CN111729687A - Preparation method and application of hydroformylation catalyst - Google Patents
Preparation method and application of hydroformylation catalyst Download PDFInfo
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- 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
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Abstract
The invention relates to a preparation method of a supported hydroformylation catalyst, which takes chloromethylated polystyrene resin as a raw material and loads rhodium and/or cobalt metal through a series of chemical conversions to form the final supported catalyst. The catalyst has high conversion rate and selectivity when catalyzing the hydroformylation of olefin, the product and the catalyst can be directly separated, the metal loss rate is low, the activity of the catalyst is stable, and the economy of the hydroformylation process is obviously improved.
Description
Technical Field
The invention relates to a preparation method and application of a hydroformylation catalyst.
Technical Field
The olefin hydroformylation reaction generally adopts a cobalt or rhodium catalyst, a homogeneous catalysis system is adopted in the industry at present, the problem of catalyst separation or recycling is inevitably caused, particularly for a high-carbon olefin catalysis system, the temperature for separating an aldol product from the catalyst is higher, the rhodium catalyst is easy to decompose and lose at high temperature, the activity is reduced, the process for separating the cobalt catalyst is complicated, certain corrosion and three wastes are caused, and the product cost is increased.
Because the catalyst and the product are not easy to separate, the research on the immobilization of the hydroformylation catalyst is widely concerned. There are many reports on supported hydroformylation catalysts, including inorganic molecular sieve, alumina, silica gel supported rhodium or cobalt catalysts, and also organic polymers such as polystyrene resin, polystyrene sulfonic acid resin, polyglycerol, polyfluoroacrylate and other supported catalysts, but these supported catalysts all have some problems, resulting in the failure of industrial use, such as low catalytic activity, poor temperature resistance, rapid activity reduction, and the failure of catalyst life to meet the use requirements.
Based on the background, a novel supported catalyst needs to be developed, the problem of separation of a product and the catalyst can be solved, the unit consumption cost of the catalyst is lower, the yield of the product is higher, the whole hydroformylation process is simpler, and the catalyst has higher stability and activity and meets the long-term use requirement.
Disclosure of Invention
The invention aims to provide a novel immobilized hydroformylation catalyst, a preparation method and application thereof, which solve the problem that reaction products and the catalyst are difficult to separate in the olefin hydroformylation process, reduce the loss of the catalyst, simultaneously can obtain products at high yield and high selectivity under mild conditions, reduce the production cost, have stable catalyst and can still maintain the activity after continuous repeated application.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method of preparing a hydroformylation catalyst comprising the steps of: (1) the method comprises the following steps of (1) carrying out nitration reaction on chloromethylated polystyrene serving as a raw material and a mixture of concentrated sulfuric acid and concentrated nitric acid to generate a catalyst intermediate A, (2) carrying out hydrolysis reaction on the intermediate A and sodium hydroxide to obtain a catalyst intermediate B, (3) carrying out reaction on the intermediate B, butyl lithium and chlorophosphite ester to generate an intermediate C, (4) soaking the intermediate C in a compound solution containing cobalt or rhodium, filtering and drying to obtain a supported hydroformylation catalyst, wherein the reaction process is shown as the following formula:
wherein R is1、R2Are identical or different alkyl, aryl, substituted alkyl, aryl, and their terminal groups may be linked to one another. n is the polymerization degree of chloromethylated polystyrene and is an integer between 100 and 10000.
In the preparation method, the mixture of concentrated sulfuric acid and concentrated nitric acid is used as a nitration reagent in the nitration reaction in the step (1), the mass concentration of the concentrated sulfuric acid and the concentrated nitric acid is 98%, the reaction temperature is 50-110 ℃, the preferred temperature is 80-100 ℃, and the reaction time is 2-10h, the preferred time is 6-8 h. The mass ratio of the chloromethylated polystyrene to the concentrated sulfuric acid to the concentrated nitric acid is 1: 0.2: 0.2 to 1: 1.5: 1.5, preferably 1: 0.5: 0.5 to 1: 1:1, filtering, washing and drying after the reaction is finished to obtain an intermediate A. The hydrolysis reaction temperature of the step (2) is 60-120 ℃, preferably 90-110 ℃, the reaction time is 5-20h, preferably 10-15h, and the mass ratio of the intermediate A to the sodium hydroxide is 1: 0.5-1: 5, preferably 1: 1-1: and 2, filtering, washing and drying after the reaction is finished to obtain an intermediate B. And (3) when the intermediate B in the step (3) reacts with butyllithium and chlorophosphite, butyllithium is firstly added at the reaction temperature of-78-10 ℃ for 0.5-3h, preferably 1-2h, and then chlorophosphite is added for reaction at the reaction temperature of-78-30 ℃, preferably-30-10 ℃ for 0.5-3h, preferably 1-2 h. The mass ratio of the intermediate B to the butyl lithium to the phosphorochloridite is 1: 0.1: 0.1-1: 0.5: 0.5, preferably 1: 0.2: 0.2-1: 0.4: 0.4. after the reaction is finished, filtering, washing and drying to obtain an intermediate C.
In the preparation method of the invention, in the step (4), the cobalt or rhodium-containing compound is one or more of dicarbonyl acetylacetone rhodium, acetylacetone triphenylphosphine carbonyl rhodium, triphenylphosphine carbonyl rhodium chloride, triphenylphosphine rhodium bromide, polymeric dicarbonyl rhodium chloride and carbonyl cobalt. The concentration of the cobalt-or rhodium-containing compound solution is 0.1 to 2mol/L, preferably 0.5 to 1 mol/L. The dipping temperature is 25-100 ℃, preferably 40-80 ℃, the dipping time is 0.5-3h, preferably 1-2h, after the reaction is finished, filtering, washing and drying at 70-110 ℃ for 24-72h to obtain the catalyst. In the catalyst loading process, the phosphite ligand and the metal center are coordinated to form the supported catalyst.
The novel immobilized hydroformylation catalyst has the following two characteristics: (1) the catalyst adopts phosphite ligands, is insensitive to oxygen and easy to synthesize, and meanwhile, the phosphite is a weak sigma-electron donor and a strong pi-electron acceptor, compared with the common phosphine ligand, the catalyst has higher hydroformylation activity, and the good coordination ability of the phosphite enables the catalyst system to be improved in the aspects of selectivity, stability and the like. (2) The strong electron-withdrawing nitro group is introduced into the polystyrene, so that the basicity of a phosphine atom on a phosphorous acid ligand is weakened, sigma-electron donor is weakened, pi-electron accepting capability is strengthened, a metal center of rhodium or cobalt is more electron-deficient, and the catalyst has higher catalyst activity in hydroformylation.
The catalyst can be used in olefin hydroformylation reaction, and the olefin comprises one or more of ethylene, propylene, n-butene, butene-1, butene-2, butadiene, isobutene, 1-pentene, cyclopentene, cyclopentadiene, 1-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, 1-nonene, 1-decene, tripropylene, tetrapropylene, dimeric n-butene, trimeric n-butene, diisobutylene and triisobutene.
The catalyst is used for catalyzing the hydroformylation reaction, the using amount of the catalyst is 0.1-10 wt%, preferably 0.5-5 wt% of the mass of the olefin, the reaction temperature is 80-120 ℃, preferably 90-110 ℃, the reaction time is 0.5-10h, preferably 2-8h, and the reaction pressure is 8-20MPaG, preferably 10-18 MPaG.
The catalyst is used for hydroformylation reaction, a bubble tower or a reaction kettle can be used for intermittent or continuous operation, after the operation is finished, an aldehyde product can be obtained by filtering, the separated catalyst is continuously recycled, no metal is lost in the continuous recycling process, and the activity of the catalyst is stable.
Compared with the prior art, the invention has the following advantages:
(1) a brand new hydroformylation catalyst is developed, and the catalyst can be directly filtered and separated from olefin raw materials and hydroformylation products after the reaction is finished, so that the cost and the difficulty of catalyst separation are greatly reduced.
(2) Can prepare aldehyde products with high selectivity and high yield, reduces the production cost, has stable activity, and does not reduce the continuous application activity.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which include, but are not limited to, the scope of the present invention.
The analytical instruments and methods used in the examples are as follows:
gas chromatograph: agilent-7820;
gas chromatographic column: 0.25mm 30m DB-5 capillary column, detector FID, vaporizer temperature 280 deg.C, column box temperature 280 deg.C, FID detector temperature 300 deg.C, argon carrying capacity 2.1mL/min, hydrogen flow 30mL/min, air flow 400mL/min, and sample injection 1.0 μ L. The conversion of the alkene and the selectivity of the product were calculated using area normalization. Temperature rising procedure: preheating to 40 deg.C, holding for 5min, and heating at 15 deg.C/min from 40 deg.C to 280 deg.C, and holding for 2 min.
An element analyzer: euro Vector EA3000
Nuclear magnetic analyzer: bruker AVANCE III 400M 400
Example 1
(1) Preparing a catalyst: 100g of chloromethylated polystyrene (avadin reagent) is added into a three-neck flask, a mixture of 40g of concentrated sulfuric acid (with the concentration of 98 wt%) and concentrated nitric acid (with the concentration of 98 wt%) in a mass ratio of 1:1 is added, the reaction temperature is 50 ℃, the reaction time is 2 hours, after the reaction is finished, filtration is carried out, 500ml of deionized water is used for washing, drying is carried out at 120 ℃ for 48 hours, 102g of resin intermediate A is obtained by weighing, 102g of intermediate A is added into 510g of 10 wt% sodium hydroxide solution, heating is carried out to 60 ℃, the reaction is carried out for 5 hours, catalyst intermediate B is generated, filtration is carried out, washing is carried out by 200ml of deionized water, drying is carried out. Adding 97g of the intermediate B into a three-neck flask, dropwise adding 97g of a butyl lithium solution with the mass concentration of 10 wt%, reacting at the temperature of-78 ℃, reacting for 0.5h, adding 9.7g of diethyl chlorophosphite, reacting at the temperature of-78 ℃, reacting for 0.5h, returning to room temperature, filtering, washing with 200ml of hexane, drying at 120 ℃ for 24h, weighing to obtain 108g of catalyst intermediate C, soaking the intermediate C in 100ml of a cobalt carbonyl toluene solution with the concentration of 2mol/L, the soaking temperature of 25 ℃, soaking for 0.5h, washing with 100ml of methanol after soaking, drying at 70 ℃ for 72h, and weighing to obtain 110g of supported hydroformylation catalyst.
The catalyst was characterized as follows:
elemental analysis: c, 59.80; h, 6.06; n, 3.68; o, 20.73; p,7.35, Co, 2.38
31P NMR:140
(2) Hydroformylation: 100g of tetrapropylene is added into a 500ml reaction kettle, 0.1g of the freshly prepared catalyst is added, the reaction kettle is replaced by nitrogen for three times, the temperature is raised to 80 ℃, synthetic gas is introduced to raise the pressure to 20MPaG, the reaction is started by stirring, the reaction time is 0.5h, the conversion rate of the tetrapropylene is 75 percent, and the selectivity of isomeric tridecanal is 95 percent.
(3) The catalyst is mechanically used: after the reaction is finished, filtering and separating the catalyst under the protection of nitrogen, continuously recycling the catalyst according to the hydroformylation process conditions in the step (2) for five times, and obtaining the following results:
conversion (%) | Selectivity (%) | |
Is used for one time | 90 | 95 |
For the second time | 89 | 96 |
For three times of use | 91 | 96 |
For four times of use | 89 | 96 |
For five times of applying | 90 | 94 |
Example 2
(1) Preparing a catalyst: 100g of chloromethylated polystyrene (avadin reagent) is added into a three-neck flask, a mixture of 300g of concentrated sulfuric acid (with the concentration of 98 wt%) and concentrated nitric acid (with the concentration of 98 wt%) in a mass ratio of 1:1 is added, the reaction temperature is 110 ℃, the reaction time is 10 hours, after the reaction is finished, filtration is carried out, 500ml of deionized water is used for washing, 110 ℃ drying is carried out for 48 hours, 103g of resin intermediate A is obtained by weighing, 103g of intermediate A is added into 1030g of 50% sodium hydroxide solution, the temperature is heated to 120 ℃, the reaction is carried out for 20 hours, catalyst intermediate B is generated, 200ml of deionized water is used for washing, 120 ℃ drying is carried out for 24 hours. Adding 95g of the intermediate B into a three-neck flask, dropwise adding 475g of a 10 wt% butyl lithium solution, reacting at 10 ℃ for 3h, adding 47.5g of dimethyl chlorophosphite, reacting at 30 ℃ for 3h, filtering, washing with 200ml of hexane, drying at 120 ℃ for 24h, weighing to obtain 109g of catalyst intermediate C, soaking the intermediate C in 100ml of a toluene solution of triphenylphosphine rhodium chloride at a concentration of 0.1mol/L and a soaking temperature of 100 ℃, soaking for 3h, washing with 100ml of methanol after soaking, drying at 110 ℃ for 24h, and weighing to obtain 111g of supported hydroformylation catalyst. The catalyst was characterized as follows:
elemental analysis: c, 56.91; h, 6.06; n, 3.68; o, 22.53; p,6.55, Rh, 3.18; cl,1.09
31P NMR:135
(2) Hydroformylation: 100g of diisobutylene is added into a 500ml reaction kettle, 10g of the freshly prepared catalyst is added, the reaction kettle is replaced by nitrogen for three times, the temperature is raised to 120 ℃, synthetic gas is introduced to boost the pressure to 8MPaG, the reaction time is 10 hours after stirring, the conversion rate of the diisobutylene is 91 percent, and the selectivity of the isononanal is 93 percent.
(3) The catalyst is mechanically used: after the reaction is finished, filtering and separating the catalyst under the protection of nitrogen, continuously recycling the catalyst according to the hydroformylation process conditions in the step (2) for five times, and obtaining the following results:
conversion (%) | Selectivity (%) | |
Is used for one time | 91 | 93 |
For the second time | 90 | 92 |
For three times of use | 91 | 94 |
For four times of use | 92 | 93 |
For five times of applying | 91 | 92 |
Example 3
(1) Preparing a catalyst: adding 100g of chloromethylated polystyrene (avadin reagent) into a three-neck flask, adding 100g of a mixture of concentrated sulfuric acid (with the concentration of 98 wt%) and concentrated nitric acid (with the concentration of 98 wt%) in a mass ratio of 1:1, reacting at 80 ℃ for 6 hours, filtering after the reaction is finished, washing with 500ml of deionized water, drying at 110 ℃ for 48 hours, weighing to obtain 110g of a resin intermediate A, adding 110g of the intermediate A into 220g of 50% sodium hydroxide solution, heating to 90 ℃, reacting for 10 hours to generate a catalyst intermediate B, washing with 200ml of deionized water, drying at 120 ℃ for 24 hours, weighing 101g of the intermediate B, adding 101g of the intermediate B into the three-neck flask, dropwise adding 202g of butyl lithium solution with the mass concentration of 10 wt%, reacting at-30 ℃, adding 20.2g of diethyl chlorophosphite after the reaction is carried out for 1 hour, reacting at-30 ℃ for 3 hours, filtering, washing by using 200ml of hexane, drying for 24h at 120 ℃, weighing to obtain 112g of the catalyst intermediate C, soaking the intermediate C in 100ml of dicarbonyl acetylacetone rhodium in toluene solution at the concentration of 0.25mol/L, the soaking temperature of 40 ℃, the soaking time of 1h, washing by using 100ml of methanol after the soaking is finished, drying for 48h at 100 ℃, and weighing to obtain 116g of the supported hydroformylation catalyst. The catalyst was characterized as follows:
elemental analysis: c, 54.71; h, 6.21; n, 3.98; o, 23.88; p,7.10, Rh, 4.12
31P NMR:140
(2) Hydroformylation: adding 100g of 1-decene into a 500ml reaction kettle, adding 0.5g of the freshly prepared catalyst, replacing the reaction kettle with nitrogen for three times, heating to 90 ℃, introducing synthetic gas, boosting the pressure to 10MPaG, stirring, starting the reaction, reacting for 2 hours, wherein the conversion rate of 1-decene is 95%, and the selectivity of undecanal is 95%.
(3) The catalyst is mechanically used: after the reaction is finished, filtering and separating the catalyst under the protection of nitrogen, continuously recycling the catalyst according to the hydroformylation process conditions in the step (2) for five times, and obtaining the following results:
conversion (%) | Selectivity (%) | |
Is used for one time | 95 | 95 |
For the second time | 94 | 95 |
For three times of use | 96 | 94 |
For four times of use | 93 | 95 |
For five times of applying | 95 | 93 |
Example 4
(1) Preparing a catalyst: adding 100g of chloromethylated polystyrene (Aladdin reagent) into a three-neck flask, adding 200g of a mixture of concentrated sulfuric acid (with the concentration of 98 wt%) and concentrated nitric acid (with the concentration of 98 wt%) in a mass ratio of 1:1, reacting at 100 ℃ for 8 hours, filtering after the reaction is finished, washing with 500ml of deionized water, drying at 110 ℃ for 48 hours, weighing to obtain 112g of a resin intermediate A, adding the intermediate A into 224g of 50% sodium hydroxide solution, heating to 110 ℃, reacting for 15 hours to generate a catalyst intermediate B, washing with 200ml of deionized water, drying at 120 ℃ for 24 hours, weighing 102g, adding 102g of the intermediate B into the three-neck flask, dropwise adding 408g of a butyl lithium solution with the mass concentration of 10 wt%, reacting at-78 ℃ for 2 hours, adding 40.8g of diphenyl chlorophosphite, reacting at 10 ℃ for 2 hours, filtering, washing with 200ml of hexane, drying at 120 ℃ for 24h, weighing to obtain 113g of catalyst intermediate C, soaking the intermediate C in 100ml of acetylacetonatocarbonyltriphenylphosphine rhodium in toluene at a concentration of 0.5mol/L, a soaking temperature of 80 ℃, a soaking time of 2h, washing with 100ml of methanol after soaking, drying at 110 ℃ for 24h, and weighing to obtain 118g of supported hydroformylation catalyst. The catalyst was characterized as follows:
elemental analysis: c, 63.93; h, 4.89; n, 2.54; o, 18.23; p, 6.73; rh, 3.68
31P NMR:152
(2) Hydroformylation: adding 100g of trimeric n-butene into a 500ml reaction kettle, adding 5g of the freshly prepared catalyst, replacing the reaction kettle with nitrogen for three times, heating to 80 ℃, introducing synthetic gas, boosting the pressure to 18MPaG, stirring, starting the reaction, wherein the reaction time is 8h, the conversion rate of the trimeric n-butene is 96%, and the selectivity of isomeric tridecanal is 94%.
(3) The catalyst is mechanically used: after the reaction is finished, filtering and separating the catalyst under the protection of nitrogen, continuously recycling the catalyst according to the hydroformylation process conditions in the step (2) for five times, and obtaining the following results:
conversion (%) | Selectivity (%) | |
Is used for one time | 93 | 95 |
For the second time | 96 | 95 |
For three times of use | 95 | 94 |
For four times of use | 93 | 95 |
For five times of applying | 95 | 93 |
Example 5
(1) Preparing a catalyst: adding 100g of chloromethylated polystyrene (Aladdin reagent) into a three-neck flask, adding 140g of concentrated sulfuric acid (with the concentration of 98 wt%) and concentrated nitric acid (with the concentration of 98 wt%) in a mass ratio of 1:1, reacting at 90 ℃ for 7h, filtering after the reaction is finished, washing with 500ml of deionized water, drying at 110 ℃ for 48h, weighing to obtain 114g of resin intermediate A, adding 114g of intermediate A into 342g of 50% sodium hydroxide solution, heating to 100 ℃, reacting for 12h to generate catalyst intermediate B, washing with 200ml of deionized water, drying at 120 ℃ for 24h, weighing 100g, adding 100g of intermediate B into the three-neck flask, dropwise adding 300g of butyl lithium solution with the mass concentration of 10 wt%, reacting at-78 ℃ for 1.5h, adding 30g of diphenyl chlorophosphite, reacting at-10 ℃ for 1.5h, filtering, washing by using 200ml of hexane, drying for 24h at 120 ℃, weighing to obtain 116g of catalyst intermediate C, soaking the intermediate C in 100ml of triphenylphosphine rhodium chloride toluene solution at the concentration of 1mol/L, the soaking temperature of 60 ℃, the soaking time of 1.5h, washing by using 100ml of methanol after the soaking is finished, drying for 24h at 110 ℃, and weighing to obtain 120g of supported hydroformylation catalyst. The catalyst was characterized as follows:
elemental analysis: c, 59.56; h, 4.77; n, 2.82; o, 19.83; p, 6.99; rh, 4.68; cl,1.3531P NMR:152
(2) Hydroformylation: 100g of triisobutene is added into a 500ml bubble tower, 2g of catalyst is added, nitrogen is used for purging and replacing for three times, the temperature is raised to 100 ℃, synthetic gas is introduced, the pressure is raised to 15MPaG, the reaction is carried out for 7 hours, the triisobutene conversion rate is 95 percent, and the selectivity of isomeric tridecanal is 92 percent.
(3) The catalyst is mechanically used: after the reaction is finished, filtering and separating the catalyst under the protection of nitrogen, continuously recycling the catalyst according to the hydroformylation process conditions in the step (2) for five times, and obtaining the following results:
conversion (%) | Selectivity (%) | |
Is used for one time | 95 | 92 |
For the second time | 94 | 91 |
For three times of use | 95 | 90 |
For four times of use | 94 | 93 |
For five times of applying | 96 | 90 |
Comparative example 1:
100g of tetrapropylene is added into a 500ml reaction kettle, 0.1g of cobalt carbonyl catalyst (alatin) is added, the reaction kettle is replaced by nitrogen for three times, the temperature is raised to 80 ℃, synthetic gas is introduced to raise the pressure to 20MPaG, the reaction is started by stirring, the reaction time is 0.5h, the conversion rate of the tetrapropylene is 35 percent, and the selectivity of isomeric tridecanal is 91 percent.
Claims (10)
1. A method for preparing a hydroformylation catalyst, comprising the steps of: (1) the method comprises the following steps of (1) carrying out nitration reaction on chloromethylated polystyrene serving as a raw material and a mixture of concentrated sulfuric acid and concentrated nitric acid to generate a catalyst intermediate A, (2) carrying out hydrolysis reaction on the intermediate A and sodium hydroxide to obtain a catalyst intermediate B, (3) carrying out reaction on the intermediate B, butyl lithium and chlorophosphite ester to generate an intermediate C, (4) soaking the intermediate C in a compound solution containing rhodium or cobalt, filtering and drying to obtain a supported hydroformylation catalyst, wherein the structures of the chloromethylated polystyrene, the chlorophosphite ester and the catalyst intermediate A, B, C are as follows:
wherein R is1、R2Are identical or different alkyl, aryl, substituted alkyl, aryl, and their terminal groups may also be linked to one another.
2. The process according to claim 1, wherein in step (1), the nitration reaction is carried out at a reaction temperature of 50 to 110 ℃, preferably 80 to 100 ℃, for a reaction time of 2 to 10 hours, preferably 6 to 8 hours, and/or the mass ratio of chloromethylated polystyrene to concentrated sulfuric acid and concentrated nitric acid is 1: 0.2: 0.2 to 1: 1.5: 1.5, preferably 1: 0.5: 0.5 to 1: 1: 1.
3. the process according to claim 1 or 2, wherein in step (2), the hydrolysis reaction temperature is 60-120 ℃, preferably 90-110 ℃, the reaction time is 5-20h, preferably 10-15h, and/or the mass ratio of intermediate A to sodium hydroxide is 1: 0.5-1: 5, preferably 1: 1-1: 2.
4. the process according to any one of claims 1 to 3, wherein in the step (3), when reacting the intermediate B with butyllithium and chlorophosphite, butyllithium is added at a temperature of-78 to 10 ℃ for 0.5 to 3 hours, preferably 1 to 2 hours, and chlorophosphite is added for reaction at a temperature of-78 to 30 ℃, preferably-30 to 10 ℃ for 0.5 to 3 hours, preferably 1 to 2 hours; and/or the mass ratio of the intermediate B to the butyl lithium to the phosphorochloridite is 1: 0.1: 0.1-1: 0.5: 0.5, preferably 1: 0.2: 0.2-1: 0.4: 0.4.
5. the process according to any one of claims 1 to 4, wherein in step (4), the rhodium-or cobalt-containing compound is one or more of dicarbonyl acetylacetonatorhodium, acetylacetonatotriphenylphosphine carbonyl rhodium, triphenylphosphine carbonyl rhodium chloride, triphenylphosphine rhodium bromide, polymeric dicarbonyl rhodium chloride, cobalt carbonyl, and/or a solution of the rhodium-or cobalt-containing compound at a concentration of 0.1 to 2mol/L, preferably 0.5 to 1 mol/L.
6. The process according to any one of claims 1 to 5, wherein in step (4), the catalyst is obtained by filtration at 70 to 110 ℃ for 24 to 72 hours and/or by impregnation at 25 to 100 ℃, preferably 40 to 80 ℃ for 0.5 to 3 hours, preferably 1 to 2 hours.
7. Use of the catalyst prepared according to the preparation process of any one of claims 1 to 6 as a catalyst for hydroformylation of olefins.
8. Use according to claim 7, wherein the olefins comprise one or more of ethylene, propylene, n-butene, butene-1, butene-2, butadiene, isobutylene, 1-pentene, cyclopentene, cyclopentadiene, 1-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, 1-nonene, 1-decene, tripropylene, tetrapropylene, di-n-butene, tri-n-butene, diisobutylene, triisobutene.
9. Use according to claim 7 or 8, characterized in that the catalyst is used in an amount of 0.1-10 wt%, preferably 0.5-5 wt%, based on the mass of the olefin, when the catalyst is used to catalyze a hydroformylation reaction; and/or the reaction temperature is 80-120 ℃, preferably 90-110 ℃; and/or the reaction time is 0.5-10h, preferably 2-8 h; and/or the reaction pressure is from 8 to 20MPaG, preferably from 10 to 18 MPaG.
10. Use according to any one of claims 7 to 9, wherein the hydroformylation reaction is carried out batchwise or continuously using a bubble column or a reaction vessel, after which the aldehyde product is obtained by filtration, and the separated catalyst is recycled.
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