CN114011474B - Olefin hydroformylation reaction method and catalytic system thereof - Google Patents

Olefin hydroformylation reaction method and catalytic system thereof Download PDF

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CN114011474B
CN114011474B CN202111504711.9A CN202111504711A CN114011474B CN 114011474 B CN114011474 B CN 114011474B CN 202111504711 A CN202111504711 A CN 202111504711A CN 114011474 B CN114011474 B CN 114011474B
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capsule body
catalytic system
hydroformylation
phosphorus
based catalyst
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CN114011474A (en
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苗志伟
应思斌
蔡岩
刘承伟
黄菊
柳磊
黄小鹏
张绍志
洪旭
王凤州
陈福泷
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ZHEJIANG XINHUA CHEMICAL CO Ltd
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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
    • 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
    • B01J31/2414—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 comprising aliphatic or saturated rings
    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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
    • 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
    • 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
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

The invention relates to an olefin hydroformylation reaction method and a catalytic system thereof. The catalyst system comprises a phosphorus-containing ligand, a metal-based catalyst and a capsule body, wherein the phosphorus-containing ligand and the metal-based catalyst are sealed in the capsule body, the capsule body is made of solid wax compounds, and the complete melting temperature of the solid wax compounds is 40-90 ℃. The solid wax compound is paraffin or palm wax. The capsule body has a hollow structure, and the phosphorus-containing ligand and the metal-based catalyst are filled in the cavity of the capsule body under the protection of inert gas, and the catalyst system is formed by sealing. The stability of the catalytic system is obviously improved, the catalytic activity and the catalytic effect of the catalyst are ensured to be fully exerted, and meanwhile, the catalytic system is very convenient to store and use.

Description

Olefin hydroformylation reaction method and catalytic system thereof
Technical Field
The invention relates to an olefin hydroformylation reaction method and a catalytic system thereof.
Background
The hydroformylation reaction of olefins, also known as oxo reaction, is a reaction that converts olefins, hydrogen and carbon monoxide to aldehydes using a transition metal-based catalyst. This reaction is industrially important because it converts olefins, which are common in the petroleum industry, to aldehydes and achieves carbon chain growth. The olefin hydroformylation reaction produces linear and branched hydroformylation products, while other types of reactions, such as isomerization of olefinic substrates to the corresponding isomerized olefins, or hydrogenation to the corresponding alkanes, etc., may also occur. The use of phosphorus-containing ligands can increase the selectivity and yield of the reaction.
Typical phosphorus-containing ligands are monodentate phosphine ligands, bidentate phosphine ligands, multidentate phosphine ligands, etc., wherein the bidentate phosphine ligands are represented by BISBI (2, 2 '-bis (diphenylphosphinomethylene) -1,1' -biphenyl) series ligands, xantphos series ligands, and Biphephos ligands having a phosphite-containing bond with large steric hindrance, etc.
However, the above-mentioned phosphorus-containing ligands are poor in stability and very sensitive to moisture and oxygen, and the phosphorus-containing ligands are chemically deteriorated after being left in the air for several minutes, so that stable storage thereof is a difficulty. Expensive equipment such as glove boxes are often required for storage and are inconvenient to use in practice. In most cases, the phosphorus-containing ligands are temporarily synthesized and used in subsequent catalytic reactions.
The metal-based catalyst and the phosphorus-containing ligand used for the olefin hydroformylation reaction form a catalytic system, wherein the metal-based catalyst is also generally sensitive to water gas, and when the olefin hydroformylation reaction is carried out in the prior art, the metal-based catalyst and the phosphorus-containing ligand can be respectively added into the reaction system to form a metal catalyst complex, and the metal-based catalyst and the phosphorus-containing ligand can also be formed into the metal catalyst complex in the solution system in advance. Chinese laid-open patent CN113522366a discloses a porous organic polymer in-situ encapsulated rhodium-based catalytic material containing monophosphine, wherein carbonyl functionalized monophosphine ligand is used as a monomer, hydrazine hydrate is used as a comonomer, and homogeneous rhodium catalyst is condensed and encapsulated in situ in inert gas atmosphere, so that the porous organic polymer in-situ encapsulated rhodium-based catalytic material containing monophosphine is constructed in one step. This patent greatly increases the stability of the catalyst, but requires functionalization and polymerization of the monophosphine ligand.
Summarizing, the catalytic system composed of the phosphorus-containing ligand and the metal-based catalyst for the olefin hydroformylation reaction in the prior art is not easy to store stably, the catalytic activity is easy to reduce, and the catalyst system is not easy to directly use when being used for catalyzing the olefin hydroformylation reaction subsequently.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides an improved catalytic system for olefin hydroformylation, which has the advantages of remarkably improved stability, ensured catalytic activity and catalytic effect of the catalyst to be fully exerted, and convenient storage and use.
In order to solve the technical problems, the invention adopts the following technical scheme:
a catalytic system for the hydroformylation of olefins, the catalytic system comprising a phosphorus-containing ligand, a metal-based catalyst and a capsule, the phosphorus-containing ligand, the metal-based catalyst being encapsulated in the capsule, the capsule being made of a solid wax compound, the solid wax compound having a complete melting temperature of 40-90 ℃.
Further, the solid wax compound is paraffin wax, palm wax, and the like.
The inventor finds out in a great number of experimental researches that the capsule body for sealing the phosphorus-containing ligand and the metal-based catalyst is prepared by adopting the solid wax compound which can be completely melted at the specific temperature, so that the capsule body can be ensured to be completely melted in the subsequent olefin hydroformylation reaction process, and further, the catalytic system is directly released in the reaction system to exert the catalytic effect, after the reaction is finished, the reaction system is cooled, the solid wax compound can be precipitated, and the solid wax compound can be removed by a filtering method and the like, so that the catalytic system is very convenient to use. The inventor verifies through experiments that the existence of the capsule in the catalytic system does not affect the catalytic reaction activity and selectivity of the phosphorus-containing ligand and the metal-based catalyst in the subsequent olefin hydroformylation reaction. In addition, the capsule body is adopted to seal the phosphorus-containing ligand and the metal-based catalyst, so that the contact of the phosphorus-containing ligand and the metal-based catalyst with water vapor and oxygen can be isolated, the storage stability of the catalyst is greatly improved, and the storage time of the catalyst is prolonged.
Preferably, the thickness of the capsule body is 0.5-3mm.
In one embodiment of the invention, the capsule body has a hollow structure, and the catalytic system is formed by filling the phosphorus-containing ligand and the metal-based catalyst in the cavity of the capsule body under the protection of inert gas and sealing.
In one embodiment of the invention, the phosphorus-containing ligand is a bidentate phosphine ligand.
Preferably, the phosphorus-containing ligand has the structure ofWherein Ar is aryl; x is C 1-5 An alkylene group of (a); r is C 1-5 Alkyl, C of (2) 3-6 Cyclic alkyl or aryl groups of (a).
More preferably, the phosphorus-containing ligand is selected from one of the following structural formulas:
in some embodiments of the invention, the metal-based catalyst is a rhodium-based catalyst and/or a cobalt-based catalyst.
More preferably, the rhodium-based catalyst is Rh (CO) 2 (acetylacetonate), rh 2 O 3 、Rh 4 (CO) 12 、Rh(CO) 16 、Rh(NO 3 ) 2 、Rh(OAc) 2 One or more of rhodium trichloride, rhodium tris (triphenylphosphine) chloride, rhodium (1, 5-cyclooctadiene) chloride dimer, or rhodium tris (triphenylphosphine) carbonyl hydride.
More preferably, the cobalt-based catalyst is one or more of cobalt chloride, potassium cobalt cyanide, cobalt acetylacetonate, bis (cyclopentanediyl) cobalt hexafluorophosphate, bis (cyclopentadienyl) cobalt, and bis (pentamethylcyclopentadienyl) cobalt hexafluorophosphate or cobalt carbonyl.
In some preferred embodiments, the molar ratio of the phosphorus-containing ligand to the metal-based catalyst is from 1 to 100:1.
the phosphorus-containing ligand and the metal catalyst sealed by the capsule body are configured according to the required amount and the molar ratio of the subsequent olefin hydroformylation reaction, so that the catalyst system can be directly used in the olefin hydroformylation reaction without weighing and adjusting the dosage of the phosphorus-containing ligand and the metal catalyst in the subsequent reaction process. And the quality of the phosphorus-containing ligand and the metal-based catalyst sealed in the capsule body can be adjusted along with the scale of the subsequent olefin hydroformylation reaction.
In some preferred embodiments, the inert gas is nitrogen or argon.
The invention further provides a process for preparing the above-described catalytic system. The preparation method of the hollow capsule body in the method comprises the following steps: forming solid wax compound on the outer surface of the mould, and then removing the shell of the mould.
Further, the preparation method of the hollow capsule body comprises the following steps: heating the solid wax compound to completely melt, inserting a mold into the melted solid wax compound, taking out the mold, cooling, and taking out the mold to obtain the hollow capsule body, wherein the mold is a glass rod.
In one embodiment of the invention, the mold is repeatedly inserted into the melted solid wax compound and removed, followed by cooling.
The invention further provides an olefin hydroformylation reaction method, which takes olefin, hydrogen and carbon monoxide as raw materials to react in the presence of the catalytic system for olefin hydroformylation reaction.
Preferably, the olefin is selected from C2-C20 linear or branched olefins.
More preferably, the olefin is selected from n-butene, n-pentene, n-hexene, isobutene or isoamylene.
Further, the reaction method comprises the following steps:
(1) Adding a solvent and the catalytic system into a high-pressure reaction kettle, and replacing the reaction kettle with nitrogen;
(2) Replacing the reaction kettle with the synthesis gas, then adding the olefin, and continuously filling the synthesis gas to raise the pressure of the reaction kettle to 1-8MPa;
(3) Heating the reaction kettle to an internal temperature of 80-140 ℃ and continuing to react for 4-16h;
(4) After the reaction is finished, cooling to enable the internal Wen Jiangzhi of the reaction kettle to be at room temperature, and then replacing the synthesis gas in the reaction kettle with nitrogen and gradually decompressing to normal pressure;
(5) Insoluble matter was removed by filtration, and the filtrate was collected and purified to give an aldehyde product.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1) The solid wax compound adopted for preparing the capsule body is chemically inert, and does not influence the catalytic reaction activity and selectivity of the catalytic system in the subsequent olefin hydroformylation reaction.
2) The stability of the catalytic system can be greatly improved by adopting the capsule body to seal the phosphorus-containing ligand and the metal-based catalyst, and the catalytic system can be stored for a long time under the condition of ordinary room temperature without expensive equipment such as a glove box and the like.
3) The catalytic system containing the capsule body can be directly put into a reaction system for use in the subsequent olefin hydroformylation reaction process, wherein the quality of the phosphorus-containing ligand and the metal-based catalyst can also be correspondingly provided with different specifications according to the requirements of subsequent reactions, and the subsequent reaction is directly taken out, so that the catalyst is very convenient.
Drawings
FIG. 1 shows a hydrogen nuclear magnetic spectrum of BISBI prepared in example 1 1 H-NMR)。
FIG. 2 shows the nuclear magnetic spectrum of BISBI prepared in example 1 31 P-NMR)。
FIG. 3 is a photograph of the hollow capsule body prepared in example 1.
FIG. 4 is a photograph of the catalytic system prepared in example 1.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention, but is not intended to limit the scope of the present invention.
Example 1
1) Synthesis of bidentate phosphine ligand 2,2 '-bis (diphenylphosphinomethylene) -1,1' -biphenyl (BISBI) with the following reaction formula:
the method comprises the following specific steps:
5g of 2,2' -dimethylbiphenyl 1 was weighed into 50mL of Dichloromethane (DCM), and then 9.3. 9.3g N-bromosuccinimide (NBS) and 225mg of Azobisisobutyronitrile (AIBN) were added thereto, followed by reflux reaction under nitrogen for 10 hours. After the reaction is finished, the system is cooled to room temperature, precipitated solids are filtered and removed, a filter cake is rinsed once by DCM, filtrate is collected, the filtrate is washed once by saturated sodium chloride, an organic phase is collected and dried by anhydrous sodium sulfate, a drying agent is filtered, a solvent is dried in a spinning manner, the remainder is recrystallized by normal hexane, a large amount of white solids are precipitated in the system after crystallization, the obtained white solids are collected by suction filtration, and 7g of 2,2' -bromomethyl biphenyl is obtained after drying. The yield in this step was 75%. 7g of the obtained product 2,2 '-bromomethyl biphenyl is placed in 100mL of dry Tetrahydrofuran (THF) to be stirred, 1.1g of magnesium powder and 10mg of iodine simple substance are added, reflux reaction is carried out for 3h under the protection of nitrogen, the system is cooled to room temperature, 4g of N, N' -tetramethyl ethylenediamine (TMEDA) is injected, stirring is carried out for 10min, finally 10g of diphenyl phosphine chloride and 50mL of toluene are injected, and the system is heated to 70 ℃ to react for 3h. The system was cooled in an ice bath, quenched with 50mL of water, the system was separated, the organic phase was collected, dried with anhydrous sodium sulfate, after drying, the solvent was removed by rotary evaporation to give a yellow oil, which was recrystallized from isopropanol to give a white powdery solid, 9.2g of white powder, 2 '-bis (diphenylphosphinomethylene) -1,1' -biphenyl (BISBI), was obtained after filtration and drying, from 2,2 '-bromomethylbiphenyl to BISBI, in a yield of 81% and from 2,2' -dimethylbiphenyl to the product, in a total reaction yield of 60.8%.
Product BISBI 1 H-NMR(400MHz,CDCl 3 ) The method comprises the following steps: delta 7.25-7.38 (m, 5H, ph), 7.09-7.17 (m, 2H, ph), 7.01-7.07 (m, 1H, ph), 6.90-6.95 (m, 1H, ph), 3.22 (dd, J=48.2, 13.6Hz,4H, CH) 2 )。 31 P-NMR(162MHz,CDCl 3 ):δ-10.5(s)。
Product BISBI 1 The H-NMR spectrum is shown in FIG. 1, 31 the P-NMR spectrum is shown in FIG. 2.
2) Preparation of the catalytic System
And (3) heating 50 parts by mass of paraffin completely melted at 70 ℃ in a beaker until the paraffin is completely melted, slowly inserting a cylindrical glass rod die into the melted paraffin, taking out the die, rapidly inserting the die into a container again after the paraffin on the surface layer of the die is cooled and solidified, repeating the steps for several times to ensure that the thickness of the paraffin attached to the die is 1mm, completely cooling, and slowly removing the die from the shell to obtain a cylindrical hollow capsule (a photo is shown in figure 3). Then, 2g of the prepared BISBI and 0.05g of metal-based catalyst tris (triphenylphosphine) rhodium carbonyl hydride were mixed in a nitrogen atmosphere, and placed in the obtained hollow capsule body, and the other end of the capsule body was sealed with the paraffin wax to prepare a catalytic system 1.
3) Application of catalytic system in hydroformylation of 1-butene
After the foregoing catalytic system 1 was stored in air at room temperature for 20 days, it was applied to olefin hydroformylation: adding a catalytic system 1 and a solvent into a 500mL stainless steel autoclave, replacing air in the autoclave with nitrogen for 5-7 times, then filling synthetic gas for 5-7 times, adding metered 1-butene, continuously filling the synthetic gas to the pressure of 2MPa, starting stirring and heating, raising the temperature in the autoclave to 90 ℃, melting the capsule in the temperature raising process to release a catalyst and a ligand, reacting for 4 hours, cooling the autoclave to room temperature after the reaction is finished, solidifying and separating paraffin in the system, filtering to remove solidified paraffin and other insoluble impurities, analyzing a product by using gas chromatography, wherein the conversion rate of 1-butene is 91.5%, and the ratio of n-valeraldehyde to 2-methyl butyraldehyde in the product is 18:1.
After the catalytic system 1 is placed in water for 20 days, the capsule body is not broken, the catalytic system is used for olefin hydroformylation, the specific process is the same as the reaction process after the former section is stored at room temperature, the conversion rate of 1-butene is 91.3% by gas chromatography analysis, and the ratio of n-valeraldehyde to 2-methyl butyraldehyde in the product is 18:1.
Example 2
The bidentate phosphine ligand BISBI synthesis, the preparation of the catalytic system 2 and the use thereof in the hydroformylation of 1-butene are substantially identical to those of example 1, except that: paraffin wax was replaced with palm wax.
Catalytic system 2 was stored in air at room temperature for 30 days with the following catalytic activity data: the conversion of 1-butene was 92.1% and the ratio of n-valeraldehyde to 2-methyl butyraldehyde in the product was 18:1.
After the catalytic system 2 was placed in water for 30 days, the capsule body was not broken, and the catalytic system was also applied to olefin hydroformylation, and the catalytic activity data were found as follows: the conversion of 1-butene was 91.7% and the ratio of n-valeraldehyde to 2-methyl butyraldehyde in the product was 18:1.
Example 3
The bidentate phosphine ligand BISBI synthesis, the preparation of the catalytic system 3 and the application thereof in the hydroformylation of 1-butene are basically the same as in example 1, except that: the metal-based catalyst was replaced by 0.05g of rhodium tris (triphenylphosphine) carbonyl hydride with 0.5g of cobalt carbonyl.
The catalytic system 3 was stored in air at room temperature for 20 days and the catalytic activity data were as follows: the conversion of the raw material is 47%, and the molar ratio of n-valeraldehyde to 2-methyl butyraldehyde is 15:1.
after the catalytic system 3 was placed in water for 20 days, the capsule body was not broken, and the same was applied to olefin hydroformylation, and the catalytic activity data were found as follows: the conversion rate of the raw materials is 46%, and the molar ratio of n-valeraldehyde to 2-methyl butyraldehyde is 15:1.
example 4
The preparation of the catalytic system 4 and its use in the hydroformylation of 1-butene are substantially identical to those of example 1, except that: using ligandsReplacing the BISBI.
Catalytic system 4 was stored in air at room temperature for 20 days with the following catalytic activity data: conversion of the starting material was 87%, molar ratio of n-valeraldehyde to 2-methyl butyraldehyde was 12:1.
after the catalytic system 4 was placed in water for 20 days, the capsule body was not broken, and the same was applied to the hydroformylation reaction, and the catalytic activity data were found as follows: conversion of raw material 88%, molar ratio of n-valeraldehyde to 2-methyl butyraldehyde 12:1.
example 5
The preparation of the catalytic system 5 and its use in the hydroformylation of 1-butene are substantially identical to those of example 1, except that: using ligandsReplacing the BISBI.
The catalytic system 5 was stored in air at room temperature for 20 days and the catalytic activity data were as follows: conversion of raw material was 83%, molar ratio of n-valeraldehyde to 2-methyl butyraldehyde was 14:1.
after the catalytic system 5 was placed in water for 20 days, the capsule body was not broken, and the same was applied to the hydroformylation reaction, and the catalytic activity data were found as follows: conversion of the starting material was 82%, molar ratio of n-valeraldehyde to 2-methyl butyraldehyde was 14:1.
the above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

Claims (11)

1. A catalytic system for the hydroformylation of olefins, characterized in that: the catalyst system comprises a phosphorus-containing ligand, a metal-based catalyst and a capsule body, wherein the phosphorus-containing ligand and the metal-based catalyst are sealed in the capsule body, the capsule body is made of solid wax compounds, and the complete melting temperature of the solid wax compounds is 40-90 ℃; the phosphorus-containing ligand is a bidentate phosphine ligand; the metal-based catalyst is a rhodium-based catalyst and/or a cobalt-based catalyst; the capsule body is of a hollow structure, and the phosphorus-containing ligand and the metal-based catalyst are filled in the cavity of the capsule body under the protection of inert gas and sealed to form the catalytic system; the solid wax compound is paraffin or palm wax; the thickness of the capsule body is 0.5-3mm; the structure of the phosphorus-containing ligand is thatWherein Ar is aryl; x is C 1-5 An alkylene group of (a); r is C 1-5 Alkyl, C of (2) 3-6 Cyclic alkyl or aryl groups of (a).
2. The catalytic system for the hydroformylation of olefins according to claim 1, characterized in that: the phosphorus-containing ligand is selected from one of the following structural formulas:
3. the catalytic system for the hydroformylation of olefins according to claim 1, characterized in that: the molar ratio of the phosphorus-containing ligand to the metal-based catalyst is 1-100:1.
4. a process for the preparation of a catalytic system for the hydroformylation of olefins according to any of claims 1 to 3, characterized in that: the preparation method comprises the steps of firstly preparing a hollow capsule body, and then filling the phosphorus-containing ligand and the metal-based catalyst into a cavity of the capsule body under the protection of inert gas and sealing.
5. The process for preparing a catalytic system for the hydroformylation of olefins according to claim 4, characterized in that: the preparation method of the hollow capsule body comprises the following steps: forming solid wax compound on the outer surface of the mould, and then removing the shell of the mould.
6. The process for preparing a catalytic system for the hydroformylation of olefins according to claim 4, characterized in that: the preparation method of the hollow capsule body comprises the following steps: heating the solid wax compound to completely melt, inserting a mold into the melted solid wax compound, taking out the mold, cooling, and taking out the mold to obtain the hollow capsule body, wherein the mold is a glass rod.
7. The process for preparing a catalytic system for the hydroformylation of olefins according to claim 6, characterized in that: repeatedly inserting the mould into the melted solid wax compound, taking out the mould, and then cooling the mould again.
8. The olefin hydroformylation reaction process with olefin and synthesis gas as material in the presence of catalyst system is characterized by comprising the following steps: the catalytic system is a catalytic system for the hydroformylation of olefins according to any of claims 1 to 3.
9. The process for the hydroformylation of olefins according to claim 8, wherein: the olefins are selected from C 2-20 Straight or branched chain olefins of (a).
10. The process for the hydroformylation of olefins according to claim 8, wherein: the olefin is selected from n-butene, n-pentene, n-hexene, isobutene or isoamylene.
11. The process for the hydroformylation of olefins according to any of claims 8 to 10, characterized in that: the method comprises the following steps:
(1) Adding a solvent and the catalytic system into a high-pressure reaction kettle, and replacing the reaction kettle with nitrogen;
(2) Replacing the reaction kettle with the synthesis gas, then adding the olefin, and continuously filling the synthesis gas to raise the pressure of the reaction kettle to 1-8MPa;
(3) Heating the reaction kettle to an internal temperature of 80-140 ℃ and continuing to react for 4-16h;
(4) After the reaction is finished, cooling to enable the internal Wen Jiangzhi of the reaction kettle to be at room temperature, and then replacing the synthesis gas in the reaction kettle with nitrogen and gradually decompressing to normal pressure;
(5) Insoluble matter was removed by filtration, and the filtrate was collected and purified to give an aldehyde product.
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