CN-119857487-B - Anti-carbon-deposition high-stability organic liquid hydrogen storage material hydrogenation catalyst and preparation method and application thereof

Abstract

The invention provides a preparation method of a hydrogenation catalyst of an anti-carbon high-stability organic liquid hydrogen storage material, which is characterized in that active metal Ni and a rare earth metal oxide auxiliary agent are loaded on a carrier by a coprecipitation method to obtain the hydrogenation catalyst. The hydrogenation catalyst prepared by the invention enhances the adsorption capacity of the catalyst and the dispersibility of active metal components by utilizing the high specific surface area carrier, effectively improves the catalytic performance, and simultaneously optimizes the reaction path by introducing the rare earth metal oxide modifier, effectively inhibits the formation of carbon deposit by forming oxygen vacancies and improving the migration rate of lattice oxygen, and remarkably enhances the anti-carbon deposit performance and the cycle stability of the catalyst. The preparation method of the hydrogenation catalyst provided by the invention has the advantages of mild process and simple required equipment, and can be used for large-scale production. In addition, the invention has higher activity, stability and cycle performance without noble metal, has good economic benefit and has wide popularization and application prospect.

Inventors

• ZHANG ZIYE
• LI JIAQI
• ZHAO YINHENG
• YANG MING
• DONG YUAN
• XU YIFAN
• YANG YIWEI

Assignees

• 中国地质大学（武汉）

Dates

Publication Date

20260508

Application Date

20250123

Claims (9)

1. 1. The application of the anti-carbon high-stability organic liquid hydrogen storage material hydrogenation catalyst in the hydrogenation reaction of N-propylcarbazole is characterized in that the reaction conditions of the application are as follows: Taking 0.2g of hydrogenation catalyst and 2.0g N-propylcarbazole, taking normal hexane as a solvent, wherein the reaction pressure is 7MPa, and the reaction temperature is 150 ℃, wherein the hydrogenation catalyst realizes the complete hydrogenation of N-propylcarbazole within 25 minutes under the reaction condition, and can still realize the complete hydrogenation of N-propylcarbazole within 120 minutes after continuously carrying out 10 times of cyclic hydrogenation tests under the condition; the preparation method of the hydrogenation catalyst comprises the following steps: S1, dissolving nickel salt, carrier metal salt and rare earth metal salt in water to obtain a first solution, respectively dissolving a precipitator and a complexing agent in water to obtain a second solution and a third solution; S2, under the water bath condition, slowly dripping the first solution and the second solution into the third solution at the same time, continuously stirring to form a precipitate, separating the precipitate, and washing to obtain a first product; s3, dispersing the first product in absolute ethyl alcohol, and removing the solvent to obtain a second product; S4, grinding the second product to obtain powder, and calcining the powder to obtain a catalyst precursor; s5, placing the catalyst precursor in a reducing atmosphere, carrying out reduction treatment, cooling, and carrying out passivation treatment to obtain a hydrogenation catalyst; the rare earth metal salt is Ce (NO 3 ) 4 ; the carrier metal salt is Al (NO 3 ) 3 ·9H 2 O; the loading of metallic nickel in the hydrogenation catalyst is 30wt.%, and the doping amount of rare earth metal oxide is 5wt.%.
2. 2. The use according to claim 1, wherein in step S1 the nickel salt comprises a combination of one or more of Ni (NO 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 O、NiSO 4 ·6H 2 O).
3. 3. The method according to claim 1, wherein in step S1, the precipitating agent comprises one or more of Na 2 CO 3 、K 2 CO 3 、NaHCO 3 、Na 2 SO 3 , and the complexing agent comprises one or more of polyethylene glycol, polydextrose, and polyfructose.
4. 4. The method according to claim 1, wherein in step S2, the water bath is at a temperature of 70-100 ℃, and in step S3, the solvent is removed by azeotropic evaporation of water and absolute ethanol under an oil bath at a temperature of 90-150 ℃.
5. 5. The use according to claim 1, wherein in step S4 the calcination treatment is carried out at a temperature of 400-800 ℃ for a time of 1-3 hours.
6. 6. The method according to claim 1, wherein in step S5, the reducing atmosphere is a mixed gas of inert gas and hydrogen gas, and the flow rate of the mixed gas is 50-90 mL/min.
7. 7. The use according to claim 1, wherein in step S5 the reduction treatment is carried out at a temperature of 550-750 ℃ for a time of 3-6 hours.
8. 8. The method according to claim 1, wherein the passivation treatment in step S5 comprises introducing a mixture of inert gas and oxygen into the cooled product for a period of 0.5-2 hours.
9. 9. The use according to claim 1, wherein the specific surface area of the hydrogenation catalyst for the anti-carbon high-stability organic liquid hydrogen storage material is 100-400m 2 /g, the pore volume is 0.2-1.4cm 3 /g, and the pore diameter is 5-25nm.

Description

Anti-carbon-deposition high-stability organic liquid hydrogen storage material hydrogenation catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of hydrogenation catalysts, and particularly relates to an anti-carbon-deposition high-stability organic liquid hydrogen storage material hydrogenation catalyst and a preparation method thereof, and application of the catalyst in organic liquid catalytic dehydrogenation. Background The organic liquid hydrogen storage technology is one of the hydrogen storage technologies which most hopefully solves the problem of hydrogen storage and transportation. The development of efficient, stable and economical hydrogenation catalysts for organic liquid hydrogen storage materials is a key to the development of this technology. Commercial catalysts currently used in the market for hydrogenation of organic liquid hydrogen storage materials usually use noble metals such as Ru, rh and the like as active components, and the high cost limits the wide application of the catalysts in industrial application. In contrast, the non-noble metal Ni has rich reserves and lower cost, and is a good choice for replacing noble metals such as Ru, rh and the like. Patent CN112675865A discloses a supported nickel-based catalyst which shows good activity for catalytic hydrogenation of NPCZ at 150 ℃ and 7MPa hydrogen pressure. However, after 5 cycles, the activity was decreased. Patent CN 117599806A discloses a nano-domain Ni Ru metal catalyst, in which the catalytic activity is reduced during the fifth cycle of the catalyst, and the completion time of hydrogenation reaction is prolonged from 60 minutes to 180 minutes. The above phenomena show that the modified nickel-based catalyst has catalytic activity comparable to that of the noble metal catalyst, but the improvement of stability still faces a great challenge. Carbon deposition is one of key factors causing the deactivation of nickel-based catalysts, and in the hydrogenation process of organic liquid hydrogen storage materials, side reactions of molecular C-C bond breakage often occur, so that carbonaceous deposits are formed on the surface of the catalyst, a large number of active sites of the catalyst are covered, and the service life of the catalyst is obviously reduced. C γ, which consists of graphitic carbon and encapsulated carbon, is the most stable and difficult form of carbon species to remove. In view of this, researchers have been actively researching and developing strategies for removing carbon from the surface C γ of nickel-based catalysts. In summary, although nickel-based catalysts exhibit activity comparable to noble metal catalysts in the hydrogenation of organic liquid hydrogen storage materials, the improvement in stability is critical to achieving widespread adoption in industrial applications. Therefore, the modification method of the nickel-based catalyst is brand-new, so that the elimination rate of the catalyst on carbon deposition is improved, the occurrence of side reactions of C-C bond breakage is inhibited, the method has important significance for effectively improving the stability and the service life of the catalyst, and the method is a technical problem to be solved by researchers. Disclosure of Invention The invention aims at providing a preparation method of a hydrogenation catalyst of an anti-carbon high-stability organic liquid hydrogen storage material, which has the advantages of mild preparation process and simple required equipment. The second purpose of the invention is to provide a hydrogenation catalyst of the organic liquid hydrogen storage material with high stability and anti-carbon deposition. The invention further aims to provide an application of the hydrogenation catalyst of the organic liquid hydrogen storage material with high stability against carbon deposition, which can show good activity and stability for hydrogenation of the organic liquid hydrogen storage material under the condition of not using noble metals. The invention provides a preparation method of a hydrogenation catalyst of an organic liquid hydrogen storage material with high stability and carbon deposit resistance, which comprises the following steps: S1, dissolving nickel salt, carrier metal salt and rare earth metal salt in water to obtain a first solution, respectively dissolving a precipitator and a complexing agent in water to obtain a second solution and a third solution; S2, under the water bath condition, slowly dripping the first solution and the second solution into the third solution at the same time, continuously stirring to form a precipitate, separating the precipitate, and washing to obtain a first product; s3, dispersing the first product in absolute ethyl alcohol, and removing the solvent to obtain a second product; S4, grinding the second product to obtain powder, and calcining the powder to obtain a catalyst precursor; and S5, placing the ca