High-entropy oxide molecular sieve interface coupling catalyst, preparation method and application

Abstract

The invention discloses a preparation method of a high-entropy oxide molecular sieve interface coupling catalyst. The preparation method comprises the following steps: 1, preparing a high-entropy metal oxide; 2, preparing an H-MCM-22 molecular sieve; 3, ball-milling the high-entropy metal oxide, the H-MCM-22 molecular sieve and the zirconium oxide balls together to obtain mixed powder; and 4, tabletting, crushing and screening the mixed powder to obtain the high-entropy oxide molecular sieve interface coupling catalyst. The invention also discloses the high-entropy oxide molecular sieve interface coupling catalyst prepared by the method and application thereof. According to the preparation method of the high-entropy oxide molecular sieve interface coupling catalyst, the high-entropy oxide molecular sieve interface coupling catalyst is composed of a high-entropy oxide composed of multi-component metal and a molecular sieve with an acidic structure regulation and control capability, and the selectivity of a C8 + component in a CO2 hydrogenation reaction is remarkably improved through an interface synergistic effect; the catalyst is simple and convenient in synthesis process, high in catalytic activity, adjustable in product distribution and suitable for large-scale preparation of high-selectivity liquid fuel.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon dioxide resource utilization and synthetic fuel, and relates to a preparation method of a high-entropy oxide molecular sieve interface coupling catalyst, and also relates to a high-entropy oxide molecular sieve interface coupling catalyst prepared by using the above preparation method and its application. Background Art

[0002] With the continuous growth of global energy demand and the promotion of the carbon neutrality goal, the resource utilization of carbon dioxide has become an important direction for green and low-carbon transformation. Converting CO2 hydrogenation into high-value liquid fuels, especially C8 components such as aviation kerosene, not only helps to mitigate the greenhouse effect but also provides a feasible path for achieving sustainable air transportation. The carbon chain length distribution of aviation fuel components is C8~C + , petroleum-based aviation kerosene mainly contains about 20% n-alkanes, 40% isoalkanes, 20% naphthenes and 20% aromatics. The total content of iso-hydrocarbons and cyclic hydrocarbons accounts for up to 80%, while the main component of bio-based aviation kerosene is isoalkanes (about 90%). 16 The core difficulty in the preparation of aviation kerosene by CO2 hydrogenation lies in that: the CO2 molecule is highly stable and requires high energy consumption for activation; the product needs to be precisely controlled to C8~C hydrocarbons (including 80% iso / cyclic components). Traditional catalysts are limited by their selectivity and stability problems. Existing iron-based, copper-based and other catalysts still have significant deficiencies in catalytic performance, C-C coupling ability and product distribution regulation, and it is difficult to meet the actual needs of efficient aviation kerosene preparation. Therefore, developing a new type, efficient and stable catalyst system has become a key problem to be solved urgently. Currently, oxide / molecular sieve bifunctional catalysts represented by In2O3 / H-ZSM-5 created by the Shanghai Advanced Research Institute of the Chinese Academy of Sciences have made important progress in the one-step synthesis of gasoline, light olefins and light aromatics by CO2 hydrogenation, but the conversion rate is low, and further processing is required to obtain ideal aviation kerosene components. 16 High-Entropy Oxides (HEOs) are new oxide materials composed of five or more metal elements in near-equimolar ratios. Due to the high-entropy effect and multi-metal synergistic effect, HEOs have rich active sites and adjustable electronic structures, and at the same time effectively inhibit sintering and reduce carbon deposition under high-temperature conditions, thus significantly improving their catalytic activity, selectivity and stability. Molecular sieve MCM-22 has an MWW topological structure. Relying on its two-dimensional pores, supercage confinement effect and adjustable acidity, it can achieve the selection of intermediate carbon numbers (such as C8~C

[0003] in methanol conversion and other reactions 16) hydrocarbons, providing an excellent platform for the synthesis of clean fuels and chemicals. Combining high entropy oxides with MCM-22 can effectively activate CO2 through the multi-metal synergistic effect, inhibit the sintering of active components and reduce carbon deposition, and selectively screen C8~C 16 The two can not only take into account CO2 activation, chain growth and structural regulation, but also greatly improve the selectivity and stability of the target product while reducing energy consumption, providing an efficient and sustainable technical path for the decarbonization of the aviation industry. Summary of the invention

[0004] The first object of the present invention is to provide a method for preparing a high entropy oxide molecular sieve interface coupling catalyst, which is composed of a high entropy oxide composed of multi-component metals and a molecular sieve (such as MCM-22) with acidic structure regulation ability, and significantly improves the C8 in CO2 hydrogenation reaction through interface synergy. + The catalyst prepared by the present invention has the advantages of simple synthesis process, high catalytic activity, adjustable product distribution, excellent stability, etc., and is suitable for large-scale preparation of highly selective liquid fuels, especially for green synthesis of aviation fuels.

[0005] The second object of the present invention is to provide a high entropy oxide molecular sieve interface coupling catalyst prepared by the above preparation method.

[0006] The third object of the present invention is to provide an application of the above-mentioned high entropy oxide molecular sieve interface coupling catalyst.

[0007] The first technical solution adopted by the present invention is a method for preparing a high entropy oxide molecular sieve interface coupling catalyst, and the specific method is as follows: Step 1, preparing high entropy metal oxide; Step 2, preparing H-MCM-22 molecular sieve; Step 3, respectively weighing high entropy metal oxide and H-MCM-22 molecular sieve, and then placing the high entropy metal oxide, H-MCM-22 molecular sieve and zirconium oxide balls in a ball mill for ball milling to obtain a mixed powder; Step 4: tablet the obtained mixed powder, crush and sieve to 60-80 mesh, and prepare a high entropy oxide molecular sieve interface coupling catalyst.

[0008] The present invention is also characterized in that: The specific method of step 1 is as follows: Step 1.1. Preparation of precursor solution: Zirconium nitrate, zinc nitrate, indium nitrate, magnesium nitrate and chromium nitrate are successively dissolved in a mixed solution composed of anhydrous ethanol and deionized water in a ratio of 1:1 according to a molar ratio of 0.35±m:0.30:0.20±m:0.10:0.05, where the value range of m is 0 to 0.1, and the total molar concentration of metals in the solution does not exceed 0.05 mol / L. Stir for 1 to 2 h to obtain a precursor solution; Step 1.2. Chelation reaction: Citric acid is added to the precursor solution, and the molar ratio of citric acid to the total metals is 1.5:1. Magnetically stir at a constant temperature of 60 °C for 2 h to form a metal-citric acid complex; Step 1.3. Formation of wet sol: The metal-citric acid complex is placed in a water bath at 60 °C, and ammonia water is slowly added dropwise to adjust the pH to 4 to 5. Continue stirring for 2 to 4 h until the solution gradually becomes viscous to obtain a wet sol; Step 1.4. Drying and calcination: The wet sol is transferred to a vacuum drying oven for drying to obtain a dry gel. After the dry gel is ground into fine powder, it is placed in a muffle furnace for the first high-temperature calcination. After naturally cooling to room temperature, it is ground again until uniform, and then the second high-temperature calcination is carried out to obtain a high-entropy metal oxide.

[0009] The specific method of Step 1.4 is as follows: The wet sol is transferred to a vacuum drying oven and dried at 80 °C for 24 h to obtain a dry gel. After grinding into fine powder, the powder is placed in a muffle furnace and heated to 400 °C at a rate of 2 °C / min, held for 2 h, naturally cooled to room temperature, ground again until uniform, and then heated to 600 °C at a rate of 5 °C / min and held for 4 h to obtain a high-entropy metal oxide.

[0010] The specific method of Step 2 is as follows: Step 2.1. Preparation of synthetic sol: At room temperature, NaOH is dissolved in deionized water, sodium aluminate and silica sol are successively added, and stirring is continued until a uniform white colloid is formed. Then, hexamethyleneimine is quantitatively injected, and stirring is continued for 30 min to obtain a synthetic sol; Step 2.2. Hydrothermal crystallization: The synthetic sol is transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle, dynamically crystallized at 150 °C for 72 h, and the stirring rate is 300 rpm. After the crystallization is completed, the reaction kettle is immediately immersed in an ice-water bath and quickly cooled to room temperature. The obtained crystallized product is separated, and the crystallized product is repeatedly washed with deionized water until the washing liquid is neutral. After drying in a blast drying oven at 120 °C for 12 h, it is calcined at 540 °C in static air for 4 h to obtain Na-MCM-22 powder; Step 2.3, Protonation treatment: Mix the above-mentioned Na-MCM-22 powder with ammonium nitrate solution, carry out ion exchange at 80 °C under constant temperature stirring for 2 h, repeat the operation 2-3 times, then filter and separate. Wash the filter cake with deionized water until the pH is 6.9-7.1, dry at 100 °C for 12 h, and then calcine in an air atmosphere at 520 °C for 4 h to finally obtain the proton-type H-MCM-22 molecular sieve.

[0011] In Step 2.1, the molar ratio of raw materials among silica sol, sodium aluminate, hexamethylenimine, deionized water and NaOH is 1: 0.03-0.01: 0.5: 40: 0.3.

[0012] In Step 2.3, the solid-liquid ratio of the mass of Na-MCM-22 powder to the volume of ammonium nitrate solution is 1 g:15 mL, and the concentration of ammonium nitrate solution is 1 mol / L.

[0013] In Step 3, the mass ratio of the high-entropy metal oxide to the H-MCM-22 molecular sieve is 0.2-5: 1, the mass ratio of the total mass of the high-entropy metal oxide and the H-MCM-22 molecular sieve to the mass of zirconia balls is 1:10, the ball milling speed is 600 rpm / min, and the ball milling time is 5 min - 60 min.

[0014] The second technical solution adopted in the present invention is a high-entropy oxide molecular sieve interface coupling catalyst, prepared by the above preparation method, including a high-entropy metal oxide and an H-MCM-22 molecular sieve, and the mass ratio of the high-entropy metal oxide to the H-MCM-22 molecular sieve is 0.2-5: 1; The chemical formula of the high-entropy metal oxide is Zr 0.35±m Zn 0.30 In 0.20±m Mg 0.10 Cr 0.05 O x , where the value range of m is 0-0.1.

[0015] The third technical solution adopted in the present invention is the application of the high-entropy oxide molecular sieve interface coupling catalyst. The high-entropy oxide molecular sieve interface coupling catalyst is used for the hydrogenation of CO2 to prepare aviation kerosene fraction, the reaction temperature is 300-400 °C, the reaction pressure is 3 MPa, and the mass space velocity is 1000-12000 mL·g cat -1 ·h -1 .

[0016] The features of the present invention also lie in: The high-entropy oxide molecular sieve interface coupling catalyst needs to be activated before use, and the activation conditions are: under the protection of an inert gas, keep the temperature constant at 250 °C - 400 °C for 2 h.

[0017] The beneficial effects of the present invention are as follows: (1) The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst of the present invention covers three core processes: controllable synthesis of high-entropy metal oxides, regulation of molecular sieve topological structure, and two-phase interface coupling. It has the advantages of strong raw material universality (the types of precursor metals can be adjusted), precise control of process parameters (crystallization temperature ≤ 200 °C), and clear product structure (phase purity > 99%); In particular, high-entropy oxides achieve uniform element distribution and controllable oxygen vacancy defect configurations through solvothermal self-assembly, and molecular sieves obtain a ten-membered ring cross-pore system of 0.41 nm × 0.54 nm through template agent regulation. The two can improve the reaction performance and selectivity of the catalyst through interface coupling; (2) The high-entropy oxide molecular sieve interface coupling catalyst of the present invention has excellent catalytic performance: in a fixed-bed reactor (P = 3 MPa, T = 320 °C, GHSV = 4000 h -1 )), this catalyst achieves a single-pass CO2 conversion rate of 25.3 ± 0.8%, and the selectivity for C8~C 16 linear alkanes reaches 58.6 - 63.2% (quantitative analysis by GC-MS), and the selectivity for CH4 is stably less than 4.7%; It is worth emphasizing that no carbon deposition (TPO detection of carbon deposition amount < 0.1 wt%) or sintering phenomenon (SBET specific surface area attenuation < 3%) occurred during the 1000-hour continuous operation of the catalyst, demonstrating the durability required for industrial applications; (3) The high-entropy oxide molecular sieve interface coupling catalyst of the present invention innovatively combines high-entropy oxides and molecular sieves to achieve the dual functions of CO2 conversion and optimization of jet fuel components. High-entropy oxides effectively break the chemical inertness of CO2 molecules through their unique multi-metal synergistic effect. At the same time, their high-entropy structure not only inhibits the sintering phenomenon of the catalyst but also significantly reduces the formation of carbon deposition; On the other hand, molecular sieves achieve selective screening of C8~C 16 products through their precise pore confinement effect and promote isomerization reactions using their acidic sites, thereby directly optimizing jet fuel components; The innovation of this dual-functional catalytic system lies in that it simultaneously takes into account the activation of CO2, carbon chain growth, and precise regulation of product structure, significantly reducing energy consumption while greatly improving the selectivity of products and the stability of the catalyst. Specific embodiments

[0018] The present invention will be described in detail below in conjunction with specific embodiments.

[0019] The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst of the present invention is as follows: Step 1, prepare high-entropy metal oxides, the specific method is as follows: Step 1.1: Preparation of precursor solution: Zirconium nitrate, zinc nitrate, indium nitrate, magnesium nitrate and chromium nitrate are successively dissolved in a mixed solution composed of anhydrous ethanol and deionized water in a ratio of 1:1 according to a molar ratio of 0.35±m:0.30:0.20±m:0.10:0.05. Here, the value range of m is 0 to 0.1, and the total molar concentration of metals in the solution does not exceed 0.05 mol / L. Stir for 1 to 2 h to obtain the precursor solution; Step 1.2: Chelation reaction: Add citric acid to the precursor solution. The molar ratio of citric acid to the total metals is 1.5:1. Stir magnetically at a constant temperature of 60 °C for 2 h to form a metal-citric acid complex; Step 1.3: Formation of wet sol: Place the metal-citric acid complex in a water bath at 60 °C, slowly add ammonia water to adjust the pH to 4 - 5, and continue stirring for 2 - 4 h until the solution gradually becomes viscous to obtain the wet sol; Step 1.4: Drying and calcination: Transfer the wet sol to a vacuum drying oven for drying to obtain a dry gel. Grind the dry gel into fine powder, then place it in a muffle furnace for the first high-temperature calcination. After naturally cooling to room temperature, grind it again until it is uniform, and then perform the second high-temperature calcination to obtain the high-entropy metal oxide.

[0020] Specifically: Transfer the wet sol to a vacuum drying oven and dry it at 80 °C for 24 h to obtain a dry gel. After grinding it into fine powder, place the powder in a muffle furnace, heat it to 400 °C at a rate of 2 °C / min, hold for 2 h to remove organic substances and nitrate radicals. After naturally cooling to room temperature, grind it again until it is uniform, and then heat it to 600 °C at a rate of 5 °C / min and hold for 4 h to promote the formation of a single phase of high-entropy oxide, denoted as HEO, to obtain the high-entropy metal oxide.

[0021] Step 2: Preparation of H-MCM-22 molecular sieve. The specific method is as follows: Step 2.1: Preparation of synthetic sol: At room temperature, dissolve NaOH in deionized water, successively add sodium aluminate and silica sol, continuously stir until a uniform white colloid is formed, and then quantitatively inject hexamethyleneimine and continue stirring for 30 min to obtain the synthetic sol; Among them, the molar ratio of raw materials between silica sol, sodium aluminate, hexamethyleneimine, deionized water and NaOH is 1:0.03 - 0.01:0.5:40:0.3, that is, the silicon-aluminum molar ratio in the H-MCM-22 molecular sieve is 30 - 100.

[0022] Step 2.2, hydrothermal crystallization: Transfer the synthesized sol to a polytetrafluoroethylene-lined autoclave, perform dynamic crystallization at 150 °C for 72 h, with a stirring rate of 300 rpm. Immediately after the crystallization is completed, immerse the autoclave in an ice-water bath and quickly cool it to room temperature. Separate the obtained crystallized product, wash the crystallized product repeatedly with deionized water until the washing solution is neutral. After drying in a blast oven at 120 °C for 12 h, calcine it at 540 °C in static air for 4 h to obtain Na-MCM-22 powder; Step 2.3, protonation treatment: Take the above-mentioned Na-MCM-22 powder and mix it with ammonium nitrate solution, perform ion exchange under constant temperature stirring at 80 °C for 2 h, repeat the operation 2 - 3 times and then filter and separate. Wash the filter cake with deionized water until the pH is 6.9 - 7.1, dry it at 100 °C for 12 h and then calcine it in an air atmosphere at 520 °C for 4 h to finally obtain proton-type H-MCM-22 molecular sieve.

[0023] Among them, the solid-liquid ratio of the mass of Na-MCM-22 powder to the volume of ammonium nitrate solution is 1 g:15 mL, and the concentration of ammonium nitrate solution is 1 mol / L.

[0024] Step 3, weigh the high-entropy metal oxide and H-MCM-22 molecular sieve respectively, and then place the high-entropy metal oxide, H-MCM-22 molecular sieve and zirconia balls in a ball mill jar for ball milling to obtain a mixed powder; Among them, the mass ratio of the high-entropy metal oxide to the H-MCM-22 molecular sieve is 0.2 - 5:1, the mass ratio of the total mass of the high-entropy metal oxide and H-MCM-22 molecular sieve to the mass of zirconia balls is 1:10, the ball milling speed is 600 rpm / min, and the ball milling time is 5 min - 60 min.

[0025] Step 4, press the obtained mixed powder, crush and screen it to 60 - 80 mesh to prepare a high-entropy oxide molecular sieve interface coupling catalyst.

[0026] The high-entropy oxide molecular sieve interface coupling catalyst of the present invention is prepared by the above preparation method, and includes a high-entropy metal oxide and an H-MCM-22 molecular sieve, and the mass ratio of the high-entropy metal oxide to the H-MCM-22 molecular sieve is 0.2 - 5:1; Furthermore, the chemical formula of the high-entropy metal oxide is Zr 0.35±m Zn 0.30 In 0.20±m Mg 0.10 Cr 0.05 O x , where the value range of m is 0 - 0.1.

[0027] Application of the high-entropy oxide molecular sieve interface coupling catalyst prepared by the present invention. The high-entropy oxide molecular sieve interface coupling catalyst is used for hydrogenating CO2 to prepare aviation kerosene fraction. The reaction temperature is 300~400 °C, the reaction pressure is 3 MPa, and the mass space velocity is 1000~12000 mL·g cat -1 ·h -1 。

[0028] Furthermore, the high-entropy oxide molecular sieve interface coupling catalyst of the present invention needs to be activated before use. The activation conditions are: under the protection of inert gas, keep the temperature constant at 250 °C~400 °C for 2 h.

[0029] Example 1 The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst in this example is as follows: Step 1. Prepare Zr 0.45 Zn 0.30 In 0.10 Mg 0.10 Cr 0.05 O x : Dissolve 0.9660 g of Zr(NO3)4·5H2O, 0.2841 g of Zn(NO3)2·6H2O, 0.2094 g of In(NO3)3·5H2O, 0.1282 g of Mg(NO3)2·6H2O, and 0.1001 g of Cr(NO3)3·9H2O in turn in a mixed solvent of 50 mL of absolute ethanol and 50 mL of deionized water, stir for 2 h until the solution is completely transparent to obtain a precursor solution; Add 1.576 g of citric acid to the precursor solution. The molar ratio of citric acid to the total metal is 1.5:1. Stir magnetically at 60 °C for 2 h to form a metal-citric acid complex; then place it in a 60 °C water bath, slowly add ammonia water to adjust the pH to 4~5, and continue to stir for 2 h until the solution gradually becomes viscous to form a transparent or semi-transparent sol to obtain a wet sol; Transfer the wet sol into a vacuum drying oven, dry at 80 °C for 24 h to obtain a dry gel. After grinding into fine powder, place the powder in a muffle furnace, heat it to 400 °C at a rate of 2 °C / min, keep it warm for 2 h to remove organic substances and nitrate ions, naturally cool to room temperature and then grind it again until it is uniform, and then heat it to 600 °C at a rate of 5 °C / min and keep it warm for 4 h to promote the formation of a high-entropy oxide single phase, denoted as HEO-1.

[0030] Step 2. Prepare H-MCM-22 molecular sieve with a silica-alumina ratio of 30. The specific method is as follows: At room temperature, 3.00 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.68 g of NaAlO2 and 50.07 g of silica sol (concentration 30 wt%) were added successively. After continuous stirring until a homogeneous white colloid was formed, 12.65 g of hexamethyleneimine was added, and stirring was continued for 30 min to obtain a synthetic sol. The synthetic sol was transferred to a polytetrafluoroethylene-lined autoclave and subjected to dynamic crystallization at 150 °C for 72 h with a stirring rate of 300 rpm. After crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The obtained crystallized product was separated, and the crystallized product was repeatedly washed with deionized water until the washing liquid was neutral. After drying in a blast oven at 120 °C for 12 h, it was calcined at 540 °C in static air for 4 h to obtain Na-MCM-22 powder. The Na-MCM-22 powder was mixed with 1 mol / L ammonium nitrate solution in a ratio of m(H-MCM-22):V(NH4NO3)=1 g:15 mL, and ion exchange was carried out under constant temperature stirring at 80 °C for 2 h. After repeating the operation 3 times, filtration and separation were carried out. The filter cake was washed with deionized water until the pH was 6.9 - 7.1, dried at 100 °C for 12 h, and then calcined in an air atmosphere at 520 °C for 4 h to finally obtain proton-type H-MCM-22(30) molecular sieve.

[0031] Step 3: Weigh 0.17 g of high-entropy metal oxide HEO-1 and 0.85 g of H-MCM-22(30) molecular sieve according to a mass ratio of 1:5, and then place the high-entropy metal oxide, H-MCM-22(30) molecular sieve and zirconia balls in a ball mill jar for ball milling. The ball-to-material ratio (mass ratio) is 10:1, the ball milling speed is 600 rpm / min, and the ball milling time is 5 min to obtain a mixed powder. Step 4: The obtained mixed powder was pressed into tablets, crushed and sieved to 60 - 80 mesh to prepare a high-entropy oxide molecular sieve interface coupling catalyst.

[0032] The high-entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed-bed reactor for catalytic reaction evaluation of carbon dioxide hydrogenation to methanol. Activation conditions: in an argon atmosphere with an airspeed of 1000 mL·gcat -1 ·h -1 at a heating rate of 10 °C / min from room temperature to 320 °C for 2 h. After activation, the activation gas argon was switched to the feed gas and introduced into the fixed-bed reactor, and the reaction temperature was adjusted to 300 °C and the reaction pressure was 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography. Among them, H2, N2, and CO2 were detected by a TCD detector, and hydrocarbon and oxygenate products were detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0033] Example 2 The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst in this example is as follows: Step 1, prepare Zr 0.45 Zn 0.30 In 0.10 Mg 0.10 Cr 0.05 O x : Dissolve 0.9660 g of Zr(NO3)4·5H2O, 0.2841 g of Zn(NO3)2·6H2O, 0.2094 g of In(NO3)3·5H2O, 0.1282 g of Mg(NO3)2·6H2O, and 0.1001 g of Cr(NO3)3·9H2O in turn in a mixed solvent of 50 mL of absolute ethanol and 50 mL of deionized water, stir for 2 h until the solution is completely transparent to obtain a precursor solution; Add 1.576 g of citric acid to the precursor solution, and the molar ratio of citric acid to the total metal is 1.5:1. Stir magnetically at a constant temperature of 60 °C for 2 h to form a metal-citric acid complex; then place it in a water bath at 60 °C, slowly add ammonia water to adjust the pH to 4-5, and continue to stir for 4 h until the solution gradually becomes viscous to form a transparent or translucent sol to obtain a wet sol; Transfer the wet sol to a vacuum drying oven, dry it at 80 °C for 24 h to obtain a dry gel. After grinding it into fine powder, place the powder in a muffle furnace, heat it to 400 °C at a rate of 2 °C / min, keep it warm for 2 h to remove organic matter and nitrate, naturally cool it to room temperature and then grind it again until it is uniform, and then heat it to 600 °C at a rate of 5 °C / min, keep it warm for 4 h to promote the formation of a high-entropy oxide single phase, denoted as HEO-1.

[0034] Step 2, prepare H-MCM-22 molecular sieve with a silica-alumina ratio of 50. The specific method is as follows: At room temperature, dissolve 3.0 g of NaOH in 180 mL of deionized water. After complete dissolution, add 0.41 g of NaAlO2 and 50.07 g of silica sol (concentration 30 wt%) in turn. Continuously stir until a uniform white colloid is formed, then add 12.65 g of hexamethyleneimine, and continue to stir for 30 min to obtain a synthesis sol; Transfer the synthesis sol to a polytetrafluoroethylene-lined autoclave, crystallize it dynamically at 150 °C for 72 h, and the stirring rate is 300 rpm. Immediately after the crystallization is completed, immerse the autoclave in an ice-water bath and quickly cool it to room temperature. Separate the obtained crystallization product, wash the crystallization product repeatedly with deionized water until the washing liquid is neutral, dry it in a blast dryer at 120 °C for 12 h, and then calcine it at 540 °C in static air for 4 h to obtain Na-MCM-22 powder; The Na-MCM-22 powder was mixed with a 1 mol / L ammonium nitrate solution at a ratio of m(H-MCM-22):V(NH4NO3) = 1 g:15 mL, and ion exchange was carried out under constant stirring at 80 °C for 2 h. After repeating the operation twice, filtration was carried out for separation. The filter cake was washed with deionized water until the pH reached 6.9 - 7.1, dried at 100 °C for 12 h, and then calcined in an air atmosphere at 520 °C for 4 h to finally obtain the proton-type H-MCM-22(50) molecular sieve.

[0035] Step 3: Weigh 0.25 g of the high-entropy metal oxide HEO-1 and 0.75 g of the H-MCM-22(50) molecular sieve according to a mass ratio of 1:3 respectively. Then, the high-entropy metal oxide, the H-MCM-22(50) molecular sieve, and zirconia balls were placed together in a ball-milling jar for ball milling. The ball-to-material ratio (mass ratio) was 10:1, the ball-milling speed was 600 rpm / min, and the ball-milling time was 15 min to obtain a mixed powder. Step 4: The obtained mixed powder was pressed into tablets, crushed and sieved to 60 - 80 mesh to prepare a high-entropy oxide molecular sieve interface-coupled catalyst.

[0036] The high-entropy oxide molecular sieve interface-coupled catalyst prepared in this example was placed in a fixed-bed reactor for catalytic reaction evaluation of carbon dioxide hydrogenation to aviation kerosene. Activation conditions: Under an argon atmosphere with a space velocity of 3600 mL·gcat -1 ·h -1 at a heating rate of 10 °C / min from room temperature to 320 °C for 2 h. After activation, the activation gas argon was switched to the feed gas and introduced into the fixed-bed reactor, and the reaction temperature was adjusted to 320 °C and the reaction pressure was adjusted to 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography. Among them, H2, N2, and CO2 were detected by a TCD detector, and hydrocarbon and oxygenate products were detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0037] Example 3 The preparation method of the high-entropy oxide molecular sieve interface-coupled catalyst in this example is as follows: Step 1: Prepare Zr 0.35 Zn 0.30 In 0.20 Mg 0.10 Cr 0.05 O x: Dissolve 0.7513 g of Zr(NO3)4·5H2O, 0.2841 g of Zn(NO3)2·6H2O, 0.4188 g of In(NO3)3·5H2O, 0.1282 g of Mg(NO3)2·6H2O, and 0.1001 g of Cr(NO3)3·9H2O successively in a mixed solvent of 50 mL of absolute ethanol and 50 mL of deionized water, and stir for 2 h until the solution becomes completely transparent to obtain a precursor solution; Add 1.576 g of citric acid to the precursor solution, and the molar ratio of citric acid to total metals is 1.5:1. Magnetically stir at a constant temperature of 60 °C for 1 h to form a metal-citric acid complex; then place it in a water bath at 60 °C, slowly add ammonia water to adjust the pH to 4 - 5, and continue stirring for 3 h until the solution gradually becomes viscous to form a transparent or semi-transparent sol, obtaining a wet sol; Transfer the wet sol into a vacuum drying oven and dry at 80 °C for 24 h to obtain a dry gel. After grinding it into fine powder, place the powder in a muffle furnace, heat it to 400 °C at a rate of 2 °C / min, hold for 2 h to remove organic substances and nitrate radicals, naturally cool to room temperature and then grind it again until it is uniform, and then heat it to 600 °C at a rate of 5 °C / min and hold for 4 h to promote the formation of a single-phase high-entropy oxide, denoted as HEO-2.

[0038] Step 2: Prepare H-MCM-22 molecular sieve with a silica-alumina ratio of 50. The specific method is as follows: At room temperature, dissolve 3.0 g of NaOH in 180 mL of deionized water. After complete dissolution, add 0.41 g of NaAlO2 and 50.07 g of silica sol (concentration of 30 wt%) successively, and continuously stir until a uniform white colloid is formed. Then add 12.65 g of hexamethylenimine and continue stirring for 30 min to obtain a synthesis sol; Transfer the synthesis sol to a polytetrafluoroethylene-lined autoclave, perform dynamic crystallization at 150 °C for 72 h with a stirring rate of 300 rpm. Immediately immerse the autoclave in an ice-water bath to quickly cool it to room temperature after crystallization. Separate the obtained crystallized product, wash the crystallized product repeatedly with deionized water until the washing liquid is neutral, dry it at 120 °C for 12 h in a forced-air dryer, and then calcine it at 540 °C in static air for 4 h to obtain Na-MCM-22 powder; Mix the Na-MCM-22 powder with a 1 mol / L ammonium nitrate solution in a ratio of m(H-MCM-22):V(NH4NO3) = 1 g:15 mL, perform ion exchange under constant stirring at 80 °C for 2 h, repeat the operation 3 times and then filter and separate. Wash the filter cake with deionized water until the pH is 6.9 - 7.1, dry it at 100 °C for 12 h and then calcine it in an air atmosphere at 520 °C for 4 h to finally obtain proton-type H-MCM-22(50) molecular sieve.

[0039] Step 3: Weigh 0.5 g of high-entropy metal oxide HEO-2 and 0.5 g of H-MCM-22(50) molecular sieve according to the mass ratio of 1:1 respectively. Then place the high-entropy metal oxide, H-MCM-22(50) molecular sieve and zirconia balls into a ball mill jar for ball milling. The ball-to-material ratio (mass ratio) is 10:1, the ball milling speed is 600 rpm / min, and the ball milling time is 30 min to obtain a mixed powder. Step 4: Press the obtained mixed powder, crush and screen it to 60-80 mesh to prepare a high-entropy oxide molecular sieve interface coupling catalyst.

[0040] Place the high-entropy oxide molecular sieve interface coupling catalyst prepared in this example into a fixed-bed reactor for catalytic reaction evaluation of carbon dioxide hydrogenation to aviation kerosene. Activation conditions: under an argon atmosphere with a space velocity of 4000 mL gcat -1 h -1 at a heating rate of 10 °C / min from room temperature to 320 °C for 2 h. After activation, switch the activation gas argon to the feed gas and introduce it into the fixed-bed reactor, and adjust to a reaction temperature of 320 °C and a reaction pressure of 3 MPa for catalytic evaluation. The reaction products are directly analyzed and detected online by chromatography. Among them, H2, N2, and CO2 are detected by a TCD detector, and hydrocarbon and oxygenate products are detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0041] Example 4 The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst in this example is as follows: Step 1: Prepare Zr 0.35 Zn 0.30 In 0.20 Mg 0.10 Cr 0.05 O x : Dissolve 0.7513 g of Zr(NO3)4·5H2O, 0.2841 g of Zn(NO3)2·6H2O, 0.4188 g of In(NO3)3·5H2O, 0.1282 g of Mg(NO3)2·6H2O, and 0.1001 g of Cr(NO3)3·9H2O in turn in a mixed solvent of 50 mL of absolute ethanol and 50 mL of deionized water, and stir for 2 h until the solution is completely transparent to obtain a precursor solution; Add 1.576 g of citric acid to the precursor solution. The molar ratio of citric acid to the total metal is 1.5:1. Magnetically stir at 60 °C for 1 h to form a metal-citric acid complex; then place it in a 60 °C water bath, slowly add ammonia water to adjust the pH to 4-5, and continue to stir for 2 h until the solution gradually becomes viscous to form a transparent or translucent sol to obtain a wet sol. Transfer the wet sol into a vacuum drying oven and dry it at 80 °C for 24 h to obtain a xerogel. After grinding it into fine powder, place the powder in a muffle furnace, heat it to 400 °C at a rate of 2 °C / min, hold for 2 h to remove organic substances and nitrate radicals, naturally cool to room temperature, grind it again until uniform, and then heat it to 600 °C at a rate of 5 °C / min and hold for 4 h to promote the formation of a single-phase high-entropy oxide, denoted as HEO-2.

[0042] Step 2: Prepare H-MCM-22 molecular sieve with a silica-alumina ratio of 100. The specific method is as follows: Under room temperature conditions, dissolve 3.00 g of NaOH in 180 mL of deionized water. After complete dissolution, add 0.20 g of NaAlO2 and 50.07 g of silica sol (concentration 30 wt%) in sequence. Continuously stir until a uniform white colloid is formed, then add 12.65 g of hexamethyleneimine and continue stirring for 30 min to obtain a synthesis sol; Transfer the synthesis sol to a polytetrafluoroethylene-lined autoclave, perform dynamic crystallization at 150 °C for 72 h, with a stirring rate of 300 rpm. Immediately immerse the autoclave in an ice-water bath to rapidly cool to room temperature after crystallization. Separate the obtained crystallization product, repeatedly wash the crystallization product with deionized water until the washing liquid is neutral, dry it in a blast dryer at 120 °C for 12 h, and then calcine it at 540 °C in static air for 4 h to obtain Na-MCM-22 powder; Mix the Na-MCM-22 powder with 1 mol / L ammonium nitrate solution at a ratio of m(H-MCM-22):V(NH4NO3)=1 g:15 mL, perform ion exchange under constant temperature stirring at 80 °C for 3 h, repeat the operation 3 times, then filter and separate. Wash the filter cake with deionized water until the pH is 6.9 - 7.1, dry it at 100 °C for 12 h, and then calcine it in an air atmosphere at 520 °C for 4 h to finally obtain proton-type H-MCM-22(100) molecular sieve.

[0043] Step 3: Weigh 0.75 g of high-entropy metal oxide HEO-2 and 0.25 g of H-MCM-22(100) molecular sieve respectively according to a mass ratio of 3:1. Then place the high-entropy metal oxide, H-MCM-22(100) molecular sieve and zirconia balls together in a ball mill jar for ball milling. The ball-to-material ratio (mass ratio) is 10:1, the ball milling speed is 600 rpm / min, and the ball milling time is 60 min to obtain a mixed powder; Step 4: Press the obtained mixed powder, crush and screen it to 60 - 80 mesh to prepare a high-entropy oxide molecular sieve interface-coupled catalyst.

[0044] The high-entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed-bed reactor for catalytic reaction evaluation of hydrogenation of carbon dioxide to aviation kerosene. Activation conditions: under an argon atmosphere with a space velocity of 6000 mL·gcat -1 ·h -1 , the temperature was raised from room temperature to 320 °C at a heating rate of 10 °C / min for 2 h. After activation, the activation gas argon was switched to the feed gas and introduced into the fixed-bed reactor, and the reaction temperature was adjusted to 340 °C and the reaction pressure was 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography. Among them, H2, N2, and CO2 were detected by a TCD detector, and hydrocarbon and oxygenate products were detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0045] Example 5 The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst in this example is as follows: Step 1. Preparation of Zr 0.25 Zn 0.30 In 0.30 Mg 0.10 Cr 0.05 O x : 0.5367 g of Zr(NO3)4·5H2O, 0.2841 g of Zn(NO3)2·6H2O, 0.6283 g of In(NO3)3·5H2O, 0.1282 g of Mg(NO3)2·6H2O, and 0.1001 g of Cr(NO3)3·9H2O were successively dissolved in a mixed solvent of 50 mL of absolute ethanol and 50 mL of deionized water, and stirred for 2 h until the solution was completely transparent to obtain a precursor solution; 1.576 g of citric acid was added to the precursor solution, and the molar ratio of citric acid to the total metal was 1.5:1. The mixture was magnetically stirred at 60 °C for 2 h to form a metal-citric acid complex; then it was placed in a 60 °C water bath, and ammonia water was slowly added dropwise to adjust the pH to 4-5, and stirring was continued for 2 h until the solution gradually became viscous to form a transparent or semi-transparent sol to obtain a wet sol; The wet sol was transferred to a vacuum drying oven and dried at 80 °C for 24 h to obtain a dry gel. After grinding into a fine powder, the powder was placed in a muffle furnace and heated to 400 °C at a rate of 2 °C / min and held for 2 h to remove organic substances and nitrate radicals. After natural cooling to room temperature, it was ground again until uniform, and then heated to 600 °C at a rate of 5 °C / min and held for 4 h to promote the formation of a high-entropy oxide single phase, denoted as HEO-3.

[0046] Step 2. Preparation of H-MCM-22 molecular sieve with a silica-alumina ratio of 100. The specific method is as follows: At room temperature, 3.00 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.20 g of NaAlO2 and 50.07 g of silica sol (concentration 30 wt%) were added in sequence. After continuous stirring until a uniform white colloid was formed, 12.65 g of hexamethyleneimine was added, and stirring was continued for 30 min to obtain a synthetic sol; The synthetic sol was transferred to a polytetrafluoroethylene-lined autoclave and subjected to dynamic crystallization at 150 °C for 72 h with a stirring rate of 300 rpm. After crystallization, the autoclave was immediately immersed in an ice-water bath and rapidly cooled to room temperature. The obtained crystallized product was separated, and the crystallized product was repeatedly washed with deionized water until the washing liquid was neutral. After drying in a blast oven at 120 °C for 12 h, it was calcined at 540 °C in static air for 4 h to obtain Na-MCM-22 powder; The Na-MCM-22 powder was mixed with a 1 mol / L ammonium nitrate solution at a ratio of m(H-MCM-22):V(NH4NO3)=1 g:15 mL, and ion exchange was carried out with constant stirring at 80 °C for 2 h. After repeating the operation 3 times, filtration and separation were carried out. The filter cake was washed with deionized water until the pH was 6.9 - 7.1, dried at 100 °C for 12 h, and then calcined in an air atmosphere at 520 °C for 4 h to finally obtain proton-type H-MCM-22(100) molecular sieve.

[0047] Step 3: Weigh 0.85 g of high-entropy metal oxide HEO-3 and 0.17 g of H-MCM-22(100) molecular sieve according to a mass ratio of 5:1. Then, the high-entropy metal oxide, H-MCM-22(100) molecular sieve, and zirconia balls were placed together in a ball mill jar for ball milling. The ball-to-material ratio (mass ratio) was 10:1, the ball milling speed was 600 rpm / min, and the ball milling time was 15 min to obtain a mixed powder; Step 4: The obtained mixed powder was pressed and crushed and screened to 60 - 80 mesh to prepare a high-entropy oxide molecular sieve interface coupling catalyst.

[0048] The high-entropy oxide molecular sieve interface coupling catalyst prepared in this example was placed in a fixed-bed reactor for catalytic reaction evaluation of carbon dioxide hydrogenation to aviation kerosene. Activation conditions: at a space velocity of 10000 mL·gcat -1 ·h -1Under an argon atmosphere, the temperature was raised from room temperature to 320 °C at a heating rate of 10 °C / min, the activation time was 2 h. After the activation was completed, the activation gas argon was switched to the raw material gas and introduced into the fixed-bed reactor, and the reaction temperature was adjusted to 360 °C and the reaction pressure was 3 MPa for catalytic evaluation. The reaction products were directly analyzed and detected online by chromatography. Among them, H2, N2, and CO2 were detected by a TCD detector, and hydrocarbon and oxygen-containing compound products were detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0049] Example 6 The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst in this example is as follows: Step 1, preparation of Zr 0.25 Zn 0.30 In 0.30 Mg 0.10 Cr 0.05 O x : 0.5367 g of Zr(NO3)4·5H2O, 0.2841 g of Zn(NO3)2·6H2O, 0.6283 g of In(NO3)3·5H2O, 0.1282 g of Mg(NO3)2·6H2O, and 0.1001 g of Cr(NO3)3·9H2O were successively dissolved in a mixed solvent of 50 mL of absolute ethanol and 50 mL of deionized water, and stirred for 2 h until the solution was completely transparent to obtain a precursor solution; 1.576 g of citric acid was added to the precursor solution, and the molar ratio of citric acid to the total metal was 1.5:1. It was magnetically stirred at 60 °C for 2 h to form a metal-citric acid complex; then placed in a 60 °C water bath, and ammonia water was slowly added dropwise to adjust the pH to 4-5, and stirred for another 2 h until the solution gradually became viscous to form a transparent or semi-transparent sol, obtaining a wet sol; The wet sol was transferred to a vacuum drying oven and dried at 80 °C for 24 h to obtain a dry gel. After grinding it into fine powder, the powder was placed in a muffle furnace, heated to 400 °C at a rate of 2 °C / min, and held for 2 h to remove organic matter and nitrate. After naturally cooling to room temperature, it was ground again until uniform, and then heated to 600 °C at a rate of 5 °C / min and held for 4 h to promote the formation of a high-entropy oxide single phase, denoted as HEO-3.

[0050] Step 2, preparation of H-MCM-22 molecular sieve with a silica-alumina ratio of 50, the specific method is as follows: At room temperature, 3.00 g of NaOH was dissolved in 180 mL of deionized water. After complete dissolution, 0.41 g of NaAlO2 and 50.07 g of silica sol (concentration 30 wt%) were successively added. After continuous stirring to form a uniform white colloid, 12.65 g of hexamethyleneimine was added, and stirring was continued for 30 min to obtain a synthesis sol; Transfer the synthesized sol to a polytetrafluoroethylene-lined autoclave, perform dynamic crystallization at 150 °C for 72 h, with a stirring rate of 300 rpm. Immediately after the crystallization is completed, immerse the autoclave in an ice-water bath and quickly cool it to room temperature. Separate the obtained crystallized product, wash the crystallized product repeatedly with deionized water until the washing liquid is neutral, dry it in a blast dryer at 120 °C for 12 h, and then calcine it at 540 °C in static air for 4 h to obtain Na-MCM-22 powder; Mix the Na-MCM-22 powder with a 1 mol / L ammonium nitrate solution at a ratio of m(H-MCM-22): V(NH4NO3) = 1 g:15 mL, carry out ion exchange under constant temperature stirring at 80 °C for 2 h, repeat the operation 3 times, then filter and separate. Wash the filter cake with deionized water until the pH is 6.9 - 7.1, dry it at 100 °C for 12 h, and then calcine it in an air atmosphere at 520 °C for 4 h to finally obtain the proton-type H-MCM-22(50) molecular sieve.

[0051] Step 3: Weigh 0.75 g of the high-entropy metal oxide HEO-3 and 0.25 g of the H-MCM-22(50) molecular sieve according to a mass ratio of 3:1. Then place the high-entropy metal oxide, H-MCM-22(50) molecular sieve, and zirconia balls together in a ball mill jar for ball milling. The ball-to-material ratio (mass ratio) is 10:1, the ball milling speed is 600 rpm / min, and the ball milling time is 30 min to obtain a mixed powder; Step 4: Press the obtained mixed powder, crush and screen it to 60 - 80 mesh to prepare a high-entropy oxide molecular sieve interface-coupled catalyst.

[0052] Place the high-entropy oxide molecular sieve interface-coupled catalyst prepared in this example in a fixed-bed reactor for catalytic reaction evaluation of carbon dioxide hydrogenation to aviation kerosene. Activation conditions: In an argon atmosphere with an airspeed of 12000 mL·gcat -1 ·h -1 , heat from room temperature to 320 °C at a heating rate of 10 °C / min, with an activation time of 2 h. After the activation is completed, switch the activation gas argon to the feed gas and introduce it into the fixed-bed reactor, adjust to a reaction temperature of 340 °C and a reaction pressure of 3 MPa for catalytic evaluation. The reaction products are directly analyzed and detected online by chromatography. Among them, H2, N2, and CO2 are detected by a TCD detector, and hydrocarbon and oxygen-containing compound products are detected by an FID detector. The catalytic evaluation results are shown in Table 1.

[0053] Table 1 Catalytic evaluation results of the high-entropy oxide molecular sieve interface-coupled catalysts obtained in Examples 1 - 6

[0054] As can be seen from Table 1, the novel catalyst coupling the high-entropy oxide with the molecular sieve exhibits good catalytic performance in the carbon dioxide hydrogenation reaction, which is specifically manifested in the following aspects: (1) High CO2 conversion rate: In all examples, the conversion rate of CO2 ranges from 17.5% to 25.9%. Among them, Example 5 (25.9%) and Example 3 (25.3%) show the best performance, indicating that the catalyst has good activity; (2) Moderate CO selectivity: The CO selectivity is between 43.3% and 55.7%, indicating that the catalyst has a certain selectivity regulation ability, can inhibit side reactions to a certain extent, and improve the selectivity of target products; (3) The hydrocarbon product distribution tends to medium and long-chain hydrocarbons: It can be seen from the table that the selectivity of CH4 is relatively low (2.6% - 4.7%), indicating that there are fewer methane by-products and good carbon chain growth ability; The proportion of C2-C7 and C8-C 16 is relatively high, and among them, C8-C 16 (heavy hydrocarbons) is as high as 64.5% in Example 3, indicating that the catalyst has strong selectivity in the direction of aromatics and is conducive to the formation of high-value-added heavy aromatics.

[0055] In summary, the coupling catalyst of the high-entropy oxide and the molecular sieve (such as H-MCM-22) realizes a relatively high CO2 conversion rate and excellent hydrocarbon distribution by regulating the metal ratio, acidic sites and interface synergistic effects. Especially, it shows good potential in the synthesis of heavy alkanes or aromatics and has high application prospects.

[0056] In the present invention, by adjusting the ratio of metal elements in the high-entropy oxide, the electronic structure and surface basicity of the active sites are regulated; by adjusting the silicon-aluminum ratio of the H-MCM-22 molecular sieve, the strength and distribution of the acidic sites are regulated, thereby adjusting the product distribution; by adjusting the mass ratio of the high-entropy oxide to the molecular sieve, the degree of interface synergistic effect between the two phases is determined; by adjusting the ball milling time, the coupling degree is regulated, further affecting the close contact in the spatial structure and the electron transfer synergistic effect between the high-entropy oxide and the molecular sieve.

[0057] The results show that an appropriate interface coupling degree can promote the effective conversion of intermediate species between HEO and ZEO, significantly improve the C-C coupling efficiency, and thus is conducive to the formation of C8-C 12 aviation fuel components. The catalyst shows good activity, selectivity and stability. In a fixed-bed reactor (P = 3 MPa, T = 320 °C, GHSV = 4000 h -1 ), the catalyst achieves a single-pass CO2 conversion rate of 25.3 ± 0.8%, and C8-C 16The selectivity of linear alkanes reached 56.8 - 63.2% (quantitative analysis by GC-MS), and the selectivity of CH4 was stably lower than 4.7%. It is worth emphasizing that no carbon deposition (the carbon deposition amount detected by TPO < 0.1 wt%) or sintering phenomenon (the decay of SBET specific surface area < 3%) occurred during the 1000-hour continuous operation of the catalyst, demonstrating the durability necessary for industrial applications and having broad application prospects in the fields of CO2 resource utilization and green synthetic fuels.

Claims

1. Preparation method of high-entropy oxide molecular sieve interface coupling catalyst, characterized in that, The specific method is as follows: Step 1: Prepare high-entropy metal oxide; Step 2: Prepare H-MCM-22 molecular sieve; Step 3: Weigh the high-entropy metal oxide and H-MCM-22 molecular sieve respectively, and then place the high-entropy metal oxide, H-MCM-22 molecular sieve and zirconia balls together in a ball milling jar for ball milling to obtain a mixed powder; Step 4: Press the obtained mixed powder, crush and screen it to 60-80 mesh to prepare a high-entropy oxide molecular sieve interface coupling catalyst.

2. The preparation method of the high-entropy oxide molecular sieve interface-coupled catalyst according to claim 1, wherein The specific method of Step 1 is as follows: Step 1.1: Prepare a precursor solution: Dissolve zirconium nitrate, zinc nitrate, indium nitrate, magnesium nitrate and chromium nitrate in a mixed solution composed of anhydrous ethanol and deionized water in a molar ratio of 0.35±m:0.30:0.20±m:0.10:0.05 in sequence, where the value range of m is 0-0.1, and the total metal molar concentration in the solution does not exceed 0.05 mol / L. Stir for 1-2 h to obtain a precursor solution; Step 1.2: Chelation reaction: Add citric acid to the precursor solution. The molar ratio of citric acid to the total metal is 1.5:

1. Stir magnetically at a constant temperature of 60 °C for 2 h to form a metal-citric acid complex; Step 1.3: Form a wet sol: Place the metal-citric acid complex in a water bath at 60 °C, slowly add ammonia water to adjust the pH to 4-5, and continue to stir for 2-4 h until the solution gradually becomes viscous to obtain a wet sol; Step 1.4: Drying and calcination: Transfer the wet sol to a vacuum drying oven for drying to obtain a dry gel. Grind the dry gel into fine powder and then place it in a muffle furnace for the first high-temperature calcination. After natural cooling to room temperature, grind it again until it is uniform, and then perform the second high-temperature calcination to obtain a high-entropy metal oxide.

3. The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst according to claim 2, wherein, The specific method of Step 1.4 is: Transfer the wet sol to a vacuum drying oven and dry it at 80 °C for 24 h to obtain a dry gel. After grinding it into fine powder, place the powder in a muffle furnace and heat it to 400 °C at a rate of 2 °C / min, hold for 2 h, naturally cool to room temperature and then grind it again until it is uniform, and then heat it to 600 °C at a rate of 5 °C / min and hold for 4 h to obtain a high-entropy metal oxide.

4. The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst according to claim 1, wherein The specific method of Step 2 is as follows: Step 2.1: Prepare a synthesis sol: At room temperature, dissolve NaOH in deionized water, add sodium aluminate and silica sol in sequence, continue to stir until a uniform white colloid is formed, and then quantitatively inject hexamethyleneimine and continue to stir for 30 min to obtain a synthesis sol; Step 2.2: Hydrothermal crystallization: Transfer the synthesis sol to a polytetrafluoroethylene-lined high-pressure reaction kettle, perform dynamic crystallization at 150 °C for 72 h, the stirring rate is 300 rpm. Immediately immerse the reaction kettle in an ice-water bath after crystallization to quickly cool it to room temperature, separate the obtained crystallization product, wash the crystallization product repeatedly with deionized water until the washing liquid is neutral, dry it in a blast dryer at 120 °C for 12 h, and then calcine it at 540 °C in static air for 4 h to obtain Na-MCM-22 powder; Step 2.3, Protonation treatment: Mix the above-mentioned Na-MCM-22 powder with ammonium nitrate solution, carry out ion exchange for 2 h under constant temperature stirring at 80 °C, repeat the operation 2-3 times and then carry out suction filtration separation. Wash the filter cake with deionized water until the pH is 6.9-7.1, dry it at 100 °C for 12 h, and then calcine it in an air atmosphere at 520 °C for 4 h to finally obtain proton-type H-MCM-22 molecular sieve.

5. The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst according to claim 4, wherein In the step 2.1, the molar ratio of raw materials among silica sol, sodium aluminate, hexamethyleneimine, deionized water and NaOH is 1:0.03-0.01:0.5:40:0.

3.

6. The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst according to claim 4, wherein, In the step 2.3, the solid-liquid ratio of the mass of Na-MCM-22 powder to the volume of ammonium nitrate solution is 1 g:15 mL, and the concentration of the ammonium nitrate solution is 1 mol / L.

7. The preparation method of the high-entropy oxide molecular sieve interface coupling catalyst according to claim 1, wherein, In the step 3, the mass ratio of the high-entropy metal oxide to the H-MCM-22 molecular sieve is 0.2-5:1, the mass ratio of the total mass of the high-entropy metal oxide and the H-MCM-22 molecular sieve to the mass of zirconia balls is 1:10, the ball milling speed is 600 rpm / min, and the ball milling time is 5 min - 60 min.

8. High-entropy oxide molecular sieve interface-coupled catalyst, characterized in that, Prepared by using the preparation method according to any one of claims 1-7, including a high-entropy metal oxide and an H-MCM-22 molecular sieve, and the mass ratio of the high-entropy metal oxide to the H-MCM-22 molecular sieve is 0.2-5:1; The chemical formula of the high-entropy metal oxide is Zr 0.35±m Zn 0.30 In 0.20±m Mg 0.10 Cr 0.05 O x , where the value range of m is 0 to 0.

1.

9. The application of the high-entropy oxide molecular sieve interface coupling catalyst according to claim 8, wherein The high-entropy oxide molecular sieve interface-coupled catalyst is used for the hydrogenation of CO2 to prepare aviation kerosene fractions, with a reaction temperature of 300-400 °C, a reaction pressure of 3 MPa, and a mass space velocity of 1000-12000 mL·g cat -1 ·h -1 。 10. Use of the high-entropy oxide molecular sieve interface coupling catalyst according to claim 9, characterized in that, Before use, the high-entropy oxide molecular sieve interface coupling catalyst needs to be activated, and the activation conditions are: under the protection of an inert gas, keep it at a constant temperature in the temperature range of 250 °C - 400 °C for 2 h.

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