WO2025232174A1 - 负载型催化剂及其制备方法与应用 - Google Patents

负载型催化剂及其制备方法与应用

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Publication number
WO2025232174A1
WO2025232174A1 PCT/CN2024/137039 CN2024137039W WO2025232174A1 WO 2025232174 A1 WO2025232174 A1 WO 2025232174A1 CN 2024137039 W CN2024137039 W CN 2024137039W WO 2025232174 A1 WO2025232174 A1 WO 2025232174A1
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Prior art keywords
catalyst
metal
supported catalyst
amount
oxide
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English (en)
French (fr)
Inventor
任行涛
吴春红
程璐
高大猛
贾志光
南杰
李明杰
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Sinopec Beijing Research Institute Of Chemical Industry Co Ltd
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute Of Chemical Industry Co Ltd
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Publication of WO2025232174A1 publication Critical patent/WO2025232174A1/zh
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/505—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration with a non-spherical or unspecified core-shell structure
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen

Definitions

  • This invention relates to the field of heterogeneous catalysts, and more specifically, to a supported catalyst, its preparation method, and its application.
  • 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.
  • 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.
  • 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%.
  • 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.
  • the preparation process of the polymer precursor is relatively cumbersome, and the carbon support requires hydrogenation treatment.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a first aspect of the present invention provides a supported catalyst, wherein the catalyst comprises 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.
  • 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:
  • the active monomer is an aromatic amine
  • the sintering conditions include: heating from room temperature to 300-400°C at a heating rate of 1-20°C/min and holding at that temperature for 1-3 hours, then heating to 400-600°C at a heating rate of 1-10°C/min and holding at that temperature for 0.5-2 hours.
  • a third aspect of the present invention provides a supported catalyst prepared by the above-described preparation method.
  • a fourth aspect of the present invention provides the application of the above-mentioned supported catalyst in the olefin carbonylation reaction.
  • the supported catalyst, its preparation method, and its application provided by the present invention achieve the following beneficial effects:
  • 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.
  • the catalyst 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.
  • aniline and/or phenylenediamine monomers are polymerized in situ on the surface of an oxide support to form a porous ⁇ -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.
  • the morphology of the nitrogen-containing polymer skeleton on the support surface can be further controlled.
  • 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.
  • Figure 1 is an XPS diagram of catalyst A1 prepared in Example 1.
  • Figure 2 is an XPS diagram of catalyst A2 prepared in Example 2.
  • a and b are the characteristic diffraction peak spectra 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.
  • c is the XRD pattern of catalyst A1 prepared in Example 1.
  • Figure 4 is a spherical aberration electron microscope image of catalyst A1 prepared in Example 1.
  • 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;
  • 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.
  • 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.
  • the catalyst contains abundant mesoporous structures, which ultimately significantly improves the catalytic activity and cycle stability of the catalyst.
  • 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.
  • 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.
  • the mass ratio of graphitized N to pyridine N is 0.1-1:1.
  • the mass ratio of the graphitized N to the pyridinized N is 0.2-1:1.
  • the content of the nitrogen carbide is 2-50 wt%, based on the total weight of the carrier.
  • the catalyst 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.
  • 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.
  • the content of the nitrogen-carbon compounds is 10-35wt%, preferably 15-35wt%, based on the total weight of the carrier.
  • 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.
  • 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.
  • the content of the support is 95-99.9 wt%, and the content of the metal is 0.1-5 wt%.
  • 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.
  • 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.
  • the content of the support is 97-99.5 wt%, and the content of the metal is 0.5-3 wt%.
  • the oxide is selected from at least one of ferric oxide, ferric oxide and ferrous oxide.
  • 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.
  • the oxide is preferably a magnetic oxide, preferably iron(III) oxide.
  • the supported catalyst is a supported magnetic catalyst.
  • the metal is selected from at least one of Rh, Pb, Ru, Ir, Co, Cs and Li.
  • the metal dispersion in the supported catalyst is 45-75%.
  • 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.
  • the dispersion of metals in the supported catalyst is 45-75%, further indicating that the supported catalyst has high catalytic efficiency.
  • 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.
  • the metal dispersion is measured using the CO pulse method.
  • 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:
  • 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.
  • the metal dispersion in the supported catalyst is 60-75%.
  • the specific surface area of the supported catalyst is 10-150 m2 /g, for example, it can be 10 m2 /g, 15 m2 /g, 20 m2 /g, 25 m2 /g, 30 m2 /g, 35 m2 /g, 40 m2 /g, 45 m2 /g, 50 m2 /g, 55 m2 /g, 60 m2/g, 65 m2 /g, 70 m2 /g, 75 m2 /g, 80 m2 /g, 85 m2 /g, 90 m2 /g, 95 m2 /g, 100 m2 /g, 105 m2 /g, 110 m2 /g, 115 m2 /g, 120 m2 /g, 125 m2/g, 130 m2 /g, 135 m2 /g, 140 m2 /g. 2 /g, 145m 2
  • 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.
  • the pore volume of the supported catalyst is 0.05-0.5 cm3 /g, for example, it can be 0.05 cm3 /g, 0.1 cm3 /g, 0.13 cm3 /g, 0.15 cm3 /g, 0.2 cm3/g, 0.25 cm3/ g, 0.3 cm3 / g, 0.35 cm3/g, 0.4 cm3/g, 0.45 cm3 /g, 0.5 cm3 /g, or any range of two values.
  • the pore volume of the intermediate pores of the supported catalyst is 0.05-0.5 cm3 /g, for example, it can be 0.05 cm3/g, 0.07 cm3 /g, 0.1 cm3/ g , 0.11 cm3/g, 0.15 cm3 /g, 0.2 cm3/g, 0.25 cm3/ g , 0.3 cm3/g, 0.35 cm3 /g, 0.4 cm3 /g, 0.45 cm3 /g, 0.5 cm3 /g, or any range of two values.
  • 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.
  • 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.
  • the specific surface area of the supported catalyst is 30-90 m2 /g.
  • the average pore size of the supported catalyst is 5-20 nm, more preferably 5-12 nm.
  • the total pore volume of the supported catalyst is 0.1-0.2 cm3 /g.
  • the total pore volume of the supported catalyst is 0.1-0.13 cm3 /g.
  • the pore volume of the mesopores in the supported catalyst is 0.07-0.2 cm3 /g.
  • the pore volume of the intermediate pores in the supported catalyst is 0.07-0.11 cm3 /g.
  • the pore volume ratio of mesopores is 70-90%.
  • the mesopore volume accounts for 70-85% of the total pore volume in the supported catalyst.
  • 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 ⁇ sub> Fe ⁇ /sub> of Fe and the characteristic peak intensity I ⁇ sub> Rh ⁇ /sub> of Rh, as measured by XRD, satisfy the following relationship:
  • I ⁇ sub>Fe ⁇ /sub> /I ⁇ sub> Rh ⁇ /sub> is greater than or equal to 345.
  • 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.
  • the characteristic peak intensities I ⁇ sub>Fe ⁇ /sub> and I ⁇ sub> Rh ⁇ /sub> of Fe and Rh, respectively, were measured by XRD.
  • 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.
  • I ⁇ sub>Fe ⁇ /sub> / I ⁇ sub>Rh ⁇ /sub> (Fe characteristic peak area / Rh characteristic peak area).
  • the characteristic peak area is obtained directly after background subtraction and peak fitting using JADE software.
  • I ⁇ sub>Fe ⁇ /sub> /I ⁇ sub> Rh ⁇ /sub> is greater than or equal to 750.
  • a second aspect of the present invention provides a method for preparing a supported catalyst, wherein the preparation method includes the following steps:
  • the active monomer is an aromatic amine
  • the sintering conditions include: heating from room temperature to 300-400°C at a heating rate of 1-20°C/min and holding at that temperature for 1-3 hours, then heating to 400-600°C at a heating rate of 1-10°C/min and holding at that temperature for 0.5-2 hours.
  • 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 ⁇ -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.
  • the prepared catalyst is used in the olefin carbonylation reaction, it can significantly improve the conversion rate, selectivity, and recycling stability.
  • 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.
  • 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.
  • 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.
  • the sintering conditions include: heating from room temperature to 300-400°C at a heating rate of 1-20°C/min, holding at that temperature for 1-3 hours, then heating to 400-600°C at a heating rate of 1-10°C/min, and holding at that temperature for 0.5-2 hours.
  • the heating rate in the first stage is 1-20°C/min, for example, it can be 1°C/min, 2°C/min, 5°C/min, 8°C/min, 10°C/min, 12°C/min, 15°C/min, 18°C/min, 20°C/min, or any range of two values;
  • the heating rate in the second stage can be 1-10°C/min, for example, it can be 1°C/min, 2°C/min, 5°C/min, 8°C/min, 10°C/min, or any range of two values.
  • the sintering conditions include: heating from room temperature to 350-400°C at a heating rate of 5-20°C/min and holding at that temperature for 1-3 hours, then heating to 400-500°C at a heating rate of 2-8°C/min and holding at that temperature for 0.5-2 hours.
  • the active monomer is selected from at least one of aniline, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.
  • 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.
  • the initiator is selected from at least one of peracetic acid, hydrogen peroxide, ammonium persulfate, and potassium persulfate.
  • the oxide support is selected from at least one of ferric oxide, ferric oxide and ferrous oxide.
  • 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.
  • 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.
  • the amount of oxide support, active monomer and initiator 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.
  • the amount of the active monomer is 10-30 wt%.
  • the amount of the initiator is 5-15 wt%.
  • the in-situ polymerization is carried out in the presence of a structure modifier.
  • 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.
  • the structure modifier is selected from at least one of polyquaternary ammonium salt, hexadecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride.
  • a specific type of surfactant is used as a structure modifier.
  • 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.
  • the structural modifier is selected from hexadecyltrimethylammonium bromide and/or hexadecyltrimethylammonium chloride.
  • 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.
  • the structure modifier e.g., hexadecyltrimethylammonium bromide (CTAB)
  • CTAB hexadecyltrimethylammonium bromide
  • the structure modifier 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.
  • CTAB hexadecyltrimethylammonium bromide
  • the amount of the structure modifier is 80-150 wt%.
  • the solvent in step (1) is preferably water.
  • the amount of solvent used 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.
  • 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.
  • 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.
  • the metal precursor in the metal precursor solution is a water-soluble metal salt capable of providing an active metal component.
  • water-soluble salt which can be a water-soluble salt commonly used in the art, such as chloride salts, carbonates, nitrates, sulfates and oxalates.
  • the active metal component is selected from at least one of Rh, Pb, Ru, Ir, Co, Cs and Li; preferably Rh and/or Co.
  • the rhodium (Rh) precursor is one or more of RhCl3 , RhCl3 ⁇ xH2O , RhCl3 ⁇ 3H2O , Rh(CO) 2 ( C5H7O2 ), and [ (C6H5)3P ] 3RhCl .
  • the cobalt (Co) precursor is one or more of Co( NO3 ) 2 , Co( NO3 ) 2 ⁇ 6H2O , CoSO4 , CoSO4 ⁇ 7H2O , CoCl2 , and CoCl2 ⁇ 6H2O .
  • 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.
  • the content of support and metal in the prepared catalyst can meet the requirements of the first aspect of this 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 5-15 wt%.
  • the concentration of the metal precursor solution there is no particular limitation on the concentration of the metal precursor solution.
  • 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%.
  • 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.
  • the surface of the support when the conditions for controlling in-situ polymerization meet the above-mentioned range, 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.
  • the conditions for the in-situ polymerization include: a polymerization temperature of 40-55°C and a polymerization time of 2-4 hours.
  • 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.
  • the active metal 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.
  • the conditions for impregnation include: an impregnation temperature of 30-50°C and an impregnation time of 5-48 hours.
  • the carrier oxide is a magnetic oxide
  • the solid-liquid separation is achieved by magnetic adsorption.
  • the drying conditions include: a drying temperature of 60-80°C and a drying time of 2-3 hours.
  • the type of protective atmosphere is not particularly limited; for example, it can be N2 or Ar.
  • the preparation method further includes: cooling the sintered product to room temperature at a rate of 1-15°C/min, for example, at a rate of 1°C/min, 2°C/min, 3°C/min, 4°C/min, 5°C/min, 6°C/min, 7°C/min, 8°C/min, 9°C/min, 10°C/min, 11°C/min, 12°C/min, 13°C/min, 14°C/min, 15°C/min, and any range of two values.
  • 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.
  • the sintered product is cooled to room temperature at a rate of 5-10 °C/min.
  • a third aspect of the present invention provides a supported catalyst prepared by the above-described preparation method.
  • a fourth aspect of the present invention provides the application of the above-mentioned supported catalyst in the olefin carbonylation reaction.
  • the olefin carbonylation reaction includes the following steps:
  • 100-1000 mg of the supported catalyst described in this invention is placed in a stainless steel high-pressure reactor.
  • C6 - C16 olefins and solvent are added.
  • the reactor is purged sequentially with inert gas and syngas to replace the existing gases. After replacement, syngas at a certain pressure is introduced.
  • the high-pressure reactor is heated to a certain temperature and maintained at a constant temperature.
  • the 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 discharged, and the catalyst and reaction mixture are separated by an external magnetic field.
  • the olefin is one or more of C6 - C16 straight-chain or branched olefins.
  • the C6 - C16 olefins include, but are not limited to, dodecene, hexene, decene, tetradecene, and octene.
  • the reaction pressure of the carbonylation reaction is 1 MPa-30 MPa
  • the reaction temperature is 60-150 °C
  • the reaction time is 0.5-15 h.
  • the volume ratio of CO to H2 in the synthesis gas is 1:1-4.
  • the solvent is toluene, cyclohexane, aldehyde, alcohol, etc.
  • 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.
  • 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 peak positions of N were referenced in literature, and peak Fit was used for fitting. The peak positions, peak areas, and FWHM (Functional Wavelength, Height, and Motion) fitting parameters were adjusted.
  • XPS X-ray photoelectron spectroscopy
  • the relative content is calculated based on the photoelectron peak area in the X-ray photoelectron energy spectrum, and the ratio of graphitized N to pyridinated N is obtained.
  • 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.
  • 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 .
  • 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.
  • 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:
  • the characteristic peak intensities I ⁇ sub>Fe ⁇ /sub> and I ⁇ sub> Rh ⁇ /sub> of Fe and Rh elements in the catalyst were measured by XRD.
  • the XRD incident angle was selected between 5-90°.
  • the interplanar spacing was calculated, determining the lattice parameters and symmetry of the material, and thus inferring its crystal structure.
  • crystalline phases typically exhibit sharp and independent diffraction peaks, while amorphous phases exhibit broad and blurred diffraction peaks.
  • Peak intensity is usually proportional to the crystalline phase content and grain size; that is, a larger peak area indicates a higher crystalline phase content and larger 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.
  • I ⁇ sub>Fe ⁇ /sub> / I ⁇ sub>Rh ⁇ /sub> (Fe characteristic peak area / Rh characteristic peak area).
  • the characteristic peak area is obtained directly after background subtraction and peak fitting using JADE software.
  • 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%.
  • 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:
  • 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.
  • Olefin conversion rate, % (Olefin content of feedstock - Olefin content of product) / Olefin content of feedstock ⁇ 100%.
  • the average particle size of the iron oxide powder was 300 nm.
  • 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.
  • the catalyst was prepared according to the method of Example 1, except that:
  • 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°C 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%.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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%.
  • 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.
  • 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.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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°C 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%.
  • 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%.
  • 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%.
  • the catalyst was prepared according to the method of Example 1, except that:
  • 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°C 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%.
  • the catalyst was prepared according to the method of Example 1, except that:
  • 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%.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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%.
  • the catalyst was prepared according to the method of Example 1, except that:
  • 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.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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°C 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%.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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°C 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%.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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°C 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%.
  • the catalyst was prepared according to the method of Example 1, except that:
  • 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°C 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%.
  • polyquaternium-7 dimethyl diallyl ammonium chloride-acrylamide copolymer
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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°C 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%.
  • the catalyst was prepared according to the method of Example 1, except that:
  • step (1) 0.95g of aniline and 0.55g of o-phenylenediamine are added;
  • 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.
  • 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.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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.
  • 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.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • 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°C 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%.
  • the catalyst was prepared according to the method of Example 1, with the following difference:
  • V always refers to the total pore volume of the catalyst
  • V ⁇ sub>medium ⁇ /sub> refers to the pore volume of the mesopores in the catalyst.
  • 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.
  • 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.
  • Figures 1 and 2 are XPS spectra of catalysts A1 and A2, respectively.
  • the spectra were calibrated for charge using external contaminant carbon (284.8 eV) as a reference.
  • peak Fit was used for fitting, adjusting peak position, peak area, and FWHM.
  • 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.
  • Figures 1 and 2 show the proportions of graphitized N and pyridinized N in the catalysts.
  • the contents of the two types of N were determined based on the XPS binding energy peak positions and peak area ratios. Specifically, the graphitized N:pyridinized N ratio of catalyst A1 was 0.2:1, and the graphitized N:pyridinized N ratio of catalyst A2 was 1.2:1.
  • Figure 3 shows the XRD diffraction pattern of catalyst A1.
  • a and b are the characteristic diffraction peak patterns of cobalt and rhodium, respectively.
  • the characteristic diffraction peak data for rhodium and cobalt are obtained from the XRD standard diffraction cards PDF#05-0685-Rh and PDF#15-0806-Co.
  • Figure 3c shows the XRD pattern of catalyst A1 prepared in Example 1.
  • the diffraction intensity produced by different crystal planes is related to the periodic arrangement density of its atoms. Sharp diffraction peaks can be detected at 30.1°, 35.5°, 43.1°, and 57.1° in Figure 3c.
  • Figure 4 is a spherical aberration electron microscope image of catalyst A1 prepared in Example 1.
  • the white high-brightness areas represent the supported metals rhodium and cobalt, and the dark areas represent the support.
  • the supported metals are distributed in a single-atom state on the support.
  • 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.
  • 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.
  • 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.
  • the catalyst of the present invention can be used for the carbonylation reaction of various carbon number olefins (hexene, decene, dodecene, tetradecene).
  • catalysts A1, A3-A6 have high conversion rates, and the conversion rate decreases only slightly after 5 cycles, indicating superior catalyst performance.

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Abstract

本发明涉及多相催化剂领域，公开了一种负载型催化剂及其制备方法和应用。该催化剂包括载体以及负载所述载体上的金属；其中，所述载体为含氮碳化物修饰的氧化物，且所述氮碳化物中的N元素包括石墨化N和吡啶化N；其中，所述石墨化N和所述吡啶化N的质量比为0.1-2：1。该负载型催化剂的载体中的氮碳化物中包含石墨化N和吡啶化N，且石墨化N和吡啶化N之间满足特定的含量关系，使得负载型催化剂中的活性金属与石墨化N和吡啶化N配位结合并产生较强的电子相互作用，活性金属分散形成活性位点，并且该催化剂中包含丰富的介孔结构，使得金属原子稳定分散且不易团聚，催化剂的催化活性以及循环稳定性显著提高。

Description

负载型催化剂及其制备方法与应用
相关申请的交叉引用
本申请要求2024年05月10日提交的中国专利申请202410578786.9的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及多相催化剂领域，具体地，涉及一种负载型催化剂及其制备方法与应用。
背景技术
烯烃羰基化反应主要是从乙烯、丙烯、丁烯等廉价原料出发，经烯烃羰基化过程合成醛、酮，酸类化合物，是一种绿色、原子经济性高的反应路径，也是当今世界最重要的工业化应用之一。羰基化学品下游的精细化学品如肥皂、医用材料、表面活性剂等产品具有广泛的用途，能够满足国民生活水平的发展需要。
烯烃羰基化催化体系中虽然均相催化剂的活性比较高，但是合成过程中需要价格昂贵的有机配体，有机配体在反应体系中容易变质和流失，因此，均相催化剂在实际应用过程中受成本和使用寿命的限制。鉴于均相催化剂存在的问题，近年来，越来越多的研究开始关注多相金属催化剂。
CN112979440A提供了一种负载型催化剂用于烯烃羰基化合成酮，以金属氧化物为载体，Rh、Ru等为活性组分，Fe、Sn、Ni、Zn等为助剂组分制备了一种负载型催化剂，其中活性金属的分散度高，其粒径小于1纳米，催化剂用于烯烃羰基化反应，产物中酮类化合物的选择性大于90％。
CN114471651A提供了一种含咪唑侧基的聚合物碳化所获得的氮掺杂的载体碳并结合镍作为基体，通过配位作用使得金属镍的分散更均匀，进一步结合钌使得该催化剂具有催化活性高、选择性好、稳定性好等优势。然而，聚合物前驱体制备过程较为繁琐，且载体碳需要加氢处理。
CN109759107A提供了一种载体碳化复合型催化剂，将碳复合的过渡金属碳化物和碳化硅组合，将活性组分的催化性能最大化发挥，催化剂的稳定性得到很大的提高。
CN115814833A公开了一种低负载量的双金属纳米催化剂，结合载体与助剂金属的几何及电子相互作用，能够有效提高羰基化产物转化效率，同时调控烯烃的羰基选择性。
CN111729687A公开了一种负载型羰基化催化剂的制备方法，该方法以氯甲基化聚苯乙烯树脂为原料，负载铑和/或钴金属，形成最终的负载型催化剂。该催化剂催化烯烃羰基化，具有较高的转化率和选择性，产物和催化剂可直接分离，金属流失率低，催化剂活性稳定，显著提高了羰基化工艺的经济性。
目前多相负载型催化剂面临普遍存在的问题，如金属位点结合不牢固导致的金属流失，分离回收程序复杂，循环过程中选择性和转化率下降等。因此，有必要开发一种载体-金属结合力强，金属利用率高、易于分离循环，且循环稳定性高的负载型催化剂。
发明内容
本发明的目的是为了克服现有技术存在负载型催化剂中载体与金属结合不牢固而导致金属流失的问题，提供一种负载型催化剂及其制备方法和应用，该负载型催化剂的载体中的氮碳化物中包含石墨化N和吡啶化N，且石墨化N和吡啶化N之间满足特定的含量关系，使得负载型催化剂中的活性金属与石墨化N和吡啶化N配位结合并产生较强的电子相互作用，活性金属分散形成催化活性位点，并且该催化剂中包含丰富的介孔结构，使得金属原子稳定分散且不易团聚，催化剂的催化活性以及循环稳定性显著提高。
为了实现上述目的，本发明第一方面提供一种负载型催化剂，其中，所述催化剂包括载体以及负载在所述载体上的金属；
其中，所述载体为含氮碳化物修饰的氧化物，且所述氮碳化物中的N元素包括石墨化N和吡啶化N；
其中，所述石墨化N和所述吡啶化N的质量比为0.1-2：1。
本发明第二方面提供一种负载型催化剂的制备方法，其特征在于，所述制备方法包括以下步骤：
(1)将氧化物载体、活性单体、引发剂与溶剂混合后，进行原位聚合后，分离、干燥得到改性载体；
(2)将金属前驱体溶液与所述改性载体进行混合、浸渍，固液分离得到固相，对所述固相进行干燥，得到催化剂前驱体；
(3)在保护性气氛的存在下，对催化剂前驱体进行烧结，得到所述负载型催化剂；
其中，所述活性单体为芳香胺；
所述烧结的条件包括：以1-20℃/min升温速率从室温升温至300-400℃后恒温1-3h后，以1-10℃/min升温速率升温至400-600℃后恒温0.5-2h。
本发明第三方面提供一种由上述制备方法制得的负载型催化剂。
本发明第四方面提供一种上述负载型催化剂在烯烃羰基化反应中的应用。
通过上述技术方案，本发明提供的负载型催化剂及其制备方法和应用获得以下有益的效果：
本发明提供的负载型催化剂的载体中的氮碳化物中包含石墨化N和吡啶化N，且石墨化N和吡啶化N之间满足特定的含量关系，使得负载型催化剂具有活性金属与石墨化N和吡啶化N配位结合形成催化活性位点，进一步地，该催化剂中包含丰富的介孔结构，最终使得催化剂的催化活性和循环稳定性得到显著提升。
进一步地，本发明提供的负载型催化剂石墨化N和所述吡啶化N的质量比满足特定的范围时，催化剂呈多介孔分布的微观结构，使得负载型催化剂中的金属活性组分能够稳定分散且不易发生团聚，降低了金属活性组分的流失率，使得催化剂的催化活性以及稳定性得到显著提升。
本发明提供的负载型催化剂的制备方法中，将苯胺和/或苯二胺单体在氧化物载体表面原位聚合形成多孔π共轭网络骨架，通过物理吸附以及金属前驱体与氮原子上电子对的配位作用结合金属，并在特定的烧结条件下对催化剂前驱体进行烧结，使得载体表面的含氮聚合物骨架转变为石墨化N和吡啶化N，通过调控分段升温程序调控石墨化N和吡啶N的比例，进而使得制得负载型催化剂活性金属电子分布得到调控，形成高度活性的金属-N活性物种，提升催化活性和选择性，以及循环使用稳定性能。
进一步地，在芳香胺，例如苯胺和/或苯二胺单体在氧化物载体表面原位聚合的过程中添加结构调节剂，能够进一步实现对载体表面的含氮聚合物骨架的形态进行调控，具体地，使得含氮聚合物在载体表面界面聚合组装形成纳米带或树枝状三维结构，充分暴露含N官能团位点与活性金属配位结合，形成高密度金属分布的结构，使得制得的催化剂中金属活性组分高度分散不易团聚，使得催化剂不易失活，金属活性组分流失率降低，催化剂活性明显提升。
附图说明
图1为实施例1制备得到的催化剂A1的XPS图。
图2为实施例2制备得到的催化剂A2的XPS图。
图3中a和b分别为金属钴和铑的特征衍射峰谱图，其中金属铑和钴的特征衍射峰数据信息来自XRD标准衍射卡片PDF#05-0685-Rh，PDF#15-0806-Co，c为实施例1制备得到的催化剂A1的XRD图。
图4为实施例1制备得到的催化剂A1的球差电镜图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种负载型催化剂，其特征在于，所述催化剂包括载体以及负载在所述载体上的金属；
其中，所述载体为含氮碳化物修饰的氧化物，且所述氮碳化物中的N元素包括石墨化N和吡啶化N；
其中，所述石墨化N和所述吡啶化N的质量比为0.1-2：1。
本发明中，负载型催化剂的载体中的氮碳化物中包含石墨化N和吡啶化N，且石墨化N和吡啶化N之间满足特定的含量关系，使得负载型催化剂具有活性金属与石墨化N和吡啶化N配位结合并产生较强的电子相互作用，活性金属分散形成催化活性位点，进一步地，该催化剂中包含丰富的介孔结构，最终使得催化剂的催化活性和循环稳定性得到显著提升。
进一步地，所述负载型催化剂的氮碳化物中包含石墨化N和吡啶化N，且石墨化N和吡啶化N之间满足特定的含量关系时，催化剂呈多介孔分布的微观结构，使得负载型催化剂中的金属活性组分能够稳定分散且不易发生团聚，降低了金属活性组分的流失率，使得催化剂的催化活性以及稳定性得到显著提升。
本发明中，所述石墨化N和所述吡啶化N的质量比为0.1-2:1，例如可以为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，以及任意两个值组成的范围，优选地，所述石墨化N和所述吡啶N的质量比为0.1-1：1。
本发明的一个优选实施方式中，所述石墨化N和所述吡啶化N的质量比为0.2-1:1。
根据本发明，以所述载体的总重量为基准，所述氮碳化物的含量为2-50wt％。
本发明中，所述载体中氮碳化物的含量满足上述范围时，使得催化剂中含有大量的介孔，进而提高催化剂的催化活性以及循环稳定性。
本发明中，以所述载体的总重量为基准，所述氮碳化物的含量为2-50wt％，例如可以为2wt％，3wt％，4wt％，5wt％，6wt％，7wt％，8wt％，9wt％，10wt％，11wt％，12wt％，13wt％，14wt％，15wt％，16wt％，17wt％，18wt％，19wt％，20wt％，21wt％，22wt％，23wt％，24wt％，25wt％，26wt％，27wt％，28wt％，29wt％，30wt％，31wt％，32wt％，33wt％，34wt％，35wt％，36wt％，37wt％，38wt％，39wt％，40wt％，41wt％，42wt％，43wt％，44wt％，45wt％，46wt％，47wt％，48wt％，49wt％，50wt％，以及任意两个值组成的范围，优选地，以所述载体的总重量为基准，所述氮碳化物的含量为10-35wt％，优选为15-35wt％。
本发明中，所述载体呈以氧化物为核，以氮碳化物为壳层的核-壳结构，其中，所述壳层的平均厚度为5-30nm，例如可以为5nm,6nm,7nm,8nm,9nm,10nm,11nm,12nm,13nm,14nm,15nm,16nm,17nm,18nm,19nm,20nm,21nm,22nm,23nm,24nm,25nm,26nm,27nm,28nm,29nm,30nm,以及任意两个值组成的范围，优选为10-25nm。
本发明中，所述壳层的厚度通过TEM电镜测得，具体地：在载体的TEM电镜图上随机选取20cm×20cm的范围，统计至少40个载体颗粒中壳层的厚度，计算平均值。
根据本发明，以所述负载型催化剂的总重量为基准，所述载体的含量为95-99.9wt％，所述金属的含量为0.1-5wt％。
本发明中，当负载型催化剂中载体和金属的含量满足上述范围时，能够使得催化剂中金属活性组分高度分散且不易团聚，进而降低活性金属组分的流失率，提高催化剂的催化活性以及循环稳定性。
本发明中，以所述负载型催化剂的总重量为基准，所述载体的含量为95-99.9wt％，例如可以为95wt％，95.5wt％，96wt％，96.5wt％，97wt％，97.5wt％，98wt％，98.5wt％，99wt％，99.5wt％，99.9wt％，以及任意两个值组成的范围，所述金属的含量为0.1-5wt％，例如可以为0.1wt％，0.5wt％，1wt％，1.5wt％，2wt％，2.5wt％，3wt％，3.5wt％，4wt％，4.5wt％，5wt％，以及任意两个值组成的范围。
进一步地，以所述负载型催化剂的总重量为基准，所述载体的含量为97-99.5wt％，所述金属的含量为0.5-3wt％。
根据本发明，所述氧化物选自四氧化三铁、三氧化二铁和氧化亚铁中的至少一种。
本发明中，所述氧化物的平均粒径为100-400nm，例如可以为100nm，150nm，200nm，250nm，300nm，350nm，400nm，以及任意两个值组成的范围，优选为200-300nm。
本发明的一个优选实施方式中，为了便于利用外磁场进行分离和回收，避免传统多相催化剂在分离与回收过程中耗时长、质量损失大的问题，优选地，所述氧化物为磁性氧化物，优选为四氧化三铁。
本发明的一个具体实施方式中，所述负载型催化剂为负载型磁性催化剂。
根据本发明，所述金属选自Rh、Pb、Ru、Ir、Co、Cs和Li中的至少一种。
根据本发明，所述负载型催化剂中金属的分散度为45-75％。
本发明中，发明人研究发现，本发明的负载型催化剂中，载体中的氮碳化物包含石墨化N和吡啶化N，且石墨化N和吡啶化N之间满足特定的含量关系时，能够使得负载型催化剂具有活性金属与石墨化N和吡啶化N配位结合形成催化活性位点，由此能够显著提高负载型催化剂中活性金属的分散度，具体地，使得负载型催化剂中金属的分散度为45-75％，进一步表明该负载型催化剂具有高的催化效率。
本发明中，所述负载型催化剂中金属的分散度是指金属在载体表面的分散程度的量化指标。
本发明中，金属的分散度采用CO脉冲法测得，具体地，测试方法包括：使用化学吸附仪，在CO气流中对催化剂样品进行脉冲滴定，至CO吸附饱和后计算金属分散度。计算公式为：
金属分散度，％＝n(CO)/n(M)×100％，其中n(CO)为CO吸附的摩尔数，n(M)为催化剂中的金属摩尔数，n(M)＝m×(w1/M1+w2/M2)，其中，m代表催化剂总质量，w1代表负载型催化剂中金属组分1在催化剂中的质量占比，M1代表金属组分1的相对原子质量；w2代表金属组分2在催化剂中的质量占比，M2代表金属组分2的相对原子质量。
本发明中，所述负载型催化剂中金属的分散度为45-75％，例如可以为45％，50％，55％，60％，65％，70％，75％，以及任意两个值组成的范围，优选地，所述负载型催化剂中金属的分散度为60-75％。
根据本发明，所述负载型催化剂的比表面积为10-150m2/g，例如可以为10m2/g，15m2/g，20m2/g，25m2/g，30m2/g，35m2/g，40m2/g，45m2/g，50m2/g，55m2/g，60m2/g，65m2/g，70m2/g，75m2/g，80m2/g，85m2/g，90m2/g，95m2/g，100m2/g，105m2/g，110m2/g，115m2/g，120m2/g，125m2/g，130m2/g，135m2/g，140m2/g，145m2/g，150m2/g，以及任意两个值组成的范围。
根据本发明，所述负载型催化剂的平均孔径为2-20nm，例如可以为2nm,3nm,4nm,5nm,6nm,7nm,8nm,9nm,10nm,11nm,12nm,13nm,14nm,15nm,16nm,17nm,18nm,19nm,20nm,以及任意两个值组成的范围。
根据本发明，所述负载型催化剂的孔容为0.05-0.5cm3/g，例如可以为0.05cm3/g，0.1cm3/g，0.13cm3/g，0.15cm3/g，0.2cm3/g，0.25cm3/g，0.3cm3/g，0.35cm3/g，0.4cm3/g，0.45cm3/g，0.5cm3/g，以及任意两个值组成的范围。
根据本发明，所述负载型催化剂中介孔的孔容为0.05-0.5cm3/g，例如可以为0.05cm3/g，0.07cm3/g，0.1cm3/g，0.11cm3/g，0.15cm3/g，0.2cm3/g，0.25cm3/g，0.3cm3/g，0.35cm3/g，0.4cm3/g，0.45cm3/g，0.5cm3/g，以及任意两个值组成的范围。
本发明中，所述负载型催化剂的比表面积、平均孔径以及孔容中的至少一种满足上述范围时，表明负载型催化剂中负载金属高度分散不易团聚，能够显著提高催化剂的催化活性和选择性。特别地，本发明的负载型催化剂中，以负载型催化剂的总孔容为基准，介孔孔容占比较高，能够达到50-90％，表明该负载型催化剂中包含丰富的介孔结构，能够进一步提高负载的金属原子的分散性。
进一步地，所述负载型催化剂的比表面积为30-90m2/g。
进一步地，所述负载型催化剂的平均孔径为5-20nm，更优选为5-12nm。
进一步地，所述负载型催化剂的总孔容为0.1-0.2cm3/g。
本发明的一个优选实施方式中，所述负载型催化剂的总孔容为0.1-0.13cm3/g。
进一步地，所述负载型催化剂中介孔的孔容为0.07-0.2cm3/g。
本发明的一个优选实施方式中，所述负载型催化剂中介孔的孔容0.07-0.11cm3/g。
进一步地，以所述负载型催化剂中孔的总孔容为基准，介孔的孔容占比为70-90％。
本发明的一个优选实施方式中，以所述负载型催化剂中孔的总孔容为基准，介孔的孔容占比为70-85％。
本发明的一个具体实施方式中，所述氧化物选自四氧化三铁、三氧化二铁和氧化亚铁中的至少一种；所述金属为Rh，或者所述金属为Rh和Co，其中，所述负载型催化剂通过XRD测得Fe元素的特征峰强度IFe与Rh元素的特征峰强度IRh满足以下关系：
IFe/IRh大于等于345。
本发明中，发明人研究发现，当负载型催化剂中以含铁氧化物作为载体，活性金属组分包含Rh时，负载型催化剂通过XRD测得的Fe元素的特征峰强度与Rh元素的特征峰强度之比满足上述范围时，表明负载型催化剂中Rh晶相的含量较低，Rh晶相的晶体粒度小，金属元素Rh的表面积更大，由此能够说明活性金属Rh在载体中分散良好。
本发明中，Fe元素的特征峰强度IFe与Rh元素的特征峰强度IRh分别通过XRD测得，具体地，测试方法为：采用粉末状样品，XRD入射角度选择5-90°，数据经JADE软件处理，并通过计算得到物相含量和比例：
IFe/IRh＝Fe特征峰面积/Rh特征峰面积。其中特征峰面积是通过JADE软件处理，扣除背景并进行峰拟合后直接得到。
进一步地，IFe/IRh大于等于750。
本发明第二方面提供一种负载型催化剂的制备方法，其中，所述制备方法包括以下步骤：
(1)将氧化物载体、活性单体、引发剂与溶剂混合后，进行原位聚合后，分离、干燥得到改性载体；
(2)将金属前驱体溶液与所述改性载体进行混合、浸渍，固液分离得到固相，对所述固相进行干燥，得到催化剂前驱体；
(3)在保护性气氛的存在下，对催化剂前驱体进行烧结，得到所述负载型催化剂；
其中，所述活性单体为芳香胺；
所述烧结的条件包括：以1-20℃/min升温速率从室温升温至300-400℃后恒温1-3h后，以1-10℃/min升温速率升温至400-600℃后恒温0.5-2h。
本发明中，所述负载型催化剂的制备方法中，将芳香胺单体在氧化物载体表面原位聚合形成多孔π共轭网络骨架，能够增加载体的吸附面积以及配位活性位点，提升对活性金属的负载率，通过物理吸附以及金属前驱体与氮原子上电子对的配位作用结合金属，并在特定的烧结条件下对催化剂前驱体进行烧结，不仅使得载体表面的含氮聚合物骨架转变为石墨化N和吡啶化N，而且显著增强了载体与金属组分之间的相互作用力，抑制了催化剂在使用过程中金属组分的流失，将制得的催化剂用于烯烃羰基化反应时，能够显著提高转化率、选择性和循环使用稳定性。
通过分段程序控温烧制，首先在较低温度区间按照一定程序烧制强化金属-载体相互作用，避免金属原子团聚，随后在较高温度区间缓慢升温烧制，使得载体碳化形成不同比例的石墨化N和吡啶化N，在提高催化剂中活性金属位点密度的同时，确保活性金属组分具有优异的分散性且不易团聚，进而提高催化剂的催化活性以及循环稳定性。
具体地，本发明中，采用梯度升温的方式对催化剂前驱体进行烧结，在较低温度区间对催化剂前驱体进行烧结，能够较好的保留含氮聚合物的三维孔结构，避免孔道塌陷。当烧结温度高于600℃时，会导致多孔结构破坏，特别是介孔结构塌陷，导致最终催化剂的比表面积不利地降低。
本发明中，所述烧结的条件包括：以1-20℃/min，升温速率从室温升温至300-400℃后恒温1-3h后，以1-10℃/min升温速率升温至400-600℃后恒温0.5-2h。
本发明中，第一阶段的升温速率为1-20℃/min，例如可以为1℃/min，2℃/min，5℃/min，8℃/min，10℃/min，12℃/min，15℃/min，18℃/min，20℃/min，以及任意两个值组成的范围；第二阶段的升温速率可以为1-10℃/min，例如可以为1℃/min，2℃/min，5℃/min，8℃/min，10℃/min，以及任意两个值组成的范围。
进一步地，所述烧结的条件包括：以5-20℃/min升温速率从室温升温至350-400℃后恒温1-3h后，以2-8℃/min升温速率升温至400-500℃后恒温0.5-2h。
本发明的一个优选实施方式中，所述活性单体选自苯胺、邻苯二胺、间苯二胺和对苯二胺中的至少一种。
本发明的一个优选实施方式中，所述活性单体选自苯胺、邻苯二胺、间苯二胺和对苯二胺中的至少两种；更优选选自苯胺、邻苯二胺、间苯二胺和对苯二胺中的任意两种，进一步优选地，所述活性单体为苯胺和选自邻苯二胺、间苯二胺和对苯二胺中的一种的苯二胺，其中，苯胺与苯二胺的质量比为1.5-2：1，例如可以为1.5:1,1.6:1，1.7:1,1.8:1,1.9:1,2:1，以及任意两个值组成的范围。
根据本发明，所述引发剂选自过氧乙酸、过氧化氢、过硫酸胺和过硫酸钾中的至少一种。
根据本发明，所述氧化物载体选自四氧化三铁、三氧化二铁和氧化亚铁中的至少一种。
根据本发明，以所述氧化物载体的用量为基准，所述活性单体的用量为2-50wt％，例如可以为2wt％,5wt％，10wt％，15wt％，20wt％，25wt％，30wt％，35wt％，40wt％，45wt％，50wt％，以及任意两个值组成的范围。
根据本发明，以所述活性单体的用量为基准，所述引发剂的用量为2-15wt％，例如可以为2wt％,3wt％，4wt％，5wt％，6wt％，7wt％，8wt％，9wt％，10wt％，11wt％，12wt％，13wt％，14wt％，15wt％，以及任意两个值组成的范围。
本发明中，控制氧化物载体、活性单体和引发剂的用量关系满足上述范围时，能够确保载体表面均匀修饰氮碳化物，并且催化剂中的石墨化N和吡啶化N能够均匀分布于催化剂的表面，与金属活性组分配位结合，进而确保活性金属组分均匀分布且不易团聚。
进一步地，以所述氧化物载体的用量为基准，所述活性单体的用量为10-30wt％。
进一步地，以所述活性单体的用量为基准，所述引发剂的用量为5-15wt％。
本发明的一个优选实施方式中，所述原位聚合在结构调节剂的存在下进行。
本发明中，在苯胺和/或苯二胺单体在氧化物载体表面原位聚合的过程中添加结构调节剂，能够进一步实现对载体表面的含氮聚合物骨架的形态进行调控，具体地，使得含氮聚合物在载体表面界面聚合组装形成纳米带或树枝状三维结构，充分暴露活性位点，提高催化剂的催化活性以及选择性。
根据本发明，所述结构调节剂选自聚季铵盐、十六烷基三甲基溴化铵和十六烷基三甲基氯化铵中的至少一种。
本发明中，采用上述特定种类的表面活性剂作为结构调节剂，通过表面活性剂分子与引发剂如过硫酸胺之间的电荷相互作用，自组装形成3D结构，凝胶或胶束软模板，通过电荷相互作用吸附苯胺和/或苯二胺单体在界面聚合组装形成纳米带或树枝状三维结构，充分暴露的含N活性位点与活性金属配位，形成高密度金属分布的结构，使得制得的催化剂中金属活性组分高度分散不易团聚，使得催化剂不易失活，金属活性组分流失率降低，催化剂活性明显提升。
进一步地，所述结构调剂选自十六烷基三甲基溴化铵和/或十六烷基三甲基氯化铵。
根据本发明，以所述活性单体的用量为基准，所述结构调节剂的用量为50-150wt％，例如可以为50wt％，60wt％，70wt％，80wt％，90wt％，100wt％，110wt％，120wt％，130wt％，140wt％，150wt％，以及任意两个值组成的范围。
本发明中，通过控制结构调节剂的用量满足上述范围时，结构调节剂(例如十六烷基三甲基溴化铵(CTAB)，能够自组装形成3D结构，凝胶或胶束软模板，能够辅助苯胺和/或苯二胺单体在界面聚合组装形成纳米带或树枝状三维结构，充分暴露的含N活性位点与活性金属配位，同时增加催化剂载体的比表面积，提供催化剂中活性金属组分的负载率的同时，降低金属活性组分的流失率，最终进一步提供催化剂的催化活性以及循环稳定性。
进一步地，以所述活性单体的用量为基准，所述结构调节剂的用量为80-150wt％。
本发明中，步骤(1)中的溶剂优选为水，对于溶剂的用量没有特别限定，只要能够使得氧化物载体、活性单体、引发剂和可选地结构调节剂充分分散均匀即可。
本发明的一个具体实施方式中，溶剂的用量使得包含溶剂和氧化物载体的混合液的质量浓度为10-50wt％，例如可以为10wt％，15wt％，20wt％，25wt％，30wt％，35wt％，40wt％，45wt％，50wt％，以及任意两个值组成的范围。
本发明的一个具体实施方式中，先将氧化物载体与溶剂混合，得到混合液后，依次将活性单体、引发剂和结构调节剂加入所述混合液中，进行原位聚合。
根据本发明，所述金属前驱体溶液中的金属前驱体为能够提供活性金属组分的水溶性金属盐。
本发明中，对于水溶性盐的种类没有特别限定，可以为本领域中常用的水溶性盐，例如氯化盐、碳酸盐、硝酸盐、硫酸盐和草酸盐等。
根据本发明，所述活性金属组分选自Rh、Pb、Ru、Ir、Co、Cs和Li中的至少一种；优选为Rh和/或Co。
本发明中，所述铑(Rh)前驱体为RhCl3、RhCl3·xH2O、RhCl3·3H2O、Rh(CO)2(C5H7O2)、[(C6H5)3P]3RhCl中的一种或多种。
本发明中，所述钴(Co)前驱体为Co(NO3)2、Co(NO3)2·6H2O、CoSO4、CoSO4·7H2O、CoCl2、CoCl2·6H2O中的一种或多种。
根据本发明，所述前驱体溶液与所述改性载体的用量使得，以所述改性载体的用量基准，所述金属前驱体的用量为2-20wt％，例如可以为2wt％，3wt％，4wt％，5wt％，6wt％，7wt％，8wt％，9wt％，10wt％，11wt％，12wt％，13wt％，14wt％，15wt％，16wt％，17wt％，18wt％，19wt％，20wt％，以及任意两个值组成的范围。
本发明中，通过控制改性载体与金属前驱体的用量满足上述关系时，能够使得制得的催化剂中载体与金属的含量满足本发明第一方面的要求。
进一步地，所述前驱体溶液与所述改性载体的用量使得，以所述改性载体的用量基准，所述金属前驱体的用量为5-15wt％。
本发明中，对于金属前驱体溶液的浓度没有特别限定，优选地，为了能够确保金属前驱体溶液中的活性金属高度分散分布，不易团聚，将其与改性载体混合浸渍时，能够使得催化剂中，活性金属组分在载体中高度分散，进而使得催化剂具有高的催化活性和高的选择性，并且具有良好的循环稳定性，控制金属前驱体溶液的浓度为0.2-6wt％，例如可以为0.2wt％，0.3wt％，0.4wt％，0.5wt％，0.6wt％，0.7wt％，0.8wt％，0.9wt％，1wt％，2wt％，3wt％，4wt％，5wt％，6wt％，以及任意两个值组成的范围，优选为0.5-3wt％。
根据本发明，所述原位聚合的条件包括：聚合温度为30-60℃，例如可以为30℃，35℃，40℃，45℃，50℃，55℃，60℃，以及任意两个值组成的范围，聚合时间为1-6h，例如可以为1h，1.5h，2h，2.5h，3h，3.5h，4h，4.5h，5h，5.5h，6h，以及任意两个值组成的范围。
本发明中，控制原位聚合的条件满足上述范围时，能够使得载体表面均匀包覆有苯胺类聚合物，经烧结后，在载体表面形成均匀的氮碳化物，且使得载体表面形成特定含量的石墨化N与吡啶化N，便于与金属配位结合，提高催化剂的催化活性以及循环稳定性。
进一步地，所述原位聚合的条件包括：聚合温度为40-55℃，聚合时间为2-4h。
根据本发明，所述浸渍的条件包括：浸渍温度为25-60℃，例如可以为25℃，30℃，35℃，40℃，45℃，50℃，55℃，60℃，以及任意两个值组成的范围，浸渍时间为2-48h，例如可以为2h，3h，5h，8h，10h，13h，15h，18h，20h，23h，25h，28h，30h，33h，35h，38h，40h，43h，45h，48h，以及任意两个值组成的范围。
本发明中，控制浸渍条件满足上述范围时，能够使得活性金属均匀负载于所述载体上，并且使得活性金属不发生团聚，进而使得制得的催化剂具有高的催化活性和选择性，且具有良好的循环稳定性。
进一步地，所述浸渍的条件包括：浸渍温度为30-50℃，浸渍时间为5-48h。
本发明中，对于所述固液分离的方式没有特别限定，可以采用本领域中常规的固液分离方式。
本发明的一个具体实施方中，所述载体氧化物为磁性氧化物时，采用磁铁吸附实现所述固液分离。
根据本发明，所述干燥条件包括：干燥温度为60-80℃，干燥时间为2-3h。
本发明中，对于所述保护性气氛的种类没有特别限定，例如可以为N2或Ar。
根据本发明，所述制备方法还包括：对烧结后产物以1-15℃/min的速率冷却至室温，例如可以以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，以及任意两个值组成的范围。
本发明中，将烧结后产物以上述特定的速率冷却至室温能够避免金属活性组分发生团聚，并且在催化剂表面形成高度活性的活性物种，最终使得催化剂具有高的催化活性和高的选择性，以及良好的循环稳定性。
进一步地，对烧结后的产物以5-10℃/min的速率冷却至室温。
本发明第三方面提供一种由上述制备方法制得的负载型催化剂。
本发明第四方面提供一种上述负载型催化剂在烯烃羰基化反应中的应用。
本发明中，对于负载型催化剂在烯烃羰基化反应中的具体应用方式没有特别限定，可以按照本领域中常规的方式进行。
本发明的一个具体实施方式中，所述烯烃羰基化反应的步骤包括：
将本发明所述的负载型催化剂100-1000mg放置于不锈钢高压反应釜中，加入原料C6-C16烯烃、溶剂，依次用惰性气体与合成气吹扫高压反应釜，进行反应釜中原有气体的置换，置换完成后通入一定压力的合成气；将高压反应釜加热升温至一定温度，保持温度恒定，在一定搅拌速率下进行羰基化反应。待反应结束后，反应釜冷却至室温，排出釜内液体，通过外加磁场分离催化剂与反应混合液。
本发明的一个具体实施方式中，所述烯烃为C6-C16直链或支链烯烃中的一种或几种。
本发明中，所述C6-C16烯烃包括但不限定于十二烯、己烯、癸烯、十四烯和辛烯等。
本发明的一个具体实施方式中，所述羰基化反应的反应压力为1MPa-30MPa，反应温度为60-150℃，反应时间为0.5-15h。
本发明的一个具体实施方式中，所述合成气中CO：H2的体积比为1:1-4。
本发明中，所述溶剂为甲苯、环己烷、醛、醇等，溶剂与烯烃的体积百分比为0.2-3：1，例如可以为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，以及任意两个值组成的范围。
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，本发明的范围并不局限于这些实施例。
以下实施例中，石墨化N、吡啶化N的含量占比通过X射线光电子能谱分谱定量测得。具体测试方法为，借助X射线光电子能谱仪测试N元素分谱，用XPS软件进行数据处理。在进行分峰拟合之前，首先对原始数据进行荷电校准，以确保各元素的结合能值准确。使用外来污染碳(如284.8eV)作为基准，通过软件Avantage进行校准，去除背景噪声并建立基准线。通过查阅文献参考N标准峰位置，使用peak Fit进行拟合处理，调整峰位置、峰面积和FWHM等拟合参数，经洛伦兹和高斯函数处理XPS N1高分辨图谱，拟合出401.5eV和398.3eV两个峰位，其中401.5eV归属于石墨化N，398.3eV归属于吡啶化N。
根据X射线光电子能谱谱图中的光电子峰面积计算相对含量，得到石墨化N和吡啶化N的比例，计算方法为：石墨化N与吡啶化N的质量比＝S(石墨N峰面积)：S(吡啶N峰面积)。
载体中壳层的厚度通过TEM电镜测得，具体地：在载体的TEM电镜图上随机选取20cm×20cm的范围，采用Nano Measurer软件测试并统计至少40个载体颗粒中壳层的厚度，计算平均值。
负载型催化剂中载体和金属的含量通过电感耦合等离子体光谱测得。其中，负载型催化剂中金属含量Q＝金属质量M1/催化剂总质量M2×100％，其中催化剂总质量M2通过天平称量得到，金属质量M1通过电感耦合等离子体光谱测试得到。负载型催化剂中载体质量Z＝催化剂总质量M2-金属质量M1。
载体中氮碳化物的含量通过EDS能谱定量分析得到。通过EDS谱峰对应的强度比进行换算，给出了各元素所占的比例。其中，氮碳化物含量＝氮元素相对含量+碳元素相对含量。
负载型催化剂的微观孔结构参数通过比表面及孔隙度分析仪ASAP 2020的测定，依据t-plot法得到孔容和比表面积。
催化剂中金属分散度采用CO脉冲法测得，具体地，测试方法包括：使用化学吸附仪，在CO气流中对催化剂样品进行脉冲滴定，至CO吸附饱和后计算金属分散度。计算公式为：
金属分散度，％＝n(CO)/n(M)×100％，其中n(CO)为CO吸附的摩尔数，n(M)为催化剂中的金属摩尔数，n(M)＝m×(w1/M1+w2/M2)，其中，m代表催化剂总质量，w1代表负载型催化剂中金属组分1在催化剂中的质量占比，M1代表金属组分1的相对原子质量；w2代表金属组分2在催化剂中的质量占比，M2代表金属组分2的相对原子质量。
催化剂中Fe元素的特征峰强度IFe与Rh元素的特征峰强度IRh通过XRD测得。其基本原理为基于布拉格方程nλ＝2d×sinθ，其中λ代表入射X射线的波长，本测试中采用铜靶对应波长λ＝0.154nm，d代表晶面间距，θ为入射光衍射角，本测试中XRD入射角度选择5-90°，通过测量衍射角和强度，结合布拉格定律，计算出晶面间距，确定材料的晶格参数和对称性，进而推断其晶体结构。XRD图谱中，晶体相通常表现为尖锐且独立的衍射峰，而非晶相则表现为宽而模糊的衍射峰。峰强度的高低通常与晶相含量、晶粒大小成正比，即峰面积越大，表示晶相含量越高，晶粒尺寸越大。因而XRD测试能够通过衍射峰提供晶体结构信息，但是不能提供原子级结构信息，即原子级分散的金属在XRD上不能形成明确的衍射峰。XRD测试的具体方法为：20-50mg粉末状样品，XRD入射角度选择5-90°，数据经JADE软件处理，借助高斯函数拟合处理衍射峰，拟合残差较小，拟合效果好。并通过计算得到物相含量和比例：
IFe/IRh＝Fe特征峰面积/Rh特征峰面积。其中特征峰面积是通过JADE软件处理，扣除背景并进行峰拟合后直接得到。
催化剂的金属流失率分别通过电感耦合等离子体光谱的测定，催化剂金属流失率＝(反应前负载型催化剂金属含量Q1-循环5次后负载型催化剂金属含量Q2)/反应前负载型催化剂金属含量Q1×100％。
催化剂用于烯烃羰基化反应时的转化率采用气相色谱测试方法测得。测试采用内标法，把一定量的纯物质作内标物，加入到已知质量的样品中，然后进行色谱分析，测定内标物和样品中几个组分的峰面积。引入相对质量校正因子，计算样品中待测组分的质量分数，由此计算转化率。计算公式为：
mi＝f×Ai/(As/ms)，其中，f为相对校正因子，通过查阅气相色谱手册获得。mi为测试样品的含量，ms为加入内标物的量，Ai和As分别为测试物i和内标物s的峰面积；
烯烃转化率，％＝(原料烯烃含量-产物烯烃含量)/原料烯烃含量×100％。
实施例以及对比例中四氧化三铁粉末的平均粒径为300nm。
实施例以及对比例所用原料均为市售品。
实施例1
(1)200g去离子水中加入2.25g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入1g苯胺和0.5g间苯二胺，0.225g过硫酸钾；在40℃下恒温搅拌5h。随后将上述混合物用去离子水洗涤至少三次置于60℃真空干燥烘箱中加热2h，得到改性载体1。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为15wt％，结构调节剂的用量为150wt％。对改性载体1中壳层的厚度
(2)称取0.17g RhCl3和0.08g Co(NO4)2，溶于20mL去离子水，配制金属前驱体溶液1(其中，Rh前驱体的质量浓度为0.40wt％，Co前驱体的质量浓度为0.43wt％)，将5g改性载体1缓慢加入预先配制金属前驱体溶液1，随后在50℃条件下恒温搅拌12h，搅拌速率300rpm，后将得到的产物用磁铁吸引分离，所得固体转移至干燥箱内，60℃下真空干燥3h，得到催化剂前体。
(3)将上述得到的催化剂前体转移至管式炉中，通入氮气30min将管式炉内空气彻底置换排净后，在氮气氛围下以5℃/min的速度从30℃升温至350℃后恒温2h，随后以2℃/min的速度升温至460℃后恒温2h。恒温过程结束后以10℃/min的速度冷却至室温后得到催化剂A1。
实施例2
按照实施例1的方法制备催化剂，不同的是：
步骤(1)与实施例1不同：200g去离子水中加入1.1g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入1g苯胺和0.5g间苯二胺，0.065g过硫酸钾；在40℃下恒温搅拌5h。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为4wt％，结构调节剂的用量为73wt％。
其余步骤与实施例1相同，制得催化剂A2。
实施例3
按照实施例1的方法制备催化剂，不同的是：
步骤(1)与实施例1不同：200g去离子水中加入0.8g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入0.4g苯胺和0.2g间苯二胺，0.055g过硫酸钾；在40℃下恒温搅拌5h。以四氧化三铁的用量为基准，活性单体的用量为12wt％，以活性单体的用量为基准，过硫酸钾的用量为9wt％，结构调节剂的用量为133wt％。
实施例4
按照实施例1的方法制备催化剂，不同的是：采用2.25g聚季铵盐-7(二甲基二烯丙基氯化铵-丙烯酰胺共聚物)代替十六烷基三甲基溴化铵。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为15wt％，结构调节剂的用量为150wt％。其余步骤与实施例1相同，制得催化剂A4。
实施例5
按照实施例1的方法制备催化剂，不同的是，采用1.5g苯胺代替实施例1的苯胺和间苯二胺。其余步骤与实施例1相同，最终得到催化剂A5。
实施例6
按照实施例1的方法制备催化剂，不同的是：采用1.5g邻苯二胺代替实施例1的苯胺和间苯二胺。其余步骤与实施例1相同，制得催化剂A6。
实施例7
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：在200g去离子水中加入0.135g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下加入0.06g苯胺和0.03g邻苯二胺，0.011g过硫酸钾；在40℃下恒温搅拌5h。以四氧化三铁的用量为基准，活性单体的用量为1.8wt％，以活性单体的用量为基准，过硫酸钾的用量为12wt％，结构调节剂的用量为150wt％。
其余步骤与实施例1相同，最终得到催化剂A7。
实施例8
按照实施例1的方法制备催化剂，不同的是：过硫酸钾的用量为0.045g。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为3wt％，结构调节剂的用量为150wt％。
其余步骤与实施例1相同，最终得到催化剂A8。
实施例9
按照实施例1的方法制备催化剂，不同的是：将过硫酸钾的用量调整为0.2g，以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为13wt％，结构调节剂的用量为150wt％。
其余步骤与实施例1相同，最终得到催化剂A9。
实施例10
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加入0.8g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入1g苯胺和0.5g间苯二胺，0.225g过氧化氢；在40℃下恒温搅拌5h。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过氧化氢的用量为15wt％，结构调节剂的用量为53wt％。
其余步骤与实施例1相同，最终得到催化剂A10。
实施例11
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加入0.45g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入0.2g苯胺和0.1g间苯二胺，0.06g过硫酸钾。以四氧化三铁的用量为基准，活性单体的用量为6wt％，以活性单体的用量为基准，过硫酸钾的用量为20wt％，结构调节剂的用量为150wt％。
其余步骤与实施例1相同，最终得到催化剂A11。
实施例12
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加入2.4g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入1.6g苯胺和0.8g对苯二胺，0.25g过硫酸钾。以四氧化三铁的用量为基准，活性单体的用量为48wt％，以活性单体的用量为基准，过硫酸钾的用量为10wt％，结构调节剂的用量为100wt％。
其余步骤与实施例1相同，最终得到催化剂A12。
实施例13
按照实施例1的方法制备催化剂，不同的是：
步骤(3)：将上述得到的催化剂前驱体转移至管式炉中，通入氮气30min将管式炉内空气彻底置换排净后，在氮气氛围下以2℃/min的速度从室温升温至350℃后恒温2h，随后以10℃/min的速度升温至460℃后恒温2h。恒温过程结束后以10℃/min的速度冷却至室温后得到催化剂A13。
实施例14
按照实施例1的方法制备催化剂，不同的是：
步骤(3)：将上述得到的催化剂前驱体转移至管式炉中，通入氮气30min将管式炉内空气彻底置换排净后，在氮气氛围下以5℃/min的速度从室温升温至300℃后恒温2h，随后以2℃/min的速度升温至530℃后恒温2h。恒温过程结束后以10℃/min的速度冷却至室温后得到催化剂A14。
实施例15
按照实施例1的方法制备催化剂，不同的是：
步骤(3)：将上述得到的催化剂前驱体转移至管式炉中，通入氮气30min将管式炉内空气彻底置换排净后，在氮气氛围下以15℃/min的速度从室温升温至300℃后恒温2h，随后以5℃/min的速度升温至500℃后恒温2h。恒温过程结束后以10℃/min的速度冷却至室温后得到催化剂A15。
实施例16
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加入2.25g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入0.9g苯胺和0.6g对苯二胺，0.225g过氧化氢；在40℃下恒温搅拌5h。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为15wt％，结构调节剂的用量为150wt％。
其余步骤与实施例1相同，最终得到催化剂A16。
实施例17
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加入2.25g十六烷基三甲基氯化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入1.1g邻苯二胺和0.4g对苯二胺，0.225g过硫酸钾；在40℃下恒温搅拌5h。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为15wt％，结构调节剂的用量为150wt％。
其余步骤与实施例1相同，最终得到催化剂A17。
实施例18
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加入4.25g十六烷基三甲基氯化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入0.5g邻苯二胺和1g对苯二胺，0.325g过硫酸钾；在40℃下恒温搅拌5h。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为22wt％，结构调节剂的用量为283wt％。
其余步骤与实施例1相同，最终得到催化剂A18。
实施例19
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加入1.25g聚季铵盐-7(二甲基二烯丙基氯化铵-丙烯酰胺共聚物)，混合均匀后加入5g四氧化三铁粉末，搅拌状态下依次加入0.5g邻苯二胺和1g对苯二胺，0.025g过硫酸钾；在40℃下恒温搅拌5h。以四氧化三铁的用量基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为1.7wt％，结构调节剂的用量为83wt％。
其余步骤与实施例1相同，最终得到催化剂A19。
实施例20
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加入5g四氧化三铁粉末，搅拌状态下依次加入1g苯胺和0.5g间苯二胺，0.225g过硫酸钾；在40℃下恒温搅拌5h，以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为15wt％，结构调节剂的用量为0wt％。
其余步骤与实施例1相同，最终得到催化剂A20。
实施例21
按照实施例1的方法制备催化剂，不同的是：
步骤(1)中加入0.95g苯胺和0.55g邻苯二胺；
步骤(3)：在氮气氛围下以5℃/min的速度从30℃升温至350℃后恒温3h，随后以2℃/min的速度升温至460℃后恒温1h。其它条件不变，得到催化剂A21。
实施例22
(1)200g去离子水中加入2.25g十六烷基三甲基溴化铵，混合均匀后加入5g磁性四氧化三铁粉末，搅拌状态下依次加入1g苯胺和0.5g间苯二胺，0.225g过硫酸钾；在40℃下恒温搅拌5h。随后将上述混合物用去离子水洗涤至少三次置于60℃真空干燥烘箱中加热2h，得到改性载体1。以四氧化三铁的用量基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为15wt％，结构调节剂的用量为150wt％。
(2)将上述得到的改性载体1转移至管式炉中，通入氮气30min将管式炉内空气彻底置换排净后，在氮气氛围下以5℃/min的速度从30℃升温至350℃后恒温2h，随后以2℃/min的速度升温至460℃后恒温2h。恒温过程结束后以10℃/min的速度冷却至室温后得到载体。
(3)称取0.17g RhCl3和0.08g Co(NO4)2，溶于20mL去离子水，配制金属前驱体溶液1(其中，Rh前驱体的质量浓度为0.40wt％，Co前驱体的质量浓度为0.43wt％)，将5g步骤(2)得到的载体缓慢加入预先配制金属前驱体溶液1，随后在50℃条件下恒温搅拌12h，搅拌速率300rpm，后将得到的产物用磁铁吸引分离，所得固体转移至干燥箱内，60℃下真空干燥3h，得到催化剂A22。
对比例1
按照实施例1的方法制备催化剂，不同的是：
步骤(3)：将上述得到的催化剂前体转移至管式炉中，通入氮气30min将管式炉内空气彻底置换排净后，在氮气氛围下以5℃/min的速度从室温升温至350℃后恒温2h，随后以1℃/min的速度升温至800℃后恒温2h。恒温过程结束后以8℃/min的速度冷却至室温后得到催化剂D1。
对比例2
按照实施例1的方法制备催化剂，不同的是：不进行步骤(1)，直接将四氧化三铁粉末用于步骤(2)。其余步骤与实施例1相同，得到催化剂D2。
对比例3
按照实施例1的方法制备催化剂，不同的是：
步骤(3)：将上述得到的催化剂前驱体转移至管式炉中，通入氮气30min将管式炉内空气彻底置换排净后，在氮气氛围下以5℃/min的速度直接升温至400℃后恒温2h。恒温过程结束后以10℃/min的速度冷却至室温后得到催化剂D3。
对比例4
按照实施例1的方法制备催化剂，不同的是：
步骤(1)：200g去离子水中加2.25g十六烷基三甲基溴化铵，混合均匀后加入5g四氧化三铁粉末，搅拌状态下加入1.5g吡咯单体，0.225g过硫酸钾；在40℃下恒温搅拌5h。以四氧化三铁的用量为基准，活性单体的用量为30wt％，以活性单体的用量为基准，过硫酸钾的用量为15wt％，结构调节剂的用量为150wt％。
其余步骤与实施例1相同，得到催化剂D4。
对比例5
按照实施例1的方法制备催化剂，不同的是：
采用5g氧化石墨烯粉末代替实施例1中的5g四氧化三铁粉末。其余步骤与实施例1相同，得到催化剂D5。
实施例以及对比例制得的改性载体以及催化剂的物化参数如表1所示。
表1

*是指石墨化N与吡咯化N的质量比。
表1续

V总是指催化剂的总孔容；
V介是指催化剂中介孔的孔容。
由表1可以看出，本发明实施例提供的负载型催化剂的载体中的氮碳化物中包含石墨化N和吡啶化N，且石墨化N和吡啶化N之间满足特定的含量关系，与活性金属配位结合形成催化活性位点，提升了催化剂的活性。同时本发明的催化剂中包含介孔结构，且介孔的孔容在催化剂的总孔容中的占比较高，提高了活性金属组分在载体中的分散稳定性，进而改善了催化剂的催化活性以及稳定性。
图1和图2分别是催化剂A1与催化剂A2的XPS图。以外来污染碳(284.8eV)作为基准对谱图进行荷电校准。通过查阅文献参考N标准峰位置，使用peak Fit进行拟合处理，调整峰位置、峰面积和FWHM等拟合参数，经洛伦兹和高斯函数处理XPS N1高分辨图谱，拟合出401.5eV和398.3eV两个峰位，其中401.5eV归属于石墨化N，398.3eV归属于吡啶化N。
由图1和图2可以看出催化剂中的石墨化N和吡啶化N含量占比，根据XPS结合能峰位置和峰面积比例确定两种类型的N含量，其中，催化剂A1的石墨化N：吡啶化N为0.2：1，催化剂A2的石墨化N：吡啶化N为1.2：1。
图3是催化剂A1的XRD衍射图。其中,a和b分别为金属钴和铑的特征衍射峰谱图，金属铑和钴的特征衍射峰数据信息来自XRD标准衍射卡片PDF#05-0685-Rh，PDF#15-0806-Co，铑(Rh)典型的特征结构衍射峰在2θ＝41.07°，47.48°，69.88°处，分别对应(111)，(200)，(220)晶面；钴(Co)典型的特征结构衍射峰在2θ＝44.22°，51.53°，75.85°，分别对应(111)，(200)，(220)晶面。图3c为实施例1制备得到的催化剂A1的XRD图。Fe3O4典型的特征结构衍射峰在2θ＝30.1°,35.5°,43.1°,57.1°处,分别对应(220)，(311)，(400)，(511)晶面，不同晶面产生的衍射强度与其原子周期性排列密度有关。图3c中30.1°,35.5°,43.1°,57.1°这几个位置可以检测到尖锐的衍射峰，衍射峰强度越大则代表其原子形成的有序排布的结晶相占比大。对于无定形结构的单原子材料，XRD图谱通常不会显示出明显的衍射峰。图3a-b钴和铑所对应的特征衍射峰位置在图3c的图谱结果中没有体现，说明在催化剂A1中没有产生两种金属的大尺寸结晶相，说明金属分散状态好。
图4是实施例1中制备得到的催化剂A1的球差电镜图，由图4可以看出图中白色高亮度区域代表负载金属铑和钴，暗色区域代表载体。负载金属在载体上呈现单原子状态分布。
测试例1
将150mg实施例以及对比例制得的催化剂与10mL 1-辛烯以及20mL甲苯混合后转移至高压反应釜内，向反应釜内通入CO/H2混合气(CO：H2体积比为1：1)，反应釜内压力在7MPa，在90℃恒温条件下反应5h，反应结束后冷却至室温，排出釜内液体，通过外加磁场分离催化剂和反应混合液，分离的催化剂循环使用5次，分别测试催化剂第1次使用时的转化率、循环5次后的转化率以及催化剂的金属流失率。1-辛烯经羰基化反应后得到的产物为壬醛。测试结果见表2。
表2
根据表2结果可以看出，本发明的催化剂用于烯烃羰基化反应时，第1次使用和循环5次后均具有较高的转化率，表明催化剂具有良好的催化活性，并且在多次循环后仍保持高的催化活性，具有优异的稳定性。与此同时，由表2可以看出，本发明提供的催化剂用于烯烃羰基化反应的过程中，催化剂中活性金属组分流失率较低，表明活性金属在载体上实现稳定负载，催化剂循环使用稳定性良好，在长周期使用过程中不易失活。
测试例2
将150mg实施例制得的催化剂分别与10mL不同的烯烃(具体详见表3)以及20mL甲苯混合后转移至高压反应釜内，向反应釜内通入CO/H2混合气(CO：H2体积比为1：1)，反应釜内压力在7MPa，在90℃恒温条件下反应5h，反应结束后冷却至室温，排出釜内液体，通过外加磁场分离催化剂和反应混合液，分离的催化剂循环使用5次，分别测试催化剂第1次使用时的转化率、循环5次后的转化率。测试结果见表3。
表3
由表3可以看出本发明的催化剂可以用于多种碳数烯烃(己烯、癸烯、十二烯，十四烯)的羰基化反应，其中催化剂A1，A3-A6都有较高的转化率，循环5次后转化率下降小，催化剂性能较优。

Claims (14)

  1. 一种负载型催化剂，其特征在于，所述催化剂包括载体以及负载在所述载体上的金属；
    其中，所述载体为含氮碳化物修饰的氧化物，且所述氮碳化物中的N元素包括石墨化N和吡啶化N；
    其中，所述石墨化N和所述吡啶化N的质量比为0.1-2：1。
  2. 根据权利要求1所述的负载型催化剂，其中，所述石墨化N和所述吡啶化N的质量比为0.1-1：1；
    优选地，以所述载体的总重量为基准，所述氮碳化物的含量为2-50wt％，优选为10-35wt％；
    优选地，所述载体呈以氧化物为核，以氮碳化物为壳层的核-壳结构；
    优选地，所述壳层的平均厚度为5-30nm，优选为10-25nm。
  3. 根据权利要求1或2所述的负载型催化剂，其中，以所述负载型催化剂的总重量为基准，所述载体的含量为95-99.9wt％，优选为97-99.5wt％，所述金属的含量为0.1-5wt％，优选为0.5-3wt％；
    优选地，所述氧化物选自四氧化三铁、三氧化二铁和氧化亚铁中的至少一种；
    优选地，所述金属选自Rh、Pb、Ru、Ir、Co、Cs和Li中的至少一种。
  4. 根据权利要求1-3中任意一项所述的负载型催化剂，其中，所述负载型催化剂中金属的分散度为45-75％，优选为60-75％。
  5. 根据权利要求1-4中任意一项所述的负载型催化剂，其中，所述负载型催化剂的比表面积为10-150m2/g，优选为30-90m2/g；
    优选地，所述负载型催化剂的平均孔径为2-20nm，优选为5-20nm；
    优选地，所述负载型催化剂的总孔容为0.05-0.5cm3/g，优选为0.1-0.2cm3/g；
    优选地，所述负载型催化剂中介孔的孔容为0.05-0.5cm3/g，优选为0.07-0.2cm3/g；
    优选地，以所述负载型催化剂中孔的总孔容为基准，介孔的孔容为50-90％，优选为70-85％。
  6. 根据权利要求1-5中任意一项所述的负载型催化剂，其中，所述氧化物选自四氧化三铁、三氧化二铁和氧化亚铁中的至少一种；所述金属为Rh，或者所述金属为Rh和Co，其中，所述负载型催化剂通过XRD测得Fe元素的特征峰强度IFe与Rh元素的特征峰强度IRh满足以下关系：
    IFe/IRh大于等于345，优选大于等于750。
  7. 一种负载型催化剂的制备方法，其特征在于，所述制备方法包括以下步骤：
    (1)将氧化物载体、活性单体、引发剂与溶剂混合后，进行原位聚合后，分离、干燥得到改性载体；
    (2)将金属前驱体溶液与所述改性载体进行混合、浸渍，固液分离得到固相，对所述固相进行干燥，得到催化剂前驱体；
    (3)在保护性气氛的存在下，对催化剂前驱体进行烧结，得到所述负载型催化剂；
    其中，所述活性单体为芳香胺；
    所述烧结的条件包括：以1-20℃/min升温速率从室温升温至300-400℃恒温1-3h后，以1-10℃/min升温速率升温至400-600℃后恒温0.5-2h，恒温过程结束后冷却至室温。
  8. 根据权利要求7所述的制备方法，其中，所述烧结的条件包括：以5-20℃/min升温速率从室温升温至350-400℃后恒温1-3h后，以2-8℃/min升温速率升温至400-500℃后恒温0.5-2h，恒温过程结束后冷却至室温。
  9. 根据权利要求7或8所述的制备方法，其中，所述活性单体选自苯胺、邻苯二胺、间苯二胺和对苯二胺中的至少一种；
    优选地，所述引发剂选自过氧乙酸、过氧化氢、过硫酸胺和过硫酸钾中的至少一种；
    优选地，所述氧化物载体选自四氧化三铁、三氧化二铁和氧化亚铁中的至少一种；
    优选地，以所述氧化物载体的用量为基准，所述活性单体的用量为2-50wt％，优选为10-30wt％；
    优选地，以所述活性单体的用量为基准，所述引发剂的用量为2-15wt％，优选为5-15wt％。
  10. 根据权利要求7-9中任意一项所述的制备方法，其中，所述原位聚合在结构调节剂的存在下进行；
    优选地，所述结构调节剂选自聚季铵盐、十六烷基三甲基溴化铵和十六烷基三甲基氯化铵中的至少一种；
    优选地，以所述活性单体的用量为基准，所述结构调节剂的用量为50-150wt％，优选为80-150wt％。
  11. 根据权利要求7-10中任意一项所述的制备方法，其中，所述金属前驱体溶液中的金属前驱体为能够提供活性金属组分的水溶性金属盐；
    优选地，所述活性金属组分选自Rh、Pb、Ru、Ir、Co、Cs和Li中的至少一种；
    优选地，所述前驱体溶液与所述改性载体的用量使得，以所述改性载体的用量为基准，所述金属前驱体的用量为2-20wt％，优选为5-15wt％；
    优选地，所述前驱体溶液的浓度为0.2-6wt％，优选为0.5-3wt％。
  12. 根据权利要求7-11中任意一项所述的制备方法，其中，所述原位聚合的条件包括：聚合温度为30-60℃，优选为40-55℃，聚合时间为1-6h，优选为2-4h；
    优选地，所述浸渍的条件包括：浸渍温度为25-60℃，优选为30-50℃，浸渍时间为2-48h，优选为5-48h；
    优选地，所述干燥条件包括：干燥温度为60-80℃，干燥时间为2-3h；
    优选地，对烧结后产物以1-15℃/min，优选5-10℃/min的速率冷却至室温。
  13. 由权利要求7-12中任意一项所述的制备方法制得的负载型催化剂。
  14. 权利要求1-6和13中任意一项所述的负载型催化剂在烯烃羰基化反应中的应用，优选地，所述烯烃为C6-C16的烯烃。
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