CN114588949A - Eggshell type catalyst for olefin hydroformylation reaction and preparation and application thereof - Google Patents

Eggshell type catalyst for olefin hydroformylation reaction and preparation and application thereof Download PDF

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CN114588949A
CN114588949A CN202210233433.6A CN202210233433A CN114588949A CN 114588949 A CN114588949 A CN 114588949A CN 202210233433 A CN202210233433 A CN 202210233433A CN 114588949 A CN114588949 A CN 114588949A
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catalyst
phosphine ligand
phosphine
eggshell
ligand
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李存耀
丁云杰
严丽
丁玉龙
姜淼
马雷
姬广军
钱磊磊
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Dalian Institute of Chemical Physics of CAS
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    • 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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    • 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
    • B01J35/397—
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    • 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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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Abstract

The invention discloses an eggshell type catalyst for olefin hydroformylation reaction and a preparation method and application thereof, wherein the eggshell type catalyst takes one, two or more than two of metals Rh, Co, Ir, Ru, Pt, Pd and Fe as active components, takes a phosphine ligand polymer bead as a carrier, and the phosphine ligand polymer bead is formed by auto-polymerization or Co-polymerization of a monodentate phosphine ligand containing an olefin group, a multidentate phosphine ligand or a secondary phosphine oxide ligand. The eggshell type catalyst is suitable for reactors such as fixed beds, slurry beds, tank reactors, trickle beds and the like. The eggshell type catalyst provided by the invention can be applied to the reactions such as olefin hydroformylation reaction, hydromethylamination, hydrocarboxylation, alcohol carbonylation reaction and the like. The catalytic performance of the catalyst is remarkably improved by adjusting the spatial distribution of the metal active component in the eggshell type catalyst, and the eggshell type catalyst for the hydroformylation reaction of the olefin, which is provided by the invention, has good stability and shows a potential industrial application prospect.

Description

Eggshell type catalyst for olefin hydroformylation reaction and preparation and application thereof
Technical Field
The invention belongs to the field of heterogeneous catalysis, and particularly relates to an eggshell type catalyst for olefin hydroformylation reaction, and a preparation method and application thereof.
Background
Olefins, carbon monoxide and a third component (H)2、H2O, ROH, etc.) to produce aldehydes or alcohols is known as hydroformylation and is of great economic and academic interest. Traditional catalysts fall into two broad categories, homogeneous and heterogeneous. The homogeneous complex catalyst generally has the advantages of mild reaction conditions, high activity and selectivity, less side reactions and the like. However, heterogeneous catalysts are easy to separate from reaction materials and products, and are easy to operate industrially, and in order to obtain a novel catalyst having the advantages of both catalysts, people put a lot of efforts into the field of heterogenization of homogeneous catalysts (eur.j.org.chem.2012, 6309-6320). Homogeneous catalyst immobilization is one of the most commonly used methods, and is achieved by covalent bond formation between a ligand and a support, but this method has a disadvantage in that an active metal is easily lost (Frontiers of Chemical Science and Engineering,2018,12, 113-.
The previous patent (CN104707660B) of the group develops a heterogeneous catalyst prepared by taking triphenylphosphine polymer as a ligand and a carrier simultaneously, the advantages of homogeneous catalysis and heterogeneous catalysis can be integrated, and the prepared catalyst has good catalytic performance and stability in the hydroformylation of ethylene.
The hydroformylation is a strongly exothermic reaction, for example, the heat of reaction for hydroformylation of ethylene to propionaldehyde is 157.06kJ/mol, and the heat of reaction for hydroformylation of propylene to n-butyraldehyde is 123.8 kJ/mol. When the heterogeneous catalyst is applied to a hydroformylation process of a fixed bed, the uniform heterogeneous catalyst can limit mass transfer and heat transfer, and hot spots are generated or a byproduct is generated through excessive reaction, so that the reaction performance of the catalyst is reduced, and even the temperature of a device is seriously fluctuated to damage the catalyst. On the other hand, the active components inside the homogeneous catalyst do not fully perform the catalytic function due to the influence of the diffusion of the reactants and products, which causes the waste of the metal active components and increases the catalyst cost.
The eggshell type catalyst is a spherical catalyst with active sites on the outer surface, and the special active metal spatial distribution of the eggshell type catalyst can improve the utilization rate of noble metals, enhance the stability of the catalyst, effectively control the reaction rate and increase the selectivity of target products. Therefore, the synthesis and application of eggshell type catalysts are attracting much attention.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide an eggshell type catalyst for olefin hydroformylation reaction, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
an eggshell type catalyst for olefin hydroformylation reaction, wherein the eggshell type catalyst takes one or more than two of metals Rh, Co, Ir, Ru, Pt, Pd and Fe as an active component and takes phosphine ligand polymer beads as a carrier;
the particle size of the phosphine ligand polymer beads ranges from 0.1 to 10mm (preferably from 0.1 to 5mm), the active component is uniformly coordinated to the surface layer of the polymer beads (the depth of the active component which is immersed from the outer surface of the carrier to the inside of the carrier), the surface layer of the carrier containing the metal active component is called an eggshell layer, and the thickness of the eggshell layer of the catalyst accounts for 0.02 to 20 percent (preferably 0.02 to 10 percent) of the particle size of the polymer beads. .
The phosphine ligand polymer beads are formed by self-polymerization of one of monodentate phosphine ligands containing alkylene groups, polydentate phosphine ligands containing alkylene groups and secondary phosphine oxide ligands containing alkylene groups or copolymerization of more than two of the monodentate phosphine ligands, the polydentate phosphine ligands and the secondary phosphine oxide ligands containing alkylene groups;
adding phosphine oxide polymer pellets into a solution containing one or more than two of precursors of active components Rh, Co, Ir, Ru, Pt, Pd and Fe, fully stirring and coordinating, and dipping active metal of the eggshell type catalyst into the polymer carrier pellets and coordinating with phosphine ligands in a carrier skeleton to form a catalyst shell layer to obtain the eggshell type catalyst;
the metal loading range of the eggshell type catalyst is 0.01-10 wt%, and the preferred range is 0.1-3 wt%.
The olefin group of the monodentate phosphine ligand, multidentate phosphine ligand or secondary phosphine oxide ligand containing olefin group used for polymerization is preferably a vinyl functional group, and the metal active component is uniformly distributed in the eggshell layer.
The monodentate phosphine ligand containing an alkenyl group is one or more than two of the following:
Figure BDA0003541198150000021
Figure BDA0003541198150000031
Figure BDA0003541198150000041
the multidentate phosphine ligand containing alkylene is selected from one or more than two of the following components:
Figure BDA0003541198150000051
the secondary phosphine oxide ligand containing alkene group is selected from one or more than two of the following:
Figure BDA0003541198150000061
the phosphine ligand polymer beads have a hierarchical pore structure, and the specific surface area is 10-3000m2A preferred range is 20 to 1000 m/g2(ii) a pore volume of 0.1-10.0cm3/g, preferably 0.2-2.0cm3/g, and a pore size distribution of 0.01-100.0nm, preferably 0.1-5.0 nm.
The preparation process of the phosphine ligand polymer beads comprises the following steps:
fully dissolving and mixing one or more than two of monodentate phosphine ligand, multidentate phosphine ligand and secondary phosphine oxide ligand containing alkylene, adding or not adding a cross-linking agent, and initiating the alkylene in the organic phosphine ligand to carry out polymerization reaction by a free radical initiator to generate the phosphine ligand polymer bead with the hierarchical pore structure; the preparation process of the eggshell type catalyst comprises the following steps: and fully stirring the precursor of the active metal component and the phosphine ligand polymer beads in a solvent, forming a firm chemical bond between the active metal component and the exposed P in the phosphine oxide polymer carrier, and evaporating the solvent to obtain the eggshell type catalyst.
The eggshell type catalyst comprises the following specific preparation steps:
a) under the inert gas atmosphere 273-473K, adding an alkylene monodentate phosphine ligand and/or polydentate phosphine ligand and/or secondary phosphine oxide ligand, adding or not adding a cross-linking agent, adding a free radical initiator, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution, wherein the preferable stirring time range is 0.1-20 hours;
b) transferring the prepolymer mixed solution prepared in the step a) into a polymerization reactor, and carrying out polymerization reaction for 1-100 hours by adopting methods such as suspension polymerization, emulsion polymerization and the like;
c) washing the solid particles obtained in the step b) by a solvent with the volume 10-1000 times of that of the solid particles, and then, vacuumizing and removing the solvent under 273-403K to obtain the phosphine ligand polymer beads with the hierarchical pore structure, namely the carrier of the eggshell type catalyst for the hydroformylation reaction of olefins;
d) adding the phosphine ligand polymer beads obtained in the step c) into a solvent containing an active metal component precursor under an inert gas atmosphere of 273-473K, stirring for 0.1-100 hours, preferably for 0.1-20 hours, and then, vacuumizing the solvent under 273-403K to obtain the eggshell type catalyst for the hydroformylation reaction of the olefin. The concentration of the active metal in the precursor solution is in the range of 0.001-1mol L-1.
The solvent in the steps a), c) and d) is one or more than two of benzene, toluene, xylene, methanol, ethanol, dichloromethane, trichloromethane, water or tetrahydrofuran;
the free radical initiator in the step a) is one or more than two of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, cyclohexanone peroxide or dibenzoyl peroxide;
the molar ratio of the monodentate olefin-group-containing phosphine ligand to the multidentate phosphine ligand in step a) is 0.01:1 to 100:1, the molar ratio of the monodentate olefin-group-containing phosphine ligand to the secondary phosphine oxide ligand is 0.01:1 to 100:1, the molar ratio of the monodentate olefin-group-containing phosphine ligand to the crosslinking agent is 0.01:1 to 100:1 when the crosslinking agent is added, and the molar ratio of the monodentate olefin-group-containing phosphine ligand to the radical initiator is 500:1 to 10:1, preferably 100:1 to 10: 1. The concentration of the secondary phosphine oxide containing alkylene in the solvent before polymerization into organic polymer beads is in the range of 0.01 to 1000g/L, preferably 0.1 to 10 g/L; the inert gas in the steps a), b) and d) is one or more than two of Ar, He, N2 and CO 2.
The active component is one or more than two of Rh, Co, Ir, Ru, Pt, Pd or Fe, wherein the precursor of Rh is RhH (CO) (PPh)3)3、Rh(CO)2(acac)、RhCl3、Rh(CH3COO)2One or more than two of the above; the precursor of Co is Co (CH)3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2One or more than two of the above; the precursor of Ir is Ir (CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4One or more than two of the above; the precursor of Ru is dichloro (cyclooctyl-1, 5-diene) ruthenium (II) and RuCl3、Ru(acac)3Dodecacarbonyltriruthenium, [ RuAr ]2(benzene)]2、[RuAr2(p-cymene)]2,[RuAr2(mesitylene)]2、[(π-ally)Ru(cod)]2、[(π-ally)Ru(nbd)]2One or more than two of the above; the precursor of Pt is Pt (acac)2、PtCl4、PtCl2(NH3)2One or more than two of the above; the precursor of Pd is Pd (CH)3COO)2、Pd(acac)2、PdCl2、Pd(PPh3)4、PdCl2(CH3CN)2One or more than two of the above; the precursor of Fe is Fe (acac)3、FeCl3、FeCl2One or more than two of FeS, ferrocene and nonacarbonyl diiron, and the metal loading range in the catalyst is 0.01-10 wt%, preferably 0.1-3 wt%. The eggshell type catalyst is applied to olefin hydroformylation reaction, hydromethylamination, hydrocarboxylation or alcohol carbonylation reaction; wherein the carbon number range of the raw material olefin is C2-C30The carbon number range of the raw material alcohol is C1-C10。
The eggshell type catalyst is suitable for reactors such as fixed beds, slurry beds, tank reactors, trickle beds and the like. The eggshell type catalyst provided by the invention can be applied to the reactions such as olefin hydroformylation reaction, hydromethylamination, hydrocarboxylation, alcohol carbonylation reaction and the like. The catalytic performance of the catalyst is remarkably improved by adjusting the spatial distribution of the metal active component in the eggshell type catalyst, and the eggshell type catalyst for the hydroformylation reaction of the olefin, which is provided by the invention, has good stability and shows a potential industrial application prospect.
The reaction principle of the invention is as follows:
the invention relates to an eggshell type catalyst prepared by self-polymerizing or copolymerizing a monodentate phosphine ligand, a multidentate phosphine ligand or a secondary phosphine oxide ligand containing alkylene into a phosphine ligand polymer bead and coordinating high-concentration P on the surface layer of the polymer bead with active metal. Because the active center is located the top layer of eggshell type catalyst, the eggshell type catalyst mass transfer and heat transfer that this patent provided are effectual, the active center high-usage. The eggshell type catalyst pellet has high polymerization crosslinking degree and high strength, and the eggshell type catalyst has high mechanical strength and long-range stability and is suitable for industrial application.
The invention has the beneficial effects that:
in order to maintain the stability of catalytic active center species, the traditional homogeneous phase and water-oil two-phase hydroformylation process usually maintains higher P/Rh ratio, so that the regulation range of the catalytic performance is limited. In addition, the eggshell type catalyst provided by the patent can remarkably improve the problems of poor mass transfer and heat transfer effects and low utilization rate of active centers of the traditional heterogeneous hydroformylation catalyst, can effectively improve mass transfer and heat transfer, and eliminates local reaction hot spots. The eggshell type catalyst has high vinyl crosslinking degree and high strength in the eggshell type catalyst body, so that the eggshell type catalyst has strong mechanical strength and long-range stability, and is suitable for industrial application.
Drawings
FIG. 1 is a phosphine ligand polymer pellet obtained in example 1.
FIG. 2 is a structural formula of a cross-linking agent used in preparation of phosphine ligand polymer beads.
Detailed Description
The following examples illustrate the invention better without limiting its scope.
The synthesis method of the vinyl monodentate phosphine ligand is disclosed in the patent (CN202110589670.1), for example, under the protection of 273K inert gas Ar, 207kg of o-chlorostyrene (1.5kmol) and 2.07kg of hydroquinone (polymerization inhibitor) are dissolved in 1000 liters of 2-methyltetrahydrofuran, stirred for 1 hour and then injected into an overhead tank of an enamel reaction kettle; the temperature of the reaction kettle is raised to 333K, 38kg of magnesium chips are placed into a 3000L enamel reaction kettle, 100L of mixed solution of o-chlorostyrene and 2-methyltetrahydrofuran is dripped into the reaction kettle, the mixed solution is continuously dripped after the initiation of a Grignard reagent (the boiling color of the solution changes into black and green), and the dripping temperature is maintained at 65 ℃. And preserving the temperature for 1 hour after the dropwise addition is finished to obtain the Grignard reagent solution.
Under the protection of inert gas Ar, transferring the prepared Grignard reagent to an overhead tank of an enamel reaction kettle, adding 70kg of phosphorus trichloride and 700 liters of 2-methyltetrahydrofuran into the enamel reaction kettle, adjusting the temperature of the reaction kettle to 0 ℃, dropwise adding the prepared Grignard reagent at 0 ℃, and continuing to react for 1 hour after dropwise adding. Under the protection of inert gas Ar of 298K, adjusting the pH of a reaction liquid to 5 by hydrochloric acid solution with the mass concentration of 2%, stirring for 1 hour to fully extinguish the reaction, standing for 2 hours, dividing the mixed liquid into two layers, taking out an upper oil layer, filtering the oil layer by a diatomite layer with the thickness of 10cm, distilling at 60 ℃ to remove the solvent to obtain a light yellow oily liquid, adding 80kg of n-heptane to heat the mixed solvent to 60 ℃ to fully dissolve, cooling to 0 ℃, recrystallizing and drying to obtain the vinyl functionalized phosphine ligand L1.
Multidentate vinyl ligand synthesis is described in (CN202111421292.2), for example, intermediate 1 can be prepared according to the procedures of the literature (Tetrahedron Letters,2010,51, 272497-2499):
Figure BDA0003541198150000091
addition of 8g of intermediate 1 to a freshly prepared phosphorus ylide reagent (13.4 g of potassium tert-butoxide added to a mixture of 42g of p-methyltriphenylphosphine bromide and 400ml of tetrahydrofuran under argon protection at 10 ℃ with stirring for 3 hours) produced the key intermediate 2:
Figure BDA0003541198150000092
10mmol of intermediate 2(29.8g) and 30g of triethylamine are dissolved in 1L of tetrahydrofuran at-5 ℃ under argon protection, and 25mmol of
Figure BDA0003541198150000093
(see Catal. Sci. Technol.,2016,6(7): 2143-. Adding 200mL saturated ammonium chloride solution at 0 deg.C for annihilation reaction, concentrating oil layer, passing through silica gel column, eluting with 20:1 eluent to obtain monomer B2 (product with nuclear magnetism and high resolution quality)Spectrum confirmed), the yield was 40%.
The synthesis method of the vinyl secondary phosphine oxide ligand is disclosed in patent (CN202111421650.X), 9g of p-chlorostyrene is dissolved in 50ml of 2-methyltetrahydrofuran under the protection of 273K argon, and the mixture is stirred uniformly for standby. 1.7g of magnesium chips are put into a flask, the temperature of the flask is raised to 333K, about 5ml of mixed solution of p-chlorostyrene and 2-methyltetrahydrofuran is dripped, the mixed solution is continuously dripped after the Grignard reagent is initiated, and the dripping temperature is maintained at 65 ℃. After the dropwise addition, the temperature is kept for 1 hour to obtain a format reagent solution of the p-chlorostyrene. Then, the temperature is reduced to 0 ℃, 4.5g of diethyl phosphite and 50ml of mixed solution are added, and the reaction is continued for 1 hour after the dropwise addition is finished. 10ml of saturated NH4Cl solution is added for annihilation reaction, the mixed solution is divided into two layers, the upper oil layer is taken out, the solvent is distilled and removed at 60 ℃ to obtain light yellow oily liquid, 10ml of n-heptane is added to heat the mixed solvent to 60 ℃ for full dissolution, then the temperature is reduced to 0 ℃ for recrystallization and drying, and 6.05g of vinyl secondary phosphine oxide ligand P1 can be obtained (the yield is about 73 percent, and the product is confirmed by nuclear magnetic and high resolution mass spectrometry).
Example 1
Preparation of phosphine ligand polymer beads: 50g of phosphine ligand L1 and 0.1g of benzoyl peroxide are dissolved in 50ml of dimethylbenzene in a 1000ml of enamel stirring reaction kettle under the protection of 298K and inert gas, 200ml of polyvinyl alcohol solution (suspending agent) with the mass concentration of 1.5% is added, the mixture is fully stirred and mixed, and the reaction temperature is raised to 90 ℃ for reaction for 2 hours. Then cooling to room temperature, filtering the particles, washing with 500mL deionized water, and vacuum drying at 60 deg.C for 5 hr to obtain phosphine ligand polymer pellets with diameter range of 0.2mm-1.0mm (figure 1) and average particle diameter of 0.7 mm.
Weighing 3.13 mg of rhodium (II) acetate in 10.0mL of dichloromethane under the protection of 298K and inert gas Ar, adding 1.0g of phosphine ligand polymer bead carrier, stirring the mixture for 24 hours under the protection of 298K and inert gas Ar, then pumping the solvent in vacuum at room temperature to obtain the eggshell type catalyst applied to the hydroformylation reaction of olefin, observing the section by an electron microscope, uniformly coordinating an active component Rh on the surface layer of the polymer bead, wherein the thickness of a catalyst layer (shell layer) containing metal Rh is 0.02mm, and the distribution of the Rh in the eggshell layer is uniform. The catalyst metal loading was found to be 0.12%.
Example 2
In example 2, phosphine ligand pellets were prepared, except that 50g of phosphine ligand L1, 5.0g of vinyl polydentate phosphine ligand B4 and 1.0g of secondary phosphine oxide ligand P6 were added in place of 50g of phosphine ligand L1, and the rest of the synthesis procedures and conditions were the same as in example 1. The diameter of the pellet is 0.2mm-1.0mm, and the average particle diameter is 0.7 mm. The active component Rh is uniformly coordinated on the surface layer of the polymer pellet by observing the section through an electron microscope, the thickness of a catalyst layer (shell layer) containing metal Rh is 0.02mm, and the distribution of Rh in an eggshell layer is uniform. The measured metal loading of the catalyst is 0.12 percent
Example 3
In example 3, an eggshell catalyst was prepared by following the same procedure as in example 1 except that 1.0mL of methylene chloride was used in place of 10mL of methylene chloride, and the beads ranged in diameter from 0.2mm to 1.0mm and had an average particle diameter of 0.7 mm. The active component Rh is uniformly coordinated on the surface layer of the polymer pellet by observing the section through an electron microscope, the thickness of a catalyst layer (shell layer) containing metal Rh is 0.005mm, and the distribution of Rh in an eggshell layer is uniform. The measured metal loading of the catalyst is 0.12 percent
Example 4
In example 4, the procedure and the catalyst synthesis process were the same as in example 1 except that the bulk polymerization process was replaced with the emulsion polymerization process, and the pellet diameter ranged from 0.2mm to 1.0mm and the average particle diameter was 0.7 mm. The active component Rh is uniformly coordinated on the surface layer of the polymer pellet by observing the section through an electron microscope, the thickness of a catalyst layer (shell layer) containing metal Rh is 0.02mm, and the distribution of Rh in an eggshell layer is uniform. The measured catalyst metal loading was 0.12%
Example 5
In example 5, a highly dispersed Co-based catalyst was obtained by using the same synthesis process and conditions as in example 1 except that the same molar number of octacarbonyldicobalt was used instead of rhodium (II) acetate, and the thickness of the catalyst layer (shell layer) was 0.02 mm.
Example 6
In example 6, a highly dispersed Ir-based catalyst having a catalyst layer (shell layer) thickness of 0.02mm was obtained by following the same synthesis procedure and conditions as in example 1 except that the same molar number of Ir (CH3COO)3 was used in place of the rhodium (II) acetate.
Example 7
In example 7, the synthesis procedure and conditions were the same as in example 1 except that the same number of moles of dodecacarbonyltriruthenium were used instead of rhodium (II) acetate, and the thickness of the catalyst layer (shell layer) was 0.02 mm.
Example 8
In example 8, the synthesis process and conditions were the same as in example 1 except that rhodium (II) acetate was replaced with the same molar number of Fe (acac)3, and the thickness of the catalyst layer (shell layer) was 0.02 mm.
Example 9
In example 9, the synthesis and conditions were the same as in example 2 except that 1.0g of CL3 shown in FIG. 2 was additionally added as a crosslinking agent in the preparation of phosphine ligand beads, and the thickness of the catalyst layer (shell layer) was 0.02 mm.
Example 10
Phosphine ligand polymer beads were prepared by the same procedure and conditions as in example 1 except that 50ml of chloroform was used instead of 50ml of xylene, and the thickness of the catalyst layer (shell layer) was 0.015 mm.
Comparative example 1
In comparative example 1, the kind and amount of the metallic Rh precursor used in the impregnation process were the same as those of example 1 except that the homogeneous catalyst was prepared by the solvothermal polymerization method mentioned in the earlier patent CN 104707660B.
The specific implementation method comprises the following steps: 50g of phosphine ligand L1 and 1g of benzoyl peroxide are dissolved in 500ml of tetrahydrofuran in a 1000ml enamel autoclave, stirred for 2 hours and kept stand under the protection of 373K nitrogen for 24 hours to carry out polymerization reaction. Then cooling to room temperature, and removing the solvent at room temperature to obtain the phosphine ligand powdery polymer.
Under the protection of 298K and inert gas, 3.13 mg of rhodium (II) acetate is weighed and dissolved in 10.0mL of dichloromethane, 1.0g of phosphine ligand powdery polymer carrier is added, the mixture is stirred for 24 hours under the protection of 298K and inert gas, and then the solvent is pumped out in vacuum at room temperature, so that the uniform powdery catalyst for the hydroformylation reaction is obtained.
Comparative example 2
In comparative example 2, except that 50g of phosphine ligand L1, 5.0g of vinyl polydentate phosphine ligand B4 and 1.0g of secondary phosphine oxide ligand P6 were added in place of 50g of phosphine ligand L1 in the preparation of a phosphine ligand powdered polymer, the rest of the synthesis procedures and conditions were the same as in comparative example 1, to obtain a hydroformylation-homogeneous powdered catalyst copolymerized with phosphine ligand L1, vinyl polydentate phosphine ligand B4 and 1.0g of secondary phosphine oxide ligand P6. The catalyst metal loading was found to be 0.12%.
Example 11
1g of the catalysts prepared in examples 1 to 10 and comparative examples 1 to 2 were charged into fixed bed reactors, respectively, and quartz sand was charged into both ends of the catalyst bed. Introducing reaction gas mixture (H)2:CO:C2H41:1:1, V/V/V), 383K, 1.0MPa, and the air speed of the reaction mixture is 4000h-1The hydroformylation reaction is carried out under the conditions. The reaction was absorbed and collected in a collection tank containing 60ml of chilled deionized water, and the reaction product propionaldehyde was completely dissolved in the water in the collection tank. The aqueous solution obtained was analysed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using ethanol as internal standard. The reaction tail gas after water absorption was analyzed on-line by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.
TABLE 1. examples 1 to 10 and comparative examples catalyst specific surface area and ethylene hydroformylation Performance
Figure BDA0003541198150000121
Examples 1 and 3 used eggshell catalysts, and comparative examples 1 and 2 used homogeneous powder catalysts (homogeneous powder catalysts were observed by electron microscopy that active component Rh was uniformly distributed in the catalyst, which is probably due to organic solvent for monomer polymerization and bulk polymerization during the preparation of the homogeneous powder catalysts, resulting in completely oleophilic surface, and stronger action force of impregnation liquid and polymer powder when active metal was loaded, thus forming homogeneous catalysts; polymer beads were prepared by suspension polymerization of water and oil phases, the surface of the polymer beads was not completely oleophilic nor completely hydrophilic, and the action force of impregnation liquid and polymer powder was weaker when active metal was loaded, thus forming eggshell catalysts), from the data in Table 1 it can be seen that the eggshell catalysts had higher ethylene hydroformylation activity under the same conditions compared to homogeneous powder catalysts, the selectivity of the product aldehyde is better. The eggshell type catalyst has the advantages that the metal is distributed on the surface layer, the special active metal space distribution can improve the utilization rate of the noble metal, enhance the stability of the catalyst, effectively control the reaction rate and increase the selectivity of a target product. In examples 5,6,7 and 8, the active metals are Co, Ir, Ru and Fe respectively, and the reactivity is lower than that of the catalyst with the active metal being Rh. When the active center is Rh, it can be seen that the ethylene hydroformylation reaction activity of the eggshell type catalyst is significantly higher than that of the corresponding comparative homogeneous type catalyst, and the aldehyde selectivity is also better.
Example 12
0.5g of the catalyst prepared in examples 1 to 10 and comparative examples 1 to 2 was charged into a 50 ml-capacity slurry bed reactor, 30ml of valeraldehyde was added as a slurry, and a reaction mixture gas (H) was introduced2:CO:C3H61:1:1), at 393K, 1.0MPa, reaction mixture air speed 2000h-1And the hydroformylation reaction was carried out at a stirring rate of 750 revolutions per minute. The reaction was absorbed and collected in a collection tank containing 60ml of cooled deionized water, and the reaction product and the slurry liquid entrained with the tail gas were all dissolved in the water in the collection tank. The aqueous solution obtained was analysed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using ethanol as internal standard. The reaction tail gas after water absorption was analyzed on-line by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 2.
TABLE 2 catalyst specific surface area and propylene hydroformylation Performance for examples 1-10 and comparative examples
Figure BDA0003541198150000131
Examples 1 and 3 used eggshell catalysts, and comparative examples 1 and 2 used corresponding homogeneous powder catalysts (homogeneous powder catalysts were observed by electron microscopy that active component Rh was uniformly distributed in the catalyst, which is probably due to organic solvent for monomer polymerization and bulk polymerization during the preparation of the homogeneous powder catalysts, resulting in completely oleophilic surface, and stronger action force of impregnation liquid and polymer powder when loading active metal, thus forming homogeneous catalysts; polymer beads were prepared by suspension polymerization of water and oil phases, the surface of the polymer beads was not completely oleophilic nor completely hydrophilic, and the action force of impregnation liquid and polymer powder was weaker when loading active metal, thus forming eggshell catalysts), from the data in Table 1 it can be seen that the hydroformylation activity of eggshell catalysts was higher than that of homogeneous powder catalysts under the same conditions, the selectivity of the product aldehyde is better, the most obvious difference is that the eggshell type catalyst is concentrated on the surface layer of the catalyst, the proportion of normal aldehyde and isomeric aldehyde of the product butyraldehyde is also regulated and controlled, and the product aldehyde has irreplaceable effect on certain occasions needing specific aldehyde. In addition, the eggshell type catalyst has the advantages that the metal is distributed on the surface layer, the special active metal space distribution can improve the utilization rate of the noble metal, enhance the stability of the catalyst, effectively control the reaction rate and increase the selectivity of a target product. In examples 5,6,7 and 8, the active metals are Co, Ir, Ru and Fe respectively, and the reactivity is lower than that of the catalyst with the active metal being Rh. When the active center is Rh, it can be seen that the hydroformylation reaction activity of the eggshell type catalyst is significantly higher than that of the corresponding comparative homogeneous type catalyst, and the selectivity to isobutyraldehyde is higher.
Example 13
0.5g of the catalysts prepared in examples 1 to 10 and comparative examples 1 to 2 was placed in a fixed bed reactor, and both ends were charged with quartz sand. The micro-feed pump maintains the flow of the 2-heptene to be 0.8ml/min, and the mass flowmeter controls the synthesis gas (H)2CO is 1:1) space velocity of 1000h-1The hydroformylation reaction is carried out under the condition of 373K and 1 MPa. The reaction was collected via an ice-bath cooled collection tank. The obtained liquid product was subjected to HP-7890N gas chromatography using HP-5 capillary column and FID detectorAnalysis, using n-propanol as an internal standard. The off-gas from the collection tank was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 3.
TABLE 3 data on specific surface area and 2-hexene reaction of catalysts synthesized in examples 1 to 10 and comparative examples 1 to 2
Figure BDA0003541198150000141
Examples 1 and 3 used eggshell catalysts, and comparative examples 1 and 2 used homogeneous powder catalysts (homogeneous powder catalysts, as observed by electron microscopy, active component Rh was uniformly distributed in the catalyst, which is probably due to organic solvent for monomer polymerization and bulk polymerization during the preparation of homogeneous powder catalysts, resulting in completely oleophilic surface, and stronger action force of impregnation liquid and polymer powder when loading active metal, thus forming homogeneous catalysts; polymer beads were prepared by suspension polymerization of water and oil phases, the surface of polymer beads was not completely oleophilic nor completely hydrophilic, and the action force of impregnation liquid and polymer powder when loading active metal was weaker, thus forming eggshell catalysts), from the data in Table 1 it can be seen that 2-hexene hydroformylation activity of eggshell catalysts was higher than that of homogeneous powder catalysts under the same conditions, the selectivity of the product aldehyde is better, the most obvious difference is that the eggshell type catalyst is concentrated on the surface layer of the catalyst, the normal aldehyde isomeric aldehyde proportion of the product aldehyde is also regulated and controlled, and the product aldehyde has irreplaceable effect on certain occasions needing specific aldehyde. In addition, the eggshell type catalyst has the advantages that the metal is distributed on the surface layer, the special active metal space distribution can improve the utilization rate of the noble metal, enhance the stability of the catalyst, effectively control the reaction rate and increase the selectivity of a target product. In examples 5,6,7 and 8, the active metals are Co, Ir, Ru and Fe respectively, and the reactivity is lower than that of the catalyst with the active metal being Rh. When the active center is Rh, the 2-hexene hydroformylation reaction activity of the eggshell type catalyst is obviously higher than that of the corresponding homogeneous catalyst in the comparative example, and the selectivity to the isomeric aldehyde is higher.
Example 14
Except that palladium acetate with the same mole number is used for replacing rhodium acetate, the synthesis process and conditions of the rest of catalysts are the same as those in example 2, and the phosphine oxide supported Pd catalyst can be obtained, and the actually measured Pd loading amount is 0.12%.
15mg of phosphine oxide-supported Pd catalyst, NH4Cl 1mmol, 5mmol of hexene reactant, and 5mL of N-methylpyrrolidone (NMP) solvent were added to a 100mL autoclave, and then 3MPa CO was charged to conduct the aminomethylation reaction.
The reaction temperature is 16 hours and 400K. Hexene conversion 67.4% and product selectivity 99.6%.
Example 15
0.5g of the catalyst in example 2, 1.0mmol of p-toluenesulfonic acid, 6mmol of cyclohexene reactant, 3mmol of methyl iodide and 50mmol of purified water were added to a 100ml autoclave, and then 2MPa CO was charged for hydrocarboxylation reaction.
The reaction time is 18 hours, the reaction temperature is 445K, the cyclohexene conversion rate is 96.7 percent, and the product selectivity is 93.2 percent.
Example 16
1g of the catalyst prepared in example 2 was charged into a fixed bed reactor, and silica sand was charged into both ends of the fixed bed reactor. Introducing reaction gas mixture (H)2CO is 1:1, V/V), at 230 deg.C and 3.5MPa, and the space velocity of reaction mixture is 3000 hr-1Conditions, methanol liquid hourly speed 4h-1The methanol carbonylation reaction is carried out. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and FID detector, using N-butanol as an internal standard. The reaction off-gas was analyzed on-line by HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 4.
TABLE 4 methanol carbonylation performance of the catalyst prepared in example 11
Figure BDA0003541198150000151

Claims (10)

1. The eggshell type catalyst for the hydroformylation reaction of olefin is characterized in that one or more than two of metals Rh, Co, Ir, Ru, Pt, Pd and Fe are used as active components, and phosphine ligand polymer beads are used as a carrier;
the particle size of the phosphine ligand polymer ball is 0.1-10mm (preferably 0.1-5mm), the active component is uniformly distributed on the surface layer of the polymer ball, the surface layer of the carrier containing the metal active component is called an eggshell layer, and the thickness of the eggshell layer of the catalyst accounts for 0.02-20% (preferably 0.02-10%) of the particle size of the polymer ball.
2. The eggshell catalyst for the hydroformylation of olefins as claimed in claim 1, wherein:
the phosphine ligand polymer beads are formed by self-polymerization of one of monodentate phosphine ligands containing alkylene groups, polydentate phosphine ligands containing alkylene groups and secondary phosphine oxide ligands containing alkylene groups or copolymerization of more than two of the monodentate phosphine ligands, the polydentate phosphine ligands and the secondary phosphine oxide ligands containing alkylene groups;
adding phosphine oxide polymer pellets into a solution containing one or more than two of precursors of active components of Rh, Co, Ir, Ru, Pt, Pd and Fe, fully stirring and coordinating, and dipping active metal of the eggshell type catalyst into the polymer carrier pellets and coordinating with phosphine ligands in a carrier skeleton to form a catalyst shell layer to obtain the eggshell type catalyst;
the metal loading range of the eggshell type catalyst is 0.01-10 wt%, and the preferred range is 0.1-3 wt%.
3. The eggshell catalyst for the hydroformylation of olefins as claimed in claim 1 or 2, wherein the olefin group of the monodentate phosphine ligand, multidentate phosphine ligand or secondary phosphine oxide ligand used for the polymerization is preferably a vinyl functional group, and the metal active component is homogeneously distributed in the eggshell layer.
4. The eggshell catalyst for the hydroformylation of olefins as claimed in claim 2 or 3, wherein:
the monodentate phosphine ligand containing an alkenyl group is one or more than two of the following:
Figure FDA0003541198140000011
Figure FDA0003541198140000021
Figure FDA0003541198140000031
Figure FDA0003541198140000041
the multidentate phosphine ligand containing alkylene is selected from one or more than two of the following components:
Figure FDA0003541198140000042
the secondary phosphine oxide ligand containing alkene group is selected from one or more than two of the following:
Figure FDA0003541198140000051
5. the eggshell catalyst for the hydroformylation of olefins as claimed in claim 1, wherein: the phosphine ligand polymer beads have a hierarchical pore structure, and the specific surface area is 10-3000m2A preferred range is 20 to 1000 m/g2(ii) a pore volume of 0.1-10.0cm3/g, preferably 0.2-2.0cm3/g, and a pore size distribution of 0.01-100.0nm, preferably 0.1-5.0 nm.
6. The process for preparing an eggshell catalyst for the hydroformylation of olefins according to any one of claims 1 to 5, wherein:
the preparation process of the phosphine ligand polymer beads comprises the following steps:
fully dissolving and mixing one or more than two of monodentate phosphine ligand, multidentate phosphine ligand and secondary phosphine oxide ligand containing alkylene, adding or not adding a cross-linking agent, and initiating the alkylene in the organic phosphine ligand to carry out polymerization reaction by a free radical initiator to generate the phosphine ligand polymer bead with the hierarchical pore structure; the preparation process of the eggshell type catalyst comprises the following steps: and fully stirring the precursor of the active metal component and the phosphine ligand polymer beads in a solvent, forming a firm chemical bond between the active metal component and the exposed P in the phosphine oxide polymer carrier, and evaporating the solvent to obtain the eggshell type catalyst.
7. The method of claim 6, wherein:
the eggshell type catalyst comprises the following specific preparation steps:
a) under the inert gas atmosphere 273-473K, adding an alkylene monodentate phosphine ligand and/or polydentate phosphine ligand and/or secondary phosphine oxide ligand, adding or not adding a cross-linking agent, adding a free radical initiator, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution, wherein the preferable stirring time range is 0.1-20 hours;
b) transferring the prepolymer mixed solution prepared in the step a) into a polymerization reactor, and carrying out polymerization reaction for 1-100 hours by adopting methods such as suspension polymerization, emulsion polymerization and the like;
c) washing the solid particles obtained in the step b) by a solvent with the volume 10-1000 times of that of the solid particles, and then, vacuumizing and removing the solvent under 273-403K to obtain the phosphine ligand polymer beads with the hierarchical pore structure, namely the carrier of the eggshell type catalyst for the hydroformylation reaction of olefins;
d) adding the phosphine ligand polymer beads obtained in the step c) into a solvent containing an active metal component precursor under an inert gas atmosphere of 273-473K, stirring for 0.1-100 hours, preferably for 0.1-20 hours, and then, vacuumizing the solvent under 273-403K to obtain the eggshell type catalyst for the hydroformylation reaction of the olefin. The concentration of the active metal in the precursor solution is in the range of 0.001-1mol L-1.
8. The method of claim 7, wherein: the solvent in the steps a), c) and d) is one or more than two of benzene, toluene, xylene, methanol, ethanol, dichloromethane, trichloromethane, water or tetrahydrofuran;
the free radical initiator in the step a) is one or more than two of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, cyclohexanone peroxide or dibenzoyl peroxide;
the molar ratio of the monodentate olefin-group-containing phosphine ligand to the multidentate phosphine ligand in step a) is 0.01:1 to 100:1, the molar ratio of the monodentate olefin-group-containing phosphine ligand to the secondary phosphine oxide ligand is 0.01:1 to 100:1, the molar ratio of the monodentate olefin-group-containing phosphine ligand to the crosslinking agent is 0.01:1 to 100:1 when the crosslinking agent is added, and the molar ratio of the monodentate olefin-group-containing phosphine ligand to the radical initiator is 500:1 to 10:1, preferably 100:1 to 10: 1. The concentration of the secondary phosphine oxide containing alkylene in the solvent before polymerization into organic polymer beads is in the range of 0.01 to 1000g/L, preferably 0.1 to 10 g/L; the inert gas in steps a), b) and d) is selected from Ar, He and N2And CO2One or more than two of them.
9. The production method according to claim 6 or 7, characterized in that: the active component is one or more than two of Rh, Co, Ir, Ru, Pt, Pd or Fe, wherein the precursor of Rh is RhH (CO) (PPh)3)3、Rh(CO)2(acac)、RhCl3、Rh(CH3COO)2One or more than two of the above; the precursor of Co is Co (CH)3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2One or more than two of the above; the precursor of Ir is Ir (CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4One or more than two of (a); the precursor of Ru is dichloro (cyclooctyl-1, 5-diene) ruthenium (II) and RuCl3、Ru(acac)3Dodecacarbonyltriruthenium, [ RuAr ]2(benzene)]2、[RuAr2(p-cymene)]2,[RuAr2(mesitylene)]2、[(π-ally)Ru(cod)]2、[(π-ally)Ru(nbd)]2One or more than two of the above; the precursor of Pt is Pt (acac)2、PtCl4、PtCl2(NH3)2One or more than two of the above; the precursor of Pd is Pd (CH)3COO)2、Pd(acac)2、PdCl2、Pd(PPh3)4、PdCl2(CH3CN)2One or more than two of the above; the precursor of Fe is Fe (acac)3、FeCl3、FeCl2One or more than two of FeS, ferrocene and nonacarbonyl diiron, and the metal loading range in the catalyst is 0.01-10 wt%, preferably 0.1-3 wt%.
10. Use of an eggshell catalyst according to any one of claims 1 to 5 in the hydroformylation of olefins, hydromethanation, hydrocarboxylation or alcohol carbonylation; wherein the carbon number range of the raw material olefin is C2-C30The carbon number range of the raw material alcohol is C1-C10。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114849787A (en) * 2022-06-10 2022-08-05 中国科学院兰州化学物理研究所 Aryl bidentate phosphine ligand polymer in-situ encapsulation rhodium-based catalytic material and preparation method and application thereof
CN115041232A (en) * 2022-06-19 2022-09-13 中海油天津化工研究设计院有限公司 Hydroformylation catalyst, preparation method and application in preparation of aldehyde from mixed olefin
CN115672329A (en) * 2022-10-12 2023-02-03 中国石油大学(华东) Co series eggshell type catalyst and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101801528A (en) * 2007-09-14 2010-08-11 Lg化学株式会社 Phosphorus-containing catalyst composition and hydroformylation process using the same
CN104707660A (en) * 2013-12-11 2015-06-17 中国科学院大连化学物理研究所 Solid heterogeneous catalyst for hydroformylation of olefins, preparation method and application thereof
CN109806911A (en) * 2017-11-21 2019-05-28 中国科学院大连化学物理研究所 A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application
RU2711579C1 (en) * 2018-11-16 2020-01-17 Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) Rhodium-containing heterogeneous catalysts for processes of producing propanal and diethyl ketone by hydroformylation of ethylene
CN113402551A (en) * 2021-05-28 2021-09-17 中国科学院大连化学物理研究所 Vinyl functionalized phosphine ligand, preparation and application thereof
CN113416211A (en) * 2021-05-28 2021-09-21 中国科学院大连化学物理研究所 Vinyl functional group phosphine ligand synthesis method, phosphine ligand and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101801528A (en) * 2007-09-14 2010-08-11 Lg化学株式会社 Phosphorus-containing catalyst composition and hydroformylation process using the same
CN104707660A (en) * 2013-12-11 2015-06-17 中国科学院大连化学物理研究所 Solid heterogeneous catalyst for hydroformylation of olefins, preparation method and application thereof
CN109806911A (en) * 2017-11-21 2019-05-28 中国科学院大连化学物理研究所 A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application
RU2711579C1 (en) * 2018-11-16 2020-01-17 Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) Rhodium-containing heterogeneous catalysts for processes of producing propanal and diethyl ketone by hydroformylation of ethylene
CN113402551A (en) * 2021-05-28 2021-09-17 中国科学院大连化学物理研究所 Vinyl functionalized phosphine ligand, preparation and application thereof
CN113416211A (en) * 2021-05-28 2021-09-21 中国科学院大连化学物理研究所 Vinyl functional group phosphine ligand synthesis method, phosphine ligand and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
宗玲博等: "有机聚合物负载铑催化剂在氢甲酰化反应中的应用研究进展", 《有机化学》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114849787A (en) * 2022-06-10 2022-08-05 中国科学院兰州化学物理研究所 Aryl bidentate phosphine ligand polymer in-situ encapsulation rhodium-based catalytic material and preparation method and application thereof
CN114849787B (en) * 2022-06-10 2023-07-28 中国科学院兰州化学物理研究所 Aryl bidentate phosphine ligand polymer in-situ encapsulation rhodium-based catalytic material and preparation method and application thereof
CN115041232A (en) * 2022-06-19 2022-09-13 中海油天津化工研究设计院有限公司 Hydroformylation catalyst, preparation method and application in preparation of aldehyde from mixed olefin
CN115041232B (en) * 2022-06-19 2023-12-12 中海油天津化工研究设计院有限公司 Hydroformylation catalyst, preparation method and application thereof in aldehyde preparation from mixed olefins
CN115672329A (en) * 2022-10-12 2023-02-03 中国石油大学(华东) Co series eggshell type catalyst and preparation method thereof

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