High-stability nickel-based catalyst and preparation method thereof

Abstract

The invention belongs to the technical field of nickel-based catalysts, and particularly provides a high-stability nickel-based catalyst and a preparation method thereof. Comprising the following steps: 1) uniformly mixing tetrabutyl titanate, polyvinylpyrrolidone and glacial acetic acid, carrying out an aging reaction to obtain a precipitate, and drying and calcining the precipitate to obtain a carrier; 2) dissolving molybdenum / cobalt composite salt in ethanol, adding triethanolamine, uniformly mixing, then dropwise adding a phosphoric acid / ethanol mixed solution, stirring for reaction, centrifuging, and decanting with ethanol to obtain a first precursor solution; dissolving nickel nitrate, cerium nitrate and a carboxyl complex in deionized water to obtain a second precursor solution; and 3) mixing the first precursor solution and the second precursor solution, adding a carrier, continuously mixing, carrying out an aging reaction, filtering, collecting the obtained solid, drying, and roasting to obtain the catalyst. The prepared catalyst has the advantages of high selectivity, high catalytic activity and good stability.

Description

Technical Field

[0001] This application belongs to the technical field of nickel-based catalysts, and particularly relates to a highly stable nickel-based catalyst and a preparation method thereof. Background Art

[0002] With the development of catalytic material technology, as a low-cost alternative to precious metals, the application fields and demand of nickel-based catalytic materials have been expanding year by year. Nickel-based catalytic materials are widely used in many fields such as hydrodeoxygenation (HDO), fine chemicals, catalytic hydrogenation, and selective hydrogenation due to their low price and wide sources.

[0003] Compared with precious metal catalysts, although nickel-based materials have low costs, their overall catalytic performance is poor. Therefore, how to design an efficient and economical nickel-based catalyst remains a challenge. To improve the reaction activity of nickel-based catalysts, they can be modified by introducing functional metals or by adjusting the carrier structure, thereby improving the performance of nickel-based catalysts.

[0004] For example, the patent document with the publication number CN120115156A discloses a preparation method of a nickel-based catalyst and the nickel-based catalyst, including: S1. completely dissolving an acid source, a cerium salt, and a solvent; S2. subjecting the solution obtained in step S1 to a hydrothermal reaction; S3. separating the solid and liquid of the product in step S2 and washing, drying, and calcining the obtained solid product to form a carrier, wherein the carrier is cerium dioxide derived from a metal-organic framework; S4. loading an active component onto the carrier, wherein the active component is metallic nickel or nickel oxide. Through this method, a nickel-based catalyst with a relatively high specific surface area and developed mesoporous channels can be prepared, which can avoid the thermal agglomeration of metallic nickel active sites and improve the stability and catalytic performance of the nickel-based catalyst.

[0005] Another example is that the patent document with the publication number CN1403195A discloses a preparation method of a nickel-based catalyst, and the catalyst is used for the partial oxidation of methane to syngas. The preparation method is to mix an aqueous solution of nickel nitrate, a solution composed of n-octane, polyoxyethylene 9-10 octylphenyl ether, and n-hexanol, and aluminum isopropoxide or tetraethyl orthosilicate, and stir at 20-60 °C; then obtain the catalyst through suction filtration, washing, drying, and calcination. The catalyst prepared by this method has a smaller particle size and a larger specific surface area compared with the traditional impregnation method. Under the operating conditions of normal pressure and a reaction temperature of 600-800 °C, it has relatively high reaction activity, and the catalyst also has anti-coking properties and high-temperature stability.

[0006] The above nickel-based catalysts have improved catalytic activity to a certain extent through the adjustment of the carrier structure and the modification of the active component, but still cannot meet the growing technical needs. How to improve the performance of nickel-based catalysts is crucial. Summary of the Invention

[0007] In view of the above problems, in order to further improve the performance of the nickel-based catalyst, the present application provides a highly stable nickel-based catalyst and a preparation method thereof.

[0008] The present application first provides a preparation method of a highly stable nickel-based catalyst, comprising the following steps: 1) Mix tetrabutyl titanate, polyvinylpyrrolidone, and glacial acetic acid evenly, and carry out an aging reaction to obtain a precipitate. After drying and calcining the precipitate, a carrier is obtained; 2) Dissolve the molybdenum / cobalt complex salt in ethanol, add triethanolamine and mix evenly, then dropwise add a phosphoric acid / ethanol mixed solution, stir and react, and then centrifuge. After decanting with ethanol, a first precursor solution is obtained; dissolve nickel nitrate, cerium nitrate, and a carboxyl complex in deionized water to obtain a second precursor solution; 3) Take the first precursor solution and the second precursor solution, mix them, add the carrier and continue to mix, then carry out an aging reaction, filter and collect the obtained solid, and obtain the product after drying and calcining.

[0009] Further, in the step 1), the dosage ratio of tetrabutyl titanate, polyvinylpyrrolidone, and glacial acetic acid is (1 - 1.5 mL):(0.2 - 0.25 g):(50 - 60 mL).

[0010] In some specific embodiments, in the step 1), the dosage ratio of tetrabutyl titanate, polyvinylpyrrolidone, and glacial acetic acid can be 1 mL:0.2 g:50 mL, 1.1 mL:0.2 g:50 mL, 1.2 mL:0.2 g:50 mL, 1.3 mL:0.2 g:50 mL, 1.4 mL:0.2 g:50 mL, 1.5 mL:0.2 g:50 mL, 1 mL:0.21 g:50 mL, 1.1 mL:0.22 g:50 mL, 1.2 mL:0.23 g:50 mL, 1.3 mL:0.24 g:50 mL, 1.4 mL:0.25 g:50 mL, 1.5 mL:0.25 g:50 mL, 1 mL:0.21 g:55 mL, 1.1 mL:0.22 g:60 mL, 1.2 mL:0.23 g:55 mL, 1.3 mL:0.24 g:60 mL, 1.4 mL:0.25 g:55 mL, 1.5 mL:0.25 g:60 mL. More preferably, generally, when the dosage ratio of tetrabutyl titanate, polyvinylpyrrolidone, and glacial acetic acid in the step 1) is 1 mL:0.25 g:55 mL, better experimental results can be obtained.

[0011] Further, in the step 1), the aging reaction is carried out at a temperature of 140 - 160 °C for 20 - 30 h.

[0012] In some specific embodiments, in step 1), the aging reaction can be carried out at temperatures of 140°C, 145°C, 150°C, 155°C, 160°C for 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h, 29 h, 30 h. More preferably, under normal circumstances, in step 1), when the aging reaction is carried out at 150°C for 24 h, better experimental results can be obtained.

[0013] Further, in step 1), drying is carried out at a temperature of 60 - 75°C for 3 - 5 h.

[0014] In some specific embodiments, in step 1), drying can be carried out at temperatures of 60°C, 65°C, 70°C, 75°C for 3 h, 3.5 h, 4 h, 4.5 h, 5 h. More preferably, in step 1), when drying is carried out at 65°C for 3.5 h, good experimental results can be obtained.

[0015] Further, in step 1), calcination is carried out in an air atmosphere at a temperature of 500 - 580°C for 3 - 5 h.

[0016] In some specific embodiments, in step 1), calcination is carried out in an air atmosphere and can be carried out at temperatures of 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C for 3 h, 3.5 h, 4 h, 4.5 h, 5 h. More preferably, under normal circumstances, in step 1), calcination is carried out in an air atmosphere at 550°C for 4 h, and better experimental results can be obtained at this time.

[0017] Further, in step 2), the dosage ratio of molybdenum / cobalt composite salt, ethanol, and triethanolamine is (0.2 - 0.5 g):(100 - 120 mL):(1 - 5 mL).

[0018] In some specific embodiments, in step 2), the dosage ratio of molybdenum / cobalt composite salt, ethanol, and triethanolamine can be 0.2 g:100 mL:1 mL, 0.25 g:100 mL:1 mL, 0.3 g:100 mL:1 mL, 0.35 g:100 mL:1 mL, 0.4 g:100 mL:1 mL, 0.45 g:100 mL:1 mL, 0.5 g:100 mL:1 mL, 0.2 g:105 mL:1 mL, 0.25 g:108 mL:1 mL, 0.3 g:110 mL:1 mL, 0.35 g:112 mL:1 mL, 0.4 g:115 mL:1 mL, 0.45 g:118 mL:1 mL, 0.5 g:120 mL:1 mL, 0.2 g:105 mL:2 mL, 0.25 g:108 mL:2.5 mL, 0.3 g:110 mL:3 mL, 0.35 g:112 mL:3.5 mL, 0.4 g:115 mL:4 mL, 0.45 g:118 mL:4.5 mL, 0.5 g:120 mL:5 mL. More preferably, under normal circumstances, in step 2), when the dosage ratio of molybdenum / cobalt composite salt, ethanol, and triethanolamine is 0.35 g:100 mL:5 mL, better experimental results can be obtained.

[0019] Further, in step 2), in the molybdenum / cobalt composite salt, the molar ratio of molybdenum to cobalt is 1:(2 - 3.5); And / or, in step 2), in the phosphoric acid / ethanol mixed solution, the volume ratio of phosphoric acid to ethanol is 1:(45 - 50); And / or, in step 2), the carboxyl complex is 1,3,5-benzenetricarboxylic acid or 1,4-benzenedicarboxylic acid.

[0020] In some specific embodiments, in step 2), in the molybdenum / cobalt composite salt, the molar ratio of molybdenum to cobalt can be 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:3.6, 1:3.8, 1:4, 1:4.1, 1:4.3, 1:4.5, 1:4.8, 1:5. More preferably, under normal circumstances, in step 2), when the molar ratio of molybdenum to cobalt in the molybdenum / cobalt composite salt is 1:2.5, better experimental results can be obtained.

[0021] In some specific embodiments, in step 2), in the phosphoric acid / ethanol mixed solution, the volume ratio of phosphoric acid to ethanol can be 1:45, 1:46, 1:47, 1:48, 1:49, 1:50. More preferably, under normal circumstances, in step 2), when the volume ratio of phosphoric acid to ethanol in the phosphoric acid / ethanol mixed solution is 1:48, better experimental results can be obtained.

[0022] In some specific embodiments, generally, when the carboxyl complex is 1,4-benzenedicarboxylic acid in step 2), better experimental results can be obtained.

[0023] Further, in step 3), the volume ratio of the first precursor solution to the second precursor solution is 1:(1.5 - 3).

[0024] Further, in step 3), the calcination is carried out in a nitrogen atmosphere at a temperature of 400 - 450 °C for 4 - 6 h.

[0025] Further, in step 3), hydroxyindanone is added while adding the carrier.

[0026] Further, the hydroxyindanone is one of 5-hydroxy-1-indanone, 4-hydroxy-1-indanone, and 6-hydroxy-1-indanone.

[0027] In some specific embodiments, generally, when 5-hydroxy-1-indanone is selected as the hydroxyindanone, better experimental results can be obtained.

[0028] In some specific embodiments, in step 3), the volume ratio of the first precursor solution to the second precursor solution can be 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3. More preferably, generally, when the volume ratio of the first precursor solution to the second precursor solution is 1:2 in step 3), better technical effects can be obtained.

[0029] In some specific embodiments, in step 3), the calcination is carried out in a nitrogen atmosphere and can be at a temperature of 400 °C, 410 °C, 420 °C, 430 °C, 440 °C, 450 °C for 4 h, 4.5 h, 5 h, 5.5 h, 6 h. More preferably, generally, in step 3), the calcination is carried out in a nitrogen atmosphere at a temperature of 400 °C for 5 h, and better experimental results can be obtained at this time.

[0030] This application also provides a highly stable nickel-based catalyst prepared by the above preparation method.

[0031] Compared with the prior art, this application has the following beneficial effects: 1. This application uses tetrabutyl titanate and polyvinylpyrrolidone as compound raw materials. After aging reaction and calcination, a spherical carrier is obtained. The carrier has a uniform scattered pore structure inside, thus obtaining a relatively high specific surface area, which can promote the reactants to quickly reach the active sites and accelerate the mass exchange rate inside and outside the catalyst pores. Moreover, after loading metal atoms such as nickel and cerium, rich active sites are formed, improving the catalytic activity and selectivity of the catalyst.

[0032] 2. This application loads a nano-inorganic polymer formed by molybdenum / cobalt composite salt on the carrier. These nano-inorganic polymers can play a protective role on the surface of the catalyst carrier, regulate the structural properties and surface microenvironment of the catalyst, inhibit the leaching of active metals, and improve the stability of the catalyst. Moreover, the doping of molybdenum / cobalt elements endows more catalytic active sites, and at the same time introduces P, N, O vacancies, enhancing the adsorption of reactants and increasing the number of acidic sites, further improving the selectivity and activity of the catalyst. In addition, the nano-inorganic polymer formed by molybdenum / cobalt composite salt can inhibit the agglomeration of metal atoms, thereby increasing the reaction rate and stability of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a schematic diagram of the test data of the hydrodeoxygenation performance of the catalysts in Examples 1-2 and Control Groups 1-2 of this application.

[0034] Figure 2 It is a TEM image of the catalyst in Example 2 of this application.

[0035] Figure 3 It is a TEM image of the catalyst in Control Group 2 of this application.

[0036] Figure 4 It is a TEM image of the nano-inorganic polymer in Example 2 of this application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] Next, the technical solutions in the embodiments of this application will be clearly and completely described in conjunction with the drawings in the embodiments of this application. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of this application.

[0038] Example 1 The preparation method of the highly stable nickel-based catalyst in this example includes the following steps: 1) Weigh accurately 1 mL of tetrabutyl titanate, 0.25 g of polyvinylpyrrolidone, and 55 mL of glacial acetic acid and place them in a sealed beaker. Stir vigorously to mix evenly. Then transfer the resulting mixture to an autoclave with a polytetrafluoroethylene liner. Then age the reaction at 150 °C for 24 h. Filter to obtain a precipitate, wash the precipitate 3 times with absolute ethanol, then transfer it to a vacuum drying oven and dry it at 65 °C for 3.5 h. Then transfer it to a muffle furnace and calcine it at 550 °C for 4 h in an air atmosphere to obtain a support; 2) Add 100 mL of ethanol to a beaker, add 0.35 g of molybdenum / cobalt complex salt to the beaker, and dissolve the molybdenum / cobalt complex salt in ethanol at a stirring speed of 600 r / min, and control the molar ratio of molybdenum to cobalt in the molybdenum / cobalt complex salt to be 1:2.5; Then add 5 mL of triethanolamine to the beaker and continue to mix evenly; Then slowly add dropwise 5 mL of phosphoric acid / ethanol mixed solution. In the phosphoric acid / ethanol mixed solution, the volume ratio of phosphoric acid to ethanol is 1:48. After stirring and reacting, centrifuge, wash with ultrapure water, and then decant with ethanol to remove the supernatant to obtain a gel. Then take 30 mL of absolute ethanol, 0.5 mL of triethanolamine and the gel and stir vigorously to obtain a first precursor solution; Dissolve 0.29 g of nickel nitrate hexahydrate, 0.434 g of cerium nitrate hexahydrate, and 0.05 g of carboxyl complex (1,4-benzenedicarboxylic acid) in 10 mL of deionized water to obtain a second precursor solution; 3) Take 5 mL of the first precursor solution and 10 mL of the second precursor solution, mix them, add 0.5 g of the support and continue to mix. Then age the reaction at room temperature for 12 h, then dry it at 50 °C for 12 h. Then transfer it to a muffle furnace and heat it up to 400 °C at a heating rate of 2.5 °C / min in a nitrogen atmosphere and calcine it for 5 h. Cool to room temperature. Then raise the temperature of the resulting product to 500 °C at a rate of 2 °C / min in a hydrogen stream of 60 mL / min and reduce it for 3 h. Cool to room temperature to obtain the product.

[0039] Example 2 The preparation method of the highly stable nickel-based catalyst in this example includes the following steps: 1) Weigh accurately 1 mL of tetrabutyl titanate, 0.25 g of polyvinylpyrrolidone, and 55 mL of glacial acetic acid and place them in a sealed beaker. Stir vigorously to mix evenly. Then transfer the resulting mixture to an autoclave with a polytetrafluoroethylene liner. Then age the reaction at 150 °C for 24 h. Filter to obtain a precipitate, wash the precipitate 3 times with absolute ethanol, then transfer it to a vacuum drying oven and dry it at 65 °C for 3.5 h. Then transfer it to a muffle furnace and calcine it at 550 °C for 4 h in an air atmosphere to obtain a support; 2) Add 100 mL of ethanol into a beaker, add 0.35 g of molybdenum / cobalt composite salt into the beaker, and dissolve the molybdenum / cobalt composite salt in ethanol at a stirring speed of 600 r / min, and control the molar ratio of molybdenum to cobalt in the molybdenum / cobalt composite salt to be 1:2.5; then add 5 mL of triethanolamine into the beaker and continue to mix evenly; then slowly dropwise add 5 mL of phosphoric acid / ethanol mixed solution, in the phosphoric acid / ethanol mixed solution, the volume ratio of phosphoric acid to ethanol is 1:48, after stirring and reacting, centrifuge, wash with ultrapure water, and then remove the supernatant by ethanol decantation to obtain a gel-like substance, and then take 30 mL of anhydrous ethanol, 0.5 mL of triethanolamine and the gel-like substance and stir vigorously to obtain a first precursor solution; dissolve 0.29 g of nickel nitrate hexahydrate, 0.434 g of cerium nitrate hexahydrate, and 0.05 g of carboxyl complex (1,4-benzenedicarboxylic acid) in 10 mL of deionized water to obtain a second precursor solution; 3) Take 5 mL of the first precursor solution and 10 mL of the second precursor solution and mix them, add 0.5 g of the carrier and 0.015 g of 5-hydroxy-1-indanone and continue to mix, then age at room temperature for 12 h, then dry at 50 °C for 12 h, then transfer to a muffle furnace, and under a nitrogen atmosphere, heat up to 400 °C at a heating rate of 2.5 °C / min, calcine for 5 h, cool to room temperature, and then raise the obtained product to 500 °C at a rate of 2 °C / min in a hydrogen stream of 60 mL / min and reduce for 3 h, and cool to room temperature to obtain.

[0040] Control Group 1 The preparation method of the catalyst in this control group includes the following steps: 1) Accurately weigh 1 mL of tetrabutyl titanate, 0.25 g of polyvinylpyrrolidone, and 55 mL of glacial acetic acid and place them in a sealed beaker, stir vigorously to mix evenly, then transfer the obtained mixed solution to an autoclave with a polytetrafluoroethylene liner, and then age at 150 °C for 24 h, filter to obtain a precipitate, wash the precipitate 3 times with anhydrous ethanol, then transfer to a vacuum drying oven and dry at 65 °C for 3.5 h, and then transfer to a muffle furnace, and calcine at 550 °C for 4 h in an air atmosphere to obtain a carrier; 2) Dissolve 0.29 g of nickel nitrate hexahydrate, 0.434 g of cerium nitrate hexahydrate, and 0.05 g of carboxyl complex (1,4-benzenedicarboxylic acid) in 10 mL of deionized water to obtain a loading solution; 3) Take 10 mL of the loading solution, add 0.5 g of the carrier and continue to mix, then age at room temperature for 12 h, then dry at 50 °C for 12 h, then transfer to a muffle furnace, and under a nitrogen atmosphere, heat up to 400 °C at a heating rate of 2.5 °C / min, calcine for 5 h, cool to room temperature, and then raise the obtained product to 500 °C at a rate of 2 °C / min in a hydrogen stream of 60 mL / min and reduce for 3 h, and cool to room temperature to obtain.

[0041] Control Group 2 The preparation method of the catalyst of this control group includes the following steps: 1) Accurately weigh 1 mL of tetrabutyl titanate, 0.25 g of polyvinylpyrrolidone, and 55 mL of glacial acetic acid, place them in a sealed beaker, stir vigorously to mix evenly, then transfer the obtained mixture to an autoclave with a polytetrafluoroethylene liner, and then age-react at 150 °C for 24 h. Filter to obtain a precipitate, wash the precipitate 3 times with absolute ethanol, then transfer it to a vacuum drying oven and dry at 65 °C for 3.5 h. Then transfer it to a muffle furnace and calcine in an air atmosphere at 550 °C for 4 h to obtain a support; 2) Mix 0.35 g of molybdenum / cobalt composite salt and 30 mL of absolute ethanol to obtain a first precursor solution, and control the molar ratio of molybdenum to cobalt in the molybdenum / cobalt composite salt to be 1:2.5; Dissolve 0.29 g of nickel nitrate hexahydrate, 0.434 g of cerium nitrate hexahydrate, and 0.05 g of carboxyl complex (1,4-benzenedicarboxylic acid) in 10 mL of deionized water to obtain a second precursor solution; 3) Take 5 mL of the first precursor solution and 10 mL of the second precursor solution, mix them, add 0.5 g of the support and continue to mix, then age-react at room temperature for 12 h, then dry at 50 °C for 12 h. Then transfer it to a muffle furnace, and under a nitrogen atmosphere, heat it to 400 °C at a heating rate of 2.5 °C / min, calcine for 5 h, cool to room temperature, and then raise the temperature of the obtained product to 500 °C at a rate of 2 °C / min in a hydrogen stream of 60 mL / min and reduce it for 3 h, and cool to room temperature to obtain.

[0042] Performance Detection 1. Take the catalysts of Examples 1-2 and Control Groups 1-2 for catalytic performance testing. Using vanillin as a model reaction, perform hydrodeoxygenation performance testing in a 30 mL four-parallel reactor. The specific steps are as follows: First, take 0.50 g of vanillin, 0.05 g of the catalyst, and 5.0 mL of ethanol and place them in a high-pressure reactor. Purge with hydrogen 5 times to remove air, then introduce hydrogen to make the pressure in the reactor reach 2.0 MPa, and then heat to 150 °C. Subsequently, keep the reaction under magnetic stirring at 500 rpm for 4 h. After the reaction is completed, take the liquid-phase product and perform quantitative and qualitative analysis through gas chromatography (Agilent Technologies 7890B, FID detector and SE-30 capillary column) and gas chromatography-mass spectrometer. The results are as Figure 1 shown. Calculate the conversion rate of vanillin and the selectivity of the target product (2-methoxy-4-methylphenol) according to the following formula: , is the amount of substance of the converted vanillin, is the amount of substance of the originally added vanillin.

[0043] , is the amount of substance of the target product generated, is the amount of substance of vanillin that has been converted.

[0044] Combined with Figure 1 it can be seen that the conversion rate of vanillin of the catalysts in Examples 1-2 is close to 100%, and the selectivity of the target product is also very high, while the selectivity of the catalysts in Control Groups 1-2 is worse than that in Example 1 and Example 2.

[0045] 2. Take the catalysts of Example 2 and Control Group 2 for transmission electron microscopy tests, and the results are as Figure 2 and Figure 3 shown; take the first precursor solution of Example 2 for transmission electron microscopy test to observe the morphology of the nano-inorganic polymer, as Figure 4 shown. It can be seen that the pores of the catalyst in Example 2 are loaded by the nano-inorganic polymer to a certain extent, thereby improving the catalytic activity and selectivity of the catalyst. Moreover, after adding the carboxyl complex and hydroxyindanone, the microstructure of the catalyst can be further improved, and the stability and catalytic activity of the catalyst can be enhanced.

[0046] Although the present application has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a highly stable nickel-based catalyst, characterized in that: It includes the following steps: 1) Mix tetrabutyl titanate, polyvinylpyrrolidone, and glacial acetic acid evenly, and carry out an aging reaction to obtain a precipitate. After drying and calcining the precipitate, a carrier is obtained; 2) Dissolve the molybdenum / cobalt composite salt in ethanol, add triethanolamine and mix evenly, then dropwise add the phosphoric acid / ethanol mixed solution, stir and react, then centrifuge, and obtain the first precursor solution after decanting with ethanol; Dissolve nickel nitrate, cerium nitrate, and the carboxyl complex in deionized water to obtain the second precursor solution; 3) Take the first precursor solution and the second precursor solution, mix them, add the carrier and continue to mix, then carry out an aging reaction, filter and collect the obtained solid, and obtain the product after drying and roasting.

2. The preparation method of the highly stable nickel-based catalyst according to claim 1, characterized in that: In the step 1), the dosage ratio of tetrabutyl titanate, polyvinylpyrrolidone, and glacial acetic acid is (1 - 1.5 mL):(0.2 - 0.25 g):(50 - 60 mL).

3. The preparation method of the highly stable nickel-based catalyst according to claim 1, characterized in that: In the step 1), the aging reaction is carried out at a temperature of 140 - 160 °C for 20 - 30 h.

4. The preparation method of the highly stable nickel-based catalyst according to claim 1, characterized in that: In the step 1), the drying is carried out at a temperature of 60 - 75 °C for 3 - 5 h.

5. The preparation method of the highly stable nickel-based catalyst according to claim 1, characterized in that: In the step 1), the calcining is carried out in an air atmosphere at a temperature of 500 - 580 °C for 3 - 5 h.

6. The preparation method of the highly stable nickel-based catalyst according to claim 1, characterized in that: In the step 2), the dosage ratio of the molybdenum / cobalt composite salt, ethanol, and triethanolamine is (0.2 - 0.5 g):(100 - 120 mL):(1 - 5 mL).

7. The preparation method of the highly stable nickel-based catalyst according to claim 1, wherein: In the step 2), in the molybdenum / cobalt composite salt, the molar ratio of molybdenum to cobalt is 1:(2 - 3.5); And / or, in the step 2), in the phosphoric acid / ethanol mixed solution, the volume ratio of phosphoric acid to ethanol is 1:(45 - 50); And / or, in the step 2), the carboxyl complex is 1,3,5-benzenetricarboxylic acid or 1,4-benzenedicarboxylic acid.

8. The preparation method of the highly stable nickel-based catalyst according to claim 1, characterized in that: In the step 3), the volume ratio of the first precursor solution to the second precursor solution is 1:(1.5 - 3).

9. The preparation method of the highly stable nickel-based catalyst according to claim 1, characterized in that: In the step 3), the roasting is carried out in a nitrogen atmosphere at a temperature of 400 - 450 °C for 4 - 6 h.

10. A highly stable nickel-based catalyst, characterized in that: It is prepared by using the preparation method as described in any one of claims 1 - 9.

Images