Catalyst with defect structure for hydrogenation and dehydrogenation reaction of organic liquid as well as preparation method and application of catalyst

Abstract

The invention belongs to the technical field of catalysis and hydrogen storage, and particularly relates to a catalyst for hydrogenation and dehydrogenation reaction of organic liquid with a defect structure as well as a preparation method and application of the catalyst. The catalyst is prepared from a catalyst carrier with a defect structure and transition metal salt through dipping, drying and thermal reduction, the catalyst carrier with the defect structure is prepared by the following steps: dipping an Al2O3 or TiO2 spherical carrier into an aqueous solution of an organic / inorganic salt containing N or F, stirring and drying to obtain a carrier; and then the dried carrier is placed in a plasma environment in a certain atmosphere to be treated, so that the catalyst carrier with the defect structure is formed. The prepared catalyst has the advantages of being excellent in reaction rate, good in catalytic activity, high in mechanical strength and the like when applied to the fixed bed hydrogenation / dehydrogenation reaction process of N-ethyl carbazole.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysis and hydrogen storage, and particularly relates to a catalyst for the hydrogenation and dehydrogenation reactions of organic liquids with a defective structure, and a preparation method and application thereof. Background Art

[0002] In recent years, hydrogen energy has received extensive attention as a clean and carbon-free energy source. However, the technologies for the safe storage and transportation of hydrogen still face many challenges and have become key issues that need to be urgently solved. The existing high-pressure gas storage methods perform poorly in terms of cost control and safety. In contrast, liquid organic hydrogen carriers (LOHCs) are considered to be a highly promising new hydrogen storage solution due to their high hydrogen storage capacity, good safety performance, ease of operation, and economy, and have made remarkable progress in recent years.

[0003] As a typical representative of LOHCs, N-ethylcarbazole has attracted great interest from researchers because it can remain liquid in the form of dodecahydro-N-ethylcarbazole (12H-NEC) at room temperature, has a hydrogen storage capacity of about 5.8% by mass, requires a relatively low hydrogen storage temperature (below 473 K), and has a relatively mild hydrogenation enthalpy (about 50.6 kJ / mol H2) (Chem. Sci., 2019, 10, 10459–10465). However, the hydrogenation and dehydrogenation reaction rates of N-heterocyclic compounds are usually slow, which limits their practical applications as liquid hydrogen storage media, especially in industrial fixed-bed reactors. In addition, when preparing shaped particle catalysts suitable for use in fixed beds, the binders that must be added may have a negative impact on the catalyst performance, further reducing the kinetic efficiency of the organic liquid hydrogenation and dehydrogenation catalysts. In view of this, especially in the emerging field of organic liquid hydrogen storage, research on highly efficient hydrogenation and dehydrogenation catalysts suitable for fixed-bed systems is particularly scarce. Therefore, it is crucial to develop new catalysts that can overcome the above obstacles and improve the catalytic efficiency.

[0004] Prior to this, we have successfully developed a series of noble and non-noble metal catalysts with high-performance hydrogenation and dehydrogenation capabilities. These include catalysts with low noble metal loading but high activity prepared using ultrasonic spray technology (such as patent application number: 202410612757.X), binary non-noble metal system catalysts synthesized by plasma ball milling method (such as patent application number: 202410196522.7), and non-noble metal catalysts produced by ultrasonic microwave hydrothermal method, etc. Although these catalysts have demonstrated excellent catalytic performance, due to mostly being in powder form, they are more suitable for batch reaction processes and are not ideal for fixed-bed reactors that require continuous operation. In previous work, spherical particle catalysts prepared by ultrasonic spray method showed excellent catalytic efficiency in batch experiments; however, challenges were encountered when attempting to apply them to fixed beds: due to the insufficient binding force between the transition metal and the carrier, the catalyst components were prone to falling off and clogging the pipeline.

[0005] In our early research, it was found that catalysts treated by plasma ball milling exhibited excellent hydrogenation and dehydrogenation catalytic performance. This is mainly attributed to the unique advantages of plasma ball milling technology: it introduces cold-field discharge plasma into the traditional mechanical ball milling process, enabling the combination of mechanical force and plasma effect, effectively promoting the refinement, alloying of powder particles, and activation of active sites. However, when preparing spherical particle catalysts suitable for fixed-bed reactors, directly applying ball milling technology becomes no longer feasible. Therefore, there is an urgent need to develop a new type of catalyst that can not only meet the requirements of large-scale fixed-bed operation but also effectively solve the challenges faced by existing technologies.

[0006] We found that: by pretreating the carrier and then placing it in a plasma environment, defect structures can be effectively introduced onto the carrier. However, if only simple plasma treatment is carried out, the defect structures generated have limited effect on improving the catalyst performance. In response to this, in this application, organic / inorganic salts containing F or N are creatively mixed into the catalyst precursor, and they decompose in the plasma environment, resulting in in-situ doping of impurity elements in the catalyst. These defects not only increase the complexity of the carrier surface but also provide a large number of active sites for subsequent transition metal loading, thereby significantly enhancing the interaction force between the transition metal and the carrier and ensuring the stability and high efficiency of the catalyst components. Summary of the Invention I. Technical problems to be solved by the present invention:

[0007] The purpose of the present invention is to provide a method for preparing and applying a catalyst for the hydrogenation and dehydrogenation reaction of organic liquids with defect structures, so as to solve the technical problems that existing powder catalysts cannot be applied to fixed beds, while commercial fixed-bed catalysts have low efficiency in the hydrogenation and dehydrogenation of organic liquids. II. Technical Solution of the Invention:

[0008] To achieve the above object, the technical solution adopted by the present invention is: a catalyst for the hydrogenation and dehydrogenation reaction of organic liquids with a defective structure, which is prepared by impregnating a catalyst carrier with a defective structure and a transition metal salt, followed by drying and thermal reduction; The catalyst carrier with a defective structure is prepared by the following steps: impregnating an Al2O3 or TiO2 spherical carrier in an aqueous solution of an organic / inorganic salt containing N or F, stirring and drying to obtain a carrier; then placing the dried carrier in a plasma environment under a certain atmosphere for treatment to form a catalyst carrier with a defective structure.

[0009] Preferably, the organic / inorganic salt containing N or F in the present invention is selected from one of urea, CN2H2, ammonium nitrate, cetyltrimethylammonium bromide or ammonium fluoride clock; the transition metal salt is selected from one or more of nickel nitrate, cobalt nitrate, palladium acetate, palladium chloride, palladium nitrate, palladium acetylacetonate, ruthenium acetate, dodecacarbonyltriruthenium or ruthenium acetylacetonate.

[0010] Preferably, the mass ratio of the organic / inorganic salt containing N or F to the spherical carrier in the present invention is (0.0002~0.005):1, and in the aqueous solution of the organic / inorganic salt containing N or F, the mass-volume ratio of the organic / inorganic salt containing N or F to water is (0.006~0.15) g:50 mL.

[0011] Preferably, the mass ratio of the catalyst carrier with a defective structure to the transition metal salt in the present invention is (0.143~29.63):30.

[0012] Preferably, the content of the transition metal in the catalyst of the present invention is 0.98~19.8%.

[0013] Preferably, the diameter of the Al2O3 or TiO2 spherical carrier in the present invention is 2~3 mm.

[0014] Another object of the present invention is to provide a method for preparing a catalyst for the hydrogenation and dehydrogenation reaction of organic liquids with a defective structure, which includes the following preparation steps: 1) Preparation of a catalyst carrier with a defective structure Impregnate an Al2O3 or TiO2 spherical carrier in an aqueous solution of an organic / inorganic salt containing N or F, stir and dry to obtain a carrier; then place the dried carrier in a plasma environment under a certain atmosphere for treatment to form a catalyst carrier with a defective structure; Preparation of the catalyst Dissolve the transition metal salt in water, then add the catalyst support prepared in step 1), stir and dry to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment under an inert atmosphere to obtain the catalyst.

[0015] Preferably, the atmosphere in the present invention is selected from one of N 2、 NH3 or H2; the discharge power of the plasma is 60 - 200 kW, the temperature is 300 - 400 °C, and the time is 1 - 6 h; the inert atmosphere is a H2 atmosphere at 600 °C or an Ar / H2 atmosphere at 300 - 450 °C.

[0016] Another object of the present invention is to provide an application of a catalyst for the hydrogenation and dehydrogenation of organic liquids with a defective structure, which is applied to the organic liquid hydrogenation reaction. The specific steps are as follows: Place the catalyst in a hydrogenation reactor of a fixed bed. After evacuating the fixed bed and maintaining the pressure, heat the reaction system to 150 °C, then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour.

[0017] Another object of the present invention is to provide an application of a catalyst for the hydrogenation and dehydrogenation of organic liquids with a defective structure, which is applied to the organic liquid dehydrogenation reaction. The specific steps are as follows: Place the catalyst in a hydrogen-evolving reactor of a fixed bed. After evacuating the fixed bed and maintaining the pressure, heat the reaction system to 200 °C. Subsequently, use a metering pump to inject 12H-N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 6 h. III. Effects and advantages of the present invention

[0018] 1) The defective state design of the organic liquid hydrogenation and dehydrogenation catalyst of the present invention can significantly enhance the interaction force between the transition metal and the support, ensure the structural stability of the catalyst during the hydrogenation and dehydrogenation process, and extend its service life. In addition, this defective state design also has a positive electronic regulation effect on the catalyst, greatly improving the hydrogenation and dehydrogenation performance of the catalyst in the fixed bed.

[0019] 2) The defective state organic liquid hydrogenation and dehydrogenation catalyst of the present invention is in the form of spherical particles and has high mechanical strength, which is suitable for fixed bed applications, laying a foundation for the industrial application of organic liquid hydrogenation and dehydrogenation catalysts.

[0020] 3) The transition metal on the defective state organic liquid hydrogenation and dehydrogenation catalyst support of the present invention has a relatively small particle size and a high dispersion degree on the spherical surface of 2 - 3 mm. Description of the drawings

[0021] Figure 1This is the macroscopic morphology diagram of the catalyst prepared in Example 1 of the present invention.

[0022] Figure 2 This is the TEM diagram of the catalyst prepared in Example 3 of the present invention. Detailed implementation manners

[0023] The present invention will be further described below in conjunction with examples and comparative examples.

[0024] A catalyst for the hydrogenation and dehydrogenation reaction of an organic liquid with a defective structure according to the present invention has a preparation technical principle as follows: Immerse a spherical carrier of Al2O3 or TiO2 in an organic / inorganic salt solution containing N or F, stir, pour out the solution, and dry the carrier. Subsequently, place the treated carrier in a plasma environment under a certain atmosphere for treatment to form a catalyst carrier with a specific defective structure. Then dissolve a transition metal salt in an appropriate solvent, and immerse the treated catalyst carrier with a specific defective structure in this solution. After the solvent is completely evaporated, a catalyst precursor can be obtained. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment in an H2 or Ar / H2 atmosphere to obtain an organic liquid hydrogenation / dehydrogenation catalyst with a defective structure. Example 1

[0025] First, dissolve 0.006 g of urea in 50 mL of water. After the urea is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the urea solution and stir and dry at 120°C. Subsequently, place the dried carrier in a nitrogen atmosphere plasma and treat it at a discharge power of 60 kW and a heating temperature of 300°C for 1 h to obtain an Al2O3-N1 carrier.

[0026] Dissolve 7.432 g of nickel nitrate in 50 mL of water, then add 30 g of the Al2O3-N1 carrier and stir and dry at 120°C to obtain a catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment in an H2 atmosphere at 600°C to obtain catalyst A1. The Ni content in catalyst A1 measured by ICP is about 5%.

[0027] Place 180 g of catalyst A1 in a fixed-bed hydrogenation reactor. After evacuating the fixed bed and maintaining the pressure for a period of time, raise the temperature of the reaction system to 150°C, and then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour. Take the product for chromatographic characterization after the reaction. The results show that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst A1 > 99%.

[0028] 180 g of catalyst A1 was placed in the hydrogen - releasing reactor of the fixed - bed. After evacuating the fixed - bed and maintaining pressure for a period of time, the reaction system was heated to 200 °C. Subsequently, a metering pump was used to inject 12H - N - ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time was 6 h. After the reaction ended, the product was taken for chromatographic characterization. The results showed that in the fixed - bed, the conversion rate of NEC from 12H - N - ethylcarbazole catalyzed by catalyst A1 was approximately 90.1%. Example 2

[0029] First, 0.03 g of CN2H2 was dissolved in 50 mL of water. After CN2H2 was completely dissolved, 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 were poured into the CN2H2 solution, and stirred and dried at 120 °C. Subsequently, the dried carrier was placed in an NH3 atmosphere plasma and treated for 3 h under the conditions of a discharge power of 130 kW and a heating temperature of 400 °C to obtain the Al2O3 - N2 carrier.

[0030] 29.63 g of cobalt nitrate was dissolved in 50 mL of water. Subsequently, 30 g of the Al2O3 - N2 carrier was added, and stirred and dried at 120 °C to obtain the catalyst precursor. Finally, the catalyst precursor was placed in a reduction furnace and reduced under an Ar / H2 atmosphere at 450 °C to obtain catalyst A2. The Co content in catalyst A2 measured by ICP was approximately 19.8%.

[0031] 180 g of catalyst A2 was placed in the hydrogenation reactor of the fixed - bed. After evacuating the fixed - bed and maintaining pressure for a period of time, the reaction system was heated to 150 °C, and then hydrogen gas at 8 MPa was cyclically charged into the reaction system. Subsequently, a metering pump was used to inject N - ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time was 1 h. After the reaction ended, the product was taken for chromatographic characterization. The results showed that in the fixed - bed, the conversion rate of N - ethylcarbazole catalyzed by catalyst A2 > 99%.

[0032] 180 g of catalyst A2 was placed in the hydrogen - releasing reactor of the fixed - bed. After evacuating the fixed - bed and maintaining pressure for a period of time, the reaction system was heated to 200 °C. Subsequently, a metering pump was used to inject 12H - N - ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time was 6 h. After the reaction ended, the product was taken for chromatographic characterization. The results showed that in the fixed - bed, the conversion rate of NEC from 12H - N - ethylcarbazole catalyzed by catalyst A2 was approximately 90.5%. Example 3

[0033] First, dissolve 0.15 g of ammonium nitrate in 50 mL of water. After the ammonium nitrate is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium nitrate solution, and stir and dry it at 120°C. Subsequently, place the dried carrier in a H2 atmosphere plasma, and treat it for 3 h under the conditions of a discharge power of 200 kW and a heating temperature of 400°C to obtain the Al2O3 - N3 carrier.

[0034] Dissolve 0.19 g of palladium acetate in 50 mL of ethanol, then add 30 g of the Al2O3 - N3 carrier, and stir and dry it at 120°C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform a reduction treatment in an Ar / H2 atmosphere at 300°C to obtain catalyst A3. The Pd content in catalyst A3 measured by ICP is about 0.3%.

[0035] Place 180 g of catalyst A3 in a fixed - bed hydrogenation reactor. After evacuating the fixed - bed and maintaining the pressure for a period of time, raise the temperature of the reaction system to 150°C, and then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N - ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour. After the reaction, take the product for chromatographic characterization. The results show that in the fixed - bed, the conversion rate of N - ethylcarbazole catalyzed by catalyst A3 is > 99%.

[0036] Place 180 g of catalyst A3 in a fixed - bed hydrogen - releasing reactor. After evacuating the fixed - bed and maintaining the pressure for a period of time, raise the temperature of the reaction system to 200°C, and then use a metering pump to inject 12H - N - ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 6 h. After the reaction, take the product for chromatographic characterization. The results show that in the fixed - bed, the conversion rate of NEC of 12H - N - ethylcarbazole catalyzed by catalyst A3 is about 91.2%. Example 4

[0037] First, dissolve 0.15 g of cetyltrimethylammonium bromide in 50 mL of water. After the cetyltrimethylammonium bromide is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the cetyltrimethylammonium bromide solution, and stir and dry it at 120°C. Subsequently, place the dried carrier in a H2 atmosphere plasma, and treat it for 6 h under the conditions of a discharge power of 120 kW and a heating temperature of 300°C to obtain the Al2O3 - N4 carrier.

[0038] Dissolve 0.143 g of palladium nitrate in 50 mL of tetrahydrofuran, then add 30 g of Al2O3-N4 support, and stir and dry at 120 °C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment in an Ar / H2 atmosphere at 300 °C to obtain catalyst A4. The Pd content in catalyst A4 measured by ICP is about 0.3%.

[0039] Place 180 g of catalyst A4 in a fixed-bed hydrogenation reactor. After evacuating the fixed bed and maintaining the pressure for a period of time, heat the reaction system to 150 °C, and then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour. After the reaction, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst A4 > 99%.

[0040] Place 180 g of catalyst A4 in a fixed-bed hydrogen evolution reactor. After evacuating the fixed bed and maintaining the pressure for a period of time, heat the reaction system to 200 °C, and then use a metering pump to inject 12H-N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 6 h. After the reaction, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of NEC of 12H-N-ethylcarbazole catalyzed by catalyst A4 is about 90.9%. Example 5

[0041] First, dissolve 0.06 g of ammonium fluoride in 50 mL of water. After the ammonium fluoride is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium fluoride solution, and stir and dry at 120 °C. Then place the dried support in a H2 atmosphere plasma and treat it for 2 h under the conditions of a discharge power of 120 kW and a heating temperature of 300 °C to obtain the Al2O3-H support.

[0042] Dissolve 0.19 g of palladium acetate in 50 mL of acetone, then add 30 g of Al2O3-H support, and stir and dry at 120 °C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment in an Ar / H2 atmosphere at 300 °C to obtain catalyst A5. The Pd content in catalyst A5 measured by ICP is about 0.3%.

[0043] 180 g of catalyst A5 was placed in the hydrogenation reactor of the fixed bed. After the fixed bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 150 °C, and then 8 MPa of hydrogen was circulated and charged into the reaction system. Subsequently, N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 1 hour. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst A5 was >99%.

[0044] 180 g of catalyst A5 was placed in the hydrogen evolution reactor of the fixed bed. After the fixed bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 200 °C. Subsequently, 12H-N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 6 h. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of NEC of 12H-N-ethylcarbazole catalyzed by catalyst A5 was approximately 91.2%. Example 6

[0045] First, 0.06 g of ammonium fluoride was dissolved in 50 mL of water. After the ammonium fluoride was completely dissolved, 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 were poured into the ammonium fluoride solution, and stirring and drying were carried out at 120 °C. Subsequently, the dried carrier was placed in a H2 atmosphere plasma and treated for 2 h under the conditions of a discharge power of 120 kW and a heating temperature of 300 °C to obtain the Al2O3-H carrier.

[0046] 0.258 g of palladium acetylacetonate was dissolved in 50 mL of water. Subsequently, 30 g of the Al2O3-H carrier was added, and stirring and drying were carried out at 120 °C to obtain the catalyst precursor. Finally, the catalyst precursor was placed in a reduction furnace and reduced under an Ar / H2 atmosphere at 300 °C to obtain catalyst A6. The Pd content in catalyst A6 measured by ICP was approximately 0.3%.

[0047] 180 g of catalyst A6 was placed in the hydrogenation reactor of the fixed bed. After the fixed bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 150 °C, and then 8 MPa of hydrogen was circulated and charged into the reaction system. Subsequently, N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 1 hour. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst A6 was >99%.

[0048] Place 180 g of catalyst A6 in the hydrogen evolution reactor of the fixed bed. After evacuating the fixed bed and maintaining the pressure for a period of time, heat the reaction system to 200 °C. Subsequently, use a metering pump to inject 12H-N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min. The total reaction time is 6 h. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of NEC of 12H-N-ethylcarbazole catalyzed by catalyst A6 is about 91.7%. Example 7

[0049] First, dissolve 0.06 g of ammonium fluoride in 50 mL of water. After the ammonium fluoride is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium fluoride solution, and stir and dry it at 120 °C. Subsequently, place the dried carrier in a H2 atmosphere plasma and treat it for 2 h under the conditions of a discharge power of 120 kW and a heating temperature of 300 °C to obtain the Al2O3-H carrier.

[0050] Dissolve 0.825 g of ruthenium acetate in 50 mL of water, then add 30 g of the Al2O3-H carrier, and stir and dry it at 120 °C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment in an Ar / H2 atmosphere at 300 °C to obtain catalyst A7. The Ru content in catalyst A7 measured by ICP is about 0.98%.

[0051] Place 180 g of catalyst A7 in the hydrogenation reactor of the fixed bed. After evacuating the fixed bed and maintaining the pressure for a period of time, heat the reaction system to 150 °C, and then circulate and charge 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min. The total reaction time is 1 h. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst A7 is > 99%. Example 8

[0052] First, dissolve 0.06 g of ammonium fluoride in 50 mL of water. After the ammonium fluoride is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium fluoride solution, and stir and dry it at 120 °C. Subsequently, place the dried carrier in a H2 atmosphere plasma and treat it for 2 h under the conditions of a discharge power of 120 kW and a heating temperature of 300 °C to obtain the Al2O3-H carrier.

[0053] Dissolve 1.898 g of dodecacarbonyltriruthenium in 50 mL of water. Subsequently, add 30 g of Al2O3-H support, and stir and dry it at 120 °C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment under an Ar / H2 atmosphere at 300 °C to obtain catalyst A8. The Ru content in catalyst A8 measured by ICP is approximately 0.99%.

[0054] Place 180 g of catalyst A8 in a fixed-bed hydrogenation reactor. After evacuating the fixed bed and maintaining the pressure for a period of time, heat the reaction system to 150 °C, and then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst A8 > 99%. Example 9

[0055] First, dissolve 0.06 g of ammonium fluoride in 50 mL of water. After the ammonium fluoride is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium fluoride solution, and stir and dry it at 120 °C. Subsequently, place the dried support in a H2 atmosphere plasma and treat it for 2 h under the conditions of a discharge power of 120 kW and a heating temperature of 300 °C to obtain the Al2O3-H support.

[0056] Dissolve 1.182 g of ruthenium acetylacetonate in 50 mL of water. Subsequently, add 30 g of Al2O3-H support, and stir and dry it at 120 °C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment under an Ar / H2 atmosphere at 300 °C to obtain catalyst A8. The Ru content in catalyst A8 measured by ICP is approximately 1%.

[0057] Place 180 g of catalyst A9 in a fixed-bed hydrogenation reactor. After evacuating the fixed bed and maintaining the pressure for a period of time, heat the reaction system to 150 °C, and then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst A9 > 99%. Example 10

[0058] First, dissolve 0.006 g of urea in 50 mL of water. After the urea is completely dissolved, pour 30 g of Al2O3 spherical particles with a density of about 0.7 g / cm 3TiO₂ spherical particles with a diameter of 2 - 3 mm were taken and stirred and dried at 120 °C. Subsequently, the dried carrier was placed in an N₂ atmosphere plasma and treated for 1 h under the conditions of a discharge power of 60 kW and a heating temperature of 300 °C to obtain the TiO₂-N1 carrier.

[0059] 7.432 g of nickel nitrate was dissolved in 50 mL of water, and then 30 g of the TiO₂-N1 carrier was added and stirred and dried at 120 °C to obtain the catalyst precursor. Finally, the catalyst precursor was placed in a reduction furnace and reduced under a H₂ atmosphere at 600 °C to obtain catalyst A1. The Ni content in catalyst A1 measured by ICP was about 5%.

[0060] 180 g of catalyst A1 was placed in a fixed-bed hydrogenation reactor. After the fixed bed was evacuated and pressurized for a period of time, the reaction system was heated to 150 °C, and then hydrogen gas at 8 MPa was circulated and charged into the reaction system. Subsequently, N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 1 hour. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst A1 > 99%.

[0061] 180 g of catalyst A1 was placed in a fixed-bed hydrogen evolution reactor. After the fixed bed was evacuated and pressurized for a period of time, the reaction system was heated to 200 °C, and then 12H-N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 6 h. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of NEC of 12H-N-ethylcarbazole catalyzed by catalyst A1 was about 89.9%. Comparative Example 1

[0062] Ordinary Al₂O₃ without defect treatment was used as the catalyst carrier.

[0063] 0.19 g of palladium acetate was dissolved in 50 mL of ethanol, and then 30 g of spherical Al₂O₃ carrier with a diameter of 2 - 3 mm was added and stirred and dried at 120 °C to obtain the catalyst precursor. Finally, the catalyst precursor was placed in a reduction furnace and reduced under an Ar / H₂ atmosphere at 300 °C to obtain catalyst B1. The Pd content in catalyst B1 measured by ICP was about 0.3%.

[0064] 180 g of catalyst B1 was placed in the hydrogenation reactor of the fixed bed. After the fixed bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 150 °C, and then hydrogen gas at 8 MPa was cyclically charged into the reaction system. Subsequently, N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 1 hour. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst B1 was approximately 79.8%.

[0065] 180 g of catalyst B1 was placed in the hydrogen-release reactor of the fixed bed. After the fixed bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 200 °C, and then 12H-N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 6 h. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of NEC of 12H-N-ethylcarbazole catalyzed by catalyst B1 was approximately 57.6%.

[0066] The poor hydrogenation and dehydrogenation performance of catalyst B1 was due to the loss of the defect design of the catalyst, and the activity of the catalyst was significantly reduced. Comparative Example 2

[0067] The temperature of plasma treatment was too low.

[0068] First, 0.15 g of ammonium nitrate was dissolved in 50 mL of water. After the ammonium nitrate was completely dissolved, 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 were poured into the ammonium nitrate solution, and stirring and drying were carried out at 120 °C. Subsequently, the dried carrier was placed in a H2 atmosphere plasma and treated for 3 h under the conditions of a discharge power of 200 kW and a heating temperature of 200 °C to obtain the Al2O3-N5 carrier.

[0069] 0.19 g of palladium acetate was dissolved in 50 mL of ethanol, and then 30 g of the Al2O3-N5 carrier was added. Stirring and drying were carried out at 120 °C to obtain the catalyst precursor. Finally, the catalyst precursor was placed in a reduction furnace and reduced under the atmosphere of Ar / H2 at 300 °C to obtain catalyst B2, and the Pd content in catalyst B2 measured by ICP was approximately 0.3%.

[0070] Place 180 g of catalyst B2 in the hydrogenation reactor of the fixed bed. After evacuating the fixed bed to a vacuum and maintaining the pressure for a period of time, heat the reaction system to 150 °C, and then circulate and charge 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst B2 is approximately 78.4%.

[0071] Place 180 g of catalyst B2 in the hydrogen-release reactor of the fixed bed. After evacuating the fixed bed to a vacuum and maintaining the pressure for a period of time, heat the reaction system to 200 °C, and then use a metering pump to inject 12H-N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 6 h. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of NEC of 12H-N-ethylcarbazole catalyzed by catalyst B2 is approximately 55.3%.

[0072] Catalyst B2 exhibits poor hydrogenation-dehydrogenation performance. The main reason is that the relatively low plasma treatment temperature is difficult to generate defects on the surface of Al2O3. In addition, at 200 °C, ammonium nitrate on the surface of Al2O3 is difficult to decompose, and only drying can be achieved, and it firmly adheres to the surface of Al2O3. Ammonium nitrate in this state has limited effect on improving the hydrogenation-dehydrogenation performance of catalyst B2. Comparative Example 3

[0073] The plasma treatment temperature is too high.

[0074] First, dissolve 0.15 g of ammonium nitrate in 50 mL of water. After the ammonium nitrate is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium nitrate solution, and stir and dry at 120 °C. Subsequently, place the dried carrier in a H2 atmosphere plasma and treat it for 3 h under the conditions of a discharge power of 200 kW and a heating temperature of 700 °C to obtain the Al2O3-N6 carrier. Unfortunately, due to the too high plasma treatment temperature, the Al2O3-N6 carrier shows signs of pulverization when taken out. For a catalyst to be applied in a fixed bed reactor, a carrier with signs of pulverization has lost its use value. Comparative Example 4

[0075] The plasma discharge power is too low.

[0076] First, dissolve 0.15 g of ammonium nitrate in 50 mL of water. After the ammonium nitrate is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3Al2O3 spherical particles with a diameter of 2 - 3 mm were taken and stirred and dried at 120 °C. Subsequently, the dried carrier was placed in an H2 atmosphere plasma and treated for 3 h under the conditions of a discharge power of 50 kW and a heating temperature of 400 °C to obtain the Al2O3-N7 carrier. 0.19 g of palladium acetate was dissolved in 50 mL of ethanol, and then 30 g of the Al2O3-N7 carrier was added and stirred and dried at 120 °C to obtain the catalyst precursor. Finally, the catalyst precursor was placed in a reduction furnace and reduced under an Ar / H2 atmosphere at 300 °C to obtain catalyst B4. The Pd content in catalyst B4 measured by ICP was approximately 0.3%.

[0077] 180 g of catalyst B4 was placed in a fixed-bed hydrogenation reactor. After the fixed bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 150 °C, and then hydrogen was circulated and charged into the reaction system at 8 MPa. Subsequently, N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 1 hour. After the reaction ended, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst B4 was approximately 78.7%.

[0078] 180 g of catalyst B4 was placed in a fixed-bed hydrogen evolution reactor. After the fixed bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 200 °C, and then 12H-N-ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 6 h. After the reaction ended, the product was taken for chromatographic characterization. The results showed that in the fixed bed, the conversion rate of NEC of 12H-N-ethylcarbazole catalyzed by catalyst B4 was approximately 55.8%.

[0079] The poor hydrogenation and dehydrogenation performance of catalyst B4 was consistent with that of catalyst B2. Comparative Example 5

[0080] The plasma discharge power was too high.

[0081] First, 0.15 g of ammonium nitrate was dissolved in 50 mL of water. After the ammonium nitrate was completely dissolved, 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 were added and stirred and dried at 120 °C. Subsequently, the dried carrier was placed in an H2 atmosphere plasma and treated for 3 h under the conditions of a discharge power of 220 kW and a heating temperature of 400 °C to obtain the Al2O3-N8 carrier. Unfortunately, due to the too high plasma discharge power, the strength of the Al2O3-N8 carrier became poor when taken out and could no longer meet the hardness requirements of the catalyst carrier for fixed beds. Comparative Example 6

[0082] The plasma treatment time is too short.

[0083] First, dissolve 0.15 g of ammonium nitrate in 50 mL of water. After the ammonium nitrate is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium nitrate solution, and stir and dry it at 120 °C. Subsequently, place the dried carrier in a H2 atmosphere plasma, and treat it for 0.5 h under the conditions of a discharge power of 200 kW and a heating temperature of 400 °C to obtain the Al2O3-N9 carrier.

[0084] Dissolve 0.19 g of palladium acetate in 50 mL of ethanol, then add 30 g of the Al2O3-N9 carrier, and stir and dry it at 120 °C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform a reduction treatment in an Ar / H2 atmosphere at 300 °C to obtain catalyst B6. The Pd content in catalyst B6 measured by ICP is about 0.3%.

[0085] Place 180 g of catalyst B6 in a fixed-bed hydrogenation reactor. After evacuating the fixed bed and maintaining the pressure for a period of time, raise the reaction system temperature to 150 °C, and then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by catalyst B6 is about 81.3%.

[0086] Place 180 g of catalyst B6 in a fixed-bed hydrogen evolution reactor. After evacuating the fixed bed and maintaining the pressure for a period of time, raise the reaction system temperature to 200 °C, and then use a metering pump to inject 12H-N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 6 h. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of NEC of 12H-N-ethylcarbazole catalyzed by catalyst B6 is about 70.5%.

[0087] Although the hydrogenation and dehydrogenation performance of catalyst B6 is improved compared with catalysts B1, B2, and B4, there is still a certain gap compared with catalysts A1 to A9. The reason for this gap is that although some defects are indeed generated in the Al2O3-N9 used in catalyst B6 during the plasma treatment process, due to the short treatment time, the density or depth of these defects is insufficient, so the improvement effect on the final hydrogenation and dehydrogenation performance of catalyst B6 is very limited. Comparative Example 7

[0088] The plasma treatment time is too long.

[0089] First, dissolve 0.15 g of ammonium nitrate in 50 mL of water. After the ammonium nitrate is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium nitrate solution, and stir and dry it at 120°C. Subsequently, place the dried carrier in a H2 atmosphere plasma, and treat it for 7 h under the conditions of a discharge power of 200 kW and a heating temperature of 400°C to obtain the Al2O3-N10 carrier. The Al2O3-N10 carrier also showed a deterioration in mechanical strength and could not be used for the next loading process. Comparative Example 8

[0090] No plasma treatment is performed.

[0091] First, dissolve 0.15 g of ammonium nitrate in 50 mL of water. After the ammonium nitrate is completely dissolved, pour 30 g of Al2O3 spherical particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 into the ammonium nitrate solution, and stir and dry it at 120°C. Subsequently, place the dried carrier in a H2 atmosphere and treat it at 400°C for 3 h to obtain the Al2O3-N11 carrier.

[0092] Dissolve 0.19 g of palladium acetate in 50 mL of ethanol, then add 30 g of the Al2O3-N11 carrier, and stir and dry it at 120°C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform a reduction treatment in an Ar / H2 atmosphere at 300°C to obtain Catalyst B8. The Pd content in Catalyst B8 measured by ICP is about 0.3%.

[0093] Place 180 g of Catalyst B8 in a fixed-bed hydrogenation reactor. After evacuating the fixed bed and maintaining the pressure for a period of time, heat the reaction system to 150°C, and then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour. After the reaction is completed, take the product for chromatographic characterization. The results show that in the fixed bed, the conversion rate of N-ethylcarbazole catalyzed by Catalyst B8 is about 70.2%.

[0094] 180 g of catalyst B8 was placed in the hydrogen - releasing reactor of the fixed - bed. After the fixed - bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 200 °C. Subsequently, 12H - N - ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 6 h. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed - bed, the conversion rate of NEC from 12H - N - ethylcarbazole catalyzed by catalyst B8 was approximately 60.6%. Its poor dehydrogenation performance was consistent with that of catalyst B1. Comparative Example 9

[0095] Do not add organic / inorganic salts containing F or N.

[0096] Take 30 g of Al2O3 spherical particles with a density of about 0.7 g / cm 3 and a diameter of 2 - 3 mm and place them under H2 atmosphere. Treat them at 400 °C for 3 h to obtain the Al2O3 - H1 support. Dissolve 0.19 g of palladium acetate in 50 mL of ethanol, then add 30 g of the Al2O3 - H1 support, and stir and dry it at 120 °C to obtain the catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform reduction treatment under an Ar / H2 atmosphere at 300 °C to obtain catalyst B9. The Pd content in catalyst B9 measured by ICP was approximately 0.3%.

[0097] 180 g of catalyst B9 was placed in the hydrogenation reactor of the fixed - bed. After the fixed - bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 150 °C, and then 8 MPa of hydrogen was cyclically charged into the reaction system. Subsequently, N - ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 1 h. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed - bed, the conversion rate of N - ethylcarbazole catalyzed by catalyst B9 was approximately 85.6%.

[0098] 180 g of catalyst B9 was placed in the hydrogen - releasing reactor of the fixed - bed. After the fixed - bed was evacuated and kept under pressure for a period of time, the reaction system was heated to 200 °C. Subsequently, 12H - N - ethylcarbazole was injected into the reactor at a flow rate of 1.5 mL / min using a metering pump, and the total reaction time was 6 h. After the reaction, the product was taken for chromatographic characterization. The results showed that in the fixed - bed, the conversion rate of NEC from 12H - N - ethylcarbazole catalyzed by catalyst B9 was approximately 83.9%.

[0099] Although catalyst B9 also exhibited more excellent catalytic performance than catalysts B1, B2, B4, and B6 without adding organic / inorganic salts containing F or N, it still could not compare with catalysts A1 - A9. This is because the Al2O3 treated with organic / inorganic salts containing F or N will produce a synergistic effect when treated in a plasma atmosphere of H2, N2, or NH3, promoting the formation of defects, making catalysts A1 - A9 exhibit better catalytic performance than catalyst B9. Comparative Example 10

[0100] Do not add organic / inorganic salts containing F or N, but treat the catalyst with plasma.

[0101] Take 30 g of spherical Al2O3 particles with a diameter of 2 - 3 mm and a density of about 0.7 g / cm 3 and place them in a H2 atmosphere plasma. Treat them for 2 h under the conditions of a discharge power of 120 kW and a heating temperature of 300 °C to obtain an Al2O3 - H2 support. Dissolve 0.19 g of palladium acetate in 50 mL of ethanol, then add 30 g of the Al2O3 - H2 support, and stir and dry it at 120 °C to obtain a catalyst precursor. Finally, place the catalyst precursor in a reduction furnace and perform a reduction treatment in an Ar / H2 atmosphere at 300 °C to obtain catalyst B10. ICP measurement shows that the Pd content in catalyst B9 is about 0.3%.

[0102] Place 180 g of catalyst B10 in a fixed - bed hydrogenation reactor. After evacuating the fixed - bed and maintaining the pressure for a period of time, raise the reaction system temperature to 150 °C, and then circulate and fill 8 MPa of hydrogen into the reaction system. Subsequently, use a metering pump to inject N - ethylcarbazole into the reactor at a flow rate of 1.5 mL / min. The total reaction time is 1 hour. After the reaction, take the product for chromatographic characterization. The results show that in the fixed - bed, the conversion rate of N - ethylcarbazole catalyzed by catalyst B9 is about 90.2%.

[0103] Place 180 g of catalyst B10 in a fixed - bed dehydrogenation reactor. After evacuating the fixed - bed and maintaining the pressure for a period of time, raise the reaction system temperature to 200 °C, and then use a metering pump to inject 12H - N - ethylcarbazole into the reactor at a flow rate of 1.5 mL / min. The total reaction time is 6 h. After the reaction, take the product for chromatographic characterization. The results show that in the fixed - bed, the conversion rate of NEC of 12H - N - ethylcarbazole catalyzed by catalyst B9 is about 86.7%.

[0104] After plasma treatment, the performance of the B10 catalyst is indeed improved compared to the B9 catalyst. However, this improvement is extremely limited and there is still a large gap compared with Examples 1-9. The reason is that H in the plasma can only act on the catalyst surface and play a certain role in improving the surface activity, but this improvement is extremely limited. In contrast, in Examples 1-9, in the plasma environment, the organic / inorganic salts containing F or N decompose, and defects are generated in situ on the catalyst. These defects not only exist on the catalyst surface but also are evenly distributed in the bulk phase, greatly improving the performance of the catalyst.

Claims

1. A catalyst for the hydrogenation and dehydrogenation reactions of organic liquids with a defective structure, characterized in that: The catalyst is prepared by impregnating a catalyst support with a defective structure with a transition metal salt, followed by drying and thermal reduction; The catalyst support with a defective structure is prepared by the following steps: impregnating an Al2O3 or TiO2 spherical support in an aqueous solution of an organic / inorganic salt containing N or F, stirring and drying to obtain a support; then placing the dried support in a plasma environment under a certain atmosphere for treatment to form a catalyst support with a defective structure.

2. The catalyst for the hydrogenation and dehydrogenation reaction of an organic liquid having a defective structure according to claim 1, wherein: The organic / inorganic salt containing N or F is selected from one of urea, CN2H2, ammonium nitrate, cetyltrimethylammonium bromide or ammonium fluorozirconate; the transition metal salt is selected from one or more of nickel nitrate, cobalt nitrate, palladium acetate, palladium chloride, palladium nitrate, palladium acetylacetonate, ruthenium acetate, dodecacarbonyltriruthenium or ruthenium acetylacetonate.

3. The catalyst for the hydrogenation and dehydrogenation reaction of an organic liquid with a defective structure according to claim 1, characterized in that: The mass ratio of the organic / inorganic salt containing N or F to the spherical support is (0.0002~0.005):1, and for the aqueous solution of the organic / inorganic salt containing N or F, the mass-volume ratio of the organic / inorganic salt containing N or F to water is (0.006~0.15) g:50 mL.

4. The catalyst for the hydrogenation and dehydrogenation reaction of an organic liquid having a defective structure according to claim 1, wherein: The mass ratio of the catalyst support with a defective structure to the transition metal salt is (0.143~29.63):

30.

5. The catalyst for the hydrogenation and dehydrogenation reaction of an organic liquid having a defective structure according to claim 1, characterized in that: The content of the transition metal in the catalyst is 0.98~19.8%.

6. The catalyst for the hydrogenation and dehydrogenation reaction of an organic liquid having a defective structure according to claim 1, characterized in that: The diameter of the Al2O3 or TiO2 spherical support is 2~3 mm.

7. A method for preparing a catalyst for the hydrogenation and dehydrogenation reaction of an organic liquid having a defective structure as described in any one of claims 1 to 6, characterized in that: The preparation steps include the following: 1) Preparation of the catalyst support with a defective structure Impregnate an Al2O3 or TiO2 spherical support in an aqueous solution of an organic / inorganic salt containing N or F, stir and dry to obtain a support; then place the dried support in a plasma environment under a certain atmosphere for treatment to form a catalyst support with a defective structure; Preparation of the catalyst Dissolve the transition metal salt in water, then add the catalyst support prepared in step 1), stir and dry to obtain a catalyst precursor, and finally place the catalyst precursor in a reduction furnace for reduction treatment under an inert atmosphere to obtain the catalyst.

8. The catalyst for the hydrogenation and dehydrogenation reaction of an organic liquid with a defective structure according to claim 7, characterized in that: The atmosphere is selected from one of N 2、 NH3 or H2; the discharge power of the plasma is 60-200 kW, the temperature is 300-400 °C, and the time is 1-6 h; the inert atmosphere is an H2 atmosphere at 600 °C or an Ar / H2 atmosphere at 300-450 °C.

9. Use of a catalyst according to any one of claims 1 to 6, characterized in that: Applied to the hydrogenation reaction of organic liquids, the specific steps are as follows: place the catalyst in a hydrogenation reactor of a fixed bed, evacuate and pressurize the fixed bed, heat the reaction system to 150 °C, then circulate and fill 8 MPa of hydrogen into the reaction system, and then use a metering pump to inject N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 1 hour.

10. Use of a catalyst according to any one of claims 1 to 6, characterized in that: Applied to the dehydrogenation reaction of organic liquids, the specific steps are as follows: place the catalyst in a hydrogen-releasing reactor of a fixed bed, evacuate and pressurize the fixed bed, heat the reaction system to 200 °C, and then use a metering pump to inject 12H-N-ethylcarbazole into the reactor at a flow rate of 1.5 mL / min, and the total reaction time is 6 h.

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