Aluminum-nickel alloy hydrogenation catalyst and method for preparing the same

Abstract

The application 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 is as follows: step 1, preparing a NiCo inner core; step 2, preparing a precursor; step 3, preparing a core-shell nanoparticle; step 4, preparing a NiAl alloy framework loaded core-shell nanoparticle; and step 5, adding the NiAl alloy framework loaded core-shell nanoparticle into an etching solution, etching, introducing O2-containing water vapor mixed gas after oxygen plasma treatment, and reacting, so that the aluminum-nickel alloy hydrogenation catalyst is obtained. The catalyst has extremely high hydrogenation activity and high reaction efficiency; the catalyst has strong stability, can keep high-efficiency catalytic capacity for a long time under complex working conditions, and has greatly prolonged service life; the catalyst has large specific surface area, rich active sites, and significantly reduced mass transfer resistance. In addition, the catalyst has stable mechanical performance and is not prone to breaking or abrasion, can adapt to high-strength industrial production environment, and guarantees long-term stable operation of the catalyst.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of alloy catalyst preparation, in particular to an aluminum-nickel alloy hydrogenation catalyst and a preparation method thereof. BACKGROUND

[0002] The aluminum-nickel alloy hydrogenation catalyst is widely used in the fields of oil hydrogenation, organic synthesis and fine chemical industry due to its high activity and low cost. The traditional aluminum-nickel alloy catalyst is prepared by melting aluminum and nickel into an alloy according to a proportion, selectively dissolving aluminum by using lye to form a porous nickel framework structure, removing aluminum by lye reaction to generate an active nickel phase with a high specific surface area, and enhancing the catalytic activity. However, the traditional preparation method has the following problems: (1) insufficient mechanical strength, the reduction of the aluminum content for supporting the alloy framework will reduce the structural stability and thermal stability of the catalyst, the catalyst is easy to break and deactivate, and it is difficult to meet the strength requirement of the catalyst for the continuous reaction system with stirring; (2) poor resistance to poisoning, impurities such as sulfides and carbon monoxide are easy to be adsorbed on the active sites of nickel, resulting in catalyst deactivation, and frequent regeneration is required; (3) high energy consumption in the traditional smelting preparation method, and the high melting point of nickel will result in poor uniformity of the alloy and reduced activity. In view of the above problems, the application provides an improved aluminum-nickel alloy catalyst and a preparation method thereof, balances the catalytic activity and mechanical strength of the aluminum-nickel alloy catalyst, improves the resistance to poisoning of the catalyst, and meets the requirements for the stability and long service life of the catalyst in the industrial catalytic process. SUMMARY

[0003] In order to solve the technical problems mentioned in the background art, the application provides a preparation method of an aluminum-nickel alloy hydrogenation catalyst.

[0004] The application provides a preparation method of an aluminum-nickel alloy hydrogenation catalyst, which adopts the following technical scheme:

[0005] The preparation method of the aluminum-nickel alloy hydrogenation catalyst comprises the following steps:

[0006] Step 1: dispersing a Ni source and a Co source in an ethylene glycol solution as an inner phase; dispersing NaBH4 and sodium citrate in deionized water as an outer phase; adjusting the flow rates of the inner phase and the outer phase through a microfluidic chip, and performing a shearing reaction at a temperature of 70-85 DEG C; centrifuging, washing and drying to obtain a NiCo core;

[0007] Step 2, disperse the NiCo core in dilute hydrochloric acid, ultrasonic treatment, add 5-8wt% 3-glycidyloxypropyltrimethoxysilane ethanol solution, react for 1-2h, centrifugal, wash, dry, get activated NiCo core; disperse the Al source and rare earth elements in deionized water, stir for 10-20min, add polyvinylpyrrolidone, continue to stir, add ammonia water to adjust pH to 8-9, age for 12-20h, get coprecipitation sol; add the activated NiCo core to the coprecipitation sol, ultrasonic dispersion, evaporate water to form a wet gel, wash, dry, get the precursor;

[0008] Step 3, heat the precursor to 400-450℃, keep for 2-3h, form amorphous Al2O3 shell layer, continue to heat to 700-900℃, keep for 3-4h, form NiAl2O4 spinel transition layer, naturally cool to room temperature, get core-shell nanoparticles;

[0009] Step 4, mix the core-shell nanoparticles, aluminum powder and nickel powder according to the mass ratio of 1-3:1:1-1.2, control the ball material ratio to be 12-15:1, under the protection of argon, use intermittent ball milling for mechanical alloying ball milling, get NiAl alloy framework loaded core-shell nanoparticles;

[0010] Step 5, add the NiAl alloy framework loaded core-shell nanoparticles to the etching solution, after etching for 15-20min at a temperature of 60-80℃, wash with deionized water until neutral, after oxygen plasma treatment, at 150-200℃, pass in water vapor mixed gas containing 1-5% O2 by volume, react for 1-3h, get the aluminum-nickel alloy hydrogenation catalyst.

[0011] Preferably, the atomic ratio of Ni to Co in the Ni source and Co source in step 1 is 3-5:1.

[0012] Preferably, the flow rate of the internal phase in step 1 is 0.4-0.6mL / min, and the flow rate ratio of the internal phase to the external phase is 1:3.

[0013] Preferably, the shear rate of the shear reaction in step 1 is 1.2×10 4 s -1 -1.5×10 4 s -1 .

[0014] Preferably, the particle size of the NiCo core in step 1 is 12-20nm.

[0015] Preferably, the Ni source in step 1 is one of Ni (NO3)3, Ni (CH3COO)2, and Ni-EDTA.

[0016] Preferably, the Co source in step 1 is one of Co (NO3)2, Co (CH3COO)2.

[0017] Preferably, the doping amount of the rare earth element in step 2 is 1.5-3at%.

[0018] Preferably, the rare earth element in step 2 is one or more of La, Ce, Nd, Sm, and Gd.

[0019] Preferably, the mass ratio of the activated NiCo inner core to the co-precipitation sol in step 2 is 1:3-5.

[0020] Preferably, the temperature rising speed in step 3 is 5-8℃.

[0021] Preferably, the intermittent ball milling condition in step 4 is that the rotation speed is 500-600 rpm, the ball milling time is 20-30 min, and the intermittent time is 5-10 min.

[0022] Preferably, the thickness of the amorphous Al2O3 shell layer in step 4 is 5-10 nm.

[0023] Preferably, the thickness of the NiAl2O4 spinel transition layer in step 4 is 2-4 nm.

[0024] Preferably, the etching solution in step 5 is that 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 min.

[0025] An aluminum-nickel alloy hydrogenation catalyst is obtained by the above method.

[0026] In summary, the present application has the following beneficial effects:

[0027] The aluminum-nickel alloy hydrogenation catalyst prepared by the present application is composed of a NiAl alloy framework and core-shell nanoparticles loaded in the NiAl alloy framework. The NiCo inner core is precisely synthesized by microfluidics. By doping a certain proportion of Co, the electronic state density of Ni is adjusted, and the H2 dissociation capacity is improved. The amorphous Al2O3 shell layer inhibits the sintering of active metals, the spinel transition layer strengthens the interfacial bonding force, reduces the loss of active components, and by doping a certain proportion of rare earth element La into the amorphous Al2O3 shell layer, La-O-Al bonds are formed, the amorphous structure is stabilized, oxygen vacancy defects are introduced, and the adsorption and dissociation of H2O / H -The adsorption activation of the shell layer is carried out, the gradient calcination optimizes the shell layer structure, the amorphous Al2O3 is formed at a lower temperature to avoid the aggregation of the inner core caused by direct high-temperature, and the spinel transition layer is formed by recrystallization at a higher temperature, so that the two-step method makes the shell layer have obvious compactness and the stability is further improved. In the etching process, benzotriazole and sodium silicate are added in the etching solution, the benzotriazole can be selectively adsorbed on the surface of the metal Ni to form a dense organic protective film through coordination, so as to avoid being dissolved by strong alkali in the etching process and affect the catalytic performance, and the sodium silicate is dissociated into silicate ions under alkaline conditions and can be adsorbed on the surface of the metal Al to form a silicate passivation film to slow down the etching rate of Al and avoid the collapse of the skeleton. The two work together to inhibit local over-etching, so that the dissolution of Al is more uniform, and a porous structure with narrow pore size distribution and good connectivity is formed. The amorphous SiO2 generated by the hydrolysis of sodium silicate can fill the pore surface to enhance the mechanical strength of the skeleton and prevent the collapse of the pore structure after etching. The residual benzotriazole and silicate after etching can be removed by plasma, avoiding the residual impurities, and the plasma treatment can further activate the surface to improve the thermal stability and sintering resistance of the catalyst. DETAILED DESCRIPTION

[0028] The application will be further described in detail below in combination with examples.

[0029] The 3-glycidyloxypropyltrimethoxysilane used in the examples and comparative examples of the application is purchased from Wuhan Kanos Technology Co., Ltd.; the polyvinylpyrrolidone is purchased from Huzhou Shenhuagomoji Material Co., Ltd.; the La (NO3)3 is purchased from Zibo Ribo Rare Earth Materials Co., Ltd.; the benzotriazole (model WP) is purchased from Wuhan Xinchuyang Chemical Co., Ltd.; and the sodium silicate is purchased from Jinan Zesheng Chemical Co., Ltd.

[0030] Examples 1-3 provide a preparation method of an aluminum-nickel alloy hydrogenation catalyst.

[0031] Example 1

[0032] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0033] Step 1, dispersing Ni (NO3)2 and Co (NO3)2 in an ethylene glycol solution according to the atomic ratio of Ni to Co as 3:1 to prepare an inner phase solution with a solid-liquid ratio of 1:20; dispersing NaBH4 and sodium citrate in deionized water as an outer phase, controlling the mass ratio of NaBH4, sodium citrate and deionized water as 2:1:100, adjusting the flow rate of the inner phase as 0.4 mL / min and the flow rate of the outer phase as 1.2 mL / min through a microfluidic chip, and performing shearing reaction under the condition that the temperature is 70℃ and the shearing rate is 1.2×10 4 s -1, centrifugation, washing, drying, and obtaining the NiCo core with a particle size of 13 nm;

[0034] Step 2, dispersing the NiCo core in 3% dilute hydrochloric acid, ultrasonic treatment for 10 min, ultrasonic power is 100 W, ultrasonic frequency is 40 KHz, adding 5 wt% 3-glycidoxypropyltrimethoxysilane ethanol solution, stirring for 1 h, stirring speed is 200 rpm, centrifugation, washing, drying, and obtaining the activated NiCo core; dispersing Al (NO3) 3 and La (NO3) 3 in deionized water, controlling the total concentration of metal ions to be 0.1 M, the doping amount of La is 1.5 at%, stirring at a stirring speed of 200 rpm for 10 min, adding 5% of the total mass of metal salt of polyvinylpyrrolidone, continuing to stir, adding 20% ammonia water to adjust the pH to 8, and aging for 12 h to obtain a coprecipitation sol; adding the activated NiCo core into the coprecipitation sol, ultrasonic dispersion for 10 min, ultrasonic power is 100 W, ultrasonic frequency is 40 KHz, evaporating water at 70℃ under stirring to form a wet gel, centrifugation, washing, and drying at 80℃ for 24 h to obtain a precursor, wherein the mass ratio of the activated NiCo core and the coprecipitation sol is 1:3;

[0035] Step 3, heating the precursor to 400℃ at a heating rate of 5℃, and keeping the temperature for 2 h to form an amorphous Al2O3 shell layer with a thickness of 5 nm, continuing to heat to 700℃, keeping the temperature for 3 h to form a NiAl2O4 spinel transition layer with a thickness of 2 nm, and naturally cooling to room temperature to obtain the core-shell nanoparticle;

[0036] Step 4, mixing the core-shell nanoparticle, aluminum powder and nickel powder according to a mass ratio of 1:1:1, controlling the ball-to-material ratio to be 12:1, and performing mechanical alloying ball milling under argon protection at a rotating speed of 500 rpm in a manner of 20 min of ball milling and 5 min of intermittent, to obtain the NiAl alloy framework loaded with the core-shell nanoparticle;

[0037] Step 5, adding the NiAl alloy framework loaded with the core-shell nanoparticle into an etching solution, etching for 15 min at a temperature of 60℃, washing with deionized water until neutral, treating with oxygen plasma for 10 min at a power of 100 W, and reacting for 1 h at 150℃ by introducing water vapor mixed gas containing 1% O2 by volume, to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: adding 1 mM benzotriazole and 1 mM sodium silicate into 0.5 M NaOH solution.

[0038] Example 2

[0039] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0040] Step 1, disperse Ni(NO3)2 and Co(NO3)2 in ethylene glycol solution according to the atomic ratio of Ni to Co being 4:1, prepare an internal phase solution with a solid-liquid ratio of 2:20; disperse NaBH4 and sodium citrate in deionized water as an external phase, control the mass ratio of NaBH4, sodium citrate and deionized water to be 2.5:1.5:100, adjust the flow rate of the internal phase to be 0.5 mL / min and the flow rate of the external phase to be 1.5 mL / min through a microfluidic chip, and perform shearing reaction under the condition of a temperature of 78℃ and a shearing rate of 1.4×10 4 s -1 , centrifuge, wash, and dry to obtain a NiCo inner core with a particle size of 15 nm;

[0041] Step 2, disperse the NiCo inner core in dilute hydrochloric acid with a mass fraction of 4%, ultrasonic treatment for 15 min with an ultrasonic power of 110 W and an ultrasonic frequency of 50 KHz, add 6wt% of 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1.5 h with a stirring speed of 300 rpm, centrifuge, wash, and dry to obtain an activated NiCo inner core; disperse Al(NO3)3 and La(NO3)3 in deionized water, control the total concentration of metal ions to be 0.2M and the doping amount of La to be 2.5at%, stir at a stirring speed of 250 rpm for 15 min, add 10% of the total mass of polyvinylpyrrolidone to the metal salt, continue to stir, add 22% of ammonia water by mass to adjust the pH to 8.5, and age for 16 h to obtain a coprecipitation sol; add the activated NiCo inner core to the coprecipitation sol, ultrasonic dispersion for 15 min with an ultrasonic power of 110 W and an ultrasonic frequency of 50 KHz, evaporate water at 75℃ under stirring to form a wet gel, centrifuge, wash, and dry at 90℃ for 30 h to obtain a precursor, wherein the mass ratio of the activated NiCo inner core to the coprecipitation sol is 1:4;

[0042] Step 3, heat the precursor to 420℃ at a heating rate of 7℃, and keep the temperature for 2.5h to form an amorphous Al2O3 shell layer with a thickness of 8 nm, continue to heat to 800℃, keep the temperature for 3.5h to form a NiAl2O4 spinel transition layer with a thickness of 3 nm, and naturally cool to room temperature to obtain core-shell nanoparticles;

[0043] Step 4, mix the core-shell nanoparticles, aluminum powder and nickel powder according to a mass ratio of 2:1:1.1, control the ball-to-material ratio to be 13:1, perform mechanical alloying ball milling under argon protection at a rotating speed of 550 rpm in a manner of 25 min of ball milling per 8 min of interval to obtain NiAl alloy framework loaded with core-shell nanoparticles;

[0044] Step 5, the core-shell nanoparticles supported on the NiAl alloy framework are added into the etching solution, after etching for 18 min at 70℃, washing with deionized water until neutral, oxygen plasma treatment for 12 min at a power of 110 W, and reaction for 2 h at 180℃ by introducing water vapor mixed gas containing 3% (volume fraction) O2, to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1.5 mM benzotriazole and 2 mM sodium silicate are added into 1 M NaOH solution.

[0045] Example 3

[0046] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0047] Step 1, Ni (NO3) 2 and Co (NO3) 2 are dispersed in ethylene glycol solution according to the 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 are dispersed in deionized water as an external phase, and the mass ratio of NaBH4, sodium citrate and deionized water is controlled to be 3:2:100; the flow rate of the internal phase is adjusted to be 0.6 mL / min and the flow rate of the external phase is adjusted to be 1.8 mL / min through a microfluidic chip; and shearing reaction is carried out at a temperature of 85℃ with a shearing rate of 1.5×10 4 s -1 , centrifugation, washing and drying to obtain a NiCo inner core with a particle size of 20 nm;

[0048] Step 2, the NiCo inner core is dispersed in dilute hydrochloric acid with a mass fraction of 6%, ultrasonic treatment is carried out for 20 min at an ultrasonic power of 120 W and an ultrasonic frequency of 60 KHz, 8wt% 3-glycidoxypropyltrimethoxysilane ethanol solution is added, stirring reaction is carried out for 2 h at a stirring speed of 400 rpm, centrifugation, washing and drying are carried out to obtain an activated NiCo inner core; Al (NO3) 3 and La (NO3) 3 are dispersed in deionized water, the total concentration of metal ions is controlled to be 0.3 M, the doping amount of La is 3at%, stirring is carried out at a stirring speed of 300 rpm for 20 min, 15% of the total mass of metal salt of polyvinylpyrrolidone is added, the pH is adjusted to be 9 by adding 25% ammonia water dropwise, and aging is carried out for 20 h to obtain a coprecipitation sol; the activated NiCo inner core is added into the coprecipitation sol, ultrasonic dispersion is carried out for 20 min at an ultrasonic power of 120 W and an ultrasonic frequency of 60 KHz, water is evaporated at 80℃ under stirring until a wet gel is formed, centrifugation, washing and drying at 100℃ for 36 h are carried out to obtain a precursor, wherein the mass ratio of the activated NiCo inner core to the coprecipitation sol is 1:5;

[0049] Step 3, the precursor is heated to 450℃ at a heating rate of 8℃, and kept for 3h to form an amorphous Al2O3 shell layer with a thickness of 10nm, and then heated to 900℃ and kept for 4h to form a NiAl2O4 spinel transition layer with a thickness of 4nm, and then naturally cooled to room temperature to obtain core-shell nanoparticles;

[0050] Step 4, the core-shell nanoparticles, aluminum powder and nickel powder are mixed according to a mass ratio of 3:1:1.2, and the ball-to-powder ratio is controlled to be 15:1, and then mechanical alloying ball milling is carried out under argon protection at a rotating speed of 600 rpm in a manner of 30 min of ball milling and 10 min of intermittent, to obtain NiAl alloy framework loaded core-shell nanoparticles;

[0051] Step 5, the NiAl alloy framework loaded core-shell nanoparticles are added into an etching solution, and after etching at 80℃ for 20 min, deionized water is used for washing until neutral, and then oxygen plasma treatment is carried out at a power of 120W for 15 min, and then the water vapor mixed gas containing 5% O2 by volume is introduced at 200℃ for 3h, to obtain an aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 2mM benzotriazole and 3mM sodium silicate are added into a 2M NaOH solution.

[0052] Comparative Example 1

[0053] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0054] Step 1, Ni(NO3)2 and Co(NO3)2 are dispersed in an ethylene glycol solution according to 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 are dispersed in deionized water as an external phase, and the mass ratio of NaBH4, sodium citrate and deionized water is controlled to be 2:1:100, the flow rate of the internal phase is adjusted to be 0.4mL / min, and the flow rate of the external phase is adjusted to be 1.2mL / min through a microfluidic chip, and then shear reaction is carried out at a temperature of 70℃, and the shear rate is 1.2×10 4 s -1 , centrifugation, washing and drying to obtain a NiCo inner core with a particle size of 13nm;

[0055] Step 2, disperse the NiCo core in 3% by mass of dilute hydrochloric acid, ultrasonic treatment for 10 min, ultrasonic power is 100 W, ultrasonic frequency is 40 KHz, add 5wt% of 3-glycidyloxypropyltrimethoxysilane ethanol solution, stirring reaction for 1h, stirring speed is 200 rpm, centrifugal, washing, drying, to get activated NiCo core; disperse Al (NO3) 3 and La (NO3) 3 in deionized water, control the total concentration of metal ions to be 0.1M, the doping amount of La is 1at%, with stirring speed of 200 rpm, stirring for 10 min, add 5% of the total mass of polyvinylpyrrolidone, continue to stir, add 20% by mass of ammonia water to adjust pH to 8, aging for 12h, to get coprecipitation sol; add the activated NiCo core to the coprecipitation sol, ultrasonic dispersion for 10 min, ultrasonic power is 100 W, ultrasonic frequency is 40 KHz, evaporate water at 70℃ under stirring to form a wet gel, centrifugal, washing, drying at 80℃ for 24h, to get the precursor, wherein the mass ratio of the activated NiCo core and the coprecipitation sol is 1:3;

[0056] Step 3, heat the precursor to 400℃ at a heating rate of 5℃, keep for 2h, form an amorphous Al2O3 shell layer with a thickness of 5nm, continue to heat to 700℃, keep for 3h, form a NiAl2O4 spinel transition layer with a thickness of 2nm, naturally cool to room temperature, to get core-shell nanoparticles;

[0057] Step 4, mix the core-shell nanoparticles, aluminum powder and nickel powder according to the mass ratio of 1:1:1, control the ball-to-material ratio to be 12:1, under argon protection, mechanical alloying ball milling is carried out at a speed of 500 rpm, with a mode of 20 min per ball milling and 5 min interval, to get the NiAl alloy framework loaded core-shell nanoparticles;

[0058] Step 5, add the NiAl alloy framework loaded core-shell nanoparticles into the etching solution, after etching for 15 min at a temperature of 60℃, wash with deionized water until neutral, treat with oxygen plasma for 10 min at a power of 100 W, pass in water vapor mixed gas containing 1% by volume of O2 at 150℃, react for 1h, to get the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: add 1 mM benzotriazole and 1 mM sodium silicate in 0.5M NaOH solution.

[0059] Comparative Example 2

[0060] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0061] Step 1, disperse Ni(NO3)2 and Co(NO3)2 in ethylene glycol solution according to the atomic ratio of Ni to Co being 2:1, prepare an internal phase solution with a solid-liquid ratio of 1:20; disperse NaBH4 and sodium citrate in deionized water as an external phase, control the mass ratio of NaBH4, sodium citrate and deionized water to be 2:1:100, adjust the flow rate of the internal phase to be 0.4 mL / min and the flow rate of the external phase to be 1.2 mL / min through a microfluidic chip, and perform shearing reaction under the condition of a temperature of 70℃ and a shearing rate of 1.2×10 4 s -1 , centrifuge, wash, and dry to obtain NiCo inner core with a particle size of 13 nm;

[0062] Step 2, disperse the NiCo inner core in dilute hydrochloric acid with a mass fraction of 3%, ultrasonic treatment for 10 min with an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, add 5wt% of 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h with a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain activated NiCo inner core; disperse Al(NO3)3 and La(NO3)3 in deionized water, control the total concentration of metal ions to be 0.1 M and the doping amount of La to be 1.5at%, stir for 10 min with a stirring speed of 200 rpm, add 5% of polyvinylpyrrolidone based on the total mass of metal salts, continue to stir, add 20% of ammonia water to adjust the pH to 8, and age for 12 h to obtain a coprecipitation sol; add the activated NiCo inner core to the coprecipitation sol, ultrasonic dispersion for 10 min with an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, evaporate water at 70℃ under stirring to form a wet gel, centrifuge, wash, and dry at 80℃ for 24 h to obtain a precursor, wherein the mass ratio of the activated NiCo inner core to the coprecipitation sol is 1:3;

[0063] Step 3, heat the precursor to 400℃ at a heating rate of 5℃, and keep the temperature for 2 h to form an amorphous Al2O3 shell layer with a thickness of 5 nm, continue to heat to 700℃, keep the temperature for 3 h to form a NiAl2O4 spinel transition layer with a thickness of 2 nm, and naturally cool to room temperature to obtain core-shell nanoparticles;

[0064] Step 4, mix the core-shell nanoparticles, aluminum powder and nickel powder according to a mass ratio of 1:1:1, control the ball-to-material ratio to be 12:1, perform mechanical alloying ball milling under argon protection at a rotating speed of 500 rpm in a manner of 20 min of ball milling and 5 min of intermittent, and obtain NiAl alloy framework loaded with core-shell nanoparticles;

[0065] Step 5, the core-shell nanoparticles supported on the NiAl alloy framework are added into the etching solution, after etching for 15 min at 60℃, washing with deionized water until neutral, oxygen plasma treatment for 10 min at a power of 100 W, and reaction for 1 h at 150℃ by introducing water vapor mixed gas containing 1% (volume fraction) O2, to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate are added into 0.5M NaOH solution.

[0066] Comparative Example 3

[0067] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0068] Step 1, Ni (NO3) 2 and Co (NO3) 2 are dispersed in ethylene glycol solution according to the 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 are dispersed in deionized water as an external phase, and the mass ratio of NaBH4, sodium citrate and deionized water is controlled to be 2:1:100; the flow rate of the internal phase is adjusted to be 0.4 mL / min and the flow rate of the external phase is adjusted to be 1.2 mL / min through a microfluidic chip; and shearing reaction is carried out at a temperature of 70℃, and the shearing rate is 1.2×10 4 s -1 , centrifugation, washing and drying to obtain a NiCo inner core with a particle size of 13 nm;

[0069] Step 2, the NiCo inner core is dispersed in dilute hydrochloric acid with a mass fraction of 3%, ultrasonic treatment is carried out for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, 5wt% 3-glycidoxypropyltrimethoxysilane ethanol solution is added, stirring reaction is carried out for 1 h at a stirring speed of 200 rpm, centrifugation, washing and drying are carried out to obtain an activated NiCo inner core; Al (NO3) 3 and La (NO3) 3 are dispersed in deionized water, the total concentration of metal ions is controlled to be 0.1M, the doping amount of La is 1.5at%, stirring is carried out at a stirring speed of 200 rpm for 10 min, 5% of polyvinylpyrrolidone based on the total mass of metal salt is added, and stirring is continued, 20% ammonia water is added dropwise to adjust the pH to 8, and aging is carried out for 12 h to obtain a coprecipitation sol; the activated NiCo inner core is added into the coprecipitation sol, ultrasonic dispersion is carried out for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, water is evaporated at 70℃ under stirring to form a wet gel, centrifugation, washing and drying at 80℃ for 24 h are carried out to obtain a precursor, wherein the mass ratio of the activated NiCo inner core to the coprecipitation sol is 1:3;

[0070] Step 3, the precursor is heated to 400℃ at a heating rate of 5℃, and kept for 2h to form an amorphous Al2O3 shell layer with a thickness of 5nm, and then heated to 700℃ and kept for 3h to form a NiAl2O4 spinel transition layer with a thickness of 2nm, and then naturally cooled to room temperature to obtain core-shell nanoparticles;

[0071] Step 4, the core-shell nanoparticles, aluminum powder and nickel powder are mixed according to a mass ratio of 1:1:1, and the ball-to-powder ratio is controlled to be 12:1, and then mechanical alloying ball milling is carried out under argon protection at a rotating speed of 500 rpm by adopting a mode of 20 min of ball milling and 5 min of intermittent, to obtain NiAl alloy framework loaded core-shell nanoparticles;

[0072] Step 5, the NiAl alloy framework loaded core-shell nanoparticles are added into an etching solution, and after etching at 60℃ for 15 min, deionized water is used for washing until neutral, and then oxygen plasma treatment is carried out at a power of 100W for 10 min, and then water vapor mixed gas containing 1% O2 by volume fraction is introduced at 150℃, and reaction is carried out for 1h, to obtain an aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1mM benzotriazole and 1mM sodium silicate are added into a 0.5M NaOH solution.

[0073] Comparative Example 4

[0074] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0075] Step 1, Ni(NO3)2 and Co(NO3)2 are dispersed in an ethylene glycol solution according to 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 are dispersed in deionized water as an external phase, and the mass ratio of NaBH4, sodium citrate and deionized water is controlled to be 2:1:100, the flow rate of the internal phase is adjusted to be 0.4mL / min, and the flow rate of the external phase is adjusted to be 1.2mL / min through a microfluidic chip, and then shear reaction is carried out at a temperature of 70℃, and the shear rate is 1.2×10 4 s -1 , centrifugation, washing and drying to obtain a NiCo inner core with a particle size of 13nm;

[0076] Step 2, the NiCo core was dispersed in 3% mass fraction dilute hydrochloric acid, ultrasonic treatment for 10 min, ultrasonic power was 100 W, ultrasonic frequency was 40 KHz, 5wt% 3-glycidoxypropyltrimethoxysilane ethanol solution was added, stirring reaction for 1 h, stirring speed was 200 rpm, centrifugation, washing, drying, and the activated NiCo core was obtained; Al (NO3) 3 and La (NO3) 3 were dispersed in deionized water, the total concentration of metal ions was controlled to be 0.1 M, the doping amount of La was 1.5 at%, stirring speed was 200 rpm, stirring for 10 min, 5% of the total mass of metal salt of polyvinylpyrrolidone was added, continued stirring, 20% mass fraction ammonia water was added dropwise to adjust pH to 8, and aging for 12 h, and the co-precipitation sol was obtained; the activated NiCo core was added into the co-precipitation sol, ultrasonic dispersion for 10 min, ultrasonic power was 100 W, ultrasonic frequency was 40 KHz, water was evaporated at 70 DEG C under stirring to form a wet gel, centrifugation, washing, drying at 80 DEG C for 24 h, and the precursor was obtained, wherein the mass ratio of the activated NiCo core and the co-precipitation sol was 1:2;

[0077] Step 3, the precursor was heated to 400 DEG C at a heating rate of 5 DEG C / min, and kept for 2 h, an amorphous Al2O3 shell layer with a thickness of 5 nm was formed, then the temperature was continuously increased to 700 DEG C, and kept for 3 h, a NiAl2O4 spinel transition layer with a thickness of 2 nm was formed, and the natural cooling to room temperature was performed, and the core-shell nanoparticle was obtained;

[0078] Step 4, the core-shell nanoparticle, aluminum powder and nickel powder were mixed according to a mass ratio of 1:1:1, the ball-to-material ratio was controlled to be 12:1, mechanical alloying ball milling was carried out under argon protection at a rotating speed of 500 rpm, and the ball milling was carried out in a mode of 20 min each ball milling and 5 min intermittent, and the NiAl alloy framework loaded core-shell nanoparticle was obtained;

[0079] Step 5, the NiAl alloy framework loaded core-shell nanoparticle was added into an etching solution, after etching for 15 min at a temperature of 60 DEG C, neutral washing with deionized water was carried out, oxygen plasma treatment was carried out at a power of 100 W for 10 min, water vapor mixed gas containing 1% O2 by volume was introduced at 150 DEG C, and reaction was carried out for 1 h, and the aluminum-nickel alloy hydrogenation catalyst was obtained.

[0080] Comparative Example 5

[0081] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0082] Step 1, disperse Ni(NO3)2 and Co(NO3)2 in ethylene glycol solution according to the atomic ratio of Ni to Co being 3:1, prepare an internal phase solution with a solid-liquid ratio of 1:20; disperse NaBH4 and sodium citrate in deionized water as an external phase, control the mass ratio of NaBH4, sodium citrate and deionized water to be 2:1:100, adjust the flow rate of the internal phase to be 0.4 mL / min and the flow rate of the external phase to be 1.2 mL / min through a microfluidic chip, and perform shearing reaction under the condition of a temperature of 70℃ and a shearing rate of 1.2×10 4 s -1 , centrifuge, wash, and dry to obtain NiCo inner core with a particle size of 13 nm;

[0083] Step 2, disperse the NiCo inner core in dilute hydrochloric acid with a mass fraction of 3%, ultrasonic treatment for 10 min with an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, add 5wt% of 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h with a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain activated NiCo inner core; disperse Al(NO3)3 and La(NO3)3 in deionized water, control the total concentration of metal ions to be 0.1 M and the doping amount of La to be 1.5at%, stir for 10 min with a stirring speed of 200 rpm, add 5% of polyvinylpyrrolidone based on the total mass of metal salts, continue to stir, add 20% of ammonia water to adjust the pH to 8, and age for 12 h to obtain a coprecipitation sol; add the activated NiCo inner core to the coprecipitation sol, ultrasonic dispersion for 10 min with an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, evaporate water at 70℃ under stirring to form a wet gel, centrifuge, wash, and dry at 80℃ for 24 h to obtain a precursor, wherein the mass ratio of the activated NiCo inner core to the coprecipitation sol is 1:6;

[0084] Step 3, heat the precursor to 400℃ at a heating rate of 5℃, and keep the temperature for 2 h to form an amorphous Al2O3 shell layer with a thickness of 5 nm, continue to heat to 700℃, keep the temperature for 3 h to form a NiAl2O4 spinel transition layer with a thickness of 2 nm, and naturally cool to room temperature to obtain core-shell nanoparticles;

[0085] Step 4, mix the core-shell nanoparticles, aluminum powder and nickel powder according to a mass ratio of 1:1:1, control the ball-to-material ratio to be 12:1, perform mechanical alloying ball milling under argon protection at a rotating speed of 500 rpm in a manner of 20 min of ball milling and 5 min of intermittent, and obtain NiAl alloy framework loaded with core-shell nanoparticles;

[0086] Step 5, the core-shell nanoparticles supported on the NiAl alloy framework are added into the etching solution, after etching for 15 min at 60℃, washing with deionized water until neutral, oxygen plasma treatment for 10 min at a power of 100 W, and reaction for 1 h at 150℃ by introducing water vapor mixed gas containing 1% (volume fraction) O2, to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate are added into 0.5M NaOH solution.

[0087] Comparative Example 6

[0088] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0089] Step 1, Ni (NO3) 2 and Co (NO3) 2 are dispersed in ethylene glycol solution according to the 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 are dispersed in deionized water as an external phase, and the mass ratio of NaBH4, sodium citrate and deionized water is controlled to be 2:1:100; the flow rate of the internal phase is adjusted to be 0.4 mL / min and the flow rate of the external phase is adjusted to be 1.2 mL / min through a microfluidic chip; and shearing reaction is carried out at a temperature of 70℃, and the shearing rate is 1.2×10 4 s -1 , centrifugation, washing and drying to obtain a NiCo inner core with a particle size of 13 nm;

[0090] Step 2, the NiCo inner core is dispersed in dilute hydrochloric acid with a mass fraction of 3%, ultrasonic treatment is carried out for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, 5wt% of 3-glycidoxypropyltrimethoxysilane ethanol solution is added, stirring reaction is carried out for 1 h at a stirring speed of 200 rpm, centrifugation, washing and drying are carried out to obtain an activated NiCo inner core; Al (NO3) 3 and La (NO3) 3 are dispersed in deionized water, the total concentration of metal ions is controlled to be 0.1M, the doping amount of La is 1.5at%, stirring is carried out at a stirring speed of 200 rpm for 10 min, 5% of polyvinylpyrrolidone of the total mass of metal salt is added, and stirring is continued, 20% of ammonia water is added dropwise to adjust the pH to 8, and aging is carried out for 12 h to obtain a coprecipitation sol; the activated NiCo inner core is added into the coprecipitation sol, ultrasonic dispersion is carried out for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, water is evaporated at 70℃ under stirring to form a wet gel, centrifugation, washing and drying at 80℃ for 24 h are carried out to obtain a precursor, wherein the mass ratio of the activated NiCo inner core and the coprecipitation sol is 1:3;

[0091] Step 3, the precursor is heated to 400℃ at a heating rate of 5℃, and the temperature is kept for 5 h, and then naturally cooled to room temperature to obtain core-shell nanoparticles;

[0092] Step 4, the core-shell nanoparticles, aluminum powder and nickel powder are mixed according to a mass ratio of 1:1:1, a ball-to-material ratio of 12:1 is controlled, mechanical alloying ball milling is performed under argon protection at a rotating speed of 500 rpm in a manner of 20 min of ball milling and 5 min of intermittent, to obtain NiAl alloy framework loaded core-shell nanoparticles;

[0093] Step 5, the NiAl alloy framework loaded core-shell nanoparticles are added into an etching solution, after etching at 60℃ for 15 min, deionized water is used for washing until neutral, oxygen plasma treatment is performed at a power of 100 W for 10 min, water vapor mixed gas containing 1% of O2 by volume fraction is introduced at 150℃, and reaction is performed for 1 h, to obtain an aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 1 mM benzotriazole and 1 mM sodium silicate are added into a 0.5M NaOH solution.

[0094] Comparative Example 7

[0095] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0096] Step 1, Ni(NO3)2 and Co(NO3)2 are dispersed in an ethylene glycol solution according to 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 are dispersed in deionized water as an external phase, a mass ratio of NaBH4, sodium citrate and deionized water is controlled to be 2:1:100, an internal phase flow rate is adjusted to be 0.4 mL / min and an external phase flow rate is adjusted to be 1.2 mL / min through a microfluidic chip, and shearing reaction is performed at a temperature of 70℃, a shearing rate is 1.2×10 4 s -1 , centrifugation, washing and drying are performed, to obtain a NiCo inner core with a particle size of 13 nm;

[0097] Step 2, disperse the NiCo core in 3% by mass of dilute hydrochloric acid, ultrasonic treatment for 10 min, ultrasonic power is 100 W, ultrasonic frequency is 40 KHz, add 5wt% of 3-glycidyloxypropyltrimethoxysilane ethanol solution, stirring reaction for 1h, stirring speed is 200 rpm, centrifugal, washing, drying, to get activated NiCo core; disperse Al (NO3) 3 and La (NO3) 3 in deionized water, control the total concentration of metal ions to be 0.1M, the doping amount of La is 1.5at%, with stirring speed of 200 rpm, stirring for 10 min, add 5% of the total mass of metal salt of polyvinylpyrrolidone, continue to stir, add 20% by mass of ammonia to adjust the pH to 8, aging for 12h, to get coprecipitation sol; add the activated NiCo core to the coprecipitation sol, ultrasonic dispersion for 10 min, ultrasonic power is 100 W, ultrasonic frequency is 40 KHz, evaporate water at 70℃ under stirring to form a wet gel, centrifugal, washing, drying at 80℃ for 24h, to get the precursor, wherein the mass ratio of the activated NiCo core and the coprecipitation sol is 1:3;

[0098] Step 3, heat the precursor to 700℃ at a heating rate of 5℃, keep for 5h, naturally cool to room temperature, to get the core-shell nanoparticles;

[0099] Step 4, mix the core-shell nanoparticles, aluminum powder and nickel powder according to the mass ratio of 1:1:1, control the ball-to-material ratio to be 12:1, under the protection of argon, mechanical alloying ball milling is carried out at a rotating speed of 500 rpm, with a mode of 20 min per ball milling and 5 min interval, to get the NiAl alloy framework loaded core-shell nanoparticles;

[0100] Step 5, add the NiAl alloy framework loaded core-shell nanoparticles into the etching solution, after etching for 15 min at a temperature of 60℃, wash with deionized water until neutral, treat with oxygen plasma for 10 min at a power of 100 W, pass in water vapor mixed gas containing 1% by volume of O2 at 150℃, and react for 1h, to get the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: add 1 mM benzotriazole and 1 mM sodium silicate into 0.5M NaOH solution.

[0101] Comparative Example 8

[0102] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0103] Step 1, disperse Ni(NO3)2 and Co(NO3)2 in ethylene glycol solution according to the atomic ratio of Ni to Co being 3:1, prepare an internal phase solution with a solid-liquid ratio of 1:20; disperse NaBH4 and sodium citrate in deionized water as an external phase, control the mass ratio of NaBH4, sodium citrate and deionized water to be 2:1:100, adjust the flow rate of the internal phase to be 0.4 mL / min and the flow rate of the external phase to be 1.2 mL / min through a microfluidic chip, and perform shearing reaction under the condition of a temperature of 70℃ and a shearing rate of 1.2×10 4 s -1 , centrifuge, wash, and dry to obtain a NiCo inner core with a particle size of 13 nm;

[0104] Step 2, disperse the NiCo inner core in dilute hydrochloric acid with a mass fraction of 3%, ultrasonic treatment for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, add 5wt% of 3-glycidyloxypropyltrimethoxysilane ethanol solution, stir for 1 h at a stirring speed of 200 rpm, centrifuge, wash, and dry to obtain an activated NiCo inner core; disperse Al (NO3)3 and La (NO3)3 in deionized water, control the total concentration of metal ions to be 0.1 M and the doping amount of La to be 1.5at%, stir at a stirring speed of 200 rpm for 10 min, add 5% of polyvinylpyrrolidone based on the total mass of metal salts, continue to stir, add 20% ammonia water to adjust the pH to 8, and age for 12 h to obtain a coprecipitation sol; add the activated NiCo inner core to the coprecipitation sol, ultrasonic dispersion for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, evaporate water at 70℃ under stirring to form a wet gel, centrifuge, wash, and dry at 80℃ for 24 h to obtain a precursor, wherein the mass ratio of the activated NiCo inner core to the coprecipitation sol is 1:3;

[0105] Step 3, heat the precursor to 400℃ at a heating rate of 5℃, and keep the temperature for 2 h to form an amorphous Al2O3 shell layer with a thickness of 5 nm, continue to heat to 700℃, keep the temperature for 3 h to form a NiAl2O4 spinel transition layer with a thickness of 2 nm, and naturally cool to room temperature to obtain a core-shell nanoparticle;

[0106] Step 4, mix the core-shell nanoparticle, aluminum powder and nickel powder according to a mass ratio of 1:1:1, control the ball-to-material ratio to be 12:1, perform mechanical alloying ball milling under argon protection at a rotating speed of 500 rpm in a manner of 20 min of ball milling and 5 min of intermittent, and obtain a NiAl alloy framework loaded with the core-shell nanoparticle;

[0107] Step 5, the core-shell nanoparticles supported on the NiAl alloy framework are added into the etching solution, after etching for 15 min at 60℃, washing with deionized water until neutral, oxygen plasma treatment for 10 min at a power of 100 W, and reaction for 1 h at 150℃ by introducing water vapor mixed gas containing 1% (volume fraction) O2, to obtain the aluminum-nickel alloy hydrogenation catalyst, wherein the etching solution is: 2 mM sodium silicate is added into 0.5 M NaOH solution.

[0108] Comparative Example 9

[0109] A preparation method of an aluminum-nickel alloy hydrogenation catalyst, comprising the following preparation steps:

[0110] Step 1, Ni (NO3) 2 and Co (NO3) 2 are dispersed in ethylene glycol solution according to the 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 are dispersed in deionized water as an external phase, and the mass ratio of NaBH4, sodium citrate and deionized water is controlled to be 2:1:100; the flow rate of the internal phase is adjusted to be 0.4 mL / min and the flow rate of the external phase is adjusted to be 1.2 mL / min through a microfluidic chip; and shearing reaction is carried out at a temperature of 70℃, and the shearing rate is 1.2×10 4 s -1 , centrifugation, washing and drying to obtain a NiCo inner core with a particle size of 13 nm;

[0111] Step 2, the NiCo inner core is dispersed in 3% (mass fraction) dilute hydrochloric acid, ultrasonic treatment is carried out for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, 5wt% 3-glycidoxypropyltrimethoxysilane ethanol solution is added, stirring reaction is carried out for 1 h at a stirring speed of 200 rpm, centrifugation, washing and drying are carried out to obtain an activated NiCo inner core; Al (NO3) 3 and La (NO3) 3 are dispersed in deionized water, the total concentration of metal ions is controlled to be 0.1 M, the doping amount of La is 1.5at%, stirring is carried out at a stirring speed of 200 rpm for 10 min, 5% of the total mass of metal salt of polyvinylpyrrolidone is added, the pH is adjusted to be 8 by adding 20% (mass fraction) ammonia water dropwise, and aging is carried out for 12 h to obtain a coprecipitation sol; the activated NiCo inner core is added into the coprecipitation sol, ultrasonic dispersion is carried out for 10 min at an ultrasonic power of 100 W and an ultrasonic frequency of 40 KHz, water is evaporated at 70℃ under stirring to form a wet gel, centrifugation, washing and drying at 80℃ for 24 h are carried out to obtain a precursor, wherein the mass ratio of the activated NiCo inner core to the coprecipitation sol is 1:3;

[0112] Step 3, the precursor is heated to 400℃ at a heating rate of 5℃, and kept for 2h to form an amorphous Al2O3 shell layer with a thickness of 5nm, and then heated to 700℃ and kept for 3h to form a NiAl2O4 spinel transition layer with a thickness of 2nm, and then naturally cooled to room temperature to obtain core-shell nanoparticles;

[0113] Step 4, the core-shell nanoparticles, aluminum powder and nickel powder are mixed according to a mass ratio of 1:1:1, and the ball-to-powder ratio is controlled to be 12:1, and then mechanical alloying ball milling is carried out under argon protection at a rotating speed of 500 rpm, and the ball milling is carried out for 20 min each time and the intermittent time is 5 min, to obtain NiAl alloy framework loaded core-shell nanoparticles;

[0114] Step 5, the NiAl alloy framework loaded core-shell nanoparticles are added into an etching solution, and after etching for 15 min at a temperature of 60℃, the etching solution is washed to neutral with deionized water, and then oxygen plasma treatment is carried out at a power of 100W for 10 min, and then the water vapor mixed gas containing 1% O2 by volume is introduced at 150℃, and the reaction is carried out for 1h, to obtain an aluminum-nickel alloy hydrogenation catalyst.

[0115] Performance test

[0116] The performance parameters of the aluminum-nickel alloy hydrogenation catalysts prepared in Examples 1-3 and Comparative Examples 1-9 are as follows:

[0117] Benzene hydrogenation conversion rate: tested according to the industry standard HG / T 5526-2019 “Aluminum-nickel alloy hydrogenation catalyst activity test method”;

[0118] Activity retention rate: tested according to the industry standard HG / T 5526-2019 “Aluminum-nickel alloy hydrogenation catalyst activity test method” after running for 1000h;

[0119] Specific surface area: tested according to the national standard GB / T 5816-1995 “Catalyst and adsorbent surface area determination method

[0120] ”;

[0121] Crushing resistance: tested according to the industry standard HG / T 5525-2019 “Aluminum-nickel alloy hydrogenation catalyst”;

[0122] The test results are shown in Table 1.

[0123] Table 1 Performance parameters of aluminum-nickel alloy hydrogenation catalysts prepared in Examples 1-3 and Comparative Examples 1-9

[0124]

[0125] As can be seen from Table 1, the aluminum-nickel alloy hydrogenation catalyst prepared in the application exhibits excellent comprehensive performance. It has extremely high hydrogenation activity, and the reaction efficiency is significantly improved; it has strong stability and can maintain high-efficiency catalytic capacity for a long time under complex working conditions, and the service life is greatly extended. At the same time, the catalyst has a large specific surface area, rich active sites, and significantly reduced mass transfer resistance. In addition, its mechanical properties are stable, not easy to break or wear, and can adapt to high-strength industrial production environment, ensuring the long-term stable operation of the catalyst.

[0126] The specific embodiments are only an explanation of the application, and are not a limitation of the application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, as long as the modifications are within the scope of the claims of the application.

Claims

1. A method for preparing an aluminum-nickel alloy hydrogenation catalyst, characterized in that, Includes the following steps: Step 1: Ni source and Co source are dispersed in ethylene glycol solution as the inner phase; NaBH4 and sodium citrate are dispersed in deionized water as the outer phase; the inner and outer phases are mixed through a microfluidic chip, subjected to shear reaction, centrifuged, washed, and dried to obtain NiCo core; Step 2: Disperse the NiCo core in dilute hydrochloric acid, add 3-glycidyl etheroxypropyltrimethoxysilane ethanol solution, react for 1-2 hours to obtain activated NiCo core; disperse the Al source and rare earth elements in deionized water, add polyvinylpyrrolidone, adjust the pH to 8-9, age to obtain coprecipitated sol; add the activated NiCo core to the coprecipitated sol, evaporate the water to form a wet gel, wash, dry to obtain the precursor; Step 3: Heat the precursor to 400-450℃ and hold for 2-3 hours to form an amorphous Al2O3 shell. Continue heating to 700-900℃ and hold for 3-4 hours to form a NiAl2O4 spinel transition layer. Cool to room temperature to obtain core-shell nanoparticles. Step 4: Mix core-shell nanoparticles, aluminum powder and nickel powder in a mass ratio of 1-3:1:1-1.2, and mechanically alloy them by intermittent ball milling under argon protection to obtain NiAl alloy framework supported core-shell nanoparticles. Step 5: Add the core-shell nanoparticles supported on the NiAl alloy framework to the etching solution. After etching, wash with deionized water until neutral. After oxygen plasma treatment, introduce a water vapor mixture containing O2 and react for 1-3 hours to obtain the aluminum-nickel alloy hydrogenation catalyst. The doping amount of rare earth elements in step 2 is 1.5-3 at%; the rare earth elements are one or more of La, Ce, Nd, Sm, and Gd; the mass ratio of the activated NiCo core to the coprecipitated sol in step 2 is 1:3-5. In step 5, the etching solution is: 1-2 mM benzotriazole and 1-3 mM sodium silicate added to 0.5-2 M NaOH solution; the oxygen plasma treatment power is 100-120 W, and the treatment time is 10-15 min.

2. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that, In step 1, the atomic ratio of Ni to Co in the Ni and Co sources is 3-5:1; the flow rate of the internal phase is 0.4-0.6 mL / min, and the flow rate ratio of the internal phase to the external phase is 1:3; the shear rate of the shear reaction is 1.2 × 10⁻⁶. 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 NiCo core has a particle size of 12-20 nm.

4. 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℃.

5. 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 as follows: the ball milling speed is 500-600 rpm, each ball milling session lasts 20-30 minutes, with an interval of 5-10 minutes.

6. The method for preparing the aluminum-nickel alloy hydrogenation catalyst according to claim 1, characterized in that, In step 3, the thickness of the amorphous Al2O3 shell is 5-10 nm; the thickness of the NiAl2O4 spinel transition layer is 2-4 nm.

7. An aluminum-nickel alloy hydrogenation catalyst prepared according to any one of claims 1-6.

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