total selectivity of high carbon aldehyde is low, the positive iso ratio is high, and olefin isomerization is serious. In the high carbon olefin hydroformylation reaction, when using rhodium / bisphosphite ligand or rhodium / phosphoramidite ligand and monodentate phosphine ligand composition as catalyst, olefin is almost completely converted, the total selectivity of high carbon aldehyde and linear high carbon aldehyde selectivity are significantly improved, and olefin isomerization is significantly reduced. The preferred bisphosphite of the present invention has the bisphosphite ligand of formula (I') structure to carry out subsequent embodiments.

[0073] Example 8

[0074] Add a toluene solution containing 0.5mmol / L acetylacetonato dicarbonyl rhodium into a stirred 100mL autoclave and stir for several minutes. Add 14g of 1-octene into the autoclave. Replace the air in the autoclave with synthesis gas 6 times. Heat to 90°C, introduce synthesis gas, keep the pressure in the autoclave constant at 1MPa, react for 1h, stop the reaction, and cool the autoclave in an ice-water bath. The reaction liquid was detected by gas chromatography, and the conversion rate of 1-octene was 96.85%, the yield of total nonanal was 4.82%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 1.72, the selectivity of total nonanal was 4.98%, the selectivity of normal nonanal was 3.15%, and the yield of 2-octene was 72.71%.

[0075] Example 9

[0076] A toluene solution containing 0.5 mmol / L of a bisphosphite ligand having the structure of formula (I') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 98.38%, the yield of total nonanal was 36.22%, the normal aldehyde / isomerized aldehyde (normal-iso ratio) was 0.91, the selectivity of total nonanal was 36.82%, the selectivity of normal nonanal was 17.59%, and the yield of 2-octene was 53.97%.

[0077] Example 10

[0078] A toluene solution containing 1 mmol / L of a bisphosphite ligand having the structure of formula (I') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 98.71%, the yield of total nonanal was 32.07%, the normal aldehyde / isomerized aldehyde (normal-iso ratio) was 0.89, the selectivity of total nonanal was 32.49%, the selectivity of normal nonanal was 15.31%, and the yield of 2-octene was 46.49%.

[0079] Embodiment 11

[0080] A toluene solution containing 1.5 mmol / L of a bisphosphite ligand having the structure of formula (I') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 97.36%, the yield of total nonanal was 11.87%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 16.2, the selectivity of total nonanal was 12.19%, the selectivity of normal nonanal was 11.48%, and the yield of 2-octene was 76.58%.

[0081] Example 12

[0082] A toluene solution containing 2 mmol / L of a bisphosphite ligand having the structure of formula (I') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 97.42%, the yield of total nonanal was 12.16%, the normal aldehyde / isomerized aldehyde (normal-iso ratio) was 16.37, the selectivity of total nonanal was 12.48%, the selectivity of normal nonanal was 11.76%, and the yield of 2-octene was 76.08%.

[0083] Embodiment 13

[0084] A toluene solution containing 3 mmol / L of a bisphosphite ligand having the structure of formula (I') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 97.58%, the yield of total nonanal was 10.09%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 13, the selectivity of total nonanal was 10.34%, the selectivity of normal nonanal was 9.6%, and the yield of 2-octene was 76.85%.

[0085] Embodiment 14

[0086] A toluene solution containing 4.5 mmol / L of a bisphosphite ligand having the structure of formula (I') and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 97.56%, the yield of total nonanal was 12.84%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 14.3, the selectivity of total nonanal was 13.16%, the selectivity of normal nonanal was 12.3%, and the yield of 2-octene was 71.98%.

[0087] Examples 8-14 compare the effects of different ratios of the bisphosphite ligand having the structure of formula (I') to rhodium concentration on the reaction, and the subsequent examples are preferably carried out with a ratio of the bisphosphite ligand having the structure of formula (I') to rhodium concentration of 3:1.

[0088] Embodiment 15

[0089] A toluene solution containing 1.5 mmol / L of a bisphosphite ligand having the structure of formula (I'), 3 mmol / L of triphenylphosphine and 0.5 mmol / L of acetylacetone dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 93.56%, the yield of total nonanal was 45.95%, the normal aldehyde / isomerized aldehyde (normal-iso ratio) was 65.31, the selectivity of total nonanal was 49.12%, the selectivity of normal nonanal was 48.37%, and the yield of 2-octene was 32.92%.

[0090] Example 16

[0091] A toluene solution containing 1.5 mmol / L of a bisphosphite ligand having the structure of formula (I'), 2 mmol / L of triphenylphosphine and 0.5 mmol / L of acetylacetone dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 96.75%, the yield of total nonanal was 45.82%, the ratio of normal aldehyde to isomeric aldehyde (normal-iso ratio) was 66.28, the selectivity of total nonanal was 47.36%, the selectivity of normal nonanal was 46.66%, and the yield of 2-octene was 25.89%.

[0092] Embodiment 17

[0093] A toluene solution containing 1.5 mmol / L of a bisphosphite ligand having the structure of formula (I'), 1.5 mmol / L of triphenylphosphine and 0.5 mmol / L of acetylacetonato dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 96.94%, the yield of total nonanal was 46.7%, the normal aldehyde / isomerized aldehyde (normal-iso ratio) was 62.11, the selectivity of total nonanal was 48.17%, the selectivity of normal nonanal was 47.41%, and the yield of 2-octene was 35.66%.

[0094] Embodiment 18

[0095] A toluene solution containing 1.5 mmol / L of a bisphosphite ligand having the structure of formula (I'), 0.5 mmol / L of triphenylphosphine and 0.5 mmol / L of acetylacetone dicarbonyl rhodium was added to a 100 mL high pressure reactor with stirring and the complexation was stirred for several minutes. 14 g of 1-octene was added to the reactor. The air in the reactor was replaced with synthesis gas 6 times. The temperature was raised to 90°C, synthesis gas was introduced, and the pressure in the reactor was kept constant at 1 MPa. The reaction was continued for 1 hour, the reaction was stopped, and the reactor was cooled in an ice-water bath. The reaction solution was detected by gas chromatography, and the conversion rate of 1-octene was 97.03%, the yield of total nonanal was 13.12%, the normal aldehyde / isomerized aldehyde (normal-iso ratio) was 17.64, the selectivity of total nonanal was 13.53%, the selectivity of normal nonanal was 12.8%, and the yield of 2-octene was 71.98%.

[0096] Examples 15-18 compare the effects of different concentration ratios of the bisphosphite ligand having the structure of formula (I'), triphenylphosphine and rhodium on the reaction, and preferably the concentration ratio of the bisphosphite ligand having the structure of formula (I'), triphenylphosphine and rhodium is 3:3:1.

[0097] Any numerical value mentioned in the present invention, if there is only an interval of two units between any minimum value and any maximum value, includes all values ​​from the minimum value to the maximum value each time increasing by one unit. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, time, etc. is declared to be 50-90, in this specification it means that 51-89, 52-88... and 69-71 and 70-71 are specifically listed. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 can be appropriately considered as a unit. These are just some specially specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0098] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A method for producing high carbon aldehydes, characterized in that: The steps include: S101: firstly dissolving a composition including a rhodium catalyst precursor, a monodentate phosphine ligand and a phosphoramidite ligand to obtain a catalyst system; S102: reacting high carbon number olefins, carbon monoxide and hydrogen under the action of the catalyst system to obtain high carbon aldehydes; Wherein, the rhodium catalyst precursor is acetylacetonato dicarbonyl rhodium; The monodentate phosphine ligand is triphenylphosphine; The phosphoramidite ligand has a structure of formula (IV'), The molar ratio of the phosphoramidite ligand, the monodentate phosphine ligand and the rhodium catalyst precursor is 3:3:0.5; The high carbon number olefin has a structure of formula (V): Wherein, R4 and R5 are independently selected from hydrogen, an alkyl group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms, and the aryl group having 6-20 carbon atoms has 0-5 substituents, and the sum of the carbon atoms of R4 and R5 is not less than 4; the aryl substituent is at least selected from nitro, halogen or an alkyl group having 1-4 carbon atoms.

2. The method for producing high carbon aldehydes according to claim 1, characterized in that In the step S102, the reaction temperature is 50°C-150°C, the reaction pressure is 0.5MPa-3MPa, and the molar ratio of the hydrogen to the carbon monoxide is 1-4:

1.

3. The method for producing high carbon aldehydes according to claim 2, characterized in that: In the step S102, the reaction temperature is 70°C-130°C, the reaction pressure is 1MPa-2MPa, and the molar ratio of the hydrogen to the carbon monoxide is 2-3:

1.

4. The method for producing high carbon aldehyde according to any one of claims 1 to 3, characterized in that: The solvent for dissolving the catalyst system is at least one selected from toluene, xylene, nonanal and decane.

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