CN114436791A - Method for producing high-carbon aldehyde by multi-ligand composite catalyst - Google Patents

Method for producing high-carbon aldehyde by multi-ligand composite catalyst Download PDF

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CN114436791A
CN114436791A CN202011204844.XA CN202011204844A CN114436791A CN 114436791 A CN114436791 A CN 114436791A CN 202011204844 A CN202011204844 A CN 202011204844A CN 114436791 A CN114436791 A CN 114436791A
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carbon
ligand
aldehyde
rhodium
carbon atoms
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C45/505—Asymmetric hydroformylation
    • 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
    • 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
    • B01J31/20—Carbonyls
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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

Abstract

The invention provides a method for producing high-carbon aldehyde by using a multi-ligand composite catalyst, which comprises 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; and (3) reacting the high carbon number olefin, carbon monoxide and hydrogen under the action of the catalyst system to obtain the high carbon number aldehyde. According to the method for producing the high-carbon aldehyde, the catalyst system with a proper active center concentration is obtained by reasonably proportioning the rhodium catalyst precursor, the monodentate phosphine ligand, the bidentate phosphine ligand, the diphosphite ligand and the phosphite ligand, 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 multi-ligand composite catalyst
Technical Field
The invention relates to a method for producing high-carbon aldehyde by using a multi-ligand composite catalyst.
Background
Hydroformylation is an important route to produce aldehydes or alcohols. Since the discovery of the German scientist Roelen in 1938, the technology is still one of the most important organic chemical production processes today for more than 70 years. Currently, over ten hydroformylation processes (also called oxo process) are adopted in industrial production, and most industrial plants take aldehydes and alcohols as main products.
The preparation of high-carbon alditol by hydroformylation of high-carbon olefin is an industrial production technology with higher comprehensive economic indexes, but the aldehyde and alcohol production technology mastered in China still concentrates on products such as C4 alcohol, C8 alcohol and the like, while high-carbon alcohol products with increasing demand year by year are still in the starting stage in China and have no high-carbon olefin hydroformylation technology with independent intellectual property rights. Currently, the global production of isononyl alcohol is mainly controlled by a few manufacturers, including Exxon Mobil, Oxeno, BASF, Kyowa Yuka, japan and taiwan southern plastic, china, wherein the production capacities of Exxon Mobil and Oxeno account for 34.6% and 28.4% of the global total production capacity, respectively, and a conventional hydroformylation process using cobalt as a catalyst is used.
The cobalt catalysis process still plays a significant role in the current hydroformylation of olefins with high carbon number, but the comprehensive economic and technical indexes of the cobalt catalysis process are far inferior to those of the rhodium catalysis process due to the factors of harsh reaction conditions, poor selectivity, more side reactions, high energy consumption, complex cobalt recovery process and the like. Research into hydroformylation of high carbon number olefins using rhodium catalysts has therefore been ongoing, mainly proceeding from two aspects: on one hand, a new rhodium catalyst of the phosphine ligand is developed from a homogeneous catalysis system, so that the catalyst has higher catalytic activity and better stability; on the other hand, the problem of water solubility of the high carbon number olefin is solved and a new two-phase catalytic system is developed from the two-phase catalytic system. The reaction activity of the two-phase catalytic system is inferior to that of the homogeneous catalytic system, particularly for high-carbon-number olefins with low water solubility, the hydroformylation is difficult to carry out due to the limitation of mass transfer, and the reaction activity of the two-phase catalytic system is lower. Thus, homogeneous catalytic systems remain a major concern for the hydroformylation of higher carbon number olefins.
The homogeneous catalysis of the hydroformylation of high carbon number olefins mainly focuses on the development of catalysts, and the emphasis is on various ligands, such as monophosphites, monoalkyl phosphides, diphosphites, dialkyl phosphides, diphosphonite amines 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 the high carbon number olefins.
Disclosure of Invention
The invention aims to solve the technical problem that the conversion rate and the selectivity can not reach higher levels at the same time in the prior art because the reaction rate of high-carbon-number olefins is low and the isomerization is serious. The method can reduce the isomerization degree of the olefin in the reaction process of the high carbon number olefin and improve the yield of the high carbon number aldehyde.
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: 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;
s102: and (3) reacting the high carbon number olefin, carbon monoxide and hydrogen under the action of the catalyst system to obtain the high carbon number aldehyde.
The method for producing the high-carbon aldehyde obtains a catalyst system with proper active center concentration by reasonably proportioning the rhodium catalyst precursor, the monodentate phosphine ligand, the bidentate phosphine ligand, the diphosphite ligand and the phosphite ligand, prepares the high-carbon aldehyde through hydroformylation reaction under the condition of carbon monoxide and hydrogen, obviously improves the selectivity of the hydroformylation reaction of the high-carbon olefin, reduces the side reaction of isomerization of the high-carbon olefin, obviously improves the normal-iso ratio of the high-carbon aldehyde in the product, and improves the yield of the high-carbon aldehyde, particularly the yield of linear high-carbon aldehyde.
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.
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 1 to 200:1, for example 30 to 170:1,50 to 150:1,80 to 120:1, 1:1,50:1,100:1,150:1,200:1, and any combination thereof. The ratio of the bidentate phosphine ligand, the phosphite ester ligand and the phosphite ester ligand is not particularly limited in the present invention, and is within the scope of the present invention as long as the present invention can be achieved.
Preferably, the molar concentration of the rhodium catalyst precursor is in the range of 0.01mmol/L to 5mmol/L, such as 1mmol/L to 4mmol/L,2mmol/L to 3mmol/L,1mmol/L,2mmol/L,3mmol/L,4mmol/L, 5mmol/L and any combination thereof.
As a specific embodiment of the present invention, the higher olefin has the structure of formula (v):
Figure BDA0002756668150000031
wherein R is4And R5Each independently selected from hydrogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms, and said aryl having 6 to 20 carbon atoms has 0 to 5 substituents thereon, and R4And R5The sum of the numbers of carbon atoms is not less than 4.
Preferably, the aryl substituent is at least one selected from nitro, halogen or alkyl having 1 to 4 carbon atoms, such as fluorine, bromine, chlorine, methyl, ethyl, propyl, butyl, and the like.
The inventor researches and discovers that the isomerization side reaction of the high-carbon olefin can be reduced, the normal-iso ratio of the high-carbon aldehyde in the product can be obviously improved, and the yield of the high-carbon aldehyde, especially the yield of linear high-carbon aldehyde, can be improved by controlling proper reaction conditions and raw material proportion.
As a specific embodiment of the present invention, in the step S102, the reaction temperature is in a range of 50 ℃ to 150 ℃, for example, 70 ℃ to 130 ℃, 90 ℃ to 110 ℃,50 ℃,100 ℃,150 ℃, and any combination thereof; the reaction pressure is in the range of 0.5MPa to 3MPa, such as 1MPa to 2MPa, 1MPa, 2MPa, 3MPa and any combination thereof.
As a specific embodiment of the present invention, the hydrogen gas (H)2) The molar ratio to the carbon monoxide (CO) is in the range of 1-4:1, such as 2-3:1, 1:1,2:1,3:1,4:1, and any combination thereof.
As a particular embodiment of the present invention, the bisphosphite ligand has the structure of formula (I):
Figure BDA0002756668150000032
wherein X is selected from C6-C28 organic divalent bridged arylene; y is1、Y2、Z1、Z2Each independently selected from one of hydrogen, tertiary butyl or methoxy.
Preferably, X is at least one selected from 1,1 '-biphenyl-2, 2' diyl, 3 '-bis-tert-butyl-5, 5' -bismethoxy-1, 1 '-biphenyl-2, 2' -diyl, 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- (p) xanthene-4, 5-diyl;
q is a single bond and/or a vacant bond for connecting two adjacent benzene rings, namely in the structure shown in the formula (I), the two adjacent benzene rings can be connected through one single bond or can be a vacant bond, namely the two adjacent benzene rings can also be connected without the single bond.
For example, in the present invention, the bisphosphite ligand may have the structure of formula (I ') or (I'):
Figure BDA0002756668150000041
as a particular embodiment of the invention, the monodentate phosphine ligand has the structure of formula (II):
Figure BDA0002756668150000042
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.
As a particular embodiment of the invention, the bidentate phosphine ligand has the structure of formula (iii):
Figure BDA0002756668150000051
wherein X is selected from organic divalent bridged arylenes of C6-C28.
Preferably, X is selected from one of 1,1 '-biphenyl-2, 2' diyl, 3 '-bis-tert-butyl-5, 5' -bismethoxy-1, 1 '-biphenyl-2, 2' -diyl, 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- (p) xanthene-4, 5-diyl.
R1、R2、R3And R4Each 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.
For example, the bidentate phosphine ligand may be of formula (iii'):
Figure BDA0002756668150000052
as a specific embodiment of the present invention, the phosphoramidite ligand has the structure of formula (IV):
Figure BDA0002756668150000053
wherein R is1At least one selected from phenyl, N-indolyl or N-carbazolyl, R2At least one selected from hydrogen, carbomethoxy, carbethoxy, cyano, halogen, n-butyl, methyl, methoxy, ethyl, ethoxy or trifluoromethyl.
For example, the phosphoramidite ligand can be of formula (iv'):
Figure BDA0002756668150000061
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 carbon aldehyde is within the scope of the present invention. As a specific embodiment of the present invention, the rhodium catalyst precursor is at least one selected from the group consisting of tris (triphenylphosphine) carbonylrhodium hydride, tris (triphenylphosphine) chlororhodium and rhodium acetylacetonate dicarbonyl; preferably, the rhodium catalyst precursor is rhodium tris (triphenylphosphonium) carbonyl hydride.
As a specific embodiment of the present invention, the solvent selected in the step S101 is required 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 the step S101, the solvent dissolving the catalyst system is at least one selected from the group consisting of toluene, xylene, nonanal, and decane.
The method for producing the high-carbon aldehyde obtains a catalyst system with proper active center concentration by reasonably proportioning the rhodium catalyst precursor, the monodentate phosphine ligand, the bidentate phosphine ligand, the diphosphite ligand and the phosphite ligand, prepares the high-carbon aldehyde through hydroformylation reaction under the condition of carbon monoxide and hydrogen, obviously improves the selectivity of the hydroformylation reaction of the high-carbon olefin, reduces the side reaction of isomerization of the high-carbon olefin, obviously improves the normal-iso ratio of the high-carbon aldehyde in the product, and improves the yield of the high-carbon aldehyde, particularly the yield of linear high-carbon aldehyde.
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 sources of material in the following examples are as follows:
1. phosphoramidite ligands having the structure of formula (iv') were purchased from carbofuran, cas: 247130-62-7;
2. bisphosphite ligands having the structure of formula (i ") are available from carbofuran, cas: 121627-17-6;
3. bidentate phosphine ligands having the structure of formula (iii') are available from carbofuran, cas: 111982-81-1;
4. the bisphosphite ligand having the structure of formula (I') is prepared by the following method, which is prepared by the laboratory:
the method comprises the following steps: oxidative coupling of 2, 4-di-tert-butylphenol
Figure BDA0002756668150000071
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 BDA0002756668150000072
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 50mmol/L triphenylphosphine and 0.5mmol/L rhodium acetylacetonate were dissolved was charged into a stirred, 100mL autoclave, 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 1h, 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 48.5%, the total nonanal yield was 39%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 3.4, the total nonanal selectivity was 80.41%, the n-nonanal selectivity was 62.14%, and the 2-octene yield was 2.6%.
Example 2
A toluene solution in which 3mmol/L of the bisphosphite ligand having the structure of the formula (III') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 46%, the total nonanal yield was 30.2%, the normal/iso-aldehyde (normal to iso ratio) was 95.1, the total nonanal selectivity was 48.21%, the n-nonanal selectivity was 46.97%, and the 2-octene yield was 6.3%.
Example 3
A toluene solution in which 3mmol/L of the bisphosphite ligand having the structure of the formula (I') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 97.08%, the total nonanal yield was 6.6%, the normal/iso-aldehyde (normal/iso ratio) was 16, the total nonanal selectivity was 6.8%, the n-nonanal selectivity was 6.4%, and the 2-octene yield was 66%.
Example 4
A toluene solution in which 3mmol/L of the bisphosphite ligand having the structure of the formula (IV') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 97.37%, the total nonanal yield was 20.78%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 133, the total nonanal selectivity was 21.34%, the n-nonanal selectivity was 21.18%, and the 2-octene yield was 44.54%.
Example 5
A toluene solution in which 3mmol/L of the bisphosphite ligand having the structure of the formula (I') and 0.5mmol/L of acetylacetonatodicarbonylrhodium were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 91.8%, the total nonanal yield was 31.4%, the normal/iso-aldehyde (normal/iso ratio) was 2.82, the total nonanal selectivity was 34.2%, the n-nonanal selectivity was 25.25%, and the 2-octene yield was 39.7%.
Example 6
A toluene solution in which 3mmol/L of the bisphosphite ligand having the structure of the formula (IV'), 3mmol/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 subjected to complexation with stirring for several minutes. 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 1h, stopping the reaction, and cooling the reaction kettle in an ice water bath. Gas chromatography detection shows that the conversion rate of 1-octene is 78.4%, the total nonanal yield is 37.8%, all the nonanal are n-nonanal, the total nonanal selectivity is 48.21%, the n-nonanal selectivity is 48.21%, and the 2-octene yield is 17.8%.
Example 7
A toluene solution in which 3mmol/L of the bisphosphite ligand having the structure of the formula (I'), 3mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, stopping the reaction, and cooling the reaction kettle in an ice water bath. The reaction liquid was subjected to gas chromatography detection, and the conversion of 1-octene was 55%, the total nonanal yield was 35%, the normal/iso-aldehyde (normal to iso ratio) was 115, the total nonanal selectivity was 63.64%, the n-nonanal selectivity was 63.09%, and the 2-octene yield was 10.8%.
Examples 1-7 compare the reaction effect of different ligands, and when rhodium/monodentate phosphine ligand is used as catalyst, the conversion rate of olefin is lower, the total selectivity of high carbon aldehyde is higher, the normal-iso ratio is lower, and the isomerization of olefin is less. In the high carbon olefin hydroformylation reaction, when rhodium/diphosphite ligand or rhodium/phosphoramidite ligand is used as a catalyst, olefin is almost completely converted, the total selectivity of high carbon aldehyde is lower, the normal-iso ratio is higher, and olefin isomerization is serious. In the high-carbon olefin hydroformylation reaction, when the rhodium/diphosphite ligand or rhodium/phosphoramidite ligand and monodentate phosphine ligand composition is used as a catalyst, the olefin is almost completely converted, the total high-carbon aldehyde selectivity and the linear high-carbon aldehyde selectivity are obviously improved, and the olefin isomerization is obviously reduced. Preferred bisphosphite ligands of the invention having the structure of formula (I') the subsequent examples were carried out.
Example 8
The toluene solution dissolved with 0.5mmol/L rhodium acetylacetonate dicarbonyl was charged into a stirred 100mL high-pressure reactor and complexed for several minutes under 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 liquid was subjected to gas chromatography detection, and the conversion of 1-octene was 96.85%, the total nonanal yield was 4.82%, the normal/iso-aldehyde (normal to iso ratio) was 1.72, the total nonanal selectivity was 4.98%, the n-nonanal selectivity was 3.15%, and the 2-octene yield was 72.71%.
Example 9
A toluene solution in which 0.5mmol/L of the bisphosphite ligand having the structure of the formula (I') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 98.38%, the total nonanal yield was 36.22%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 0.91, the total nonanal selectivity was 36.82%, the n-nonanal selectivity was 17.59%, and the 2-octene yield was 53.97%.
Example 10
A toluene solution in which 1mmol/L of the bisphosphite ligand having the structure of the formula (I') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 98.71%, the total nonanal yield was 32.07%, the normal/iso-aldehyde (normal to iso ratio) was 0.89, the total nonanal selectivity was 32.49%, the n-nonanal selectivity was 15.31%, and the 2-octene yield was 46.49%.
Example 11
A toluene solution in which 1.5mmol/L of the bisphosphite ligand having the structure of the formula (I') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 97.36%, the total nonanal yield was 11.87%, the normal/iso-aldehyde (n-iso ratio) was 16.2, the total nonanal selectivity was 12.19%, the n-nonanal selectivity was 11.48%, and the 2-octene yield was 76.58%.
Example 12
A toluene solution in which 2mmol/L of bisphosphite ligand having the structure of the formula (I') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and was subjected to a complex stirring for several minutes. 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 1h, 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 97.42%, the total nonanal yield was 12.16%, the normal/iso-aldehyde (n-iso ratio) was 16.37, the total nonanal selectivity was 12.48%, the n-nonanal selectivity was 11.76%, and the 2-octene yield was 76.08%.
Example 13
A toluene solution in which 3mmol/L of the bisphosphite ligand having the structure of the formula (I') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 97.58%, the total nonanal yield was 10.09%, the normal/iso-aldehyde (normal to iso ratio) was 13, the total nonanal selectivity was 10.34%, the n-nonanal selectivity was 9.6%, and the 2-octene yield was 76.85%.
Example 14
A toluene solution in which 4.5mmol/L of the bisphosphite ligand having the structure of the formula (I') and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 97.56%, the total nonanal yield was 12.84%, the normal/iso-aldehyde (normal to iso ratio) was 14.3, the total nonanal selectivity was 13.16%, the n-nonanal selectivity was 12.3%, and the 2-octene yield was 71.98%.
Examples 8-14 compare the effect of different bisphosphite ligands having the structure of formula (I ') on the reaction at a rhodium concentration ratio, preferably a bisphosphite ligand having the structure of formula (I') to rhodium concentration ratio of 3:1 to carry out the subsequent examples.
Example 15
A toluene solution in which 1.5mmol/L of the bisphosphite ligand having the structure of the formula (I'), 3mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, 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 93.56%, the total nonanal yield was 45.95%, the n-aldehyde/iso-aldehyde (n-iso ratio) was 65.31, the total nonanal selectivity was 49.12%, the n-nonanal selectivity was 48.37%, and the 2-octene yield was 32.92%.
Example 16
A toluene solution in which 1.5mmol/L of the bisphosphite ligand having the structure of the formula (I'), 2mmol/L of triphenylphosphine and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complex was stirred for several minutes. 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 1h, stopping the reaction, and cooling the reaction kettle in an ice water bath. Gas chromatography detection of the reaction liquid shows that the conversion rate of 1-octene is 96.75%, the total nonanal yield is 45.82%, the normal aldehyde/iso-aldehyde (normal-iso ratio) is 66.28, the total nonanal selectivity is 47.36%, the n-nonanal selectivity is 46.66%, and the 2-octene yield is 25.89%.
Example 17
A toluene solution in which 1.5mmol/L of the bisphosphite ligand having the structure of the formula (I'), 1.5mmol/L of triphenylphosphin and 0.5mmol/L of rhodium acetylacetonate are dissolved is charged into a 100mL autoclave equipped with a stirrer, and the complexing is carried out 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 1h, 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 yield of total nonanal was 46.7%, the normal/iso-aldehyde (normal to iso ratio) was 62.11, the selectivity for total nonanal was 48.17%, the selectivity for n-nonanal was 47.41%, and the yield of 2-octene was 35.66%.
Example 18
A toluene solution in which 1.5mmol/L of the bisphosphite ligand having the structure of the formula (I'), 0.5mmol/L of triphenylphosphin and 0.5mmol/L of rhodium acetylacetonate dicarbonyl were dissolved was charged into a 100mL autoclave equipped with a stirrer, and the complexation was carried out with stirring for several minutes. 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 1h, 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 97.03%, the yield of total nonanal was 13.12%, the normal/iso-aldehyde (normal to iso ratio) was 17.64, the selectivity for total nonanal was 13.53%, the selectivity for n-nonanal was 12.8%, and the yield of 2-octene was 71.98%.
Examples 15-18 compare the effect of different bisphosphite ligands having the structure of formula (I '), triphenylphosphine and rhodium concentration ratios on the reaction, preferably the bisphosphite ligand having the structure of formula (I'), triphenylphosphine and rhodium concentration ratio is 3:3: 1.
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 with reference to exemplary embodiments, but 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 (10)

1. A method for producing a high-carbon aldehyde, comprising the steps of:
s101: 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;
s102: and (3) reacting the high carbon number olefin, carbon monoxide and hydrogen under the action of the catalyst system to obtain the high carbon number aldehyde.
2. The process for producing higher aldehydes as claimed in claim 1, wherein the molar ratio of the sum of said bisphosphite ligand and said monodentate phosphine ligand to said rhodium catalyst precursor is 1 to 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 30 to 170: 1; more preferably, the molar ratio of the sum of the bisphosphite ligand and the monodentate phosphine ligand to the rhodium catalyst precursor is from 50 to 150: 1; further 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;
preferably, the molar concentration of the rhodium catalyst precursor is 0.01mmol/L to 5 mmol/L; more preferably, the molar concentration of the rhodium catalyst precursor is from 1mmol/L to 4 mmol/L; further preferably, the molar concentration of the rhodium catalyst precursor is 2mmol/L to 3 mmol/L.
3. The method for producing high-carbon aldehydes according to claim 1 or 2, wherein the high-carbon number olefins have a structure of formula (v):
Figure FDA0002756668140000011
wherein R is4And R5Each independently selected from hydrogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms, and said aryl having 6 to 20 carbon atoms has 0 to 5 substituents thereon, and R4And R5The sum of the number of carbon atoms is not less than 4; preferably, the aryl substituent is at least one selected from nitro, halogen or alkyl having 1 to 4 carbon atoms.
4. The method for producing higher aldehydes as claimed in any one of claims 1 to 3, wherein, in the step S102, the reaction temperature is 50 ℃ to 150 ℃, the reaction pressure is 0.5MPa to 3MPa, and the molar ratio of the hydrogen to the carbon monoxide is 1 to 4: 1; preferably, the reaction temperature is 70 ℃ to 130 ℃, and/or the reaction pressure is 1MPa to 2MPa, and/or the molar ratio of the hydrogen to the carbon monoxide is 2 to 3: 1.
5. The process for producing a higher aldehyde according to any one of claims 1 to 4, wherein the bisphosphite ligand has the structure of formula (I):
Figure FDA0002756668140000021
wherein X is selected from C6-C28 organic divalent bridged arylene; preferably, X is at least one selected from 1,1 '-biphenyl-2, 2' diyl, 3 '-bis-tert-butyl-5, 5' -bismethoxy-1, 1 '-biphenyl-2, 2' -diyl, 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- (p) xanthene-4, 5-diyl;
Y1、Y2、Z1、Z2each independently selected from one of hydrogen, tertiary butyl or methoxy;
q is a single bond and/or a vacant bond connecting two adjacent benzene rings.
6. The method for producing a high-carbon aldehyde according to any one of claims 1 to 5, wherein the monodentate phosphine ligand has the structure of formula (II):
Figure FDA0002756668140000022
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.
7. The method for producing a high carbon aldehyde according to any one of claims 1 to 6, wherein the bidentate phosphine ligand has the structure of formula (III):
Figure FDA0002756668140000023
wherein X is selected from C6-C28 organic divalent bridged arylene; preferably, X is selected from one of 1,1 '-biphenyl-2, 2' diyl, 3 '-bis-tert-butyl-5, 5' -bismethoxy-1, 1 '-biphenyl-2, 2' -diyl, 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- (p) xanthene-4, 5-diyl;
R1、R2、R3and R4Each 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.
8. The method for producing a high-carbon aldehyde according to any one of claims 1 to 7, wherein the phosphoramidite ligand has the structure of formula (IV):
Figure FDA0002756668140000031
wherein R is1At least one selected from phenyl, N-indolyl or N-carbazolyl, R2At least one selected from hydrogen, carbomethoxy, carbethoxy, cyano, halogen, n-butyl, methyl, methoxy, ethyl, ethoxy or trifluoromethyl.
9. The method for producing higher aldehydes according to any one of claims 1 to 8, wherein the rhodium catalyst precursor is at least one member selected from the group consisting of tris (triphenylphosphine) rhodium carbonylhydride, tris (triphenylphosphine) rhodium chloroxide and rhodium acetylacetonate dicarbonyl; preferably, the rhodium catalyst precursor is tris (triphenylphosphine) rhodium carbonyl hydride.
10. The method for producing high-carbon aldehydes as claimed in any one of claims 1 to 9, wherein the solvent for dissolving the catalyst system is at least one selected from the group consisting of toluene, xylene, nonanal and decane.
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