Aluminum-nickel alloy hydrogenation catalyst and preparation method thereof

Abstract

The invention relates to the technical field of alloy catalyst preparation, in particular to an aluminum-nickel alloy hydrogenation catalyst and a preparation method thereof.The preparation method of the catalyst comprises the steps that 1, a NiCo inner core is prepared; step 2, preparing a precursor; step 3, preparing core-shell nanoparticles; step 4, preparing NiAl alloy skeleton loaded core-shell nanoparticles; and step 5, adding the NiAl alloy skeleton loaded core-shell nanoparticles into an etching solution, etching, carrying out oxygen plasma treatment, introducing water vapor mixed gas containing O2, and reacting to obtain the aluminum-nickel alloy hydrogenation catalyst. The catalyst is extremely high in hydrogenation activity and high in reaction efficiency; the catalyst has the advantages of high stability, long-term high-efficiency catalytic capability under complex working conditions, greatly prolonged service life, large specific surface area, abundant active sites and obviously reduced mass transfer resistance. In addition, the catalyst is stable in mechanical performance, not prone to breakage or abrasion and suitable for a high-strength industrial production environment, and long-term stable operation of the catalyst is guaranteed.

Description

Technical Field

[0001] The present application relates to the technical field of alloy catalyst preparation, and more specifically, to an aluminum-nickel alloy hydrogenation catalyst and a preparation method thereof. Background Art

[0002] Aluminum-nickel alloy hydrogenation catalysts are widely used in oil hydrogenation, organic synthesis, and fine chemical industries due to their high activity and low cost. Traditional aluminum-nickel alloy catalysts are prepared by melting aluminum and nickel in proportion to form an alloy, then selectively dissolving aluminum with alkaline solution to form a porous nickel skeleton structure. The aluminum is removed by alkaline solution reaction to generate an active nickel phase with a high specific surface area, thereby enhancing the catalytic activity. However, the traditional preparation method has the following problems: (1) Insufficient mechanical strength. Due to the reduction of the aluminum content supporting the alloy skeleton, the structural stability and thermal stability of the catalyst will be reduced. The catalyst is easily broken and deactivated, making it difficult to meet the catalyst strength requirements of a continuously operating reaction system with stirring; (2) Poor resistance to poisoning. Impurities such as sulfide and carbon monoxide are easily adsorbed on the nickel active sites, resulting in catalyst deactivation and the need for frequent regeneration; (3) Traditional smelting preparation methods have high energy consumption, and the high melting point of nickel will lead to poor alloy uniformity and reduced activity. In response to the above problems, this application proposes an improved aluminum-nickel alloy catalyst and its preparation method, which balances the catalytic activity and mechanical strength of the aluminum-nickel alloy catalyst, improves the catalyst's anti-poisoning ability, and meets the requirements for catalyst stability and long life in industrial catalysis processes. Summary of the Invention

[0003] In order to solve the technical problems mentioned in the background technology, the present application provides a method for preparing an aluminum-nickel alloy hydrogenation catalyst.

[0004] This application provides a method for preparing an aluminum-nickel alloy hydrogenation catalyst, which adopts the following technical solution: A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Dispersing Ni and Co sources in ethylene glycol solution as the inner phase; dispersing NaBH4 and sodium citrate in deionized water as the outer phase; adjusting the flow rates of the inner and outer phases through a microfluidic chip, performing a shear reaction at a temperature of 70-85°C, centrifuging, washing, and drying to obtain a NiCo core; Step 2: Disperse the NiCo core in dilute hydrochloric acid, ultrasonically treat, add 5-8wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, react for 1-2 hours, centrifuge, wash, and dry to obtain an activated NiCo core; disperse the Al source and rare earth element in deionized water, stir for 10-20 minutes, add polyvinyl pyrrolidone, continue stirring, add ammonia water dropwise to adjust the pH to 8-9, and age for 12-20 hours to obtain a coprecipitation sol; add the activated NiCo core to the coprecipitation sol, ultrasonically disperse, evaporate water to form a wet gel, wash, and dry to obtain a precursor; Step 3: heating the precursor to 400-450°C and holding the temperature for 2-3 hours to form an amorphous Al2O3 shell layer, then heating the precursor to 700-900°C and holding the temperature for 3-4 hours to form a NiAl2O4 spinel transition layer, and then cooling the precursor to room temperature to obtain core-shell nanoparticles. Step 4: mixing the core-shell nanoparticles, aluminum powder, and nickel powder in a mass ratio of 1-3:1:1-1.2, controlling the ball-to-material ratio to be 12-15:1, and performing mechanical alloying ball milling by intermittent ball milling under argon protection to obtain NiAl alloy skeleton-loaded core-shell nanoparticles; Step 5: Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60-80°C for 15-20 minutes, wash with deionized water until neutral, treat with oxygen plasma, and then introduce a water vapor mixture containing 1-5% O2 by volume at 150-200°C for 1-3 hours to obtain an aluminum-nickel alloy hydrogenation catalyst.

[0005] Preferably, the atomic ratio of Ni to Co in the Ni source and the Co source in step 1 is 3-5:1.

[0006] Preferably, in step 1, the flow rate of the inner phase is 0.4-0.6 mL / min, and the flow rate ratio of the inner phase to the outer phase is 1:3.

[0007] Preferably, the shear rate of the shear reaction in step 1 is 1.2×10 4 s -1 -1.5×10 4 s -1 .

[0008] Preferably, the particle size of the NiCo core in step 1 is 12-20 nm.

[0009] Preferably, the Ni source in step 1 is one of Ni (NO3)3, Ni (CH3COO)2, and Ni-EDTA.

[0010] Preferably, the Co source in step 1 is one of Co (NO3)2 and Co (CH3COO)2.

[0011] Preferably, the doping amount of the rare earth element in step 2 is 1.5-3at%.

[0012] Preferably, the rare earth element in step 2 is one or more of La, Ce, Nd, Sm, and Gd.

[0013] Preferably, the mass ratio of the activated NiCo core to the coprecipitated sol in step 2 is 1:3-5.

[0014] Preferably, the heating rate in step 3 is 5-8°C.

[0015] Preferably, the intermittent ball milling conditions in step 4 are: at a rotation speed of 500-600 rpm, each ball milling time is 20-30 min, and the intermittent time is 5-10 min.

[0016] Preferably, the thickness of the amorphous Al2O3 shell in step 4 is 5-10 nm.

[0017] Preferably, the thickness of the NiAl2O4 spinel transition layer in step 4 is 2-4 nm.

[0018] Preferably, the etching solution in step 5 is: 1-2 mM benzotriazole and 1-3 mM sodium silicate are added to 0.5-2 M NaOH solution; the oxygen plasma treatment power is 100-120 W, and the treatment time is 10-15 minutes.

[0019] An aluminum-nickel alloy hydrogenation catalyst is obtained by the method.

[0020] In summary, this application has the following beneficial effects: The aluminum-nickel alloy hydrogenation catalyst prepared in this application consists of a NiAl alloy skeleton and core-shell nanoparticles loaded in the NiAl alloy skeleton. The NiCo core is precisely synthesized by microfluidics. By doping a certain proportion of Co, the electronic state density of Ni is adjusted to improve the H2 dissociation ability; the amorphous Al2O3 shell inhibits the sintering of active metals, and the spinel transition layer strengthens the interfacial bonding force and reduces the loss of active components. By doping a certain proportion of rare earth element La into the amorphous Al2O3 shell, La-O-Al bonds are formed, the amorphous structure is stabilized, oxygen vacancy defects are introduced, and the H2O / H -The adsorption activation and gradient calcination optimize the shell structure. Amorphous Al2O3 is first formed at a lower temperature to avoid core agglomeration caused by direct high temperatures. Recrystallization to a spinel transition layer occurs at higher temperatures. This two-step process significantly densifies the shell and further improves its stability. During the etching process, benzotriazole and sodium silicate are added to the etchant. Benzotriazole selectively adsorbs on the Ni surface, forming a dense organic protective film through coordination, preventing dissolution by strong bases during etching and affecting catalytic performance. Sodium silicate dissociates into silicate ions under alkaline conditions, which adsorb onto the Al surface to form a silicate passivation film, slowing the Al etching rate and preventing skeleton collapse. The combined effect of these two processes inhibits localized overetching, promotes more uniform Al dissolution, and forms a porous structure with a narrow pore size distribution and good connectivity. The amorphous SiO2 formed by the hydrolysis of sodium silicate fills the pore surfaces, enhancing the mechanical strength of the skeleton and preventing pore collapse after etching. The benzotriazole and silicate remaining after etching can be removed by plasma to avoid impurity residues. At the same time, plasma treatment can further activate the surface, and water vapor oxidation can synergistically improve the thermal stability and sintering resistance of the catalyst. DETAILED DESCRIPTION

[0021] The present application is further described in detail below with reference to the embodiments.

[0022] 3-Glycidyloxypropyltrimethoxysilane used in the examples and comparative examples of the present application was purchased from Wuhan Kanos Technology Co., Ltd.; polyvinyl pyrrolidone was purchased from Huzhou Shenhua Polymer Materials Co., Ltd.; La (NO3)3 was purchased from Zibo Ruibokang Rare Earth Materials Co., Ltd.; benzotriazole (model: WP) was purchased from Wuhan Xinchuyang Chemical Co., Ltd.; and sodium silicate was purchased from Jinan Zesheng Chemical Co., Ltd.

[0023] Examples 1-3 provide a method for preparing an aluminum-nickel alloy hydrogenation catalyst.

[0024] Example 1 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 3:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:3. Step 3: The precursor was heated to 400°C at a heating rate of 5°C and kept at this temperature for 2 hours to form an amorphous Al2O3 shell layer with a thickness of 5 nm. The temperature was further raised to 700°C and kept at this temperature for 3 hours to form a NiAl2O4 spinel transition layer with a thickness of 2 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate added to 0.5 M NaOH solution.

[0025] Example 2 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 4:1 to prepare an internal phase solution with a solid-liquid ratio of 2:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2.5:1.5:100. The flow rate of the internal phase was adjusted to 0.5 mL / min and the flow rate of the external phase was adjusted to 1.5 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 78°C and a shear rate of 1.4×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 15 nm; Step 2: Disperse the NiCo core in 4% dilute hydrochloric acid, ultrasonically treat for 15 min, with an ultrasonic power of 110 W and an ultrasonic frequency of 50 kHz, add 6 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir and react for 1.5 h, with a stirring speed of 300 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; (NO3)3 and La(NO3)3 were dispersed in deionized water, the total metal ion concentration was controlled to be 0.2M, the La doping amount was 2.5at%, the stirring speed was 250rpm, and the stirring was carried out for 15 minutes. Polyvinyl pyrrolidone (10% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 22% was added dropwise to adjust the pH to 8.5, and the mixture was aged for 16 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol, and ultrasonic dispersion was carried out for 15 minutes. The ultrasonic power was 110W and the ultrasonic frequency was 50KHz. The water was evaporated under stirring at 75°C to form a wet gel. The mixture was centrifuged, washed, and dried at 90°C for 30 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:4. Step 3: The precursor was heated to 420°C at a heating rate of 7°C and kept at this temperature for 2.5 hours to form an amorphous Al2O3 shell layer with a thickness of 8 nm. The temperature was further raised to 800°C and kept at this temperature for 3.5 hours to form a NiAl2O4 spinel transition layer with a thickness of 3 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 2:1:1.1, with a ball-to-material ratio of 13:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 550 rpm, with each ball milling lasting 25 minutes and an interval of 8 minutes, to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5: Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at 70°C for 18 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 110W for 12 minutes, and introduce a water vapor mixture containing 3% O2 by volume at 180°C. React for 2 hours to obtain an aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1.5mM benzotriazole and 2mM sodium silicate added to 1M NaOH solution.

[0026] Example 3 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 5:1 to prepare an internal phase solution with a solid-liquid ratio of 3:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 3:2:100. The flow rate of the internal phase was adjusted to 0.6 mL / min and the flow rate of the external phase was adjusted to 1.8 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 85°C and a shear rate of 1.5×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 20 nm; Step 2: Disperse the NiCo core in 6% dilute hydrochloric acid, ultrasonically treat for 20 min, with an ultrasonic power of 120 W and an ultrasonic frequency of 60 kHz, add 8 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 2 h, stir at 400 rpm, centrifuge, wash, and dry to obtain the activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.3M, the doping amount of La was 3at%, the stirring speed was 300 rpm, and the stirring was carried out for 20 minutes. Polyvinyl pyrrolidone (15% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 25% was added dropwise to adjust the pH to 9. The mixture was aged for 20 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol, and ultrasonic dispersion was carried out for 20 minutes. The ultrasonic power was 120 W and the ultrasonic frequency was 60 kHz. The water was evaporated under stirring at 80°C to form a wet gel. The mixture was centrifuged, washed, and dried at 100°C for 36 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:5. Step 3: The precursor was heated to 450°C at a heating rate of 8°C and kept at this temperature for 3 hours to form an amorphous Al2O3 shell layer with a thickness of 10 nm. The temperature was further raised to 900°C and kept at this temperature for 4 hours to form a NiAl2O4 spinel transition layer with a thickness of 4 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 3:1:1.2, with a ball-to-material ratio of 15:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 600 rpm, with each ball milling lasting 30 minutes and a rest period of 10 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at 80°C for 20 min, wash with deionized water until neutral, treat with oxygen plasma at a power of 120 W for 15 min, and introduce a water vapor mixture containing 5% O2 by volume at 200°C for 3 h to obtain an aluminum-nickel alloy hydrogenation catalyst. The etching solution is: 2 mM benzotriazole and 3 mM sodium silicate added to 2M NaOH solution.

[0027] Comparative Example 1 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 3:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1at%, the stirring speed was 200 rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100 W and the ultrasonic frequency was 40 kHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:3. Step 3: The precursor was heated to 400°C at a heating rate of 5°C and kept at this temperature for 2 hours to form an amorphous Al2O3 shell layer with a thickness of 5 nm. The temperature was further raised to 700°C and kept at this temperature for 3 hours to form a NiAl2O4 spinel transition layer with a thickness of 2 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate added to 0.5 M NaOH solution.

[0028] Comparative Example 2 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 2:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:3. Step 3: The precursor was heated to 400°C at a heating rate of 5°C and kept at this temperature for 2 hours to form an amorphous Al2O3 shell layer with a thickness of 5 nm. The temperature was further raised to 700°C and kept at this temperature for 3 hours to form a NiAl2O4 spinel transition layer with a thickness of 2 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate added to 0.5 M NaOH solution.

[0029] Comparative Example 3 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 6:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:3. Step 3: The precursor was heated to 400°C at a heating rate of 5°C and kept at this temperature for 2 hours to form an amorphous Al2O3 shell layer with a thickness of 5 nm. The temperature was further raised to 700°C and kept at this temperature for 3 hours to form a NiAl2O4 spinel transition layer with a thickness of 2 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate added to 0.5 M NaOH solution.

[0030] Comparative Example 4 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 3:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:2. Step 3: The precursor was heated to 400°C at a heating rate of 5°C and kept at this temperature for 2 hours to form an amorphous Al2O3 shell layer with a thickness of 5 nm. The temperature was further raised to 700°C and kept at this temperature for 3 hours to form a NiAl2O4 spinel transition layer with a thickness of 2 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate added to 0.5 M NaOH solution.

[0031] Comparative Example 5 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 3:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10min. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12h to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10min. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70℃ to form a wet gel. The mixture was centrifuged, washed, and dried at 80℃ for 24h to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:6. Step 3: The precursor was heated to 400°C at a heating rate of 5°C and kept at this temperature for 2 hours to form an amorphous Al2O3 shell layer with a thickness of 5 nm. The temperature was further raised to 700°C and kept at this temperature for 3 hours to form a NiAl2O4 spinel transition layer with a thickness of 2 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate added to 0.5 M NaOH solution.

[0032] Comparative Example 6 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 3:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:3. Step 3: heating the precursor to 400°C at a heating rate of 5°C, keeping the temperature for 5 hours, and naturally cooling to room temperature to obtain core-shell nanoparticles; Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate added to 0.5 M NaOH solution.

[0033] Comparative Example 7 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 3:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:3. Step 3: heating the precursor to 700°C at a heating rate of 5°C, keeping the temperature for 5 hours, and naturally cooling to room temperature to obtain core-shell nanoparticles; Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at a temperature of 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate added to 0.5 M NaOH solution.

[0034] Comparative Example 8 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 3:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:3. Step 3: The precursor was heated to 400°C at a heating rate of 5°C and kept at this temperature for 2 hours to form an amorphous Al2O3 shell layer with a thickness of 5 nm. The temperature was further raised to 700°C and kept at this temperature for 3 hours to form a NiAl2O4 spinel transition layer with a thickness of 2 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 2 mM sodium silicate added to 0.5 M NaOH solution.

[0035] Comparative Example 9 A method for preparing an aluminum-nickel alloy hydrogenation catalyst comprises the following steps: Step 1: Ni(NO3)2 and Co(NO3)2 were dispersed in ethylene glycol solution at an atomic ratio of Ni to Co of 3:1 to prepare an internal phase solution with a solid-liquid ratio of 1:20; NaBH4 and sodium citrate were dispersed in deionized water as the external phase, and the mass ratio of NaBH4, sodium citrate and deionized water was controlled to be 2:1:100. The flow rate of the internal phase was adjusted to 0.4 mL / min and the flow rate of the external phase was adjusted to 1.2 mL / min through a microfluidic chip. The shear reaction was carried out at a temperature of 70°C and a shear rate of 1.2×10 4 s -1 , centrifuged, washed, and dried to obtain NiCo cores with a particle size of 13 nm; Step 2: Disperse the NiCo core in 3% dilute hydrochloric acid, ultrasonically treat for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, add 5 wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo core; Al (NO3)3 and La (NO3)3 was dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1M, the doping amount of La was 1.5at%, the stirring speed was 200rpm, and the mixture was stirred for 10 minutes. Polyvinyl pyrrolidone (5% of the total mass of the metal salt) was added, and the stirring was continued. Ammonia water with a mass fraction of 20% was added dropwise to adjust the pH to 8. The mixture was aged for 12 hours to obtain a coprecipitation sol. The activated NiCo core was added to the coprecipitation sol and ultrasonically dispersed for 10 minutes. The ultrasonic power was 100W and the ultrasonic frequency was 40KHz. The water was evaporated under stirring at 70°C to form a wet gel. The mixture was centrifuged, washed, and dried at 80°C for 24 hours to obtain a precursor, wherein the mass ratio of the activated NiCo core to the coprecipitation sol was 1:3. Step 3: The precursor was heated to 400°C at a heating rate of 5°C and kept at this temperature for 2 hours to form an amorphous Al2O3 shell layer with a thickness of 5 nm. The temperature was further raised to 700°C and kept at this temperature for 3 hours to form a NiAl2O4 spinel transition layer with a thickness of 2 nm. The precursor was naturally cooled to room temperature to obtain core-shell nanoparticles. Step 4: The core-shell nanoparticles, aluminum powder, and nickel powder were mixed in a mass ratio of 1:1:1, with a ball-to-material ratio of 12:1. Under argon protection, the mixture was subjected to mechanical alloying ball milling at a speed of 500 rpm, with each ball milling lasting 20 minutes and a rest period of 5 minutes to obtain NiAl alloy skeleton-loaded core-shell nanoparticles. Step 5. Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution, etch at 60°C for 15 minutes, wash with deionized water until neutral, treat with oxygen plasma at a power of 100 W for 10 minutes, and introduce a water vapor mixture containing 1% O2 by volume at 150°C. React for 1 hour to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 2 mM benzotriazole added to 0.5 M NaOH solution.

[0036] Performance Testing The performance parameters of the aluminum-nickel alloy hydrogenation catalysts prepared in Examples 1-3 and Comparative Examples 1-9 of the present application are as follows: Benzene hydrogenation conversion rate: tested in accordance with industry standard HG / T 5526-2019 "Test Method for Activity of Aluminum-Nickel Alloy Hydrogenation Catalysts"; Activity retention rate: Refer to the industry standard HG / T 5526-2019 "Test method for activity of aluminum-nickel alloy hydrogenation catalysts" and test the catalytic activity after 1000 hours of operation; Specific surface area: Refer to the national standard GB / T 5816-1995 "Determination of surface area of catalysts and adsorbents" 》Test; Crushing resistance: tested in accordance with the industry standard HG / T 5525-2019 "Aluminum-nickel alloy hydrogenation catalyst"; The test results are shown in Table 1.

[0037] Table 1 Performance parameters of the aluminum-nickel alloy hydrogenation catalysts prepared in Examples 1-3 and Comparative Examples 1-9

[0038] As shown in Table 1, the aluminum-nickel alloy hydrogenation catalyst prepared in this application exhibits excellent overall performance. Its hydrogenation activity is extremely high, significantly improving reaction efficiency; its stability allows it to maintain high catalytic performance over long periods of time under complex operating conditions, significantly extending its service life. Furthermore, the catalyst has a large specific surface area, abundant active sites, and significantly reduced mass transfer resistance. Furthermore, its mechanical properties are stable, making it resistant to breakage and wear, making it suitable for high-intensity industrial production environments and ensuring the catalyst's long-term stable operation.

[0039] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A method for preparing an aluminum-nickel alloy hydrogenation catalyst, characterized in that: The following steps are involved: Step 1: Disperse the Ni source and the Co source in an ethylene glycol solution as the inner phase; disperse NaBH4 and sodium citrate in deionized water as the outer phase; mix the inner and outer phases through a microfluidic chip, perform a shear reaction, centrifuge, wash, and dry to obtain a NiCo core; Step 2: Disperse the NiCo core in dilute hydrochloric acid, add 3-glycidyloxypropyltrimethoxysilane ethanol solution, and react for 1-2 hours to obtain an activated NiCo core; disperse the Al source and rare earth elements in deionized water, add polyvinyl pyrrolidone, adjust the pH to 8-9, and age to obtain a coprecipitation sol; add the activated NiCo core to the coprecipitation sol, evaporate the water to form a wet gel, wash, and dry to obtain a precursor; Step 3: heating the precursor to 400-450°C and holding the temperature for 2-3 hours to form an amorphous Al2O3 shell layer, then heating the precursor to 700-900°C and holding the temperature for 3-4 hours to form a NiAl2O4 spinel transition layer, and then cooling the precursor to room temperature to obtain core-shell nanoparticles. Step 4: mixing the core-shell nanoparticles, aluminum powder, and nickel powder in a mass ratio of 1-3:1:1-1.2, and performing mechanical alloying ball milling by intermittent ball milling under argon protection to obtain NiAl alloy skeleton-loaded core-shell nanoparticles; Step 5: Add the NiAl alloy skeleton-loaded core-shell nanoparticles to the etching solution. After etching, wash with deionized water until neutral. After oxygen plasma treatment, introduce a water vapor mixed gas containing O2 and react for 1-3 hours to obtain the aluminum-nickel alloy hydrogenation catalyst.

2. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that: The atomic ratio of Ni to Co in the Ni source and the Co source in step 1 is 3-5:1; the flow rate of the inner phase is 0.4-0.6 mL / min, and the flow rate ratio of the inner phase to the outer phase is 1:3; the shear rate of the shear reaction is 1.2×10 4 s -1 -1.5×10 4 s -1 .

3. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that: The particle size of the NiCo core is 12-20 nm.

4. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that: The doping amount of the rare earth element in step 2 is 1.5-3at%; the rare earth element is one or more of La, Ce, Nd, Sm, and Gd.

5. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that: The mass ratio of the activated NiCo core to the coprecipitated sol in step 2 is 1:3-5.

6. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that: The heating rate in step 3 is 5-8°C.

7. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that: The intermittent ball milling conditions in step 4 are: a rotation speed of 500-600 rpm, each ball milling time of 20-30 min, and an interval of 5-10 min.

8. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that: The thickness of the amorphous Al2O3 shell layer in step 4 is 5-10 nm; the thickness of the NiAl2O4 spinel transition layer is 2-4 nm.

9. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that: The etching solution in step 5 is: 1-2 mM benzotriazole and 1-3 mM sodium silicate are added to 0.5-2 M NaOH solution; the oxygen plasma treatment power is 100-120 W, and the treatment is carried out for 10-15 minutes.

10. An aluminum-nickel alloy hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 9.

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