CN114433240A - Method for producing high-carbon aldehyde by using high-carbon olefin - Google Patents

Method for producing high-carbon aldehyde by using high-carbon olefin Download PDF

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CN114433240A
CN114433240A CN202011203939.XA CN202011203939A CN114433240A CN 114433240 A CN114433240 A CN 114433240A CN 202011203939 A CN202011203939 A CN 202011203939A CN 114433240 A CN114433240 A CN 114433240A
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carbon
aldehyde
ligand
rhodium
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李爽
随山红
董岩
朱丽琴
包天舒
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

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Abstract

The invention provides a method for producing high-carbon aldehyde by using high-carbon olefin, which comprises the following steps: dissolving a rhodium catalyst precursor, a bisphosphite ligand and a monodentate phosphine ligand to obtain a catalyst system; and (3) preparing high carbon aldehyde from high carbon number olefin, carbon monoxide and hydrogen under the catalytic action of the catalyst system. According to the method for producing the high-carbon aldehyde, the monodentate phosphine ligand, the diphosphite ligand and the old catalyst precursor are reasonably proportioned to obtain the catalyst system with a proper active center concentration, the high-carbon aldehyde is prepared through hydroformylation under the conditions of carbon monoxide and hydrogen, the selectivity of hydroformylation of high-carbon olefin is obviously improved, the isomerization side reaction of the high-carbon olefin is reduced, the normal-iso ratio of the high-carbon aldehyde in the product is obviously improved, and the yield of the high-carbon aldehyde, especially the yield of linear high-carbon aldehyde, is improved.

Description

Method for producing high-carbon aldehyde by using high-carbon olefin
Technical Field
The invention designs a method for producing high-carbon aldehyde by using high-carbon olefin.
Background
Chain monohydric alcohols containing six or more carbon atoms are collectively called higher alcohols, and higher alcohols are an important group of base materials and can be used for the synthesis of various fine chemicals, such as plasticizers, surfactants, antifoaming agents, detergents, stabilizers, and the like. The downstream products of the method are widely applied to the fields of food, medicine, agriculture, paper making, mechanical mining, daily chemical industry, petrochemical industry and the like. Higher alcohols can be prepared by hydrogenation of the corresponding higher aldehydes, which can be prepared by hydroformylation of higher olefins.
The hydroformylation reaction system requires a certain gas pressure, and the aldehyde in the product is usually in the form of linear aldehyde and branched aldehyde. Generally, the linear aldehydes in the product have much higher market value than branched aldehydes. The linear high carbon alcohol ester has good intermiscibility with resin, and greatly improves the processing performance of the product. The product has good appearance, good resistance to adverse effects of external environment, good fracture resistance, long service life, good insulation property, low environmental pollution, and no precipitation of plasticizer. Therefore, in order to better describe the linear selectivity of the product when researching the hydroformylation reaction, the concept of positive-to-differential ratio (n: i) is introduced, and the amount of the linear product is one of important indexes for measuring the quality of the hydroformylation reaction.
In the hydroformylation reaction, the difficulty of the reaction is greatly influenced by the structure of the olefin, the olefin with smaller steric hindrance is easier to react, and the reaction rate of the olefin with long carbon chain and the internal olefin is lower. The homogeneous catalysis of high carbon olefin hydroformylation technology mainly focuses on the development of catalysts, and focuses on various ligands, such as monophosphites, monoalkyl phosphides, diphosphites, dialkyl phosphides, diphosphonites and ionic ligands. The problems of conversion and selectivity not being able to reach simultaneously high levels are common due to the low reaction rate and the severe isomerization of higher olefins.
Disclosure of Invention
The method for producing the high-carbon aldehyde can effectively reduce the side reaction of isomerization of the high-carbon olefin, the high-carbon aldehyde normal-to-iso ratio can even reach more than 95, the yield can reach more than 45 percent, and particularly the yield of the linear high-carbon aldehyde is improved.
To achieve the object of the present invention, the present invention provides a method for producing a high-carbon aldehyde, comprising the steps of:
s101: dissolving a rhodium catalyst precursor, a bisphosphite ligand and a monodentate phosphine ligand to obtain a catalyst system;
s102: and (3) preparing high carbon aldehyde from high carbon number olefin, carbon monoxide and hydrogen under the catalytic action of the catalyst system.
In the present invention, the high-carbon olefin means an olefin having not less than 6 carbon atoms, and the high-carbon aldehyde means an aldehyde having not less than 6 carbon atoms.
According to the method for producing the high-carbon aldehyde, the monodentate phosphine ligand, the diphosphite ligand and the old catalyst precursor are reasonably proportioned to obtain the catalyst system with a proper active center concentration, the high-carbon aldehyde is prepared through hydroformylation under the conditions of carbon monoxide and hydrogen, the selectivity of hydroformylation of high-carbon olefin is obviously improved, the isomerization side reaction of the high-carbon olefin is reduced, the normal-iso ratio of the high-carbon aldehyde in the product is obviously improved, and the yield of the high-carbon aldehyde, especially the yield of linear high-carbon aldehyde, is improved.
The inventor researches and discovers that by controlling proper reaction conditions, the occurrence of side reactions can be further reduced, and the normal-to-iso ratio of the high-carbon aldehyde in the product and the yield of the linear high-carbon aldehyde can be improved.
As a specific embodiment of the present invention, the reaction temperature of step S102 is 50 ℃ to 150 ℃, such as 80 ℃ to 120 ℃,50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃,100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃,150 ℃ and any combination thereof.
As a specific embodiment of the present invention, the reaction pressure of step S102 is in the range of 0.5MPa to 3MPa, such as 1.5MPa to 2.5MPa, 1MPa, 2MPa, 3MPa and any combination thereof.
In the present invention, the higher olefins have the structure of formula (i):
Figure BDA0002756398990000021
wherein R is4And R5Each independently selected from hydrogen, alkyl having 1 to 20 carbon atoms, or alkyl having 6 to 20 carbon atoms and said alkyl having 6 to 20 carbon atoms further having 0 to 5 aryl substituents thereon, and R4And R5The sum of the carbon atoms of (a) is not less than 4; preferably, the aryl substituents are selected from nitro, fluoro, chloro, bromo, methyl, ethyl, propyl and/or butyl.
As a specific embodiment of the present invention, the molar ratio of the bisphosphite ligand to the monodentate phosphine ligand may range from about 1:15 to about 25, such as 1:15,1:20,1:25, and any combination thereof.
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 in the range of about 1 to 200:1, such as 80 to 120:1,50:1,100:1,150:1,200:1, and any combination thereof.
The monodentate phosphine ligand of the present invention is not particularly limited, and is within the scope of the present invention as long as the present invention can be achieved. Specifically, in the present invention, the monodentate phosphine ligand has the structure of formula (ii):
Figure BDA0002756398990000031
wherein R is1、R2And R3Each independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl or cycloalkenyl groups having 5 to 20 carbon atoms, and aryl groups having 6 to 36 carbon atoms.
The rhodium catalyst precursor with a suitable concentration can improve the conversion rate of the high carbon number olefin, and specifically, in the present invention, the mass concentration of the rhodium catalyst precursor is about 0.01mmol/L to 5mmol/L, such as 1mmol/L,2mmol/L,3mmol/L,4mmol/L,5mmol/L and any combination thereof.
The present invention is not particularly limited in the selection of the rhodium catalyst precursor, and a rhodium catalyst precursor which can be applied to the present invention and can improve the yield of high carbon aldehydes is within the scope of the present invention. As a specific embodiment of the present invention, the rhodium catalyst precursor is selected from at least one of tris (triphenylphosphine) rhodium carbonyl hydride, tris (triphenylphosphine) rhodium chloride and rhodium acetylacetonate dicarbonyl, for example rhodium acetylacetonate dicarbonyl and/or tris (triphenylphosphine) rhodium carbonyl hydride.
In the present invention, the bisphosphite ligand has the structure of formula (III):
Figure BDA0002756398990000032
the rhodium catalyst precursor, the bisphosphite ligand and the monodentate phosphine ligand of the present invention may be commercially available or may be self-prepared in a laboratory, and the present invention is not particularly limited thereto.
The solvent selected in the step S101 is required to be able to dissolve the rhodium catalyst precursor, the bisphosphite, the monodentate phosphine ligand, and the high-carbon-number olefin well. As a specific embodiment of the present invention, in the step S101, the solvent dissolving the catalyst system is at least one selected from the group consisting of toluene, xylene, nonanal, and decane.
According to the method for producing the high-carbon aldehyde, the monodentate phosphine ligand, the diphosphite ligand and the old catalyst precursor are reasonably proportioned to obtain the catalyst system with a proper active center concentration, the high-carbon aldehyde is prepared through hydroformylation under the conditions of carbon monoxide and hydrogen, the selectivity of hydroformylation of high-carbon olefin is remarkably improved, the isomerization side reaction of the high-carbon olefin can be effectively reduced, the normal-to-iso ratio of the high-carbon aldehyde can even reach more than 95, the yield reaches more than 45%, and especially the yield of linear high-carbon aldehyde is improved.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
The bisphosphite ligands having the structure of formula (III) in the following examples were prepared as follows:
the method comprises the following steps: oxidative coupling of 2, 4-di-tert-butylphenol
Figure BDA0002756398990000041
Solid NaOH, sodium dodecyl sulfate, deionized water and di-tert-butylphenol are added into a three-neck flask and heated to 80 ℃. And slowly dropwise adding 30% hydrogen peroxide into the solution, and reacting for 1 hour at the temperature of 90 ℃. The filter cake was washed with acetonitrile and filtered again, which was repeated three times. The white solid product is obtained as the target product.
Step two: phosphonite esterification
Figure BDA0002756398990000051
Biphenol and phosphorus trichloride were added to a three-necked flask and reacted for 1 hour. Tetrahydrofuran was then added and heated to 60 degrees celsius. Dissolving the product prepared in the step one in 2-methyltetrahydrofuran, adding the solution, and reacting for 1 hour. And washing the crude product with acetonitrile, filtering, repeating for three times, and washing with methanol for two times to obtain a white solid target product.
[ example 1 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 50 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction solution was subjected to gas chromatography, and found that the conversion of 1-octene was 27.03%, the total nonanal yield was 11.39%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 112, the total nonanal selectivity was 42.14%, the n-nonanal selectivity was 41.77%, and the 2-octene yield was 7.51%.
[ example 2 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 70 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction liquid was subjected to gas chromatography, and the conversion of 1-octene was 90.33%, the total nonanal yield was 32.83%, the normal/iso-aldehyde (normal to iso ratio) was 55.6, the total nonanal selectivity was 36.34%, the n-nonanal selectivity was 35.7%, and the 2-octene yield was 39.18%.
[ example 3 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 80 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction solution was subjected to gas chromatography, and the conversion of 1-octene was 95.98%, the total nonanal yield was 46.23%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 69.69, the total nonanal selectivity was 48.17%, the n-nonanal selectivity was 47.49%, and the 2-octene yield was 34.67%.
[ example 4 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction solution was subjected to gas chromatography, and the conversion of 1-octene was 96.94%, the total nonanal yield was 46.7%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 62.11, the total nonanal selectivity was 48.17%, the n-nonanal selectivity was 47.41%, and the 2-octene yield was 35.66%.
[ example 5 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 100 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction solution was subjected to gas chromatography, and found that the conversion of 1-octene was 97.35%, the total nonanal yield was 35.63%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 41.95, the total nonanal selectivity was 36.63%, the n-nonanal selectivity was 35.77%, and the 2-octene yield was 46.68%.
[ example 6 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 120 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 1MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction liquid was subjected to gas chromatography, and the conversion of 1-octene was 98.12%, the total nonanal yield was 24.14%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 15.53, the total nonanal selectivity was 26.4%, the n-nonanal selectivity was 23.11%, and the 2-octene yield was 64.73%.
[ example 7 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the kettle constant at 0.5MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in ice-water bath. The reaction solution was subjected to gas chromatography, and the conversion of 1-octene was 97.06%, the total nonanal yield was 34.73%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 98, the total nonanal selectivity was 35.79%, the n-nonanal selectivity was 35.07%, and the 2-octene yield was 45.18%.
[ example 8 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 1.5MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in ice water bath. The reaction liquid was subjected to gas chromatography, and the conversion of 1-octene was 97.18%, the total nonanal yield was 28.78%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 31.78, the total nonanal selectivity was 29.58%, the n-nonanal selectivity was 28.68%, and the 2-octene yield was 49.3%.
[ example 9 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 2MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction solution was subjected to gas chromatography, and the conversion of 1-octene was 97.42%, the total nonanal yield was 27.72%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 31.4, the total nonanal selectivity was 28.44%, the n-nonanal selectivity was 27.56%, and the 2-octene yield was 49.35%.
[ example 10 ]
A toluene solution in which 1.5mmol/L of ligand (III), 1.5mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the mixture was complexed for several minutes with stirring. 14g of 1-octene was added to the kettle. The air in the kettle was replaced with synthesis gas 6 times. Heating to 90 ℃, introducing synthesis gas, keeping the pressure in the reaction kettle constant at 3MPa, reacting for 1 hour, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction liquid was subjected to gas chromatography, and the conversion of 1-octene was 96.48%, the total nonanal yield was 28.32%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 27.3, the total nonanal selectivity was 29.35%, the n-nonanal selectivity was 28.32%, and the 2-octene yield was 46.19%.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (9)

1. A method for producing a high-carbon aldehyde, comprising the steps of:
s101: dissolving a rhodium catalyst precursor, a bisphosphite ligand and a monodentate phosphine ligand to obtain a catalyst system;
s102: and (3) preparing high carbon aldehyde from high carbon number olefin, carbon monoxide and hydrogen under the catalytic action of the catalyst system.
2. The method for producing higher aldehydes as claimed in claim 1, wherein the reaction temperature of the step S102 is 50 ℃ to 150 ℃; preferably, the reaction temperature of the step S102 is 80-120 ℃; preferably, the reaction temperature of the step S102 is 90 ℃; and/or the presence of a gas in the atmosphere,
the reaction pressure is 0.5MPa-3 MPa; preferably, the reaction pressure is 1.5MPa-2.5 MPa; preferably, the reaction pressure is 1 MPa.
3. The method for producing higher aldehydes according to claim 1 or 2, wherein the higher olefins have the structure of formula (i):
Figure FDA0002756398980000011
wherein R is4And R5Each independently selected from hydrogen, alkyl having 1 to 20 carbon atoms, or alkyl having 6 to 20 carbon atoms and said alkyl having 6 to 20 carbon atoms further having 0 to 5 aryl substituents thereon, and R4And R5The sum of the carbon atoms of (a) is not less than 4; preferably, the aryl substituents are selected from nitro, fluoro, chloro, bromo, methyl, ethyl, propyl and/or butyl.
4. The process for producing a high-carbon aldehyde according to any one of claims 1 to 3, wherein the molar ratio of the bisphosphite ligand to the monodentate phosphine ligand is from 1:15 to 25; preferably, the molar ratio of the bisphosphite ligand to the monodentate phosphine ligand is 1: 20; and/or the presence of a gas in the gas,
the molar ratio of the sum of the bisphosphite ligand and the monodentate phosphine ligand to the rhodium catalyst precursor is 1-200: 1; preferably, the molar ratio of the sum of the bisphosphite ligand and the monodentate phosphine ligand to the rhodium catalyst precursor is from 80 to 120: 1.
5. The method for producing a high-carbon aldehyde according to any one of claims 1 to 4, wherein the monodentate phosphine ligand has the structure of formula (II):
Figure FDA0002756398980000021
wherein R is1、R2And R3Each independently selected from the group consisting of 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.
6. The method for producing higher aldehydes according to any one of claims 1 to 5, wherein the molar concentration of the rhodium catalyst precursor is 0.01mmol/L to 5 mmol/L.
7. The method for producing high carbon aldehydes according to any one of claims 1 to 6, wherein the rhodium catalyst precursor is at least one member selected from the group consisting of tris (triphenylphosphine) rhodium carbonyl hydride, tris (triphenylphosphine) rhodium chloride and rhodium acetylacetonate dicarbonyl; preferably, the rhodium catalyst precursor is selected from rhodium acetylacetonate dicarbonyl and/or tris (triphenylphosphine) rhodium carbonyl hydride.
8. The method according to any one of claims 1 to 7, wherein the bisphosphite ligand has the structure of formula (III):
Figure FDA0002756398980000022
9. the method for producing high-carbon aldehydes as claimed in any one of claims 1 to 8, wherein the solvent for dissolving the catalyst system in step S101 is at least one selected from the group consisting of toluene, xylene, nonanal and decane.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115290789A (en) * 2022-08-04 2022-11-04 鲁西催化剂有限公司 Method for evaluating activity of rhodium-containing catalyst working solution

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364950A (en) * 1992-09-29 1994-11-15 Union Carbide Chimicals & Plastics Technology Corporation Process for stabilizing phosphite ligands in hydroformylation reaction mixtures
RU2352552C1 (en) * 2007-11-01 2009-04-20 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Catalyst of olefins c2-c20 hydroformilation, method of obtaining it (versions) and method of obtaining aldehydes c3-c21
CN101681776A (en) * 2007-04-09 2010-03-24 Lg化学株式会社 Catalyst composition including phosphite ligands and hydroformylation method using the same
US20110144392A1 (en) * 2008-08-19 2011-06-16 Brammer Michael A Hydroformylation process using a symmetric bisphosphite ligand for improved control over product isomers
CN102266796A (en) * 2006-12-22 2011-12-07 中国科学院上海有机化学研究所 Propylene hydroformylation catalyzing system and method
CN102911021A (en) * 2012-11-12 2013-02-06 青岛三力本诺化学工业有限公司 Method for preparing aldehyde through linear chain olefin hydroformylation
CN103990495A (en) * 2014-04-24 2014-08-20 上海华谊（集团）公司 Olefin hydroformylation catalyst
CN104058944A (en) * 2014-04-24 2014-09-24 上海华谊（集团）公司 Method for preparing aldehyde through alkene hydroformylation reaction
CN104370718A (en) * 2014-11-07 2015-02-25 中国海洋石油总公司 Method for preparing valeraldehyde by etherified C4 hydroformylation
CN105566081A (en) * 2015-12-15 2016-05-11 上海华谊（集团）公司 Method for preparing aldehyde through olefin hydroformylation
CN106000470A (en) * 2016-06-06 2016-10-12 四川大学 Catalyst used for hydroformylation of olefin, and preparation method and application thereof
CN106431869A (en) * 2016-10-09 2017-02-22 上海华谊（集团）公司 Method for producing aldehydes through olefin hydroformylation reaction
CN111348995A (en) * 2020-04-14 2020-06-30 万华化学集团股份有限公司 Method for preparing aldehyde by olefin hydroformylation
CN111606792A (en) * 2020-06-29 2020-09-01 成都欣华源科技有限责任公司 Method for preparing high-carbon aldehyde

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364950A (en) * 1992-09-29 1994-11-15 Union Carbide Chimicals & Plastics Technology Corporation Process for stabilizing phosphite ligands in hydroformylation reaction mixtures
CN102266796A (en) * 2006-12-22 2011-12-07 中国科学院上海有机化学研究所 Propylene hydroformylation catalyzing system and method
CN101681776A (en) * 2007-04-09 2010-03-24 Lg化学株式会社 Catalyst composition including phosphite ligands and hydroformylation method using the same
RU2352552C1 (en) * 2007-11-01 2009-04-20 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Catalyst of olefins c2-c20 hydroformilation, method of obtaining it (versions) and method of obtaining aldehydes c3-c21
US20110144392A1 (en) * 2008-08-19 2011-06-16 Brammer Michael A Hydroformylation process using a symmetric bisphosphite ligand for improved control over product isomers
CN102911021A (en) * 2012-11-12 2013-02-06 青岛三力本诺化学工业有限公司 Method for preparing aldehyde through linear chain olefin hydroformylation
CN103990495A (en) * 2014-04-24 2014-08-20 上海华谊（集团）公司 Olefin hydroformylation catalyst
CN104058944A (en) * 2014-04-24 2014-09-24 上海华谊（集团）公司 Method for preparing aldehyde through alkene hydroformylation reaction
CN104370718A (en) * 2014-11-07 2015-02-25 中国海洋石油总公司 Method for preparing valeraldehyde by etherified C4 hydroformylation
CN105566081A (en) * 2015-12-15 2016-05-11 上海华谊（集团）公司 Method for preparing aldehyde through olefin hydroformylation
CN106000470A (en) * 2016-06-06 2016-10-12 四川大学 Catalyst used for hydroformylation of olefin, and preparation method and application thereof
CN106431869A (en) * 2016-10-09 2017-02-22 上海华谊（集团）公司 Method for producing aldehydes through olefin hydroformylation reaction
CN111348995A (en) * 2020-04-14 2020-06-30 万华化学集团股份有限公司 Method for preparing aldehyde by olefin hydroformylation
CN111606792A (en) * 2020-06-29 2020-09-01 成都欣华源科技有限责任公司 Method for preparing high-carbon aldehyde

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘雯静;袁茂林;付海燕;李瑞祥;陈华;: "铑/双膦配体催化均相内烯烃氢甲酰化反应的研究进展", 催化学报, no. 06 *
张之翔;曾永康;黄琼淋;张宇;高武;: "异丁烯氢甲酰化合成异戊醛的研究", 应用化工, no. 03 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115290789A (en) * 2022-08-04 2022-11-04 鲁西催化剂有限公司 Method for evaluating activity of rhodium-containing catalyst working solution

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