CN117046519A - Co-based multi-phase catalyst loaded with nitrogen-containing porous organic ligand polymer and application thereof - Google Patents

Co-based multi-phase catalyst loaded with nitrogen-containing porous organic ligand polymer and application thereof Download PDF

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CN117046519A
CN117046519A CN202310695205.5A CN202310695205A CN117046519A CN 117046519 A CN117046519 A CN 117046519A CN 202310695205 A CN202310695205 A CN 202310695205A CN 117046519 A CN117046519 A CN 117046519A
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nitrogen
catalyst
ligand
ligand polymer
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王玉清
姜淼
严丽
丁健
赫文秀
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Inner Mongolia University of Science and Technology
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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
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/18—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
    • B01J31/1805—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 the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Abstract

The application discloses a nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst and application thereof, belonging to the technical field of heterogeneous catalysis; the catalyst consists of a metal component and an organic nitrogen ligand polymer, wherein the metal component is metal Co, and the organic nitrogen ligand polymer is a polymer with a large specific surface area and a multistage pore structure formed by solvothermal polymerization of vinyl functionalized organic nitrogen ligands; the catalyst of the application shows high reaction activity, high target product aldehyde selectivity and good reaction stability in the hydroformylation reaction of high-carbon-end olefin and internal olefin; such heterogeneous catalysts are suitable for use in fixed bed, slurry bed, tank reactors and the like. Compared with the traditional triphenylphosphine ligand polymer supported Co-based catalyst for catalyzing the hydroformylation reaction of high-carbon olefin, the catalyst has higher catalytic activity and aldehyde selectivity, and meanwhile, the novel Co-based multi-phase catalyst is adopted, so that the cost of separating and recycling the catalyst can be reduced, and the catalyst is more suitable for large-scale industrial production.

Description

Co-based multi-phase catalyst loaded with nitrogen-containing porous organic ligand polymer and application thereof
Technical Field
The application relates to the technical field of heterogeneous catalysis, in particular to a Co-based multi-phase catalyst loaded by a nitrogen-containing porous organic ligand polymer and application thereof.
Background
The design synthesis of porous organic polymer (porous organic polymer, POPs) materials is one of the new hot spots in the research field of porous materials, and the porous materials are mainly formed by covalent bonding of small organic molecules. Compared with the traditional inorganic microporous materials and metal organic frame Materials (MOFs), the frameworks of POPs are composed of pure organic molecules and are mutually connected through covalent bonds, so that the POPs have open pore channels and excellent pore properties. Compared with soluble polymers, POPs have the advantages of large specific surface area, developed pores and easy separation; more importantly, due to the diversity of organic chemical synthesis methods, a rich synthesis path and a rich construction mode are provided for the construction of an organic molecular network, the material can have corresponding properties by purposefully introducing functionalized organic molecules, and the pore properties of the material can be regulated and controlled by regulating the structure of the organic molecules. In addition, in most cases, covalently linked organic microporous polymers have a more stable molecular network structure while maintaining the pore properties of the material than molecular network systems that are not covalently linked. In addition, the porous organic polymer containing the ligand can be used as a carrier and also can be used as a ligand, and the metal active unit with catalytic activity can be introduced into the porous organic polymer at fixed points, so that the metal active unit is highly dispersed in the porous organic polymer carrier in a single-atom form, thereby being beneficial to stabilizing metal active sites, reducing loss of metal active components and greatly improving the utilization efficiency of metal.
Currently, catalysts reported in literature for olefin hydroformylation reactions mainly comprise homogeneous catalysts composed of metal and alkylphosphine ligands, phosphite ligands, phosphonite amide ligands, nitrogen ligands and the like, and heterogeneous catalysts composed of two-phase catalysis and homogeneous catalyst immobilization, commonly used carriers for immobilization such as activated carbon, silica, molecular sieves, heteropolyacids, mesoporous materials, functional organic polymers, metal organic framework materials and the like (Catal. Sci. Technical, 2022,12,4962-4982; chem. Commun.,2023,59,2126; front. Chem. Sci. Eng.2018, 113-123). The homogeneous catalyst has high activity, high normal aldehyde selectivity, difficult separation from products, complex process and trace metal impurities which cause fatal defects to downstream products. On the other hand, the heterogeneous catalyst still has the problems of poor activity and selectivity, easy loss of active components, poor reusability and the like.
2021, beller et al (ACS Sustainable chem. Eng.,2021,9,5148-5154) reported the use of phosphine oxide ligand modified Co-based catalysts in the hydroformylation of 1-octene under mild reaction conditions (60-80 ℃,4mpa,24 h), high total aldehyde selectivity, low total alcohol content, and higher linear nonanal selectivity, but the system is homogeneous catalysis and still faces the problems of difficult separation and recovery of the catalyst, etc.
In 2019, fang et al (Chemistry Select,2019,4 (35): 10447-10451) selected molecular sieves A with different pore diameters as carriers, and NaBH4 as a reducing agent by an isovolumetric impregnation method, to prepare a series of supported Co-based catalysts. In the hydroformylation reaction of 1-hexene, the conversion rate of olefin reaches 74.2%, and the aldehyde-to-iso ratio of the product is 1.93. However, the activity of the active compound is still to be improved, the circulation stability is poor, and the active component is easy to run off.
BAUER et al (Nat Commun,2020,11 (1): 1059) applied Metal Organic Frameworks (MOFs) to Co2 (CO) 8 catalyzed hydroformylation reactions. The research shows that proper micropores in MOFs material can increase the generation rate of branched aldehyde so as to increase the selectivity of the MOFs material, but the MOFs material has poor hydrothermal stability, the raw materials are expensive, and the recycling stability data are not provided.
In 2020, lee et al (Fuel, 2020, 269:117397) prepared a single crystal Co3O4 nano catalyst with different morphologies by a hydrothermal synthesis method, in a hydroformylation reaction of 1-heptene, the same metal Co oxide Co3O4 has different morphologies and exposed crystal faces, the reaction results are different, for example, the reaction is carried out for 12 hours under the conditions of 170 ℃ and 4MPa, the conversion rate of 1-heptene of the octahedral Co3O4 catalyst reaches 88%, the selectivity of C8 aldehyde is 75.2%, and the positive-to-negative ratio of aldehyde is not reported. However, the reaction conditions are still too severe, and the reaction time is relatively long.
The vinyl polymerized porous organic polymer material has the characteristics of high specific surface area, hierarchical pore structure, easy modification and the like. As a catalytic material, the active center in the pore canal can be utilized in a large amount due to the unique swelling property. Vinyl polymeric porous organic polymer materials have been widely used as supports and ligand supported Rh-based catalysts in olefin hydroformylation reactions, achieving excellent catalytic activity, selectivity and stability (Journal ofCatalysis,368 (2018) 197-206.Applied Catalysis A:General,551 (2018) 98-105.j.catalyst, 353 (2017) 123-132). However, the heterogeneous catalytic systems described above all use the noble metal Rh as catalyst and are expensive.
Disclosure of Invention
The application aims to provide a nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst and application thereof, wherein a homogeneous phase ligand multi-phase strategy is adopted, a homogeneous phase nitrogen-containing ligand is introduced into vinyl (vinyl), and the vinyl is polymerized in an autoclave by a solvothermal polymerization method to form the nitrogen-containing porous organic polymer with high specific surface area and a multi-stage pore structure, and the nitrogen-containing porous organic polymer supported Co-based multi-phase catalyst is obtained after metal Co is self-supported.
The application adopts the following technical scheme:
according to a first aspect of the present disclosure, the present application provides a nitrogen-containing porous organic ligand polymer-supported Co-based multi-phase catalyst consisting of a metal component and an organic nitrogen ligand polymer; the metal component is metal Co, and the organic nitrogen ligand polymer is generated by solvothermal polymerization of vinyl functionalized organic nitrogen ligands; the vinyl functionalized organic nitrogen ligand is any one or a combination of a plurality of L1, L2 and L3:
further, the organic nitrogen ligand polymer is prepared by ligand L1 self-polymerization or copolymerization of L1 and L2 or L3.
Further, the organic nitrogen ligand polymer has a hierarchical pore structure, and the specific surface area is 100-3000 m 2 And/g, contains micropores, mesopores and macropores, and has a pore volume of 0.1-5 cm 3 And/g, wherein the pore size distribution is 0.1-50 nm.
According to a second aspect of the present disclosure, the present application provides a method for preparing the above catalyst:
a) At 273-473K (preferably 298-373K), N 2 Adding vinyl functionalized nitrogen ligand, adding or not adding cross-linking agent, adding free radical initiator, mixing and stirring to obtain mixed solution.
b) Transferring the mixed solution obtained in the step a) into a synthesis autoclave, wherein 323K-473 and 473K, N 2 And (3) under the atmosphere, adopting a solvothermal polymerization method, standing for 1-100 h (preferably 20-80 h) to carry out polymerization reaction, and vacuumizing to remove the solvent after the completion of the polymerization reaction to obtain the organic nitrogen ligand polymer.
c) Placing the organic nitrogen ligand polymer in a solvent containing a metal active component Co, wherein 323K-473K, N 2 Stirring for 0.5-100 h (preferably 5-50 h) under the atmosphere, and vacuum pumping the solvent to obtain the nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst.
Further, the solvent in the steps a) and c) is one or more of benzene, toluene, methanol, ethanol, tetrahydrofuran, dichloromethane or chloroform.
Further, the cross-linking agent in the step a) is one or more of styrene, ethylene, propylene, divinylbenzene or 1,3, 5-tri-ethynylbenzene.
Further, the free radical initiator is one or more than two of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile. The weight ratio of the free radical initiator to the organic nitrogen ligand monomer is 1:100-1:5.
Further, the molar ratio of the vinyl functionalized organic nitrogen ligand in step a) is 0.01:1100:1 (preferably 0.1:1 to 1:1), the molar ratio of the organic nitrogen ligand to the crosslinking agent is 0.01:110:1 (preferably 0.1:1 to 1:1) and the molar ratio of the organic nitrogen ligand to the radical initiator is 300:110:1 (preferably 50:1 to 10:1) when the crosslinking agent is added.
Further, the precursor of the metal component Co is derived from Co (OAc) 2 、Co(acac) 2 、Co(acac) 3 、Co(NO 3 ) 2 、CoCl 2 One or more of the metals Co is/are carried in the amount of 1-50 wt%.
According to a third aspect of the present disclosure, the present application provides the use of the above catalyst, the use of the above nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst in the hydroformylation of high olefins, the reaction of high carbon end olefins and internal olefins (C5-C12) with synthesis gas (CO/H) in the presence of the Co-based multi-phase catalyst 2 ) The hydroformylation reaction is carried out in a trickle bed, a slurry bed or a kettle reactor, wherein the reaction temperature is preferably 323-523K, the reaction pressure is preferably 0.5-15 MPa, and the liquid hourly space velocity is preferably 0.05-8.0 h -1 The gas space velocity is preferably 500 to 10000h -1 。
The reaction principle of the application is as follows: according to the application, a homogeneous phase ligand containing nitrogen is introduced into vinyl by adopting a homogeneous phase ligand multiphase strategy, and polymerized in an autoclave by utilizing a solvothermal polymerization method to form a porous organic polymer containing nitrogen with high specific surface area and multistage pore structure, and after metal Co is loaded, a porous organic polymer containing nitrogen loaded Co-based multi-phase catalyst is obtained. The advantages of the porous organic polymer carrier (high specific surface area and multistage pore structure) and the ligand (coordination with Co, immobilization of metal Co, co loss prevention and Co electron and space effect regulation) are fully integrated. The porous organic polymer material can seal and limit the reaction substrate in the nano-scale pores, so as to increase the substrate concentration on the catalytic site; the vinyl porous organic polymer synthesized by solvothermal polymerization shows better swelling characteristics. The catalyst has the advantages of extremely high activity, higher product aldehyde selection, higher stability and the like due to the characteristics.
The application has the beneficial effects that: the application provides a nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst, wherein the coordination formed by N atoms and metals in a nitrogen-containing ligand is beneficial to the high dispersion of active metals, the utilization efficiency of the metals is improved, and the nitrogen-containing porous organic ligand polymer is not easy to run off. The polymer has a porous grade structure with high specific surface area, has the dual functions of a carrier and a ligand, and greatly improves the catalytic activity. The heterogeneous catalyst can remarkably improve the catalytic activity and the product aldehyde selectivity in the hydroformylation reaction of high-carbon olefins, particularly in the hydroformylation reaction of internal olefins. The novel Co-based multi-phase catalyst can reduce the cost of separating and recycling the catalyst, and is beneficial to realizing large-scale industrialized application.
Drawings
FIG. 1 is a block diagram of a typical vinyl functionalized nitrogen-containing monomer of the present application.
FIG. 2 is a schematic diagram of the synthetic technical route of the Co-based multi-phase catalyst supported by the porous organic polymer containing nitrogen.
FIG. 3 is a block diagram of a cross-linking agent used in the polymerization of the present application.
FIG. 4 is a 1H spectrum of a vinyl functionalized triphenylnitrogen monomer of example 1 of the application.
FIG. 5 is a 13C spectrum of a vinyl functionalized tri-basic nitrogen of example 1 of the present application.
FIG. 6 is a cobalt-based pre-loaded POL-NPh of example 1 of this application 3 SEM images and EDS mapping images of (a-d).
FIG. 7 is a cobalt-based supported (e-h) Co/POL-NPh of example 1 of this application 3 SEM and EDS mapping of the catalyst.
FIG. 8 is a graph of example 1 of the present application at N 2 Catalyst thermogravimetry curve under atmosphere, (a) POL-NPh 3 (b)Co/POL-NPh 3 。
FIG. 9 is a sample of POL-NPh3 (1) and Co/POL-NPh of this application 3 N of catalyst (2) 2 Adsorption and desorption isotherms.
FIG. 10 is a sample of POL-NPh of this application 3 (a) And Co/POL-NPh 3 Pore size distribution curve of catalyst (b).
FIG. 11 is a sample of POL-NPh of example 1 3 FT-IR diagram of (c).
FIG. 12 is a graph of Co/POL-NPh of example 1 3 FT-IR diagram of catalyst.
Detailed Description
The following describes the technical scheme of the present application in detail by means of specific examples, but the content of the present application is not limited to the following examples only. The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
At 298K and inert gas N 2 1.0g of tris (4-vinylbenzene) based nitrogen ligand was dissolved in 10mL of tetrahydrofuran under a protective atmosphere, 25mg of azobisisobutyronitrile, a radical initiator, was added to the above solution, and stirred for 30min. The resulting mixture was transferred to an autoclave and polymerized at 373K by solvothermal polymerization for 24h. After the polymerized solution is cooled to room temperature, the solvent is pumped away under the condition of 302K to obtain the nitrogen-containing porous organic polymer (the yield is 100 percent), and the nitrogen-containing porous organic polymer is named as POL-NPh 3 The specific surface area is 1120.8m by the characterization of nitrogen adsorption and desorption test 2 Per gram, a total pore volume of 1.57cm 3 And/g, the NLDFT method has pore size distribution of 0.2-80 nm.
The porous organic polymer containing nitrogen loads Co-based multi-phase catalyst: at 298K and inert gas N 2 Under a protective atmosphere, 0.3345g Co (OAc) was weighed out 2 Dissolving in 25mL absolute ethanol solvent, adding 1g of the prepared nitrogen-containing porous organic polymer, stirring for 24h, filtering, washing with absolute ethanol for three times, and vacuum pumping the obtained solid mixture 348K to remove the solvent to obtain the nitrogen-containing porous organic polymer supported Co-based multi-phase catalyst named Co/POL-NPh 3 The specific surface area is 1054.6m by the characterization of nitrogen adsorption and desorption test 2 Per gram, a total pore volume of 2.33cm 3 And/g, the NLDFT method has pore size distribution of 0.2-80 nm. From Co/POL-NPh 3 Catalyst and POL-NPh 3 Carrier bodyThe thermogravimetric curve of (2) shows that under the nitrogen atmosphere, the catalyst has obvious skeleton decomposition weightlessness peak at the temperature of more than 430 ℃. From Co/POL-NPh 3 Catalyst and POL-NPh 3 The FT-IR diagram of the support shows that Co in the catalyst interacts with the N atom in the ligand.
The Co-based multi-phase catalyst prepared by the method is filled into an autoclave, then 1-hexene raw material and toluene solvent are added, and the hydroformylation reaction is carried out under the conditions of 423K,3.0MPa and 4 hours of reaction time. The reaction product was collected by centrifugation and the separated product was analyzed on an Agilent 7890A gas chromatograph with a hydrogen flame detector (FID) equipped with HP-5 capillary, with n-propanol as an internal standard, calculated using the internal standard method, and the reaction results are shown in table 1.
Example 2
In example 2, the same procedure as in example 1 was repeated except that 0.8g of the tris (4-vinylbenzene) based nitrogen ligand, 0.2g of the bis (4-vinylbenzene) based nitrogen ligand was dissolved in 10mL of tetrahydrofuran, and the reaction results were shown in Table 1.
Example 3
In example 3, the same procedure as in example 1 was repeated except that 0.6g of the tris (4-vinylbenzene) based nitrogen ligand, 0.4g of the bis (4-vinylbenzene) based nitrogen ligand was dissolved in 10mL of tetrahydrofuran, and the reaction results were shown in Table 1.
Example 4
In example 4, the same procedure as in example 1 was repeated except that 0.8g of the tris (4-vinylbenzene) based nitrogen ligand, 0.2g of the mono (4-vinylbenzene) based nitrogen ligand was dissolved in 10mL of tetrahydrofuran, and the reaction results were shown in Table 1.
Example 5
In example 5, the same procedure as in example 1 was repeated except that 0.6g of the tris (4-vinylbenzene) based nitrogen ligand, 0.4g of the mono (4-vinylbenzene) based nitrogen ligand was dissolved in 10mL of tetrahydrofuran, and the reaction results were shown in Table 1.
Example 6
In example 6, the procedure was the same as in example 1 except that 2.5mg of the radical initiator azobisisobutyronitrile was added instead of 25mg of the radical initiator azobisisobutyronitrile, and the reaction results are shown in Table 1.
Example 7
In example 7, except for weighing 0.158g Co (OAc) 2 Instead of 0.3345g Co (OAc) 2 The other procedures were the same as in example 1, and the reaction results are shown in Table 1.
Example 8
In example 8, except that 0.0305g Co (OAc) was weighed out 2 Instead of 0.3345g Co (OAc) 2 The other procedures were the same as in example 1, and the reaction results are shown in Table 1.
Example 9
In example 9, except for weighing 0.5375g Co (NO 3 ) 2 Instead of 0.3345g Co (OAc) 2 The other procedures were the same as in example 1, and the reaction results are shown in Table 1.
Example 10
In example 10, except 0.2475g of CoCl was weighed 2 Instead of 0.3345g Co (OAc) 2 The other procedures were the same as in example 1, and the reaction results are shown in Table 1.
Example 11
In example 11, except that 0.487g Co (acac) was weighed out 2 Instead of 0.3345g Co (OAc) 2 The other procedures were the same as in example 1, and the reaction results are shown in Table 1.
Example 12
In example 12, the reaction results are shown in Table 1, except that the hydroformylation reaction temperature 373K was used in place of the hydroformylation evaluation reaction temperature 423K.
Example 13
In example 13, the reaction results are shown in Table 1, except that the hydroformylation reaction pressure of 2.0MPa was used in place of the hydroformylation evaluation reaction pressure of 3 MPa.
Example 14
In example 14, the reaction results are shown in Table 1, except that the hydroformylation reaction time of 24 hours was used in place of the hydroformylation evaluation reaction time of 4 hours.
Example 15
In example 15, the reaction results are shown in Table 1, except that the hydroformylation reaction raw material 1-octene was used in place of the hydroformylation reaction raw material 1-hexene.
Example 16
In example 16, the reaction results are shown in Table 1, except that 2-octene as the hydroformylation reaction raw material was used in place of 1-hexene as the hydroformylation reaction raw material.
Comparative example 1
In comparative example 1, except that SiO was used 2 Carrier replaces nitrogen-containing porous organic polymer POL-NPh 3 The procedure used for the preparation of the catalyst and the subsequent evaluation of the heterogeneous hydroformylation reaction was the same as in example 1, and the reaction results are shown in Table 1.
Comparative example 2
In comparative example 2, except that the phosphine-containing porous organic polymer POL-PPh was used 3 Carrier replaces nitrogen-containing porous organic polymer POL-NPh 3 The procedure used for the preparation of the catalyst and the subsequent evaluation of the heterogeneous hydroformylation reaction was the same as in example 1, and the reaction results are shown in Table 1.
Comparative example 3
In comparative example 3, except that Al is used 2 O 3 Carrier replaces nitrogen-containing porous organic polymer POL-NPh 3 The procedure used for the preparation of the catalyst and the subsequent evaluation of the heterogeneous hydroformylation reaction was the same as in example 1, and the reaction results are shown in Table 1.
TABLE 1Co/POL-NPh 3 Multiphase catalyst high-carbon olefin hydroformylation reaction result
As can be seen from the reaction data of examples 1-5 above, co/POL-NPh when the nitrogen ligand L1 is selected for self-polymerization 3 The heterogeneous catalyst high-carbon olefin hydroformylation reaction shows optimal olefin conversion rate and product aldehyde selectivity. From the data of example 1 and example 6, it can be seen thatThe proper amount of free radical initiator can help to increase the conversion of olefin and the selectivity of aldehyde. As can be seen from the data of examples 1, 7-8 and 9-11, the Co-based loading and the type of the precursor, co (OAc), affect the hydroformylation reaction performance of the higher olefins 2 Co/POL-NPh with Co loading of 10wt% 3 The multiphase catalyst has optimal high-carbon olefin hydroformylation reaction performance. As can be seen from the data of examples 1, 12 and 13, the high temperature and high pressure are advantageous for increasing Co/POL-NPh 3 The multiphase catalyst has high-carbon olefin hydroformylation reaction performance. The data of example 1 and example 16 shows that Co/POL-NPh 3 The heterogeneous catalyst has excellent reaction performance in high-carbon internal olefin hydroformylation reaction. The data of example 1 and comparative examples 1-3 show that the Co-based catalyst supported by POL-NPh3 as a carrier shows the optimal performance in the hydroformylation of high-carbon olefins. According to the results of the reaction data of examples 1-16 and comparative examples 1-3, the Co-based multi-phase catalyst provided by the application is applied to the hydroformylation reaction of high-carbon end olefins and internal olefins, and the novel multi-phase catalyst has excellent reaction activity and selectivity and good reaction stability, and provides an economical and industrialized multi-phase Co-based catalyst for the hydroformylation of high-carbon olefins.
The above examples are only illustrative of the application and are not intended to be limiting of the embodiments. Other variations in various forms will be apparent to those of ordinary skill in the art in view of the foregoing description. And obvious variations thereof are contemplated as falling within the scope of the application. Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Claims (10)

1. A Co-based multi-phase catalyst supported by a nitrogen-containing porous organic ligand polymer, characterized in that the catalyst consists of a metal component and an organic nitrogen ligand polymer; the metal component is metal Co, and the organic nitrogen ligand polymer is generated by solvothermal polymerization of vinyl functionalized organic nitrogen ligands; the vinyl functionalized organic nitrogen ligand is any one or a combination of a plurality of L1, L2 and L3:
2. the nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst according to claim 1, wherein the organic nitrogen ligand polymer is prepared by ligand L1 self-polymerization or copolymerization of L1 with L2 or L3.
3. The Co-supported heterogeneous catalyst of a nitrogen-containing porous organic ligand polymer according to claim 1, wherein the organic nitrogen ligand polymer has a multi-stage pore structure and a specific surface area of 100 to 3000m 2 And/g, contains micropores, mesopores and macropores, and has a pore volume of 0.1-5 cm 3 And/g, wherein the pore diameter distribution is 0.1-50 nm.
4. The nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst according to claim 1, wherein the catalyst is prepared by:
a) At 273-473K, N 2 Adding a vinyl functionalized nitrogen ligand, adding or not adding a cross-linking agent, then adding a free radical initiator, mixing and stirring to prepare a mixed solution;
b) Transferring the mixed solution obtained in the step a) into a synthesis autoclave, wherein 323K-473K and N are respectively added 2 Under the atmosphere, a solvothermal polymerization method is adopted, standing is carried out for 1-100 h for polymerization reaction, and after the completion, the solvent is pumped out in vacuum to obtain the organic nitrogen ligand polymer;
c) Placing the organic nitrogen ligand polymer in a solvent containing a metal active component Co, wherein the solvent contains 323K-473K and N 2 Stirring for 0.5-100 h under the atmosphere and vacuumAnd (3) removing the solvent to obtain the nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst.
5. The Co-based multi-phase catalyst supported on a nitrogen-containing porous organic ligand polymer according to claim 4, wherein the solvent in steps a) and c) is one or more of benzene, toluene, methanol, ethanol, tetrahydrofuran, methylene chloride or chloroform; the cross-linking agent in the step a) is one or more than two of styrene, ethylene, propylene, divinylbenzene or 1,3, 5-tri-ethynyl benzene; the free radical initiator is one or more than two of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or azodiisoheptonitrile; the weight ratio of the free radical initiator to the organic nitrogen ligand monomer is 1:100-1:5.
6. The nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst according to claim 4, wherein the molar ratio of vinyl functionalized organic nitrogen ligand in step a) is 0.01:1100:1, the molar ratio of organic nitrogen ligand to crosslinker is 0.01:110:1, and the molar ratio of organic nitrogen ligand to free radical initiator is 300:110:1, with crosslinker added.
7. The nitrogen-containing porous organic ligand polymer supported Co-based multi-phase catalyst according to claim 4, wherein the precursor of the metallic component Co is derived from Co (OAc) 2 、Co(acac) 2 、Co(acac) 3 、Co(NO 3 ) 2 、CoCl 2 One or more of the metals Co is/are carried in the amount of 1-50 wt%.
8. Use of a catalyst according to any one of claims 1 to 3 for catalyzing the hydroformylation of high olefins.
9. The application of the catalyst according to claim 8, wherein the high-carbon olefin comprises C5-C12 high-carbon end olefin and internal olefin.
10. The use of the catalyst according to claim 8, wherein the high-carbon end olefins and internal olefins are subjected to hydroformylation with synthesis gas in the presence of a Co-based multi-phase catalyst in a trickle bed, slurry bed or kettle reactor, wherein the reaction temperature is 323-523K, the reaction pressure is 0.5-15 MPa, and the liquid hourly space velocity is 0.05-8.0 h -1 The gas space velocity is 500-10000 h -1 。
CN202310695205.5A 2023-06-13 2023-06-13 Co-based multi-phase catalyst loaded with nitrogen-containing porous organic ligand polymer and application thereof Pending CN117046519A (en)

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