CN110981709B - Method for preparing aldehyde by hydroformylation of internal olefin - Google Patents
Method for preparing aldehyde by hydroformylation of internal olefin Download PDFInfo
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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
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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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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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
- 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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- 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
- 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 preparing aldehyde by hydroformylating internal olefin, which is characterized in that a water-soluble rhodium compound, a water-soluble diphosphine ligand, an additive, deionized water and the internal olefin are added into a reaction kettle with a stirrer and a thermocouple, then, synthesis gas mixed by hydrogen and carbon monoxide in a volume ratio of 1:1 is used for replacing for 3-5 times, then, the pressure is increased to 1.0-5.0 MPa, the reaction is carried out for 2-10 hours at the temperature of 60-120 ℃, reactants are taken out after cooling, and the product aldehyde is obtained through separation.
Description
Technical Field
The invention belongs to the field of organic compound synthesis, and particularly relates to a method for preparing aldehyde by hydroformylation of internal olefin.
Background
Hydroformylation refers to the reaction of olefins with synthesis gas (H)2+ CO) in the presence of a catalyst to form branched and linear aldehydes having more than one carbon. Since the discovery of this reaction in 1938 by professor Otto Roelen, hydroformylation has become one of the most important chemical reactions in industrial applications today. In recent years, researchers pay attention to the hydroformylation reaction of some special olefins such as internal olefin and cyclic olefin, the substrates are cheap and easy to obtain, and the product aldehyde has wide market demand, can be used as an intermediate for fine chemical synthesis, and has high added value. For example, iso-decyl alcohol obtained by condensing and hydrogenating n-valeraldehyde generated by hydroformylation of byproduct 2-butene in crude oil processing can be used for preparing high-grade plasticizer with excellent performance; such as tricyclodecanedialdehyde from the hydroformylation of dicyclopentadiene, the diols reduced by hydrogenation can be esterified with acrylic acid to give acrylates which can be used for the preparation of adhesives and sealants. However, hydroformylation of such olefins tends to be more difficult to achieve desirable reactivity and selectivity than conventional olefins. And few reports also show that homogeneous catalysis is adopted, and the separation of the catalyst and the product and the recycling of the catalyst are always difficult after the catalytic reaction is finished. Although water-organic two-phase catalysis has unique advantages in this regard, reports on the use of internal olefin hydroformylation reactions to produce aldehydes have been relatively rare. Therefore, the present invention aims to provide a containerIn a process for preparing aldehydes by aqueous-organic two-phase hydroformylation of olefins, the product after the reaction can be separated from the catalyst by two-phase separation.
The invention patent 201610943755.4 discloses a catalyst for hydroformylation of internal olefins, its preparation method and application, the catalyst of the invention is oil soluble catalyst, the catalytic system is homogeneous catalytic system, its disadvantage is that the catalyst is difficult to separate from the product, can't realize recycling, difficult to apply industrially. Especially for higher boiling products, the high temperatures required for distillative separation are highly likely to deactivate the catalyst. The method provided by the patent can realize the separation of the catalyst and the product and the recycling of the catalyst, the selectivity of the product aldehyde can be ensured by the catalyst, the mass transfer problem of the reaction is improved, and the activity, the selectivity and the stability of a composite catalyst system are balanced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing aldehyde by internal olefin hydroformylation, which is characterized by comprising the following steps: in a water-organic two-phase catalytic system, a bidentate or tridentate chelated catalyst is formed by a water-soluble diphosphine ligand and a rhodium compound by utilizing a special chelating point, aldehyde with high conversion rate and high selectivity is obtained by adding an additive and changing conditions, and the catalyst can be recycled by two-phase separation.
The invention is realized by the following technical scheme:
a method for preparing aldehyde by hydroformylating internal olefin comprises the steps of adding a water-soluble rhodium compound, a water-soluble diphosphine ligand, a certain amount of additive and deionized water into a reaction kettle with a stirrer and a thermocouple to be completely dissolved, adding the internal olefin, then replacing for 3-5 times by using synthesis gas (hydrogen and carbon monoxide in a volume ratio of 1:1), pressurizing to 1.0-5.0 MPa, reacting for 2-10 hours at the temperature of 60-120 ℃, cooling, taking out a reactant, and performing two-phase separation to obtain a product aldehyde.
The structural formula of the water-soluble diphosphine ligand is as follows:
wherein the content of the first and second substances,
z is one of N or CH;
m is one of lithium, sodium, potassium, rubidium, cesium and francium alkali metal;
R1is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl;
R2is H, C4One of the following alkyl or alkoxy groups.
The water-soluble rhodium compound is RhCl3·3H2O、HRh(CO)[(m-C6H4SO3Na)3P]3、RhCl[(m-C6H4SO3Na)3P]3Or RhCl [ (CO) [ (m-C)6H4SO3Na]2At least one of (1).
Preferably, the water-soluble diphosphine ligand is:
the concentration of the metal rhodium in water is 4 multiplied by 10-4～9×10-3mol/L。
The concentration of the water-soluble diphosphine ligand in water is 8 multiplied by 10-4～0.54mol/L
The molar ratio of the internal olefin to the rhodium compound is 100-10000.
The internal olefin is C4-C12A substituted internal olefin or a cyclic olefin. Preferably 2-hexene, 2-octene, 2,4, 4-trimethyl-2-pentene, 3, 4-dimethyl-2-hexene, cyclohexene, norbornene, norborneolA diene or a dicyclopentadiene.
The additive can be one or more of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, didodecyl dimethyl ammonium bromide, docosyl trimethyl ammonium iodide, dodecyl hexadecyl dimethyl ammonium bromide and hexadecyl pyridine chloride. The concentration of the additive in water is 0.1-20mmol/L, preferably 1-10 mmol/L.
The invention has the beneficial effects that:
1) the water-organic two-phase catalytic system makes the rhodium compound and the phosphine ligand remain in the water layer after the catalytic reaction is finished, and the rhodium compound and the phosphine ligand are quickly separated from the organic layer. The separation of the catalyst and the product aldehyde is realized, and the deactivation and decomposition of the rhodium catalyst easily caused by high-temperature distillation are avoided.
2) The ligand has two or three coordination points to complex with rhodium, which can ensure the selectivity of the catalyst.
3) Compared with the existing homogeneous catalyst system, the catalyst system has better catalytic activity under a milder condition by adding the additive, and the improvement of the selectivity of the internal olefin hydroformylation product aldehyde by providing the water-soluble diphosphine ligand containing multiple coordination sites is realized for the first time.
4) The water is used as the solvent to meet the requirement of 'green chemistry'.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Sequentially adding water-soluble rhodium compound HRh (CO) [ (m-C) into a clean high-pressure reaction kettle with a magnetic stirrer6H4SO3Na)3P]3(0.026g), water-soluble ligand L1(0.7g), deionized water 15mL, and surfactant twelveAlkyl trimethyl ammonium bromide (6.2mg) and 2-hexene (5mL), synthesis gas for the reaction kettle (H)21:1) replacing for three times, and then filling synthetic gas to 1 MPa; the reaction was carried out at 60 ℃ for 10 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, and carefully taking out an upper organic phase hydroformylation product to be analyzed by a gas chromatograph: the 2-hexene conversion was 90%, the aldehyde selectivity was 95%, and the ratio of normal aldehyde to isomeric aldehyde was 10.
Example 2
Sequentially adding a water-soluble rhodium compound RhCl into a clean high-pressure reaction kettle with a magnetic stirrer3·3H2O (3.68mg), water-soluble ligand L2(0.31g), deionized water 12mL, surfactant dodecyl trimethyl ammonium bromide (6.2mg) and 2-octene (5mL), syngas for the reaction kettle (H)21:1) replacing for three times, and then injecting synthetic gas to 3 MPa; the reaction was carried out at 80 ℃ for 6 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, and carefully taking out an upper organic phase hydroformylation product to be analyzed by a gas chromatograph: the conversion of 2-octene was 95%, the selectivity for aldehyde was 97%, and the ratio of normal aldehyde to isomeric aldehyde was 8.5.
Example 3
Sequentially adding a water-soluble rhodium compound RhCl [ (m-C) into a clean high-pressure reaction kettle with a magnetic stirrer6H4SO3Na)3P]3(11mg), water-soluble ligand L3(14mg), deionized water 15mL, surfactant cetyl trimethyl ammonium bromide (10.9mg) and 2-decene (10mL), synthesis gas for reaction kettle (H)21:1) replacing for three times, and then filling synthetic gas to 2 MPa; the reaction was carried out at 110 ℃ for 3 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, and carefully taking out an upper organic phase hydroformylation product to be analyzed by a gas chromatograph: the 2-decene conversion was 88%, the aldehyde selectivity was 90%, and the ratio of normal aldehyde to isomeric aldehyde was 5.5.
Example 4
Sequentially adding a water-soluble rhodium compound RhCl [ (m-C) into a clean high-pressure reaction kettle with a magnetic stirrer6H4SO3Na)3P]3(0.49g), water-soluble ligand L4(2g), deionized water 32mL, surfactant didodecyldimethylammonium bromide (18.4mg), and mixed butenes (2.5mL, 50% 2-butene content), syngas for the reaction kettle (H)21:1) replacing for three times, and then injecting synthetic gas to 3 MPa; the reaction was carried out at 110 ℃ for 5 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, and carefully taking out an upper organic phase hydroformylation product to be analyzed by a gas chromatograph: the mixed butene conversion was 82% and the ratio of normal aldehyde to iso aldehyde was 8.
Example 5
Sequentially adding a water-soluble rhodium compound RhCl [ (m-C) into a clean high-pressure reaction kettle with a magnetic stirrer6H4SO3Na)3P]3(0.205g), water-soluble ligand L5(0.82g), deionized water 15mL, surfactant octadecyl trimethyl ammonium bromide (29.4mg) and butene dimer (10mL), synthesis gas for the reaction kettle (H)21:1) replacing for three times, and then filling synthetic gas to 5 MPa; the reaction was carried out at 90 ℃ for 3 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, carefully taking out an upper organic phase hydroformylation product, and analyzing the yield by using a gas chromatograph: the mixed butene conversion was 88% and the ratio of normal aldehyde to iso aldehyde was 6.
Example 6
Sequentially adding water-soluble rhodium compound HRh (CO) [ (m-C) into a clean high-pressure reaction kettle with a magnetic stirrer6H4SO3Na)3P]3(0.037g), water-soluble ligand L6(0.27g), deionized water 10mL, behenyl trimethyl ammonium iodide (19.8mg), and butene trimer (18mL), synthesis gas (H) for the reactor21:1) replacing for three times, and then injecting synthesis gas to 4 MPa; the reaction was carried out at 110 ℃ for 5 hours. After the reaction is finished, the reaction is carried outCooling the kettle to room temperature, discharging redundant synthesis gas, transferring the product into a clean test tube, standing until the product is obviously layered, carefully taking out the upper layer organic phase hydroformylation product, and analyzing the yield by a gas chromatograph: butene dimer conversion was 85%, aldehyde selectivity was 90%, and the ratio of normal to iso aldehyde was 5.5.
Example 7
Sequentially adding a water-soluble rhodium compound RhCl into a clean high-pressure reaction kettle with a magnetic stirrer3·3H2O (8.9mg), water-soluble ligand L6(0.13g), deionized water 20mL, dodecylhexadecyldimethylammonium bromide (62mg) and norbornene (4mL), Synthesis gas for reaction kettle (H)21:1) replacing for three times, and then injecting synthesis gas to 4 MPa; the reaction was carried out at 120 ℃ for 2 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, and carefully taking out an upper organic phase hydroformylation product to be analyzed by a gas chromatograph: the norbornene conversion was 95% and the aldehyde selectivity was 98%.
Example 8
Sequentially adding a water-soluble rhodium compound RhCl into a clean high-pressure reaction kettle with a magnetic stirrer3·3H2O (3.68mg), water-soluble ligand L2(0.31g), deionized water 28mL, cetylpyridinium chloride (57mg) and norbornadiene (5mL), synthesis gas for reaction kettle (H)21:1) replacing for three times, and then injecting synthetic gas to 3 MPa; the reaction was carried out at 80 ℃ for 4 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, carefully taking out an upper organic phase hydroformylation product, and analyzing the product yield by using a gas chromatograph: the norbornadiene conversion rate is 99 percent, the aldehyde selectivity is more than 99 percent, and the ratio of the dialdehyde to the monoaldehyde is 54.
Example 9
Sequentially adding a water-soluble rhodium compound RhCl [ (CO) m-C into a clean high-pressure reaction kettle with a magnetic stirrer6H4SO3Na)3P]2(0.018g) water-soluble ligand L3(0.56g) and20mL of ionic water, surfactants dodecyl trimethyl ammonium bromide (61mg) and cyclohexene (5mL), synthesis gas for reaction kettle (H)21:1) replacing for three times, and then injecting synthetic gas to 3 MPa; the reaction was carried out at 100 ℃ for 3 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, and carefully taking out an upper organic phase hydroformylation product to be analyzed by a gas chromatograph: the cyclohexene conversion rate is 98%, and the aldehyde selectivity is more than 99%.
Example 10
Sequentially adding a water-soluble rhodium compound RhCl [ (CO) m-C into a clean high-pressure reaction kettle with a magnetic stirrer6H4SO3Na)3P]2(0.022g), water-soluble ligand L3(0.42g), deionized water 15mL, diethylene glycol (0.09mL) and dicyclopentadiene (1.2mL), syngas for the reaction kettle (H)21:1) replacing for three times, and then injecting synthetic gas to 3 MPa; the reaction was carried out at 100 ℃ for 3 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, transferring a product into a clean test tube, standing until the product is obviously layered, and carefully taking out an upper organic phase hydroformylation product to be analyzed by a gas chromatograph: the dicyclopentadiene conversion was 96%, the aldehyde selectivity was 92% and the ratio of dialdehyde to monoaldehyde was 4.3.
Example 11
Sequentially adding a water-soluble rhodium compound RhCl [ (CO) m-C into a clean high-pressure reaction kettle with a magnetic stirrer6H4SO3Na)3P]2(0.118g), water-soluble ligand L1(6g), deionized water 12mL, cetyltrimethylammonium bromide (6.6mg), and dicyclopentadiene (5mL), Synthesis gas for the reaction kettle (H)21:1) replacing for three times, and then injecting synthetic gas to 3 MPa; the reaction was carried out at 100 ℃ for 3 hours. After the reaction is finished, cooling the reaction kettle to room temperature, discharging redundant synthesis gas, taking out an upper layer organic phase product, adding a new batch of dicyclopentadiene for repeated reaction, wherein the conversion rate of the dicyclopentadiene in the first circulation is 96 percent, the selectivity of aldehyde is 92 percent, and the ratio of dialdehyde to monoaldehyde is 4.0. Second cycle dicyclopentadiene conversion 94%, aldehyde selectivity 92% of dialdehyde to monoaldehyde was 4.0. The conversion rate of dicyclopentadiene in the third cycle is 92%, the selectivity of aldehyde is 90%, and the ratio of dialdehyde to monoaldehyde is 4.0. The conversion rate of dicyclopentadiene in the fourth cycle is 90%, the selectivity of aldehyde is 88%, and the ratio of dialdehyde to monoaldehyde is 3.8. The fifth cycle had 88% dicyclopentadiene conversion and 88% aldehyde selectivity, with a ratio of dialdehyde to monoaldehyde of 3.8.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A process for the hydroformylation of internal olefins to produce aldehydes, characterized in that: dissolving a water-soluble rhodium compound, a water-soluble diphosphine ligand and an additive in deionized water, adding internal olefin, reacting for 2-10 hours at the pressure of hydrogen and carbon monoxide synthetic gas of 1.0-5.0 MPa and the temperature of 60-120 ℃, cooling, taking out a reactant, and separating to obtain a product aldehyde;
the structural formula of the water-soluble diphosphine ligand is as follows:
wherein the content of the first and second substances,
m is one of lithium, sodium, potassium, rubidium, cesium and francium alkali metal;
R1is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
R2is H, C4The following alkoxy groups;
the additive is selected from one or more of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, didodecyl dimethyl ammonium bromide, docosyl trimethyl ammonium iodide, dodecyl hexadecyl dimethyl ammonium bromide and hexadecyl pyridine chloride;
the internal olefin is C4-C12A substituted internal olefin or a cyclic olefin.
2. The method of claim 1, wherein the water-soluble rhodium compound has a concentration of 4 x 10-4～9×10-3mol/L, the concentration of the water-soluble diphosphine ligand is 8 multiplied by 10-40.54mol/L, and the concentration of the additive is 1-10 mmol/L.
3. A method according to claim 1, wherein the water-soluble bisphosphine ligand is:
4. a process according to claim 1, wherein the water-soluble rhodium compound is RhCl3·3H2O、HRh(CO)[(m-C6H4SO3Na)3P]3、RhCl[(m-C6H4SO3Na)3P]3Or RhCl [ (CO) [ (m-C)6H4SO3Na)3P]2At least one of (1).
5. The method of claim 1, wherein the molar ratio of the internal olefin to the rhodium compound is 100 to 10000.
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