CN113578393A - Composition and method for preparing aldehyde by two-phase catalytic hydroformylation - Google Patents
Composition and method for preparing aldehyde by two-phase catalytic hydroformylation Download PDFInfo
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- CN113578393A CN113578393A CN202010362103.8A CN202010362103A CN113578393A CN 113578393 A CN113578393 A CN 113578393A CN 202010362103 A CN202010362103 A CN 202010362103A CN 113578393 A CN113578393 A CN 113578393A
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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
- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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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
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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
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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
- B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
- B01J2531/96—Water
Abstract
The invention relates to a composition for preparing aldehyde by two-phase catalytic hydroformylation, which comprises: rhodium catalyst and asymmetric quaternary ammonium salt type gemini surfactant. The invention also relates to a method for preparing aldehydes by two-phase catalytic hydroformylation. When the composition provided by the invention is used for preparing aldehyde by two-phase catalytic hydroformylation, the conversion rate of olefin and the selectivity of aldehyde can be obviously improved, and meanwhile, the production cost is also reduced.
Description
Technical Field
The invention relates to a composition for preparing aldehyde by two-phase catalytic hydroformylation and a method for preparing aldehyde by two-phase catalytic hydroformylation.
Background
In recent years, with the rapid development of plastic processing, automobile industry, cable industry and building industry worldwide, the demand for plasticizers is increasing globally, and further the demand for plasticizer alcohol is increasing rapidly, especially the demand for higher alcohols above C6.
Currently, the hydroformylation production process in industry is mainly divided into homogeneous catalysis and two-phase catalysis. Homogeneous catalysis has the advantages of high reaction rate, high activity and the like, but products and catalysts need to be separated by adopting a distillation method. As the carbon chain grows, the boiling point of the hydroformylation reaction product, high carbon aldehyde, increases, and higher temperatures are required to separate the product. The rhodium catalyst with high activity is easy to deactivate at high temperature, so the high-temperature distillation used in the homogeneous catalysis process can cause the loss of the noble metal catalyst, and the production cost is increased.
In order to overcome the above-mentioned disadvantages of homogeneous phase reaction for preparing aldehydes, two-phase catalytic processes (especially oil-water two-phase catalysis) were developed, mainly due to the following reasons: on one hand, the product and the catalyst are easy to separate in the oil-water two-phase catalytic reaction process, high-temperature operation is not needed, the deactivation of the rhodium catalyst is avoided, the use efficiency is increased, and the production cost is reduced; on the other hand, the solvent used in the process is water, so that the use of organic solvents is reduced, and the requirement of 'green chemistry' is met. At present, the oil-water two-phase catalysis process is applied to the industrial production of preparing aldehyde by the hydroformylation of low-carbon olefin. However, the poor solubility (some are even completely insoluble) of the high-carbon olefin with the carbon number of above C6 in water leads to slow mass transfer rate, affects reaction activity, and limits the application of the oil-water two-phase catalysis process in the industrial production of hydroformylation of the high-carbon olefin, so that the problem of slow mass transfer rate of the high-carbon olefin in the oil-water two-phase catalysis process is particularly important to solve.
Chinese patent CN105418394 discloses a water-soluble ligand containing alcoholic hydroxyl segments, which has good solubility in water and can ensure that the catalyst can be recycled by simple oil-water separation after the reaction is finished, but the problem of mass transfer of high-carbon olefin in water is not solved by the increase of the solubility of the ligand.
In order to solve the problem of high-carbon olefin mass transfer, Chinese patent CN1562932 discloses a method for preparing aldehyde by using ionic liquid to carry out hydroformylation reaction, and although the method is easy to realize the separation of catalyst and product and has the advantages of high yield, high selectivity and the like, the ionic liquid has complicated synthesis steps, is easy to cause environmental pollution and has extremely high cost; furthermore, U.S. Pat. No. 6,5205 discloses a hydroformylation process in a microemulsion, which increases the mass transfer rate of water-insoluble higher olefins in water, but requires the use of a large amount of an emulsifier, and thus causes problems such as difficulty in post-treatment and high cost. The journal of chemistry (2013, volume 71, 844-848) published a study on the promotion of 1-octene hydroformylation water/oil two-phase reaction by a novel cationic surfactant, and although the surfactant not only quickens the reaction speed but also improves the normal/iso ratio of aldehyde compared with the traditional cationic surfactant, the usage amount of the surfactant is still higher, so that the emulsion of the solution is easy to cause and the difficulty of the two-phase separation at the later stage is brought.
Although the mass transfer problem of the high-carbon olefin in water is solved by changing the solvent or adding the solubilizer, the problems of large usage amount of the solubilizer, high cost and the like exist, so that the improvement of the type of the solubilizer is urgently needed to remove the limitation of the oil-water two-phase catalytic process in the industrial production of the hydroformylation of the high-carbon olefin.
Disclosure of Invention
In the oil-water two-phase reaction process, the reaction rate is slow or even no reaction is caused due to the low solubility of the high-carbon olefin in water. In order to solve the above technical problems, the present invention provides a composition for two-phase catalytic hydroformylation to produce aldehydes, comprising: rhodium catalyst and asymmetric quaternary ammonium salt type gemini surfactant.
According to a preferred embodiment of the present invention, the molar ratio of the asymmetric quaternary ammonium salt type gemini surfactant to the rhodium catalyst is 20:1 to 0.08:1, preferably 10:1 to 0.1:1, more preferably 5:1 to 0.5: 1.
According to a preferred embodiment of the present invention, the structure of the asymmetric quaternary ammonium salt type gemini surfactant is represented by formula (I),
in the formula (I), R1And R2Same or different is C6-C22Alkyl groups of (a); r3、R4And R5Identical or different from C1-C6Alkyl and hydroxy substituted C1-C6An alkyl group; m is hydroxy or hydrogen; x-Selected from halide ions, preferably from Br-And Cl-。
According to a preferred embodiment of the invention, in formula (I), R1And R2Is C10-C18Alkyl group of (1).
According to a preferred embodiment of the invention, in formula (I), R1Is C14-C18Such as C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, which may be linear or branched, preferably linear.
According to a preferred embodiment of the invention, in formula (I), R2Is C14-C18Such as C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, which may be linear or branched, preferably linear.
According to the invention, C1-C6Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, which may be straight or branched.
According to the invention, C is substituted by hydroxy1-C6Alkyl means, as defined above for C1-C6Examples of groups formed by substitution of one or more hydrogens of the alkyl group with one or more hydroxyl groups include, but are not limited to, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, and the like.
According to a preferred embodiment of the present invention, the rhodium catalyst is a water-soluble rhodium catalyst comprising a rhodium complex and an organophosphinic compound; preferably, the amount of the organophosphinic compound is 0.5mol to 200mol, preferably 3mol to 70mol, more preferably 15mol to 50mol, with respect to 1mol of the central metallic rhodium atom of the rhodium catalyst.
According to a preferred embodiment of the invention, the rhodium complex is at least one of rhodium trichloride hydrate, rhodium acetylacetonate dicarbonyl, bis (trisulfonated triphenylphosphine trisodium) rhodium monochlorocarbonyl, bis (disulfonated triphenylphosphine disodium) rhodium monochlorocarbonyl, bis (monosulfonated triphenylphosphine monosodium) rhodium monochlorocarbonyl, and tris (trisulfonated triphenylphosphine trisodium) rhodium monohydromonocarboxyl.
According to a preferred embodiment of the present invention, the organic phosphine compound (i.e. phosphine ligand) is at least one of tri-sodium tri-sulfonated triphenylphosphine, di-sodium di-sulfonated triphenylphosphine and mono-sodium mono-sulfonated triphenylphosphine, which are water soluble.
When the composition provided by the invention is used for preparing aldehyde by two-phase catalytic hydroformylation, the conversion rate of olefin and the selectivity of aldehyde can be obviously improved, and meanwhile, the production cost is also reduced.
Thus, in another aspect, the invention also provides a process for the preparation of aldehydes by two-phase catalytic hydroformylation, which comprises reacting an olefin feedstock with carbon monoxide and hydrogen in the presence of a solution of a composition according to the invention and water to form an aldehyde.
The asymmetric quaternary ammonium salt gemini surfactant is added in the hydroformylation reaction, so that the defects that the hydroformylation reaction rate of high-carbon olefin above C6 is low in the existing two-phase water-soluble rhodium-phosphine catalysis process, the concentration required by adding the conventional surfactant is high, two-phase emulsification is generated, the phase separation is difficult, and the loss of the rhodium catalyst is increased are overcome, the use efficiency of the rhodium catalyst is improved, and the production cost is reduced.
The water used in the present invention is preferably deionized water.
According to a preferred embodiment of the present invention, the concentration of rhodium in the solution is from 0.1mmol/L to 2mmol/L, preferably from 0.2mmol/L to 1.6mmol/L, more preferably from 0.7mmol/L to 1.6mmol/L, in terms of rhodium metal atoms.
According to a preferred embodiment of the present invention, the concentration of said asymmetric quaternary ammonium salt type gemini surfactant is 0.01mmol/L to 5mmol/L, preferably 0.1mmol/L to 3mmol/L, more preferably 0.1mmol/L to 2 mmol/L. According to some embodiments, the quaternary ammonium salt surfactant is present in a concentration of 0.08mmol/L to 3 mmol/L.
According to a preferred embodiment of the invention, the olefinic feedstock is a C6+ olefin, preferably octene.
According to a preferred embodiment of the invention, the reaction temperature is between 50 ℃ and 120 ℃, preferably between 90 ℃ and 110 ℃.
According to a preferred embodiment of the invention, the reaction pressure is between 0.1MPa and 10MPa, preferably between 0.1MPa and 4 MPa.
According to a preferred embodiment of the invention, the reaction time is from 1 hour to 8 hours, preferably from 2 hours to 5 hours.
According to a preferred embodiment of the invention, the molar ratio of the olefinic feedstock to the rhodium catalyst (based on the central metal rhodium atom of the rhodium catalyst) is from 100000:1 to 500:1, preferably from 10000:1 to 1000:1, more preferably from 8000:1 to 1000: 1.
According to a preferred embodiment of the invention, the molar ratio of carbon monoxide to hydrogen is between 0.9 and 1.1:1, preferably 1: 1.
According to a preferred embodiment of the invention, the olefinic hydrocarbon feedstock is premixed with the solution for a time period in the range of from 0 to 10 minutes, preferably from 1 to 5 minutes, more preferably from 1 to 3 minutes, before being contacted with the carbon monoxide and hydrogen.
The invention improves the reaction rate of the hydroformylation of the high-carbon olefin by adding a small amount of the asymmetric quaternary ammonium salt gemini surfactant, avoids the serious emulsification after the addition of the high-concentration surfactant, reduces the loss of the rhodium catalyst, reduces the production cost and improves the possibility of the water/oil two-phase catalytic process in the industrial production of the hydroformylation of the high-carbon olefin.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Preparation example 1
The asymmetric quaternary ammonium salt type gemini surfactant described in example 1 is prepared according to patent CN 104587890B, and the specific synthetic route is as follows.
Preparation example 2
The procedure for preparing the asymmetric quaternary ammonium salt type gemini surfactant used in example 2 was identical to that of preparation example 1 except that the raw material di-n-octyl methyl tertiary amine was changed to di-n-decyl methyl tertiary amine.
Preparation example 3
The procedure for preparing the unsymmetrical quaternary ammonium salt-type gemini surfactant used in example 3 was identical to that of preparation example 1, except that the starting di-n-octyl methyl tertiary amine was changed to di-n-hexadecylmethyl tertiary amine.
Preparation example 4
The procedure for preparing the asymmetric quaternary ammonium salt type gemini surfactant used in example 4 was identical to that of preparation example 1 except that epichlorohydrin was changed to 1, 3-dichloropropane as a raw material.
Preparation example 5
The procedure for preparing the gemini surfactant of asymmetric quaternary ammonium salt type used in example 5 was identical to that of preparation example 1 except that methyldiethanolamine as a raw material was changed to triethylamine.
Preparation example 6
The procedure for preparing the asymmetric quaternary ammonium salt type gemini surfactant used in example 6 was identical to that of preparation example 1 except that methyldiethanolamine as a raw material was changed to N, N-diethylmethylamine.
Example 1
The monohydro-carbonyltris (trisulfonated triphenylphosphine trisodium salt) rhodium HRh (CO) (TPPTS)3Trisulfonated triphenylphosphine trisodium salt TPPTS, and surfactant (compound with a structure shown in formula (I), R1，R2Is an octyl group; r3，R4Is hydroxyethyl; r5Is methyl; m is hydroxy, X-Is Cl-Has the concrete structure of
) And deionized water to prepare 25mL of aqueous solution, adding the aqueous solution into a 50mL stainless steel high-pressure reaction kettle with a stirrer and a thermocouple, uniformly stirring to ensure that the concentration of rhodium in the solution is 0.8mmol/L, the concentration of TPPTS is 24mmol/L, the concentration of a surfactant is 1mmol/L, and replacing the synthesis gas in the reaction kettle for 3 times. Adding 1-octene to make the volume ratio of oil phase to water phase 1: 5. Premixing and stirring for 2min at a pressure of 2MPa and a temperature of 100 deg.C, introducing synthetic gas (CO: H)21:1), after the reaction was completed, the reaction product was cooled and taken out, and analyzed by gas chromatography, and the test results are shown in table 1.
Example 2
The experimental procedure is as in example 1, wherein the gemini surfactant of the asymmetric quaternary ammonium salt type is structurally modified (compound of formula (I), wherein R is1，R2Is n-decyl; r3，R4Is hydroxyethyl; r5Is methyl; m is hydroxy, X-Is Cl-) The rest of the experimental conditions were unchanged, and the test results are shown in table 1.
Example 3
The experimental procedure is as in example 1, wherein the gemini surfactant of the asymmetric quaternary ammonium salt type is structurally modified (compound of formula (I), wherein R is1，R2Is n-hexadecyl; r3，R4Is hydroxyethyl; r5Is methyl; m is hydroxy, X-Is Cl-) The rest of the experimental conditions were unchanged, and the test results are shown in table 1.
Example 4
The experimental procedure is as in example 3, wherein the gemini surfactant of the asymmetric quaternary ammonium salt type is structurally modified (compound of formula (I), wherein R is1，R2Is n-hexadecyl; r3，R4Is hydroxyethyl; r5Is methyl; m is hydrogen, X-Is Cl-) The rest of the experimental conditions were unchanged, and the test results are shown in table 1.
Example 5
The experimental procedure is as in example 3, wherein the unsymmetrical quaternary ammonium salt form of bisThe structure of the surfactant is changed (the compound of the formula (I), wherein R1，R2Is n-hexadecyl; r3，R4，R5Is ethyl; m is hydroxy, X-Is Cl-) The rest of the experimental conditions were unchanged, and the test results are shown in table 1.
Example 6
The experimental procedure is as in example 3, wherein the gemini surfactant of the asymmetric quaternary ammonium salt type is structurally modified (compound of formula (I), wherein R is1，R2Is n-hexadecyl; r3Is hydroxyethyl; r4，R5Is ethyl; m is hydroxy, X-Is Cl-) The rest of the experimental conditions were unchanged, and the test results are shown in table 1.
Examples 7 to 9
The experimental procedure was the same as in example 3, wherein the concentrations of the asymmetric quaternary ammonium salt type gemini surfactant were changed to 0.05mmol/L, 1.5mmol/L and 3mmol/L, respectively, and the rest of the experimental conditions were unchanged, and the test results are shown in Table 1.
Examples 10 to 11
The experimental procedure was the same as in example 3, wherein the rhodium concentration in the solution was changed to 2mmol/L and 0.1mmol/L, respectively, and the rest of the experimental conditions were unchanged, and the test results are shown in Table 1.
Comparative example 1
The experimental procedure is the same as in example 3, wherein no surfactant is added, the rest of the experimental conditions are unchanged, and the test results are as follows: the conversion rate of 1-octene is less than 10%.
As can be seen from comparative example 1, the catalyst has a lower reactivity without the addition of a surfactant.
Comparative example 2
The experimental procedure is the same as in example 3, wherein the asymmetric quaternary ammonium salt type gemini surfactant is replaced by cationic surfactant CTAB, and the rest of the experimental conditions are unchanged, and the test results are as follows: the 1-octene conversion was 15.1%.
As can be seen from comparative example 2, the use of the same concentration of the conventional cationic surfactant is less reactive than the asymmetric quaternary ammonium salt type gemini surfactant.
TABLE 1
| Examples | CRhodium，mmol/L | CWatch (A)，mmol/L | Olefin conversion,% | Aldehyde selectivity,% |
| 1 | 0.8 | 0.4 | 61.3 | 83.5 |
| 2 | 0.8 | 0.4 | 83.8 | 85.1 |
| 3 | 0.8 | 0.4 | 93.3 | 90.3 |
| 4 | 0.8 | 0.4 | 90.1 | 87.5 |
| 5 | 0.8 | 0.4 | 92.5 | 88.2 |
| 6 | 0.8 | 0.4 | 91.7 | 87.9 |
| 7 | 0.8 | 0.05 | 67.9 | 86.1 |
| 8 | 0.8 | 1.5 | 94.7 | 89.0 |
| 9 | 0.8 | 3 | 93.8 | 90.1 |
| 10 | 2 | 0.4 | 94.3 | 88.7 |
| 11 | 0.1 | 0.4 | 62.1 | 80.3 |
(Note: C)RhodiumAs the concentration of the rhodium catalyst in solution, CWatch (A)Is the concentration of the surfactant in the solution. )
When the composition provided by the invention is used for preparing aldehyde by two-phase catalytic hydroformylation, the conversion rate of olefin and the selectivity of aldehyde can be obviously improved, and meanwhile, the production cost is also reduced.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.
Claims (10)
1. A composition for two-phase catalytic hydroformylation to produce aldehydes, comprising: rhodium catalyst and asymmetric quaternary ammonium salt type gemini surfactant.
2. The composition according to claim 1, wherein the molar ratio of the gemini surfactant of asymmetric quaternary ammonium salt type to the rhodium catalyst is from 20:1 to 0.08:1, preferably from 10:1 to 0.1:1, more preferably from 5:1 to 0.5: 1.
3. The composition according to claim 1 or 2, wherein the asymmetric quaternary ammonium salt type gemini surfactant has a structure represented by formula (I),
wherein R is1And R2Same or different is C6-C22Alkyl of (2), preferablyIs selected as C10-C18Alkyl groups of (a); r3、R4And R5Identical or different from C1-C6Alkyl and hydroxy-substituted C of1-C6Preferably selected from methyl, ethyl, propyl, butyl, hydroxymethyl and hydroxyethyl; m is hydroxy or hydrogen; x-Selected from halide ions, preferably from Br-And Cl-。
4. The composition of any one of claims 1-3, wherein the rhodium catalyst is a water-soluble rhodium catalyst comprising a rhodium complex and an organophosphinic compound; preferably, the amount of the organophosphinic compound is 0.5mol to 200mol, preferably 3mol to 70mol, more preferably 15mol to 50mol, with respect to 1mol of the central metallic rhodium atom of the rhodium catalyst.
5. The composition of claim 4, wherein the rhodium complex is at least one of rhodium trichloride hydrate, rhodium acetylacetonate dicarbonyl, bis (trisulfonated triphenylphosphine trisodium) rhodium monochlorocarbonyl, bis (disulfonated triphenylphosphine disodium) rhodium monochlorocarbonyl, bis (monosulfonated triphenylphosphine monosodium) rhodium monochlorocarbonyl, and tris (trisulfonated triphenylphosphine trisodium) rhodium monohydromonocarboxyl; and/or the organic phosphine compound is at least one of water-soluble tri-sodium sulfonated triphenylphosphine salt, di-sodium sulfonated triphenylphosphine salt and mono-sodium sulfonated triphenylphosphine salt.
6. A process for the preparation of aldehydes by two-phase catalytic hydroformylation, comprising reacting an olefin feedstock with carbon monoxide and hydrogen in the presence of a solution of a composition according to any one of claims 1 to 5 and water to produce aldehydes.
7. The method of claim 6, wherein the concentration of rhodium in the solution is 0.1mmol/L to 2mmol/L, preferably 0.2mmol/L to 1.6mmol/L, more preferably 0.7mmol/L to 1.6mmol/L, calculated as rhodium metal atom; and/or the concentration of the asymmetric quaternary ammonium salt type surfactant is 0.01mmol/L-5mmol/L, preferably 0.1mmol/L-3mmol/L, and more preferably 0.1mmol/L-2 mmol/L.
8. The process according to claim 6 or 7, characterized in that the olefinic feedstock is a C6+ olefin, preferably octene; and/or the reaction temperature is 50-120 ℃, preferably 90-110 ℃; and/or the reaction pressure is 0.1MPa to 10MPa, preferably 0.1MPa to 4 MPa; and/or the reaction time is from 1 hour to 8 hours, preferably from 2 hours to 5 hours.
9. The process according to any one of claims 6 to 8, characterized in that the molar ratio of the olefinic feedstock to the rhodium catalyst is from 100000:1 to 500:1, preferably from 10000:1 to 1000:1, more preferably from 8000:1 to 1000: 1.
10. A process according to any one of claims 6 to 9, characterised in that the olefinic hydrocarbon feedstock is premixed with the solution for a time period in the range 0 to 10 minutes, preferably 1 to 5 minutes, more preferably 1 to 3 minutes, before being contacted with the carbon monoxide and hydrogen.
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| CN109896939A (en) * | 2017-12-07 | 2019-06-18 | 中国石油化工股份有限公司 | Composition and method for biphasic catalysis preparing aldehyde by hydroformylation |
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