Supported catalyst as well as preparation method and application thereof

Abstract

The invention relates to the field of heterogeneous catalysts, and discloses a supported catalyst as well as a preparation method and application thereof. The catalyst comprises a carrier and metal loaded on the carrier, wherein the carrier is an oxide modified by a nitrogen-containing carbide, and the N element in the nitrogen-containing carbide comprises graphitized N and pyridinized N; wherein the mass ratio of the graphitized N to the pyridinized N is (0.1-2): 1. Nitrogen carbide in a carrier of the supported catalyst contains graphitized N and pyridinized N, and the graphitized N and the pyridinized N meet a specific content relationship, so that active metal in the supported catalyst is coordinated and combined with the graphitized N and the pyridinized N to generate relatively strong electron interaction, the active metal is dispersed to form active sites, and the active sites are separated from the active metal. And the catalyst contains abundant mesoporous structures, so that metal atoms are stably dispersed and are not easy to agglomerate, and the catalytic activity and the cycling stability of the catalyst are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of heterogeneous catalysts, and more specifically, to a supported catalyst, its preparation method, and its application. Background Technology

[0002] Olefin carbonylation is a reaction that synthesizes aldehydes, ketones, and acids from inexpensive raw materials such as ethylene, propylene, and butene. It is a green and atom-economical reaction pathway and one of the most important industrial applications in the world today. Downstream fine chemicals derived from carbonyl chemicals, such as soaps, medical materials, and surfactants, have a wide range of applications and can meet the needs of national living standards development.

[0003] While homogeneous catalysts exhibit high activity in olefin carbonylation catalysis systems, their synthesis requires expensive organic ligands, which are prone to degradation and loss during the reaction process. Therefore, the practical application of homogeneous catalysts is limited by cost and lifespan. Given these limitations, in recent years, increasing research has focused on heterogeneous metal catalysts.

[0004] CN112979440A provides a supported catalyst for the carbonylation of olefins to synthesize ketones. The supported catalyst is prepared using metal oxides as supports, Rh and Ru as active components, and Fe, Sn, Ni and Zn as auxiliary components. The active metals have high dispersion and a particle size of less than 1 nanometer. The catalyst is used in the carbonylation reaction of olefins, and the selectivity of ketone compounds in the product is greater than 90%.

[0005] CN114471651A discloses a nitrogen-doped carbon support obtained by carbonizing a polymer containing imidazole side groups, combined with nickel as the matrix. Coordination of the nickel metal results in more uniform dispersion, and the further combination with ruthenium gives the catalyst advantages such as high catalytic activity, good selectivity, and good stability. However, the preparation process of the polymer precursor is relatively cumbersome, and the carbon support requires hydrogenation treatment.

[0006] CN109759107A provides a supported carbonized composite catalyst that combines carbon-composite transition metal carbides and silicon carbide, maximizing the catalytic performance of the active components and greatly improving the stability of the catalyst.

[0007] CN115814833A discloses a low-load bimetallic nanocatalyst that, by combining the geometric and electronic interactions between the support and the auxiliary metal, can effectively improve the conversion efficiency of carbonylation products and simultaneously regulate the carbonyl selectivity of olefins.

[0008] CN111729687A discloses a method for preparing a supported carbonylation catalyst. This method uses chloromethylated polystyrene resin as a raw material, and supports rhodium and / or cobalt metal to form the final supported catalyst. This catalyst exhibits high conversion and selectivity in the carbonylation of olefins, allows for direct separation of the product and catalyst, has a low metal loss rate, and demonstrates stable catalyst activity, significantly improving the economics of the carbonylation process.

[0009] Currently, multiphase supported catalysts face common problems, such as metal loss due to weak metal site bonding, complex separation and recovery procedures, and decreased selectivity and conversion during recycling. Therefore, it is necessary to develop a supported catalyst with strong support-metal bonding, high metal utilization, easy separation and recycling, and high cycling stability. Summary of the Invention

[0010] The purpose of this invention is to overcome the problem of metal loss caused by weak bonding between the support and metal in existing supported catalysts. This invention provides a supported catalyst, its preparation method, and its application. The nitrogen carbides in the support of this supported catalyst contain graphitized N and pyrided N, and the graphitized N and pyrided N satisfy a specific content relationship. This allows the active metal in the supported catalyst to coordinate with the graphitized N and pyrided N and generate strong electronic interactions. The active metal disperses to form catalytic active sites. Furthermore, the catalyst contains abundant mesoporous structures, which ensures stable dispersion of metal atoms and prevents agglomeration. This significantly improves the catalytic activity and cycle stability of the catalyst.

[0011] To achieve the above objectives, a first aspect of the present invention provides a supported catalyst, wherein the catalyst comprises a support and a metal supported on the support;

[0012] The support is an oxide modified with nitrogen carbides, and the nitrogen element in the nitrogen carbides includes graphitized nitrogen and pyridinized nitrogen.

[0013] The mass ratio of graphitized N to pyridinized N is 0.1-2:1.

[0014] A second aspect of the present invention provides a method for preparing a supported catalyst, characterized in that the preparation method includes the following steps:

[0015] (1) After mixing the oxide support, active monomer, initiator and solvent, in-situ polymerization is carried out, followed by separation and drying to obtain the modified support;

[0016] (2) The metal precursor solution is mixed with the modified support and impregnated, and the solid phase is obtained by solid-liquid separation. The solid phase is dried to obtain the catalyst precursor.

[0017] (3) The catalyst precursor is sintered in the presence of a protective atmosphere to obtain the supported catalyst;

[0018] The active monomer is an aromatic amine;

[0019] The sintering conditions include: heating from room temperature to 300-400℃ at a heating rate of 1-20℃ / min and holding at that temperature for 1-3 hours, then heating to 400-600℃ at a heating rate of 1-10℃ / min and holding at that temperature for 0.5-2 hours.

[0020] A third aspect of the present invention provides a supported catalyst prepared by the above-described preparation method.

[0021] A fourth aspect of the present invention provides the application of the above-mentioned supported catalyst in the olefin carbonylation reaction.

[0022] Through the above technical solutions, the supported catalyst, its preparation method, and its application provided by the present invention achieve the following beneficial effects:

[0023] The nitrogen carbides in the support of the supported catalyst provided by the present invention contain graphitized N and pyrided N, and the graphitized N and pyrided N satisfy a specific content relationship, so that the supported catalyst has active metals that coordinate with graphitized N and pyrided N to form catalytic active sites. Furthermore, the catalyst contains abundant mesoporous structures, which ultimately significantly improves the catalytic activity and cycle stability of the catalyst.

[0024] Furthermore, when the mass ratio of graphitized N to pyridinized N in the supported catalyst provided by the present invention meets a specific range, the catalyst exhibits a multi-mesoporous microstructure, which enables the metal active components in the supported catalyst to be stably dispersed and less prone to agglomeration, thereby reducing the loss rate of the metal active components and significantly improving the catalytic activity and stability of the catalyst.

[0025] In the preparation method of the supported catalyst provided by this invention, aniline and / or phenylenediamine monomers are polymerized in situ on the surface of an oxide support to form a porous π-conjugated network framework. The metal is combined through physical adsorption and coordination between the metal precursor and the electron pairs on the nitrogen atoms. The catalyst precursor is sintered under specific sintering conditions, so that the nitrogen-containing polymer framework on the support surface is transformed into graphitized N and pyridineized N. The ratio of graphitized N and pyridineized N is controlled by regulating the segmented heating program, thereby regulating the active metal electron distribution of the prepared supported catalyst, forming highly active metal-N active species, improving catalytic activity and selectivity, as well as the stability of recycling.

[0026] Furthermore, by adding a structure modifier during the in-situ polymerization of aromatic amines, such as aniline and / or phenylenediamine monomers, on the surface of an oxide support, the morphology of the nitrogen-containing polymer skeleton on the support surface can be further controlled. Specifically, the nitrogen-containing polymers are polymerized and assembled at the interface of the support surface to form nanoribbons or dendritic three-dimensional structures, fully exposing N-containing functional group sites to coordinate and bind with active metals, forming a high-density metal distribution structure. This results in highly dispersed metal active components in the prepared catalyst that are not prone to agglomeration, making the catalyst less susceptible to deactivation, reducing the loss rate of metal active components, and significantly improving the catalyst activity. Attached Figure Description

[0027] Figure 1 The image shows the XPS plot of catalyst A1 prepared in Example 1.

[0028] Figure 2 The image shows the XPS plot of catalyst A2 prepared in Example 2.

[0029] Figure 3 In the diagram, a and b are the characteristic diffraction peak spectra of cobalt and rhodium, respectively. The characteristic diffraction peak data of rhodium and cobalt are obtained from the XRD standard diffraction cards PDF#05-0685-Rh and PDF#15-0806-Co. c is the XRD pattern of catalyst A1 prepared in Example 1.

[0030] Figure 4 This is a spherical aberration electron microscope image of catalyst A1 prepared in Example 1. Detailed Implementation

[0031] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0032] A first aspect of the present invention provides a supported catalyst, characterized in that the catalyst comprises a support and a metal supported on the support;

[0033] The support is an oxide modified with nitrogen carbides, and the nitrogen element in the nitrogen carbides includes graphitized nitrogen and pyridinized nitrogen.

[0034] The mass ratio of graphitized N to pyridinized N is 0.1-2:1.

[0035] In this invention, the nitrogen carbides in the support of the supported catalyst contain graphitized N and pyrided N, and the graphitized N and pyrided N satisfy a specific content relationship, which enables the supported catalyst to coordinate with the active metal and graphitized N and pyrided N and generate strong electronic interactions. The active metal is dispersed to form catalytic active sites. Furthermore, the catalyst contains abundant mesoporous structures, which ultimately significantly improves the catalytic activity and cycle stability of the catalyst.

[0036] Furthermore, the nitrogen carbides of the supported catalyst contain graphitized N and pyridinated N, and when the graphitized N and pyridinated N satisfy a specific content relationship, the catalyst exhibits a multi-mesoporous microstructure, which enables the metal active components in the supported catalyst to be stably dispersed and not prone to agglomeration, reducing the loss rate of the metal active components and significantly improving the catalytic activity and stability of the catalyst.

[0037] In this invention, the mass ratio of graphitized N to pyridine N is 0.1-2:1, for example, it can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, or any range of two values. Preferably, the mass ratio of graphitized N to pyridine N is 0.1-1:1.

[0038] In a preferred embodiment of the present invention, the mass ratio of the graphitized N to the pyridinized N is 0.2-1:1.

[0039] According to the present invention, the content of the nitrogen carbide is 2-50 wt%, based on the total weight of the carrier.

[0040] In this invention, when the content of nitrogen carbides in the support meets the above-mentioned range, the catalyst contains a large number of mesopores, thereby improving the catalytic activity and cycle stability of the catalyst.

[0041] In this invention, based on the total weight of the carrier, the content of the nitrogen-carbon compound is 2-50 wt%, for example, it can be 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, or 28 wt%. The content of the nitrogen-carbon compounds is 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, and any range of two values. Preferably, the content of the nitrogen-carbon compounds is 10-35wt%, preferably 15-35wt%, based on the total weight of the carrier.

[0042] In this invention, the carrier has a core-shell structure with an oxide core and a nitride shell. The average thickness of the shell is 5-30 nm, for example, it can be 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, 30 nm, or any two of these values, preferably 10-25 nm.

[0043] In this invention, the thickness of the shell layer is measured by TEM electron microscopy. Specifically, a 20cm×20cm area is randomly selected on the TEM electron microscopy image of the carrier, and the thickness of the shell layer in at least 40 carrier particles is counted and the average value is calculated.

[0044] According to the present invention, based on the total weight of the supported catalyst, the content of the support is 95-99.9 wt%, and the content of the metal is 0.1-5 wt%.

[0045] In this invention, when the content of the support and the metal in the supported catalyst meets the above-mentioned range, the active metal component in the catalyst can be highly dispersed and not easily agglomerated, thereby reducing the loss rate of the active metal component and improving the catalytic activity and cycle stability of the catalyst.

[0046] In this invention, based on the total weight of the supported catalyst, the content of the support is 95-99.9 wt%, for example, it can be 95 wt%, 95.5 wt%, 96 wt%, 96.5 wt%, 97 wt%, 97.5 wt%, 98 wt%, 98.5 wt%, 99 wt%, 99.5 wt%, 99.9 wt%, or any two of these values; the content of the metal is 0.1-5 wt%, for example, it can be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, or any two of these values.

[0047] Furthermore, based on the total weight of the supported catalyst, the content of the support is 97-99.5 wt%, and the content of the metal is 0.5-3 wt%.

[0048] According to the present invention, the oxide is selected from at least one of ferric oxide, ferric oxide and ferrous oxide.

[0049] In this invention, the average particle size of the oxide is 100-400 nm, for example, it can be 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, or any two of these values, preferably 200-300 nm.

[0050] In a preferred embodiment of the present invention, in order to facilitate separation and recovery using an external magnetic field and avoid the problems of long time consumption and large mass loss in the separation and recovery process of traditional heterogeneous catalysts, the oxide is preferably a magnetic oxide, preferably iron(III) oxide.

[0051] In one specific embodiment of the present invention, the supported catalyst is a supported magnetic catalyst.

[0052] According to the present invention, the metal is selected from at least one of Rh, Pb, Ru, Ir, Co, Cs and Li.

[0053] According to the present invention, the metal dispersion in the supported catalyst is 45-75%.

[0054] In this invention, the inventors discovered that in the supported catalyst of this invention, the nitrogen carbides in the support contain graphitized N and pyrided N, and when graphitized N and pyrided N satisfy a specific content relationship, the supported catalyst can have active metals coordinated with graphitized N and pyrided N to form catalytic active sites, thereby significantly improving the dispersion of active metals in the supported catalyst. Specifically, the dispersion of metals in the supported catalyst is 45-75%, further indicating that the supported catalyst has high catalytic efficiency.

[0055] In this invention, the dispersion degree of the metal in the supported catalyst refers to a quantitative indicator of the degree of dispersion of the metal on the surface of the support.

[0056] In this invention, the metal dispersion is measured using the CO pulse method. Specifically, the test method includes: using a chemisorption analyzer, pulse titrating the catalyst sample in a CO gas stream until CO adsorption saturation is achieved, and then calculating the metal dispersion. The calculation formula is:

[0057] Metal dispersion, % = n(CO) / n(M) × 100%, where n(CO) is the number of moles of CO adsorbed, n(M) is the number of moles of metal in the catalyst, n(M) = m × (w1 / M1 + w2 / M2), where m represents the total mass of the catalyst, w1 represents the mass percentage of metal component 1 in the supported catalyst, M1 represents the relative atomic mass of metal component 1; w2 represents the mass percentage of metal component 2 in the catalyst, M2 represents the relative atomic mass of metal component 2.

[0058] In this invention, the metal dispersion in the supported catalyst is 45-75%, for example, it can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, or any range of two values. Preferably, the metal dispersion in the supported catalyst is 60-75%.

[0059] According to the present invention, the specific surface area of ​​the supported catalyst is 10-150 m². 2 / g, for example, can be 10m 2 / g, 15m 2 / g, 20m 2 / g, 25m 2 / g, 30m 2 / g, 35m 2 / g, 40m 2 / g, 45m 2 / g, 50m 2 / g, 55m 2 / g, 60m 2 / g, 65m 2 / g, 70m 2 / g, 75m2 / g, 80m 2 / g, 85m 2 / g, 90m 2 / g, 95m 2 / g, 100m 2 / g, 105m 2 / g, 110m 2 / g, 115m 2 / g, 120m 2 / g, 125m 2 / g, 130m 2 / g, 135m 2 / g, 140m 2 / g, 145m 2 / g, 150m 2 / g, and a range consisting of any two values.

[0060] According to the present invention, the average pore size of the supported catalyst is 2-20 nm, for example, it can be 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, and any range of two values.

[0061] According to the present invention, the pore volume of the supported catalyst is 0.05-0.5 cm³. 3 / g, for example, can be 0.05cm 3 / g, 0.1cm 3 / g, 0.13cm 3 / g, 0.15cm 3 / g, 0.2cm 3 / g, 0.25cm 3 / g, 0.3cm 3 / g, 0.35cm 3 / g, 0.4cm 3 / g, 0.45cm 3 / g, 0.5cm 3 / g, and a range consisting of any two values.

[0062] According to the present invention, the pore volume of the mesopores in the supported catalyst is 0.05-0.5 cm³. 3 / g, for example, can be 0.05cm 3 / g, 0.07cm 3 / g, 0.1cm 3 / g, 0.11cm 3 / g, 0.15cm 3 / g, 0.2cm3 / g, 0.25cm 3 / g, 0.3cm 3 / g, 0.35cm 3 / g, 0.4cm 3 / g, 0.45cm 3 / g, 0.5cm 3 / g, and a range consisting of any two values.

[0063] In this invention, when at least one of the specific surface area, average pore size, and pore volume of the supported catalyst meets the above-mentioned ranges, it indicates that the supported metal in the supported catalyst is highly dispersed and not prone to agglomeration, which can significantly improve the catalytic activity and selectivity of the catalyst. In particular, in the supported catalyst of this invention, based on the total pore volume of the supported catalyst, the proportion of mesoporous pore volume is relatively high, reaching 50-90%, indicating that the supported catalyst contains abundant mesoporous structures, which can further improve the dispersion of the supported metal atoms.

[0064] Furthermore, the specific surface area of ​​the supported catalyst is 30-90 m². 2 / g.

[0065] Furthermore, the average pore size of the supported catalyst is 5-20 nm, more preferably 5-12 nm.

[0066] Furthermore, the total pore volume of the supported catalyst is 0.1-0.2 cm³. 3 / g.

[0067] In a preferred embodiment of the present invention, the total pore volume of the supported catalyst is 0.1-0.13 cm³. 3 / g.

[0068] Furthermore, the pore volume of the mesopores in the supported catalyst is 0.07-0.2 cm³. 3 / g.

[0069] In a preferred embodiment of the present invention, the pore volume of the intermediate pores in the supported catalyst is 0.07-0.11 cm³. 3 / g.

[0070] Furthermore, based on the total pore volume of the supported catalyst, the pore volume ratio of mesopores is 70-90%.

[0071] In a preferred embodiment of the present invention, the mesopore volume accounts for 70-85% of the total pore volume in the supported catalyst.

[0072] In one specific embodiment of the present invention, the oxide is selected from at least one of iron(III) oxide, ferric oxide, and ferrous oxide; the metal is Rh, or the metal is Rh and Co, wherein the characteristic peak intensity I of Fe element is measured by XRD of the supported catalyst. Fe The characteristic peak intensity I of Rh element Rh The following relationship must be satisfied:

[0073] I Fe / I Rh Greater than or equal to 345.

[0074] In this invention, the inventors discovered that when an iron oxide is used as a support in a supported catalyst and the active metal component contains Rh, if the ratio of the characteristic peak intensity of Fe to the characteristic peak intensity of Rh measured by XRD in the supported catalyst meets the above-mentioned range, it indicates that the content of the Rh crystal phase in the supported catalyst is low, the crystal particle size of the Rh crystal phase is small, and the surface area of ​​the metal element Rh is larger. This demonstrates that the active metal Rh is well dispersed in the support.

[0075] In this invention, the characteristic peak intensity I of Fe element Fe The characteristic peak intensity I of Rh element Rh The results were obtained by XRD. Specifically, the testing method was as follows: powdered samples were used, the XRD incident angle was selected between 5-90°, the data were processed by JADE software, and the phase content and proportion were calculated.

[0076] I Fe / I Rh =Fe characteristic peak area / Rh characteristic peak area. The characteristic peak area is obtained directly after processing with JADE software, removing background and performing peak fitting.

[0077] Furthermore, I Fe / I Rh Greater than or equal to 750.

[0078] A second aspect of the present invention provides a method for preparing a supported catalyst, wherein the preparation method includes the following steps:

[0079] (1) After mixing the oxide support, active monomer, initiator and solvent, in-situ polymerization is carried out, followed by separation and drying to obtain the modified support;

[0080] (2) The metal precursor solution is mixed with the modified support and impregnated, and the solid phase is obtained by solid-liquid separation. The solid phase is dried to obtain the catalyst precursor.

[0081] (3) The catalyst precursor is sintered in the presence of a protective atmosphere to obtain the supported catalyst;

[0082] The active monomer is an aromatic amine;

[0083] The sintering conditions include: heating from room temperature to 300-400℃ at a heating rate of 1-20℃ / min and holding at that temperature for 1-3 hours, then heating to 400-600℃ at a heating rate of 1-10℃ / min and holding at that temperature for 0.5-2 hours.

[0084] In this invention, the method for preparing the supported catalyst involves in-situ polymerization of aromatic amine monomers on the surface of an oxide support to form a porous π-conjugated network framework. This increases the adsorption area and coordination active sites of the support, thereby improving the loading rate of the active metal. The metal is bound through physical adsorption and coordination between the metal precursor and the electron pairs on the nitrogen atoms. The catalyst precursor is then sintered under specific sintering conditions. This not only transforms the nitrogen-containing polymer framework on the support surface into graphitized N and pyridinated N, but also significantly enhances the interaction between the support and the metal components, suppressing the loss of metal components during catalyst use. When the prepared catalyst is used in the olefin carbonylation reaction, it can significantly improve the conversion rate, selectivity, and recycling stability.

[0085] By using segmented temperature-controlled calcination, the metal-support interaction is first enhanced by calcination in a lower temperature range according to a certain program, thus preventing metal atom aggregation. Subsequently, the temperature is slowly increased in a higher temperature range, which causes the support to carbonize and form graphitized N and pyridinated N in different proportions. This increases the density of active metal sites in the catalyst while ensuring that the active metal components have excellent dispersibility and are not prone to aggregation, thereby improving the catalytic activity and cycle stability of the catalyst.

[0086] Specifically, in this invention, a gradient heating method is used to sinter the catalyst precursor. Sintering the catalyst precursor at a lower temperature range can better preserve the three-dimensional porous structure of the nitrogen-containing polymer and avoid pore collapse. When the sintering temperature exceeds 600°C, it will cause damage to the porous structure, especially the collapse of the mesoporous structure, resulting in an unfavorable reduction in the specific surface area of ​​the final catalyst.

[0087] In this invention, the sintering conditions include: heating from room temperature to 300-400℃ at a heating rate of 1-20℃ / min, holding at that temperature for 1-3 hours, then heating to 400-600℃ at a heating rate of 1-10℃ / min, and holding at that temperature for 0.5-2 hours.

[0088] In this invention, the heating rate in the first stage is 1-20℃ / min, for example, it can be 1℃ / min, 2℃ / min, 5℃ / min, 8℃ / min, 10℃ / min, 12℃ / min, 15℃ / min, 18℃ / min, 20℃ / min, or any range of two values; the heating rate in the second stage can be 1-10℃ / min, for example, it can be 1℃ / min, 2℃ / min, 5℃ / min, 8℃ / min, 10℃ / min, or any range of two values.

[0089] Furthermore, the sintering conditions include: heating from room temperature to 350-400℃ at a heating rate of 5-20℃ / min and holding at that temperature for 1-3 hours, then heating to 400-500℃ at a heating rate of 2-8℃ / min and holding at that temperature for 0.5-2 hours.

[0090] In a preferred embodiment of the present invention, the active monomer is selected from at least one of aniline, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.

[0091] In a preferred embodiment of the present invention, the active monomer is selected from at least two of aniline, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine; more preferably, it is selected from any two of aniline, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine; even more preferably, the active monomer is aniline and phenylenediamine selected from one of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine, wherein the mass ratio of aniline to phenylenediamine is 1.5-2:1, for example, it can be 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, and any range of two values.

[0092] According to the present invention, the initiator is selected from at least one of peracetic acid, hydrogen peroxide, ammonium persulfate, and potassium persulfate.

[0093] According to the present invention, the oxide support is selected from at least one of ferric oxide, ferric oxide and ferrous oxide.

[0094] According to the present invention, based on the amount of the oxide support, the amount of the active monomer is 2-50 wt%, for example, it can be 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, and any range of two values.

[0095] According to the present invention, based on the amount of the active monomer, the amount of the initiator is 2-15 wt%, for example, it can be 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, and any range of two values.

[0096] In this invention, when the amount of oxide support, active monomer and initiator is controlled to meet the above range, it can be ensured that the support surface is uniformly modified with nitrogen carbides, and that graphitized N and pyridinated N in the catalyst can be uniformly distributed on the surface of the catalyst and combine with the active metal components, thereby ensuring that the active metal components are uniformly distributed and not easily agglomerated.

[0097] Furthermore, based on the amount of the oxide support, the amount of the active monomer is 10-30 wt%.

[0098] Furthermore, based on the amount of the active monomer, the amount of the initiator is 5-15 wt%.

[0099] In a preferred embodiment of the present invention, the in-situ polymerization is carried out in the presence of a structure modifier.

[0100] In this invention, adding a structure modifier during the in-situ polymerization of aniline and / or phenylenediamine monomers on the surface of an oxide support can further regulate the morphology of the nitrogen-containing polymer skeleton on the support surface. Specifically, it enables the nitrogen-containing polymer to polymerize and assemble at the interface of the support surface to form nanoribbons or dendritic three-dimensional structures, fully exposing active sites and improving the catalytic activity and selectivity of the catalyst.

[0101] According to the present invention, the structure modifier is selected from at least one of polyquaternary ammonium salt, hexadecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride.

[0102] In this invention, a specific type of surfactant is used as a structure modifier. Through the charge interaction between surfactant molecules and initiators such as ammonium persulfate, a 3D structure is formed by self-assembly. A gel or micelle soft template is formed by the adsorption of aniline and / or phenylenediamine monomers through charge interaction, which then polymerize and assemble at the interface to form nanoribbons or dendritic three-dimensional structures. The fully exposed nitrogen-containing active sites coordinate with the active metal to form a structure with a high-density metal distribution. This results in a highly dispersed and non-aggregated metal active component in the prepared catalyst, making the catalyst less prone to deactivation, reducing the loss rate of metal active components, and significantly improving the catalyst activity.

[0103] Furthermore, the structural modifier is selected from hexadecyltrimethylammonium bromide and / or hexadecyltrimethylammonium chloride.

[0104] According to the present invention, based on the amount of the active monomer, the amount of the structure modifier is 50-150 wt%, for example, it can be 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 100 wt%, 110 wt%, 120 wt%, 130 wt%, 140 wt%, 150 wt%, and any range of two values.

[0105] In this invention, by controlling the amount of structure modifier to meet the above-mentioned range, the structure modifier (e.g., hexadecyltrimethylammonium bromide (CTAB)) can self-assemble into a 3D structure, a gel or micelle soft template, which can assist aniline and / or phenylenediamine monomers in the interfacial polymerization assembly to form nanoribbons or dendritic three-dimensional structures, fully exposing N-containing active sites and coordinating with active metals, while increasing the specific surface area of ​​the catalyst support, providing the loading rate of active metal components in the catalyst, and reducing the loss rate of active metal components, ultimately further improving the catalytic activity and cycle stability of the catalyst.

[0106] Furthermore, based on the amount of the active monomer, the amount of the structure modifier is 80-150 wt%.

[0107] In this invention, the solvent in step (1) is preferably water. There is no particular limitation on the amount of solvent used, as long as the oxide carrier, active monomer, initiator and optional structure modifier are sufficiently and evenly dispersed.

[0108] In one specific embodiment of the present invention, the amount of solvent used is such that the mass concentration of the mixture containing the solvent and the oxide carrier is 10-50 wt%, for example, it can be 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, and any range of two values.

[0109] In one specific embodiment of the present invention, the oxide support is first mixed with a solvent to obtain a mixture, and then the active monomer, initiator and structure modifier are added to the mixture in sequence to carry out in-situ polymerization.

[0110] According to the present invention, the metal precursor in the metal precursor solution is a water-soluble metal salt capable of providing an active metal component.

[0111] In this invention, there is no particular limitation on the type of water-soluble salt, which can be a water-soluble salt commonly used in the art, such as chloride salts, carbonates, nitrates, sulfates and oxalates.

[0112] According to the present invention, the active metal component is selected from at least one of Rh, Pb, Ru, Ir, Co, Cs and Li; preferably Rh and / or Co.

[0113] In this invention, the rhodium (Rh) precursor is one or more of RhCl3, RhCl3·xH2O, RhCl3·3H2O, Rh(CO)2(C5H7O2), and [(C6H5)3P]3RhCl.

[0114] In this invention, the cobalt (Co) precursor is one or more of Co(NO3)2, Co(NO3)2·6H2O, CoSO4, CoSO4·7H2O, CoCl2, and CoCl2·6H2O.

[0115] According to the present invention, the amounts of the precursor solution and the modified carrier are such that, based on the amount of the modified carrier, the amount of the metal precursor is 2-20 wt%, for example, it can be 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, and any range of two values.

[0116] In this invention, by controlling the amount of modified support and metal precursor to satisfy the above-mentioned relationship, the content of support and metal in the prepared catalyst can meet the requirements of the first aspect of this invention.

[0117] Furthermore, the amounts of the precursor solution and the modified carrier are such that, based on the amount of the modified carrier, the amount of the metal precursor is 5-15 wt%.

[0118] In this invention, there is no particular limitation on the concentration of the metal precursor solution. Preferably, in order to ensure that the active metal in the metal precursor solution is highly dispersed and not prone to agglomeration, when it is mixed and impregnated with the modified support, the active metal component in the catalyst is highly dispersed in the support, thereby giving the catalyst high catalytic activity and high selectivity, as well as good cycle stability. The concentration of the metal precursor solution is controlled to be 0.2-6 wt%, for example, it can be 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, or any two of these values, preferably 0.5-3 wt%.

[0119] According to the present invention, the conditions for the in-situ polymerization include: a polymerization temperature of 30-60°C, for example, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, or any range of two values; and a polymerization time of 1-6 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, or any range of two values.

[0120] In this invention, when the conditions for controlling in-situ polymerization meet the above-mentioned range, the surface of the support can be uniformly coated with aniline polymers. After sintering, uniform nitrogen carbides are formed on the surface of the support, and a specific amount of graphitized N and pyridinated N are formed on the surface of the support, which facilitates coordination and combination with metals, thereby improving the catalytic activity and cycle stability of the catalyst.

[0121] Furthermore, the conditions for the in-situ polymerization include: a polymerization temperature of 40-55℃ and a polymerization time of 2-4 hours.

[0122] According to the present invention, the impregnation conditions include: an impregnation temperature of 25-60°C, for example, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, or any range of two values; and an impregnation time of 2-48h, for example, 2h, 3h, 5h, 8h, 10h, 13h, 15h, 18h, 20h, 23h, 25h, 28h, 30h, 33h, 35h, 38h, 40h, 43h, 45h, 48h, or any range of two values.

[0123] In this invention, when the impregnation conditions are controlled to meet the above-mentioned range, the active metal can be uniformly loaded on the support and the active metal can be prevented from agglomerating, thereby making the prepared catalyst have high catalytic activity and selectivity, and good cycle stability.

[0124] Furthermore, the conditions for impregnation include: an impregnation temperature of 30-50°C and an impregnation time of 5-48 hours.

[0125] In this invention, there is no particular limitation on the method of solid-liquid separation, and conventional solid-liquid separation methods in the art can be used.

[0126] In one specific embodiment of the present invention, when the carrier oxide is a magnetic oxide, the solid-liquid separation is achieved by magnetic adsorption.

[0127] According to the present invention, the drying conditions include: a drying temperature of 60-80°C and a drying time of 2-3 hours.

[0128] In this invention, the type of protective atmosphere is not particularly limited; for example, it can be N2 or Ar.

[0129] According to the present invention, the preparation method further includes: cooling the sintered product to room temperature at a rate of 1-15℃ / min, for example, at a rate of 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min, 10℃ / min, 11℃ / min, 12℃ / min, 13℃ / min, 14℃ / min, 15℃ / min, and any range of two values.

[0130] In this invention, cooling the sintered product to room temperature at the specific rate mentioned above can prevent the agglomeration of the metal active components and form highly active species on the catalyst surface, ultimately giving the catalyst high catalytic activity, high selectivity, and good cycle stability.

[0131] Furthermore, the sintered product is cooled to room temperature at a rate of 5-10 °C / min.

[0132] A third aspect of the present invention provides a supported catalyst prepared by the above-described preparation method.

[0133] A fourth aspect of the present invention provides the application of the above-mentioned supported catalyst in the olefin carbonylation reaction.

[0134] In this invention, there are no particular limitations on the specific application of supported catalysts in olefin carbonylation reactions; they can be carried out in accordance with conventional methods in the art.

[0135] In one specific embodiment of the present invention, the olefin carbonylation reaction includes the following steps:

[0136] 100-1000 mg of the supported catalyst described in this invention was placed in a stainless steel high-pressure reactor, and raw material C6-C was added. 16 Olefins and solvents are sequentially purged from a high-pressure reactor with inert gas and syngas to replace the existing gases. After replacement, syngas at a certain pressure is introduced. The high-pressure reactor is then heated to a certain temperature and maintained at a constant temperature, and a carbonylation reaction is carried out under a certain stirring rate. After the reaction is complete, the reactor is cooled to room temperature, the liquid inside is drained, and the catalyst and reaction mixture are separated by an external magnetic field.

[0137] In one specific embodiment of the present invention, the olefin is C6-C. 16 One or more of straight-chain or branched olefins.

[0138] In this invention, the C6-C 16 Alkenes include, but are not limited to, dodecene, hexene, decene, tetradecene, and octene.

[0139] In one specific embodiment of the present invention, the reaction pressure of the carbonylation reaction is 1 MPa-30 MPa, the reaction temperature is 60-150 °C, and the reaction time is 0.5-15 h.

[0140] In one specific embodiment of the present invention, the volume ratio of CO to H2 in the synthesis gas is 1:1-4.

[0141] In this invention, the solvent is toluene, cyclohexane, aldehyde, alcohol, etc., and the volume percentage of the solvent to the olefin is 0.2-3:1, for example, it can be 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, and any range of two values.

[0142] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only, and the scope of the present invention is not limited to these embodiments.

[0143] In the following embodiments, the content ratios of graphitized N and pyridinized N were quantitatively determined by X-ray photoelectron spectroscopy (XPS). Specifically, the N elemental spectrum was measured using an XPS spectrometer, and the data was processed using XPS software. Before peak fitting, the raw data was first calibrated to ensure the accuracy of the binding energy values ​​for each element. An external contaminant carbon (e.g., 284.8 eV) was used as a reference, and calibration was performed using Avantage software to remove background noise and establish a baseline. The standard N peak positions were referenced in literature, and peak fitting was performed using Peak Fit. Fitting parameters such as peak position, peak area, and FWHM were adjusted. The XPS N1 high-resolution spectrum was processed using Lorentz and Gaussian functions, resulting in two peak positions at 401.5 eV and 398.3 eV. The 401.5 eV peak was assigned to graphitized N, and the 398.3 eV peak to pyridinized N.

[0144] The relative content of graphitized N and pyridinized N is calculated based on the photoelectron peak area in the X-ray photoelectron spectroscopy spectrum. The calculation method is: mass ratio of graphitized N to pyridinized N = S (石墨N峰面积) :S (吡啶N峰面积) .

[0145] The thickness of the shell in the carrier was measured by TEM electron microscopy. Specifically, a 20cm×20cm area was randomly selected on the TEM electron microscopy image of the carrier, and the thickness of the shell in at least 40 carrier particles was measured and counted using Nano Measurer software, and the average value was calculated.

[0146] The contents of the support and metal in the supported catalyst were determined by inductively coupled plasma spectroscopy. Specifically, the metal content Q in the supported catalyst is calculated as: metal mass M1 / ​​total catalyst mass M2 × 100%, where the total catalyst mass M2 was obtained by weighing using a balance, and the metal mass M1 was obtained by inductively coupled plasma spectroscopy. The support mass Z in the supported catalyst is calculated as: total catalyst mass M2 - metal mass M1.

[0147] The content of nitrogen carbides in the support was obtained by quantitative analysis using EDS energy dispersive spectroscopy. The proportion of each element was calculated by converting the intensity ratios of the corresponding EDS peaks. Specifically, the nitrogen carbide content = relative nitrogen content + relative carbon content.

[0148] The micropore structure parameters of the supported catalyst were determined by ASAP 2020 specific surface area and porosity analyzer, and the pore volume and specific surface area were obtained by t-plot method.

[0149] The metal dispersion in the catalyst was determined using the CO pulse method. Specifically, the test method included: pulse titration of the catalyst sample in a CO gas stream using a chemisorption analyzer until CO adsorption saturation, followed by calculation of the metal dispersion. The calculation formula is as follows:

[0150] Metal dispersion, % = n(CO) / n(M) × 100%, where n(CO) is the number of moles of CO adsorbed, n(M) is the number of moles of metal in the catalyst, n(M) = m × (w1 / M1 + w2 / M2), where m represents the total mass of the catalyst, w1 represents the mass percentage of metal component 1 in the supported catalyst, M1 represents the relative atomic mass of metal component 1; w2 represents the mass percentage of metal component 2 in the catalyst, M2 represents the relative atomic mass of metal component 2.

[0151] The characteristic peak intensity I of Fe element in the catalyst Fe The characteristic peak intensity I of Rh element RhThe XRD pattern is obtained through XRD. Its basic principle is based on Bragg's equation nλ = 2d × sinθ, where λ represents the wavelength of the incident X-rays (λ = 0.154 nm for a copper target), d represents the interplanar spacing, and θ is the diffraction angle. In this test, the XRD incident angle is selected between 5-90°. By measuring the diffraction angle and intensity, and combining this with Bragg's law, the interplanar spacing is calculated, determining the lattice parameters and symmetry of the material, and thus inferring its crystal structure. In XRD patterns, crystalline phases typically exhibit sharp and independent diffraction peaks, while amorphous phases exhibit broad and blurred diffraction peaks. The peak intensity is usually proportional to the crystalline phase content and grain size; that is, the larger the peak area, the higher the crystalline phase content and the larger the grain size. Therefore, XRD testing can provide crystal structure information through diffraction peaks, but it cannot provide atomic-level structural information; that is, atomically dispersed metals cannot form distinct diffraction peaks on XRD. The specific method for XRD testing is as follows: 20-50 mg of powdered sample; XRD incident angle selected between 5-90°; data processed using JADE software; diffraction peaks were adjusted using Gaussian function fitting, resulting in a small fitting residual and good fitting effect. The phase content and proportion were then calculated.

[0152] I Fe / I Rh =Fe characteristic peak area / Rh characteristic peak area. The characteristic peak area is obtained directly after processing with JADE software, removing background and performing peak fitting.

[0153] The catalyst metal loss rate was determined by inductively coupled plasma spectroscopy. Catalyst metal loss rate = (metal content of supported catalyst before reaction Q1 - metal content of supported catalyst after 5 cycles Q2) / metal content of supported catalyst before reaction Q1 × 100%.

[0154] The conversion rate of the catalyst in the olefin carbonylation reaction was determined by gas chromatography. The test employed the internal standard method, where a certain amount of pure substance was added to a known mass of sample as an internal standard, followed by chromatographic analysis to determine the peak areas of the internal standard and several components in the sample. A relative mass correction factor was introduced to calculate the mass fraction of the analyte in the sample, thereby calculating the conversion rate. The calculation formula is as follows:

[0155] mi = f × Ai / (As / ms), where f is the relative correction factor, obtained by consulting the gas chromatography handbook. mi is the content of the test sample, ms is the amount of internal standard added, and Ai and As are the peak areas of analyte i and internal standard s, respectively.

[0156] Olefin conversion rate, % = (Olefin content of feedstock - Olefin content of product) / Olefin content of feedstock × 100%.

[0157] In the examples and comparative examples, the average particle size of the iron oxide powder was 300 nm.

[0158] All raw materials used in the examples and comparative examples are commercially available products.

[0159] Example 1

[0160] (1) Add 2.25g of hexadecyltrimethylammonium bromide to 200g of deionized water, mix well, then add 5g of iron(III) oxide powder. While stirring, add 1g of aniline, 0.5g of m-phenylenediamine, and 0.225g of potassium persulfate sequentially. Stir at 40℃ for 5 hours. Then wash the mixture with deionized water at least three times and heat in a vacuum drying oven at 60℃ for 2 hours to obtain modified carrier 1. Based on the amount of iron(III) oxide, the amount of active monomer is 30wt%, and based on the amount of active monomer, the amount of potassium persulfate is 15wt%, and the amount of structure modifier is 150wt%. The thickness of the shell layer in modified carrier 1...

[0161] (2) Weigh 0.17g RhCl3 and 0.08g Co(NO4)2, dissolve them in 20mL of deionized water, and prepare metal precursor solution 1 (wherein, the mass concentration of Rh precursor is 0.40wt% and the mass concentration of Co precursor is 0.43wt%). Slowly add 5g of modified support 1 to the pre-prepared metal precursor solution 1, and then stir at 50℃ for 12h at a stirring rate of 300rpm. The obtained product is then separated by magnetic attraction. The obtained solid is transferred to a drying oven and vacuum dried at 60℃ for 3h to obtain the catalyst precursor.

[0162] (3) The catalyst precursor obtained above was transferred to a tube furnace. Nitrogen gas was introduced for 30 min to completely replace and purge the air in the tube furnace. Then, under a nitrogen atmosphere, the temperature was increased from 30°C to 350°C at a rate of 5°C / min and held at that temperature for 2 h. Subsequently, the temperature was increased to 460°C at a rate of 2°C / min and held at that temperature for 2 h. After the isothermal process, the temperature was cooled to room temperature at a rate of 10°C / min to obtain catalyst A1.

[0163] Example 2

[0164] The catalyst was prepared according to the method of Example 1, with the following difference:

[0165] Step (1) differs from Example 1: 1.1g of hexadecyltrimethylammonium bromide was added to 200g of deionized water, mixed thoroughly, and then 5g of iron(III) oxide powder was added. While stirring, 1g of aniline, 0.5g of m-phenylenediamine, and 0.065g of potassium persulfate were added sequentially. The mixture was stirred at 40℃ for 5 hours. Based on the amount of iron(III) oxide, the amount of active monomer was 30wt%, and based on the amount of active monomer, the amount of potassium persulfate was 4wt%, and the amount of structure modifier was 73wt%.

[0166] The remaining steps are the same as in Example 1, and catalyst A2 is obtained.

[0167] Example 3

[0168] The catalyst was prepared according to the method of Example 1, with the following difference:

[0169] Step (1) differs from Example 1: 0.8g of cetyltrimethylammonium bromide was added to 200g of deionized water, mixed thoroughly, and then 5g of iron(III) oxide powder was added. While stirring, 0.4g of aniline, 0.2g of m-phenylenediamine, and 0.055g of potassium persulfate were added sequentially. The mixture was stirred at 40°C for 5 hours. Based on the amount of iron(III) oxide, the amount of active monomer was 12wt%, and based on the amount of active monomer, the amount of potassium persulfate was 9wt%, and the amount of structure modifier was 133wt%.

[0170] Example 4

[0171] The catalyst was prepared according to the method of Example 1, except that 2.25 g of polyquaternium-7 (dimethyl diallyl ammonium chloride-acrylamide copolymer) was used instead of hexadecyltrimethylammonium bromide. Based on the amount of iron oxide, the amount of active monomer was 30 wt%, and based on the amount of active monomer, the amount of potassium persulfate was 15 wt%, and the amount of structure modifier was 150 wt%. The remaining steps were the same as in Example 1, yielding catalyst A4.

[0172] Example 5

[0173] The catalyst was prepared according to the method of Example 1, except that 1.5 g of aniline was used instead of aniline and m-phenylenediamine in Example 1. The remaining steps were the same as in Example 1, and catalyst A5 was finally obtained.

[0174] Example 6

[0175] The catalyst was prepared according to the method of Example 1, except that 1.5 g of o-phenylenediamine was used instead of aniline and m-phenylenediamine in Example 1. The remaining steps were the same as in Example 1, and catalyst A6 was obtained.

[0176] Example 7

[0177] The catalyst was prepared according to the method of Example 1, with the following difference:

[0178] Step (1): Add 0.135g of cetyltrimethylammonium bromide to 200g of deionized water, mix well, then add 5g of iron oxide powder. While stirring, add 0.06g of aniline, 0.03g of o-phenylenediamine, and 0.011g of potassium persulfate; stir at 40℃ for 5h. Based on the amount of iron oxide, the amount of active monomer is 1.8wt%, based on the amount of active monomer, the amount of potassium persulfate is 12wt%, and the amount of structure modifier is 150wt%.

[0179] The remaining steps are the same as in Example 1, and catalyst A7 is finally obtained.

[0180] Example 8

[0181] The catalyst was prepared according to the method of Example 1, except that the amount of potassium persulfate was 0.045 g. Based on the amount of iron oxide, the amount of active monomer was 30 wt%, based on the amount of active monomer, the amount of potassium persulfate was 3 wt%, and the amount of structure modifier was 150 wt%.

[0182] The remaining steps are the same as in Example 1, and catalyst A8 is finally obtained.

[0183] Example 9

[0184] The catalyst was prepared according to the method of Example 1, except that the amount of potassium persulfate was adjusted to 0.2 g, the amount of active monomer was 30 wt% based on the amount of iron oxide, the amount of potassium persulfate was 13 wt% based on the amount of active monomer, and the amount of structure modifier was 150 wt%.

[0185] The remaining steps are the same as in Example 1, and catalyst A9 is finally obtained.

[0186] Example 10

[0187] The catalyst was prepared according to the method of Example 1, with the following difference:

[0188] Step (1): Add 0.8g of cetyltrimethylammonium bromide to 200g of deionized water, mix well, then add 5g of iron(III) oxide powder. While stirring, add 1g of aniline, 0.5g of m-phenylenediamine, and 0.225g of hydrogen peroxide in sequence; stir at 40℃ for 5h. Based on the amount of iron(III) oxide, the amount of active monomer is 30wt%, based on the amount of active monomer, the amount of hydrogen peroxide is 15wt%, and the amount of structure modifier is 53wt%.

[0189] The remaining steps are the same as in Example 1, and catalyst A10 is finally obtained.

[0190] Example 11

[0191] The catalyst was prepared according to the method of Example 1, with the following difference:

[0192] Step (1): Add 0.45g of cetyltrimethylammonium bromide to 200g of deionized water, mix well, then add 5g of iron(III) oxide powder. While stirring, add 0.2g of aniline, 0.1g of m-phenylenediamine, and 0.06g of potassium persulfate in sequence. Based on the amount of iron(III) oxide, the amount of active monomer is 6wt%, based on the amount of active monomer, the amount of potassium persulfate is 20wt%, and the amount of structure modifier is 150wt%.

[0193] The remaining steps are the same as in Example 1, and catalyst A11 is finally obtained.

[0194] Example 12

[0195] The catalyst was prepared according to the method of Example 1, with the following difference:

[0196] Step (1): Add 2.4g of cetyltrimethylammonium bromide to 200g of deionized water, mix well, then add 5g of iron(III) oxide powder. While stirring, add 1.6g of aniline, 0.8g of p-phenylenediamine, and 0.25g of potassium persulfate in sequence. Based on the amount of iron(III) oxide, the amount of active monomer is 48wt%, based on the amount of active monomer, the amount of potassium persulfate is 10wt%, and the amount of structure modifier is 100wt%.

[0197] The remaining steps are the same as in Example 1, and catalyst A12 is finally obtained.

[0198] Example 13

[0199] The catalyst was prepared according to the method of Example 1, with the following difference:

[0200] Step (3): The catalyst precursor obtained above was transferred to a tube furnace. Nitrogen gas was introduced for 30 minutes to completely replace and purge the air from the tube furnace. Under a nitrogen atmosphere, the temperature was increased from room temperature to 350°C at a rate of 2°C / min and held at that temperature for 2 hours. Then, the temperature was increased to 460°C at a rate of 10°C / min and held at that temperature for 2 hours. After the isothermal process, the temperature was cooled to room temperature at a rate of 10°C / min to obtain catalyst A13.

[0201] Example 14

[0202] The catalyst was prepared according to the method of Example 1, with the following difference:

[0203] Step (3): The catalyst precursor obtained above was transferred to a tube furnace. Nitrogen gas was introduced for 30 minutes to completely replace and purge the air from the tube furnace. Under a nitrogen atmosphere, the temperature was increased from room temperature to 300°C at a rate of 5°C / min and held at that temperature for 2 hours. Then, the temperature was increased to 530°C at a rate of 2°C / min and held at that temperature for 2 hours. After the isothermal process, the temperature was cooled to room temperature at a rate of 10°C / min to obtain catalyst A14.

[0204] Example 15

[0205] The catalyst was prepared according to the method of Example 1, with the following difference:

[0206] Step (3): The catalyst precursor obtained above was transferred to a tube furnace. Nitrogen gas was introduced for 30 minutes to completely replace and purge the air from the tube furnace. Under a nitrogen atmosphere, the temperature was increased from room temperature to 300°C at a rate of 15°C / min and held at that temperature for 2 hours. Then, the temperature was increased to 500°C at a rate of 5°C / min and held at that temperature for 2 hours. After the isothermal process, the temperature was cooled to room temperature at a rate of 10°C / min to obtain catalyst A15.

[0207] Example 16

[0208] The catalyst was prepared according to the method of Example 1, with the following difference:

[0209] Step (1): Add 2.25g of cetyltrimethylammonium bromide to 200g of deionized water, mix well, then add 5g of iron(III) oxide powder. While stirring, add 0.9g of aniline, 0.6g of p-phenylenediamine, and 0.225g of hydrogen peroxide in sequence; stir at 40℃ for 5h. Based on the amount of iron(III) oxide, the amount of active monomer is 30wt%, and based on the amount of active monomer, the amount of potassium persulfate is 15wt%, and the amount of structure modifier is 150wt%.

[0210] The remaining steps are the same as in Example 1, and catalyst A16 is finally obtained.

[0211] Example 17

[0212] The catalyst was prepared according to the method of Example 1, with the following difference:

[0213] Step (1): Add 2.25g of cetyltrimethylammonium chloride to 200g of deionized water, mix well, then add 5g of iron oxide powder. While stirring, add 1.1g of o-phenylenediamine, 0.4g of p-phenylenediamine, and 0.225g of potassium persulfate in sequence; stir at 40℃ for 5h. Based on the amount of iron oxide, the amount of active monomer is 30wt%, based on the amount of active monomer, the amount of potassium persulfate is 15wt%, and the amount of structure modifier is 150wt%.

[0214] The remaining steps are the same as in Example 1, and catalyst A17 is finally obtained.

[0215] Example 18

[0216] The catalyst was prepared according to the method of Example 1, with the following difference:

[0217] Step (1): Add 4.25g of cetyltrimethylammonium chloride to 200g of deionized water, mix well, then add 5g of iron(III) oxide powder. While stirring, add 0.5g of o-phenylenediamine, 1g of p-phenylenediamine, and 0.325g of potassium persulfate in sequence; stir at 40℃ for 5h. Based on the amount of iron(III) oxide, the amount of active monomer is 30wt%, based on the amount of active monomer, the amount of potassium persulfate is 22wt%, and the amount of structure modifier is 283wt%.

[0218] The remaining steps are the same as in Example 1, and catalyst A18 is finally obtained.

[0219] Example 19

[0220] The catalyst was prepared according to the method of Example 1, with the following difference:

[0221] Step (1): Add 1.25g of polyquaternium-7 (dimethyl diallyl ammonium chloride-acrylamide copolymer) to 200g of deionized water, mix well, then add 5g of iron oxide powder. While stirring, add 0.5g of o-phenylenediamine, 1g of p-phenylenediamine, and 0.025g of potassium persulfate in sequence; stir at 40℃ for 5h. Based on the amount of iron oxide, the amount of active monomer is 30wt%, based on the amount of active monomer, the amount of potassium persulfate is 1.7wt%, and the amount of structure modifier is 83wt%.

[0222] The remaining steps are the same as in Example 1, and catalyst A19 is finally obtained.

[0223] Example 20

[0224] The catalyst was prepared according to the method of Example 1, with the following difference:

[0225] Step (1): Add 5g of iron oxide powder to 200g of deionized water, and add 1g of aniline, 0.5g of m-phenylenediamine, and 0.225g of potassium persulfate in sequence while stirring. Stir at 40℃ for 5h. Based on the amount of iron oxide, the amount of active monomer is 30wt%, based on the amount of active monomer, the amount of potassium persulfate is 15wt%, and the amount of structure modifier is 0wt%.

[0226] The remaining steps are the same as in Example 1, and catalyst A20 is finally obtained.

[0227] Example 21

[0228] The catalyst was prepared according to the method of Example 1, with the following difference:

[0229] In step (1), 0.95g of aniline and 0.55g of o-phenylenediamine are added;

[0230] Step (3): Under a nitrogen atmosphere, the temperature was increased from 30°C to 350°C at a rate of 5°C / min and held at that temperature for 3 hours. Then, the temperature was increased to 460°C at a rate of 2°C / min and held at that temperature for 1 hour. Other conditions remained unchanged, and catalyst A21 was obtained.

[0231] Example 22

[0232] (1) Add 2.25g of cetyltrimethylammonium bromide to 200g of deionized water, mix well, then add 5g of magnetic iron oxide powder. While stirring, add 1g of aniline, 0.5g of m-phenylenediamine, and 0.225g of potassium persulfate in sequence; stir at 40℃ for 5h. Then wash the above mixture with deionized water at least three times and heat in a vacuum drying oven at 60℃ for 2h to obtain modified carrier 1. Based on the amount of iron oxide, the amount of active monomer is 30wt%, based on the amount of active monomer, the amount of potassium persulfate is 15wt%, and the amount of structure modifier is 150wt%.

[0233] (2) The modified support 1 obtained above was transferred to a tube furnace. Nitrogen gas was introduced for 30 min to completely replace and purge the air in the tube furnace. Under a nitrogen atmosphere, the temperature was increased from 30°C to 350°C at a rate of 5°C / min and held at that temperature for 2 h. Then, the temperature was increased to 460°C at a rate of 2°C / min and held at that temperature for 2 h. After the isothermal process, the temperature was cooled to room temperature at a rate of 10°C / min to obtain the support.

[0234] (3) Weigh 0.17g RhCl3 and 0.08g Co(NO4)2, dissolve them in 20mL of deionized water, and prepare metal precursor solution 1 (wherein, the mass concentration of Rh precursor is 0.40wt% and the mass concentration of Co precursor is 0.43wt%). Slowly add 5g of the support obtained in step (2) to the pre-prepared metal precursor solution 1, and then stir at 50℃ for 12h at a stirring rate of 300rpm. Then, the obtained product is separated by attraction with a magnet, and the obtained solid is transferred to a drying oven and vacuum dried at 60℃ for 3h to obtain catalyst A22.

[0235] Comparative Example 1

[0236] The catalyst was prepared according to the method of Example 1, with the following difference:

[0237] Step (3): The catalyst precursor obtained above was transferred to a tube furnace. Nitrogen gas was introduced for 30 minutes to completely replace and purge the air from the tube furnace. Under a nitrogen atmosphere, the temperature was increased from room temperature to 350°C at a rate of 5°C / min and held at that temperature for 2 hours. Then, the temperature was increased to 800°C at a rate of 1°C / min and held at that temperature for 2 hours. After the isothermal process, the temperature was cooled to room temperature at a rate of 8°C / min to obtain catalyst D1.

[0238] Comparative Example 2

[0239] The catalyst was prepared according to the method of Example 1, except that step (1) was omitted and iron(III) oxide powder was directly used in step (2). The remaining steps were the same as in Example 1, and catalyst D2 was obtained.

[0240] Comparative Example 3

[0241] The catalyst was prepared according to the method of Example 1, with the following difference:

[0242] Step (3): The catalyst precursor obtained above was transferred to a tube furnace. Nitrogen gas was introduced for 30 minutes to completely replace and purge the air in the tube furnace. The temperature was then directly increased to 400°C at a rate of 5°C / min under a nitrogen atmosphere and held at that temperature for 2 hours. After the holding period, the temperature was cooled to room temperature at a rate of 10°C / min to obtain catalyst D3.

[0243] Comparative Example 4

[0244] The catalyst was prepared according to the method of Example 1, with the following difference:

[0245] Step (1): Add 2.25g of cetyltrimethylammonium bromide to 200g of deionized water, mix well, then add 5g of iron oxide powder, and add 1.5g of pyrrole monomer and 0.225g of potassium persulfate while stirring; stir at 40℃ for 5h. Based on the amount of iron oxide, the amount of active monomer is 30wt%, based on the amount of active monomer, the amount of potassium persulfate is 15wt%, and the amount of structure modifier is 150wt%.

[0246] The remaining steps are the same as in Example 1, and catalyst D4 is obtained.

[0247] Comparative Example 5

[0248] The catalyst was prepared according to the method of Example 1, with the following difference:

[0249] 5g of graphene oxide powder was used instead of 5g of iron oxide powder in Example 1. The remaining steps were the same as in Example 1, and catalyst D5 was obtained.

[0250] The physicochemical parameters of the modified supports and catalysts prepared in the examples and comparative examples are shown in Table 1.

[0251] Table 1

[0252]

[0253]

[0254] * refers to the mass ratio of graphitized N to pyrrolic N.

[0255] Table 1 (continued)

[0256]

[0257]

[0258] V always refers to the total pore volume of the catalyst;

[0259] Vmedium refers to the pore volume of the mesopores in the catalyst.

[0260] As shown in Table 1, the nitrogen carbides in the support of the supported catalyst provided in this embodiment of the invention include graphitized N and pyridinated N, and graphitized N and pyridinated N satisfy a specific content relationship, which coordinates with the active metal to form catalytic active sites, thereby improving the catalyst activity. Simultaneously, the catalyst of this invention contains a mesoporous structure, and the pore volume of the mesopores accounts for a high proportion of the total pore volume of the catalyst, improving the dispersion stability of the active metal component in the support, thereby improving the catalytic activity and stability of the catalyst.

[0261] Figure 1 and Figure 2 The XPS spectra for catalysts A1 and A2 are shown below. The spectra were calibrated for charge using external contaminant carbon (284.8 eV) as a reference. Based on literature review and reference to the standard N peak position, peak fitting was performed, adjusting peak position, peak area, and FWHM. After processing the XPS N1 high-resolution spectrum with Lorentz and Gaussian functions, two peaks at 401.5 eV and 398.3 eV were fitted, with 401.5 eV attributed to graphitized N and 398.3 eV attributed to pyridinized N.

[0262] Depend on Figure 1 and Figure 2 The proportions of graphitized N and pyridinized N in the catalyst can be seen. The content of the two types of N can be determined based on the position and peak area ratio of the XPS binding energy peak. Specifically, the ratio of graphitized N to pyridinized N in catalyst A1 is 0.2:1, and the ratio of graphitized N to pyridinized N in catalyst A2 is 1.2:1.

[0263] Figure 3This is the XRD diffraction pattern of catalyst A1. Among them, a and b are the characteristic diffraction peak patterns of cobalt and rhodium, respectively. The characteristic diffraction peak data of rhodium and cobalt are from the XRD standard diffraction cards PDF#05-0685-Rh and PDF#15-0806-Co. The typical characteristic structure diffraction peaks of rhodium (Rh) are at 2θ = 41.07°, 47.48°, and 69.88°, corresponding to the (111), (200), and (220) crystal planes, respectively. The typical characteristic structure diffraction peaks of cobalt (Co) are at 2θ = 44.22°, 51.53°, and 75.85°, corresponding to the (111), (200), and (220) crystal planes, respectively. Figure 3 c is the XRD pattern of catalyst A1 prepared in Example 1. The typical characteristic diffraction peaks of Fe3O4 are at 2θ = 30.1°, 35.5°, 43.1°, and 57.1°, which correspond to the (220), (311), (400), and (511) crystal planes, respectively. The diffraction intensity produced by different crystal planes is related to the periodic arrangement density of its atoms. Figure 3 Sharp diffraction peaks can be detected at positions 30.1°, 35.5°, 43.1°, and 57.1° in XRD pattern c. Higher peak intensities indicate a larger proportion of ordered crystalline phase. For amorphous single-atom materials, XRD patterns typically do not show obvious diffraction peaks. Figure 3 The characteristic diffraction peak positions corresponding to cobalt and rhodium are at... Figure 3 The fact that c is not reflected in the spectrum results indicates that no large-sized crystalline phases of the two metals were produced in catalyst A1, indicating that the metal dispersion is good.

[0264] Figure 4 This is a spherical aberration electron microscope image of catalyst A1 prepared in Example 1. Figure 4 As can be seen in the figure, the bright white areas represent the loaded metals rhodium and cobalt, while the dark areas represent the support. The loaded metals are distributed in a single-atom state on the support.

[0265] Test Example 1

[0266] 150 mg of the catalyst prepared in the examples and comparative examples was mixed with 10 mL of 1-octene and 20 mL of toluene and transferred to a high-pressure reactor. A CO / H2 mixture (CO:H2 volume ratio of 1:1) was introduced into the reactor, and the pressure inside the reactor was maintained at 7 MPa. The reaction was carried out at a constant temperature of 90 °C for 5 h. After the reaction, the mixture was cooled to room temperature, and the liquid inside the reactor was discharged. The catalyst and the reaction mixture were separated by an external magnetic field. The separated catalyst was recycled 5 times. The conversion rate of the catalyst during the first use, the conversion rate after 5 cycles, and the metal loss rate of the catalyst were tested. The product obtained by the carbonylation reaction of 1-octene was nonanal. The test results are shown in Table 2.

[0267] Table 2

[0268]

[0269]

[0270] As shown in Table 2, the catalyst of this invention exhibits high conversion rates in both the first use and after five cycles when used in the olefin carbonylation reaction, indicating good catalytic activity. Furthermore, it maintains high catalytic activity even after multiple cycles, demonstrating excellent stability. Simultaneously, Table 2 also shows that the catalyst provided by this invention exhibits a low loss rate of active metal components during the olefin carbonylation reaction, indicating stable loading of the active metal on the support, good catalyst stability during cycling, and minimal deactivation during long-term use.

[0271] Test Example 2

[0272] 150 mg of the catalyst prepared in the examples was mixed with 10 mL of different olefins (see Table 3 for details) and 20 mL of toluene, and then transferred to a high-pressure reactor. A CO / H2 mixture (CO:H2 volume ratio of 1:1) was introduced into the reactor. The pressure inside the reactor was 7 MPa, and the reaction was carried out at a constant temperature of 90 °C for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and the liquid inside the reactor was discharged. The catalyst and the reaction mixture were separated by an external magnetic field. The separated catalyst was recycled 5 times. The conversion rate of the catalyst during the first use and the conversion rate after 5 cycles were tested. The test results are shown in Table 3.

[0273] Table 3

[0274] Test case catalyst olefin types product First-time conversion rate / % Conversion rate after 5 cycles / % Test Case B1 A1 Dodecene Tridealdehyde 96.9 96.4 Test Case B2 A2 Dodecene Tridealdehyde 90.8 90.0 Test Case B3 A3 decene Undecaldehyde 94.8 94.1 Test case B4 A4 decene Undecaldehyde 93.7 92.2 Test Case B5 A5 Hexene heptanal 97.4 95.3 Test Case B6 A6 Hexene heptanal 96.6 94.2 Test Case B7 A7 Tetradecene Decidaldehyde 78.3 75.1 Test case B8 A8 Tetradecene Decidaldehyde 89.5 88.6 Test case B9 A9 Dodecene Tridealdehyde 93.6 92.9 Test case B10 A10 Dodecene Tridealdehyde 86.3 83.1

[0275] As can be seen from Table 3, the catalyst of the present invention can be used for the carbonylation reaction of various carbon number olefins (hexene, decene, dodecene, tetradecene). Among them, catalysts A1, A3-A6 have high conversion rates, and the conversion rate decreases only slightly after 5 cycles, indicating superior catalyst performance.

[0276] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A supported catalyst, characterized in that, The catalyst includes a support and a metal supported on the support; The support is an oxide modified with nitrogen carbides, and the nitrogen element in the nitrogen carbides includes graphitized nitrogen and pyridinized nitrogen. The mass ratio of graphitized N to pyridinized N is 0.1-2:

1.

2. The supported catalyst according to claim 1, wherein, The mass ratio of the graphitized N to the pyridinized N is 0.1-1:1; Preferably, the content of the nitrogen carbide is 2-50 wt%, more preferably 10-35 wt%, based on the total weight of the carrier; Preferably, the carrier has a core-shell structure with an oxide core and a nitride shell; Preferably, the average thickness of the shell layer is 5-30 nm, and more preferably 10-25 nm.

3. The supported catalyst according to claim 1 or 2, wherein, Based on the total weight of the supported catalyst, the content of the support is 95-99.9 wt%, preferably 97-99.5 wt%, and the content of the metal is 0.1-5 wt%, preferably 0.5-3 wt%. Preferably, the oxide is selected from at least one of iron(III) oxide, ferric oxide, and ferrous oxide; Preferably, the metal is selected from at least one of Rh, Pb, Ru, Ir, Co, Cs and Li.

4. The supported catalyst according to any one of claims 1-3, wherein, The metal dispersion in the supported catalyst is 45-75%, preferably 60-75%.

5. The supported catalyst according to any one of claims 1-4, wherein, The specific surface area of ​​the supported catalyst is 10-150 m². 2 / g, preferably 30-90m 2 / g; Preferably, the average pore size of the supported catalyst is 2-20 nm, more preferably 5-20 nm; Preferably, the total pore volume of the supported catalyst is 0.05-0.5 cm³. 3 / g, preferably 0.1-0.2cm 3 / g; Preferably, the pore volume of the mesopores in the supported catalyst is 0.05-0.5 cm³. 3 / g, preferably 0.07-0.2cm 3 / g; Preferably, based on the total pore volume of the supported catalyst, the pore volume of the mesopores is 50-90%, more preferably 70-85%.

6. The supported catalyst according to any one of claims 1-5, wherein, The oxide is selected from at least one of iron(III) oxide, ferric oxide, and ferrous oxide; the metal is Rh, or the metal is Rh and Co, wherein the characteristic peak intensity I of Fe element is measured by XRD. Fe The characteristic peak intensity I of Rh element Rh The following relationship must be satisfied: I Fe / I Rh 345 or greater, preferably 750 or greater.

7. A method for preparing a supported catalyst, characterized in that, The preparation method includes the following steps: (1) After mixing the oxide support, active monomer, initiator and solvent, in-situ polymerization is carried out, followed by separation and drying to obtain the modified support; (2) The metal precursor solution is mixed with the modified support and impregnated, and the solid phase is obtained by solid-liquid separation. The solid phase is dried to obtain the catalyst precursor. (3) The catalyst precursor is sintered in the presence of a protective atmosphere to obtain the supported catalyst; The active monomer is an aromatic amine; The sintering conditions include: heating from room temperature to 300-400℃ at a heating rate of 1-20℃ / min and holding at that temperature for 1-3 hours, then heating to 400-600℃ at a heating rate of 1-10℃ / min and holding at that temperature for 0.5-2 hours, and finally cooling to room temperature after the holding process is completed.

8. The preparation method according to claim 7, wherein, The sintering conditions include: heating from room temperature to 350-400℃ at a heating rate of 5-20℃ / min and holding at that temperature for 1-3 hours, then heating to 400-500℃ at a heating rate of 2-8℃ / min and holding at that temperature for 0.5-2 hours, and finally cooling to room temperature after the holding process is completed.

9. The preparation method according to claim 7 or 8, wherein, The active monomer is selected from at least one of aniline, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine; Preferably, the initiator is selected from at least one of peracetic acid, hydrogen peroxide, ammonium persulfate, and potassium persulfate; Preferably, the oxide support is selected from at least one of ferric oxide, ferric oxide, and ferrous oxide; Preferably, based on the amount of the oxide support, the amount of the active monomer is 2-50 wt%, preferably 10-30 wt%. Preferably, the amount of the initiator is 2-15 wt%, more preferably 5-15 wt%, based on the amount of the active monomer.

10. The preparation method according to any one of claims 7-9, wherein, The in-situ polymerization is carried out in the presence of a structure modifier; Preferably, the structure modifier is selected from at least one of polyquaternary ammonium salt, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride; Preferably, based on the amount of the active monomer, the amount of the structure modifier is 50-150 wt%, more preferably 80-150 wt%.

11. The preparation method according to any one of claims 7-10, wherein, The metal precursor in the metal precursor solution is a water-soluble metal salt that can provide active metal components; Preferably, the active metal component is selected from at least one of Rh, Pb, Ru, Ir, Co, Cs, and Li; Preferably, the amounts of the precursor solution and the modified carrier are such that, based on the amount of the modified carrier, the amount of the metal precursor is 2-20 wt%, preferably 5-15 wt%. Preferably, the concentration of the precursor solution is 0.2-6 wt%, more preferably 0.5-3 wt%.

12. The preparation method according to any one of claims 7-11, wherein, The conditions for the in-situ polymerization include: a polymerization temperature of 30-60℃, preferably 40-55℃, and a polymerization time of 1-6h, preferably 2-4h; Preferably, the impregnation conditions include: an impregnation temperature of 25-60℃, more preferably 30-50℃, and an impregnation time of 2-48h, more preferably 5-48h; Preferably, the drying conditions include: a drying temperature of 60-80℃ and a drying time of 2-3 hours; Preferably, the sintered product is cooled to room temperature at a rate of 1-15°C / min, more preferably 5-10°C / min.

13. A supported catalyst prepared by any one of claims 7-12.

14. The use of the supported catalyst according to any one of claims 1-6 and 13 in the carbonylation reaction of olefins, preferably, the olefin being C6-C. 16 olefins.

Images