Supported cobalt-based high-entropy oxide catalyst and application thereof in preparation of propylene through propane dehydrogenation
The preparation of supported cobalt-based high-entropy oxide catalysts has solved the problems of toxicity and precious metals in existing catalysts, improved the efficiency of propane dehydrogenation to propylene, and achieved low-cost and high-activity catalytic effects.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-11-18
- Publication Date
- 2026-05-19
AI Technical Summary
Existing Cr-based and Pt-based catalysts suffer from toxicity and noble metal properties. In the process of propane dehydrogenation to propylene, the active metal ions of single-component transition metal oxides are easily reduced, resulting in a decrease in catalytic activity. Existing methods are difficult to effectively improve the activity and stability of catalysts.
By using supported cobalt-based high-entropy oxide catalysts and controlling their composition and preparation methods, CoxM3-xO4 with a spinel structure was prepared. The catalyst was then loaded onto molecular sieves, oxides, or nitride supports using citric acid complexation impregnation or mechanical ball milling to improve catalytic activity.
It achieves high catalytic activity at a low cost and in an environmentally friendly manner, significantly improving the efficiency of propane dehydrogenation to propylene, and is suitable for industrial scale-up.
Smart Images
Figure HDA0005139846590000011 
Figure HDA0005139846590000012
Abstract
Description
Technical Field
[0001] This invention relates to the preparation of a supported high-entropy oxide catalyst and its application in the dehydrogenation of propane to propylene, belonging to the fields of catalysis and chemical engineering. Technical Background
[0002] Propylene is an important chemical raw material, and its demand is increasing year by year. Propane dehydrogenation to propylene (PDH) technology is one of the important ways to increase propylene production and make rational use of shale gas. In view of the toxicity of Cr-based catalysts and the precious metal nature of Pt-based catalysts currently used in industry, the development of inexpensive, non-toxic and environmentally friendly non-precious metal PDH catalysts has extremely important scientific significance and practical value.
[0003] Transition metal oxides such as Zn and Co possess excellent CH bond activation capabilities and are inexpensive and environmentally friendly, showing potential to replace commercial PDH catalysts. However, single-component transition metals often face problems such as excessive reduction of active metal ions, reduced active species, and decreased PDH activity. Rationally selecting different methods to stabilize active species and thus improve PDH activity and stability is a key challenge in propane dehydrogenation. Current research mostly focuses on optimizing the support, selecting suitable promoters, or incorporating active elements such as Zn and Co into the molecular sieve framework to improve the PDH activity of the catalyst. While these methods have some effect, the results are not particularly ideal. Summary of the Invention
[0004] To address the above problems, this invention provides a method for preparing a supported high-entropy oxide catalyst and its application in propane dehydrogenation to propylene. A highly active propane dehydrogenation catalyst is prepared by controlling the composition, content, and preparation method of the high-entropy oxide catalyst. This invention offers a simple synthesis method and improves the catalytic activity of Co-based catalysts for propane dehydrogenation.
[0005] The present invention aims to provide a supported cobalt-based high-entropy oxide catalyst, wherein the catalyst comprises a cobalt-based high-entropy oxide and a support, and the mass percentage of the cobalt-based high-entropy oxide in the catalyst is 1-10%; wherein the cobalt-based high-entropy oxide is composed of Co. x M 3-x O4 has a spinel structure, wherein M is four or more of Mg, Ca, Ni, Zn, V, Mn, Zr, Ga, Sn, and Ti; and x ranges from 0.5 to 2.5.
[0006] Based on the above technical solution, preferably, x is 1.0 to 2.0.
[0007] Based on the above technical solution, preferably, the molar ratio of each element in M to any other element is 1:0.8 to 1.2, and more preferably, the molar ratio of each element in M is close to equimolar.
[0008] Based on the above technical solution, preferably, the mass ratio of cobalt-based high-entropy oxide in the catalyst is 1-8%.
[0009] Based on the above technical solution, preferably, M is four or more of Mg, Zn, Mn, Zr, Ga, and Sn.
[0010] Based on the above technical solution, preferably, the carrier is one or more of molecular sieves, oxides, and nitrides.
[0011] Based on the above technical solution, preferably, the molecular sieve is one or more of MFI type or dealuated Beta type molecular sieves; the MFI type is one or more of S-1 and TS-1; preferably, the molar ratio of Si to Ti in the TS-1 molecular sieve is 10 to 60:1; the oxide is one or more of Al2O3, SiO2, mesoporous MCM-41, SBA-15, TiO2, ZrO2 and CeO2; the nitride is one or more of carbon nitride, boron nitride and silicon nitride.
[0012] The present invention also aims to provide a method for preparing the above-mentioned supported high-entropy oxide catalyst, wherein the method for preparing the supported high-entropy oxide catalyst is a citric acid complexation impregnation method or a mechanical ball milling method.
[0013] Based on the above technical solution, preferably, the citric acid complexation impregnation method includes the following steps:
[0014] (1) Cobalt-based high-entropy oxide (Co x M 3-x O4) The precursor material is dissolved in water or ethanol solvent and stirred for 0.5 to 3 hours;
[0015] (2) Add a certain proportion of citric acid and ethylene glycol to the mixed solution obtained in step (1), and stir for 0.5–3 h to allow them to complex; wherein the cobalt-based high-entropy oxide (Co x M 3-x The molar ratio of O4 precursor material to citric acid is 1:1.0–2.0; the molar ratio of citric acid to ethylene glycol is 1:0.1–0.5.
[0016] (3) Add the mixed solution obtained in step (2) to the carrier, sonicate for 0.5-3 hours, stir for 2-5 hours, let stand for 12-24 hours, then dry at 60-100℃ for 6-12 hours, and continue to dry at 120-150℃ for 12-24 hours.
[0017] (4) The catalyst prepared in step (3) is calcined at 520-800℃ for 2-10 hours to obtain the target catalyst.
[0018] Based on the above technical solution, preferably, in step (1), the molar ratio of the cobalt-based high-entropy oxide precursor material to water or ethanol solvent is 1:100 to 300, and more preferably 1:100 to 200.
[0019] Based on the above technical solution, preferably, the mechanical ball milling method includes the following steps:
[0020] (1) Cobalt-based high-entropy oxide (Co x M 3-x O4) The precursor material and the carrier are placed in a ball mill jar, and water or ethanol solvent is added, or no additional solvent is added, and the mixture is ball milled for 3 to 10 hours.
[0021] (2) Dry the powder after ball milling in step (1) at 60-100℃ and grind it evenly;
[0022] (3) The supported catalyst prepared in step (3) is calcined at 520-800℃ for 2-10 hours to obtain the target catalyst.
[0023] Based on the above technical solution, preferably, in step (1), when water or ethanol solvent is added, the mass ratio of the carrier to water or ethanol solvent is 1:0.4 to 2.
[0024] Based on the above technical solution, preferably, the cobalt-based high-entropy oxide precursor material is one or more of the following: metal nitrates, chlorides, acetates, carbonates, citrates, acetylacetone salts, and oxides.
[0025] Based on the above technical solution, preferably, when the cobalt-based high-entropy oxide contains V, oxalic acid needs to be added to the cobalt-based high-entropy oxide precursor material, wherein the molar ratio of V to oxalic acid is 1:1 to 3.
[0026] Another object of the present invention is to provide the application of the above-mentioned supported high-entropy catalyst in the propane dehydrogenation to propylene reaction, wherein the reaction conditions are: reaction temperature 520-650℃, reaction pressure 0.01-0.1 MPa, and propane mass hourly space velocity 0.4-50 h⁻¹. -1 Preferably, the propane concentration is 10-80%.
[0027] Beneficial effects:
[0028] Compared with existing technologies, the propane dehydrogenation to propylene catalyst obtained by the method of this invention has the advantages of low cost and environmental friendliness, and exhibits higher catalytic activity than single cobalt-based metal oxides. The preparation method provided by this invention is simple, widely applicable, and easy to scale up industrially. Attached Figure Description
[0029] This invention appendix Figure 2 , of which:
[0030] Figure 1 This is a comparison graph of the propylene formation rate between Comparative Example 1 and Examples 1-4.
[0031] Figure 2 This is a transmission electron microscope (TEM) image of the catalyst from Example 2. From... Figure 2 The interplanar spacings of 0.471 nm, 0.291 nm, and 0.249 nm correspond to the (111), (220), and (311) crystal planes of the spinel oxide, respectively, confirming that the supported high-entropy oxide prepared in the examples has a spinel structure. Detailed Implementation
[0032] The following specific embodiments will further illustrate the content of the present invention and should not be construed as limiting the present invention in any way.
[0033] Comparative Example 1
[0034] Dissolve 0.363 g of cobalt nitrate hexahydrate in 5 mL of water and stir for 1 h; add 0.314 g of citric acid monohydrate and 0.018 g of ethylene glycol, and mix and stir for 1 h. Add the above mixed solution dropwise to 12.8 g of S-1 molecular sieve (specific surface area 460 m² / g). 2 The catalyst was ultrasonically treated for 2 hours, stirred for 2 hours, and then allowed to stand for 16 hours. It was then dried in an oven at 80℃ for 6 hours and then in an oven at 120℃ for 12 hours. The prepared catalyst was calcined at 700℃ for 5 hours. 0.15 g of the catalyst was used in the propane dehydrogenation to propylene reaction. The feed gas was 25% propane (diluted with nitrogen), the reaction temperature was 580℃, the reaction pressure was 0.1 MPa, and the mass hourly space velocity (HHSV) was 7.9 h⁻¹. -1 The propylene selectivity was 96.2%, and the propylene formation rate was... Performance comparison Figure 1 As shown.
[0035] Comparative Example 2
[0036] 0.5 g of the catalyst from Example 1 was used in the propane dehydrogenation to propylene reaction. The reactant gas was 50% propane (diluted with nitrogen), the reaction temperature was 580 °C, the reaction pressure was 0.1 MPa, and the reaction mass hourly space velocity (WHSV) was 2.4 h⁻¹. -1 The propane conversion rate was 47.6%, and the propylene selectivity was 59%.
[0037] Example 1
[0038] 0.121 g of cobalt nitrate hexahydrate, 0.07 g of zirconium nitrate pentahydrate, 0.04 g of magnesium nitrate hexahydrate, 0.06 g of manganese nitrate (50% by mass), 0.05 g of nickel nitrate hexahydrate, and 0.05 g of zinc nitrate hexahydrate were dissolved in 3.0 mL of water and stirred for 1 h. Then, 0.42 g of citric acid monohydrate and 0.03 g of ethylene glycol were added and stirred for 2 h. The above mixture was then added dropwise to 4.9 g of S-1 molecular sieve (specific surface area 460 m²). 2 The catalyst was ultrasonically treated for 2 hours, stirred for 2 hours, and then allowed to stand for 16 hours before being dried in an oven at 80°C for 12 hours. The prepared catalyst was then calcined at 600°C for 3 hours. 0.15 g of the catalyst was used in a propane dehydrogenation reaction to produce propylene. The reactant gas was 25% propane (diluted with nitrogen), the reaction temperature was 580°C, the reaction pressure was 0.1 MPa, and the mass hourly space velocity (HHSV) was 7.9 h⁻¹. -1 The propane conversion rate was 43.6%, the propylene selectivity was 93.2%, and the propylene formation rate was... Performance comparison Figure 1 As shown.
[0039] Example 2
[0040] 0.24 g of cobalt nitrate hexahydrate, 0.04 g of zirconium nitrate pentahydrate, 0.02 g of magnesium nitrate hexahydrate, 0.03 g of manganese nitrate (50% by mass), 0.02 g of nickel nitrate hexahydrate, and 0.05 g of zinc nitrate hexahydrate were dissolved in 3.0 mL of water and stirred for 1 h. Then, 0.42 g of citric acid monohydrate and 0.03 g of ethylene glycol were added, and the mixture was stirred for 2 h. The above mixture was then added dropwise to 4.9 g of S-1 molecular sieve (specific surface area 460 m²). 2 The catalyst was subjected to ultrasonic treatment for 2 hours, stirred for 2 hours, and then allowed to stand for 16 hours. It was then dried in an oven at 80°C for 12 hours. The prepared catalyst was calcined at 600°C for 3 hours. A transmission electron microscope (TEM) image of the catalyst is shown below. Figure 2 As shown, 0.15 g of catalyst was used in the propane dehydrogenation to propylene reaction. The reactant gas was 25% propane (diluted with nitrogen), the reaction temperature was 580 °C, the reaction pressure was 0.1 MPa, and the mass hourly space velocity (HHSV) was 7.9 h⁻¹. -1 The propane conversion rate was 43.6%, the propylene selectivity was 88.1%, and the propylene formation rate was... Performance comparison Figure 1 As shown.
[0041] Example 3
[0042] 0.48 g of cobalt nitrate hexahydrate, 0.07 g of zirconium nitrate pentahydrate, 0.04 g of calcium nitrate tetrahydrate, 0.06 g of manganese nitrate (50% by mass), 0.04 g of stannous chloride dihydrate, and 0.05 g of zinc nitrate hexahydrate were dissolved in 5.0 mL of water and stirred for 1 h. Then, 0.72 g of citric acid monohydrate and 0.06 g of ethylene glycol were added and stirred for 2 h. The above mixture was then added dropwise to 9.8 g of TS-1 (Si / Ti molar ratio 36, specific surface area 446 m²). 2 The catalyst was ultrasonically treated in a molecular sieve (g) for 2 hours, stirred for 2 hours, allowed to stand for 16 hours, and then dried in an oven at 80°C for 12 hours. The prepared catalyst was calcined at 600°C for 3 hours. 0.15 g of the catalyst was used in a propane dehydrogenation reaction to propylene, with 25% propane (diluted with nitrogen) as the feed gas, at a reaction temperature of 580°C, a reaction pressure of 0.1 MPa, and a mass hourly space velocity (HHSV) of 7.9 h⁻¹. -1 The propylene selectivity was 97.2%, and the propylene formation rate was... Performance comparison Figure 1 .
[0043] Example 4
[0044] 0.30 g of cobalt nitrate hexahydrate, 0.02 g of gallium nitrate hexahydrate, 0.02 g of zirconium nitrate pentahydrate, 0.01 g of magnesium nitrate hexahydrate, 0.02 g of manganese nitrate (50% by mass), and 0.01 g of nickel nitrate hexahydrate were dissolved in 4.0 mL of water and stirred for 1 h. Then, 0.72 g of citric acid monohydrate and 0.06 g of ethylene glycol were added and stirred for 2 h. The above mixture was then added dropwise to 6.5 g of TS-1 (Si / Ti molar ratio 36, specific surface area 446 m²). 2 The catalyst was ultrasonically treated in a molecular sieve (g) for 2 hours, stirred for 2 hours, allowed to stand for 16 hours, and then dried in an oven at 80°C for 12 hours. The prepared catalyst was calcined at 600°C for 3 hours. 0.15 g of the catalyst was used in a propane dehydrogenation reaction to propylene, with 25% propane (diluted with nitrogen) as the feed gas, at a reaction temperature of 580°C, a reaction pressure of 0.1 MPa, and a mass hourly space velocity (HHSV) of 7.9 h⁻¹. -1 The propylene selectivity was 96.8%, and the propylene formation rate was... Performance comparison Figure 1 .
[0045] Example 5
[0046] 0.24 g of cobalt nitrate hexahydrate, 0.04 g of zirconium nitrate pentahydrate, 0.02 g of magnesium nitrate hexahydrate, 0.03 g of manganese nitrate (50% by mass), and 0.02 g of nickel nitrate hexahydrate were dissolved in 4.0 mL of water and stirred for 1 h. Then, 0.36 g of citric acid monohydrate and 0.02 g of ethylene glycol were added and stirred for 2 h. The above mixture was then added dropwise to 6.5 g of S-1 molecular sieve (specific surface area 460 m²). 2 The catalyst was ultrasonically treated for 2 hours, stirred for 2 hours, and then allowed to stand for 16 hours before being dried in an oven at 80°C for 12 hours. The prepared catalyst was then calcined at 600°C for 3 hours. 0.15 g of the catalyst was used in a propane dehydrogenation reaction to produce propylene. The reactant gas was 25% propane (diluted with nitrogen), the reaction temperature was 580°C, the reaction pressure was 0.1 MPa, and the mass hourly space velocity (HHSV) was 7.9 h⁻¹. -1 The propylene selectivity was 95.3%, and the propylene formation rate was...
[0047] Example 6
[0048] 0.48 g of cobalt nitrate hexahydrate, 0.07 g of zirconium nitrate pentahydrate, 0.04 g of calcium nitrate tetrahydrate, 0.06 g of manganese nitrate (50% by mass), 0.04 g of stannous chloride dihydrate, and 0.05 g of zinc nitrate hexahydrate were dissolved in 4.2 mL of water and stirred for 1 h. Then, 0.72 g of citric acid monohydrate and 0.06 g of ethylene glycol were added and stirred for 2 h. The above mixture was then added dropwise to 8.7 g of mesoporous MCM-41 (specific surface area 830 m²). 2 The catalyst was ultrasonically treated for 2 hours, stirred for 2 hours, and then allowed to stand for 16 hours before being dried in an oven at 80°C for 12 hours. The prepared catalyst was then calcined at 600°C for 3 hours. 0.15 g of the catalyst was used in a propane dehydrogenation reaction to produce propylene. The reactant gas was 25% propane (diluted with nitrogen), the reaction temperature was 580°C, the reaction pressure was 0.1 MPa, and the mass hourly space velocity (HHSV) was 7.9 h⁻¹. -1 The propylene selectivity was 96.8%, and the propylene formation rate was...
[0049] Example 7
[0050] Dissolve 0.30 g of cobalt nitrate hexahydrate, 0.02 g of zinc nitrate hexahydrate, 0.02 g of zirconium nitrate pentahydrate, 0.01 g of magnesium nitrate hexahydrate, 0.02 g of manganese nitrate (50% by mass), 0.005 g of ammonium metavanadate, and 0.01 g of oxalic acid in 5.0 mL of water and stir for 1 h. Then add 0.72 g of citric acid monohydrate and 0.06 g of ethylene glycol and stir for 2 h. Then add the above mixed solution dropwise to 6.5 g of TS-1 (Si / Ti molar ratio 36, specific surface area 446 m²). 2The catalyst was ultrasonically treated in a molecular sieve (g) for 2 hours, stirred for 2 hours, allowed to stand for 16 hours, and then dried in an oven at 80°C for 12 hours. The prepared catalyst was calcined at 600°C for 3 hours. 0.15 g of the catalyst was used in a propane dehydrogenation reaction to propylene, with 25% propane (diluted with nitrogen) as the feed gas, at a reaction temperature of 580°C, a reaction pressure of 0.1 MPa, and a mass hourly space velocity (HHSV) of 7.9 h⁻¹. -1 The propylene selectivity was 96.8%, and the propylene formation rate was...
[0051] Example 8
[0052] The following ingredients were added: 0.24 g cobalt nitrate hexahydrate, 0.04 g zirconium nitrate pentahydrate, 0.02 g magnesium nitrate hexahydrate, 0.03 g manganese nitrate tetrahydrate, 0.02 g stannous chloride dihydrate, 0.02 g zinc nitrate hexahydrate, and 4.9 g TS-1 (Si / Ti molar ratio 36, specific surface area 446 m²). 2 The molecular sieve (g) was placed in a ball mill jar, and 20.1g of ethanol was added. The mixture was ball-milled for 5 hours. The powder was then dried at 70℃ and ground until homogeneous; subsequently, it was calcined at 650℃ for 3 hours. 0.15g of the catalyst was used in the propane dehydrogenation to propylene reaction. The reactant gas was 25% propane (diluted with nitrogen), the reaction temperature was 580℃, the reaction pressure was 0.1MPa, and the mass hourly space velocity (HHSV) was 7.9h. -1 The propylene selectivity was 86.8%, and the propylene formation rate was...
[0053] Example 9
[0054] 0.5 g of the catalyst from Example 2 was used in the propane dehydrogenation to propylene reaction. The reactant gas was 25% propane (diluted with nitrogen), the reaction temperature was 580 °C, the reaction pressure was 0.1 MPa, and the mass hourly space velocity (HHSV) was 1.2 h⁻¹. -1 The propane conversion rate was 37%, and the propylene selectivity was 93.2%.
[0055] Example 10
[0056] 0.5 g of the catalyst from Example 2 was used in the propane dehydrogenation to propylene reaction. The reactant gas was 50% propane (diluted with nitrogen), the reaction temperature was 580 °C, the reaction pressure was 0.1 MPa, and the reaction mass hourly space velocity (WHSV) was 2.4 h⁻¹. -1 The propane conversion rate was 33.8%, and the propylene selectivity was 94.2%.
[0057] Example 11
[0058] 0.5 g of the catalyst from Example 2 was used in the propane dehydrogenation to propylene reaction. The reactant gas was 50% propane (diluted with nitrogen), the reaction temperature was 580 °C, the reaction pressure was 0.1 MPa, and the reaction mass hourly space velocity (WHSV) was 2.4 h⁻¹. -1 The propane conversion rate was 33.8%, and the propylene selectivity was 94.2%.
[0059] As can be seen from the comparison of the above examples and comparative examples, the propane dehydrogenation performance of the supported high-entropy oxide catalyst designed in this invention is higher than that of single cobalt-based oxides, which significantly improves the catalytic activity of cobalt-based catalysts.
Claims
1. A supported cobalt-based high-entropy oxide catalyst, characterized in that: The catalyst comprises a cobalt-based high-entropy oxide and a support, wherein the mass percentage of the cobalt-based high-entropy oxide is 1–10%; the cobalt-based high-entropy oxide is composed of Co. x M 3-x O4 has a spinel structure, wherein M is one or more of Mg, Ca, Ni, Zn, V, Mn, Zr, Ga, Sn, and Ti, and x is 0.5 to 2.
5.
2. The supported cobalt-based high-entropy oxide catalyst according to claim 1, characterized in that: The molar ratio of each element in M to any other element is 1:0.8 to 1.
2.
3. The supported cobalt-based high-entropy oxide catalyst according to claim 1, characterized in that: The carrier is one or more of molecular sieves, oxides, and nitrides.
4. The supported cobalt-based high-entropy oxide catalyst according to claim 1, characterized in that: The molecular sieve is one or more of MFI type or dealuated Beta type molecular sieves; the MFI type molecular sieve is one or more of S-1 and TS-1; the oxide is one or more of Al2O3, SiO2, mesoporous MCM-41, SBA-15, TiO2, ZrO2 and CeO2; the nitride is one or more of carbon nitride, boron nitride and silicon nitride.
5. The method for preparing the supported high-entropy oxide catalyst according to any one of claims 1-4, characterized in that: The supported high-entropy oxide catalyst is prepared by citric acid complexation impregnation or mechanical ball milling.
6. The preparation method according to claim 5, characterized in that: The citric acid complexation impregnation method includes the following steps: (1) Dissolve the cobalt-based high-entropy oxide precursor material in water or ethanol solvent and stir for 0.5 to 3 hours; (2) Add citric acid and ethylene glycol to the mixed solution obtained in step (1) and stir for 0.5 to 3 hours; wherein the molar ratio of cobalt-based high-entropy oxide precursor material to citric acid is 1:1.0 to 2.0; and the molar ratio of citric acid to ethylene glycol is 1:0.1 to 0.
5. (3) Add the mixed solution obtained in step (2) to the carrier, sonicate for 0.5-3 hours, stir for 2-5 hours, let stand for 12-24 hours, then dry at 60-100℃ for 6-12 hours, and continue to dry at 120-150℃ for 12-24 hours. (4) The catalyst prepared in step (3) is calcined at 520-800℃ for 2-10 hours to obtain the target catalyst.
7. The preparation method according to claim 5, characterized in that: The mechanical ball milling method includes the following steps: (1) Place the cobalt-based high-entropy oxide precursor material and the carrier in a ball milling jar, add water or ethanol solvent, or do not add any solvent, and ball mill for 3 to 10 hours; (2) Dry the powder after ball milling in step (1) at 60-100℃ and grind it evenly; (3) The supported catalyst prepared in step (3) is calcined at 520-800℃ for 2-10 hours to obtain the target catalyst.
8. The application according to claim 6 or 7, characterized in that: The high-entropy oxide precursor materials are one or more of the following: metal nitrates, chlorides, acetates, carbonates, citrates, acetylacetone salts, oxalates, and oxides. In step (1) of the citric acid complex impregnation method, the molar ratio of the cobalt-based high-entropy oxide precursor material to water or ethanol solvent is 1:100 to 300. In step (1) of the mechanical ball milling method, when water or ethanol solvent is added, the mass ratio of the carrier to the solvent is 1:0.4 to 2.
9. The application of the supported cobalt-based high-entropy oxide catalyst according to any one of claims 1-4 in the propane dehydrogenation to propylene reaction.
10. The application according to claim 9, characterized in that: The reaction conditions were: reaction temperature 520–650℃, reaction pressure 0.01–0.1 MPa, and propane mass hourly space velocity (HHSV) 0.4–50 h⁻¹. -1 .