A highly stable nickel-based catalyst and its preparation method

Abstract

The present application belongs to the technical field of nickel-based catalysts, and specifically provides a highly stable nickel-based catalyst and a preparation method thereof. The process comprises the following steps: 1) uniformly mixing tetrabutyl titanate, polyvinyl pyrrolidone, and glacial acetic acid, performing an aging reaction to obtain a precipitate, drying the precipitate, and calcining the precipitate to obtain a carrier; 2) dissolving a molybdenum / cobalt composite salt in ethanol, adding triethanolamine and mixing uniformly, then dripping a phosphoric acid / ethanol mixed solution, stirring the reaction and 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; 3) mixing the first precursor solution and the second precursor solution, adding the carrier and continuing to mix, then performing an aging reaction, filtering and collecting the obtained solid, drying, and then calcining. The catalyst prepared by the present application has the advantages of high selectivity, high catalytic activity, and good stability.

Description

Technical Field

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

[0002] With the development of catalytic material technology, the application and demand for nickel-based catalytic materials, as low-cost alternatives to precious metals, are expanding year by year. Due to their low price and wide availability, nickel-based catalytic materials are widely used in a variety of fields, including hydrodeoxygenation (HDO), fine chemicals, catalytic hydrogenation, and selective hydrogenation.

[0003] Compared to precious metal catalysts, nickel-based materials, while inexpensive, have inferior overall catalytic performance. Therefore, designing efficient and economical nickel-based catalysts remains a challenge. To enhance the reactivity of nickel-based catalysts, their performance can be improved by modifying them with functional metals or by adjusting the support structure.

[0004] For example, patent application publication number CN120115156A discloses a method for preparing a nickel-based catalyst and a nickel-based catalyst, comprising: 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. performing solid-liquid separation on the product of step S2 and washing, drying, and calcining the resulting solid product to form a support, wherein the support is metal-organic framework-derived cerium dioxide; and S4. loading an active component onto the support, wherein the active component is metallic nickel or nickel oxide. This method can produce a nickel-based catalyst with a high specific surface area and well-developed mesoporous channels, preventing thermal agglomeration of metallic nickel active sites and improving the stability and catalytic performance of the nickel-based catalyst.

[0005] For example, patent application publication number CN1403195A discloses a method for preparing a nickel-based catalyst for use in the partial oxidation of methane to produce synthesis gas. The preparation method involves mixing an aqueous solution of nickel nitrate, a solution consisting of n-octane, polyoxyethylene 9-10 octylphenyl ether, and n-hexanol, with aluminum isopropoxide or tetraethyl orthosilicate, and stirring at 20-60°C. The catalyst is then filtered, washed, dried, and calcined to produce the catalyst. Compared to conventional impregnation methods, the catalyst prepared by this method has a smaller particle size and a larger specific surface area. Under normal pressure and a reaction temperature of 600-800°C, it exhibits high reactivity, resistance to carbon deposition, and high-temperature stability.

[0006] The above-mentioned nickel-based catalysts have improved their catalytic activity to a certain extent through structural adjustment of the carrier and modification of the active components, but they 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 nickel-based catalysts, the present application provides a highly stable nickel-based catalyst and a preparation method thereof.

[0008] This application first provides a method for preparing a highly stable nickel-based catalyst, comprising the following steps:

[0009] 1) Tetrabutyl titanate, polyvinyl pyrrolidone, and glacial acetic acid are uniformly mixed, and an aging reaction is performed to obtain a precipitate, which is then dried and calcined to obtain a support;

[0010] 2) dissolving a molybdenum / cobalt complex salt in ethanol, adding triethanolamine and mixing uniformly, 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 the carboxyl complex in deionized water to obtain a second precursor solution;

[0011] 3) Mix the first precursor solution and the second precursor solution, add the carrier and continue mixing, then age and react, filter and collect the resulting solid, dry and then calcine to obtain the product.

[0012] Furthermore, in step 1), the usage ratio of tetrabutyl titanate, polyvinyl pyrrolidone, and glacial acetic acid is (1-1.5 mL): (0.2-0.25 g): (50-60 mL).

[0013] In some specific embodiments, in step 1), the usage ratio of tetrabutyl titanate, polyvinyl pyrrolidone, 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, and 1.1 mL:0.22 g:50 mL. More preferably, under normal circumstances, in step 1), when the usage ratio of tetrabutyl titanate, polyvinyl pyrrolidone, and glacial acetic acid is 1 mL:0.25 g:55 mL, better experimental results can be achieved.

[0014] Furthermore, in step 1), the aging reaction is carried out at a temperature of 140-160° C. for 20-30 hours.

[0015] In some specific embodiments, in step 1), the aging reaction can be carried out at 140°C, 145°C, 150°C, 155°C, or 160°C for 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 hours. More preferably, in general, better experimental results can be achieved when the aging reaction is carried out at 150°C for 24 hours in step 1).

[0016] Furthermore, in step 1), the drying is performed at a temperature of 60-75° C. for 3-5 hours.

[0017] In some specific embodiments, in step 1), the drying can be performed at 60°C, 65°C, 70°C, or 75°C for 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours. More preferably, in step 1), the drying is performed at 65°C for 3.5 hours, which can achieve good experimental results.

[0018] Furthermore, in step 1), the calcination is carried out in an air atmosphere at a temperature of 500-580° C. for 3-5 hours.

[0019] In some specific embodiments, in step 1), calcination is carried out in an air atmosphere at 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, or 580°C for 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours. More preferably, in step 1), calcination is carried out in an air atmosphere at 550°C for 4 hours, which can achieve better experimental results.

[0020] Furthermore, in the step 2), the usage ratio of the molybdenum / cobalt composite salt, ethanol, and triethanolamine is (0.2-0.5 g):(100-120 mL):(1-5 mL).

[0021] In some specific embodiments, in step 2), the usage ratio of molybdenum / cobalt composite salt, ethanol and triethanolamine can be 0.2g:100mL:1mL, 0.25g:100mL:1mL, 0.3g:100mL:1mL, 0.35g:100mL:1mL, 0.4g:100mL:1mL, 0.45g:100mL:1mL, 0.5g:100mL:1mL, 0.2g:105mL:1mL, 0.25g:108mL:1mL, 0.3g:1 10mL:1mL, 0.35g:112mL:1mL, 0.4g:115mL:1mL, 0.45g:118mL:1mL, 0.5g:120mL:1mL, 0.2g:105mL:2mL, 0.25g:108mL:2.5mL, 0.3g:110mL:3mL, 0.35g:112mL:3.5mL, 0.4g:115mL:4mL, 0.45g:118mL:4.5mL, 0.5g:120mL:5mL. More preferably, under normal circumstances, in step 2), when the usage ratio of molybdenum / cobalt composite salt, ethanol, and triethanolamine is 0.35g:100mL:5mL, better experimental results can be obtained.

[0022] Furthermore, in step 2), the molar ratio of molybdenum to cobalt in the molybdenum / cobalt composite salt is 1:(2-3.5);

[0023] And / or, in step 2), in the phosphoric acid / ethanol mixed solution, the volume ratio of phosphoric acid to ethanol is 1:(45-50);

[0024] And / or, in step 2), the carboxyl complex is 1,3,5-benzenetricarboxylic acid or 1,4-benzenedicarboxylic acid.

[0025] In some specific embodiments, in step 2), the molar ratio of molybdenum to cobalt in the molybdenum / cobalt composite salt may 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, or 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.

[0026] In some specific embodiments, in step 2), the volume ratio of phosphoric acid to ethanol in the phosphoric acid / ethanol mixed solution can be 1:45, 1:46, 1:47, 1:48, 1:49, or 1:50. More preferably, under normal circumstances, in step 2), a volume ratio of phosphoric acid to ethanol in the phosphoric acid / ethanol mixed solution of 1:48 can achieve better experimental results.

[0027] In some specific embodiments, generally, in step 2), when the carboxyl complex is 1,4-benzenedicarboxylic acid, better experimental results can be obtained.

[0028] Furthermore, in step 3), the volume ratio of the first precursor solution to the second precursor solution is 1:(1.5-3).

[0029] Furthermore, in step 3), the calcination is carried out in a nitrogen atmosphere at a temperature of 400-450° C. for 4-6 hours.

[0030] Furthermore, in step 3), hydroxyindane is added at the same time as the carrier.

[0031] Furthermore, the hydroxyindanone is one of 5-hydroxy-1-indanone, 4-hydroxy-1-indanone and 6-hydroxy-1-indanone.

[0032] In some specific embodiments, under normal circumstances, when the hydroxyindanone is 5-hydroxy-1-indanone, better experimental results can be obtained.

[0033] In some specific embodiments, in step 3), the volume ratio of the first precursor liquid to the second precursor liquid 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, or 1:3. More preferably, under normal circumstances, in step 3), a volume ratio of the first precursor liquid to the second precursor liquid of 1:2 can achieve better technical effects.

[0034] In some specific embodiments, in step 3), the calcination is carried out under a nitrogen atmosphere at 400°C, 410°C, 420°C, 430°C, 440°C, or 450°C for 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours. More preferably, in general, in step 3), the calcination is carried out under a nitrogen atmosphere at 400°C for 5 hours, which can achieve better experimental results.

[0035] The present application also provides a highly stable nickel-based catalyst, which is prepared using the above-mentioned preparation method.

[0036] Compared with the prior art, this application has the following beneficial effects:

[0037] 1. This application uses tetrabutyl titanate and polyvinyl pyrrolidone as compound raw materials, and obtains a spherical carrier after aging reaction and calcination. The interior of the carrier has a uniform scattered pore structure, thereby obtaining a higher specific surface area, which can promote the reactants to quickly reach the active site and accelerate the material exchange rate inside and outside the catalyst pores. Moreover, after loading metal atoms such as nickel and cerium, rich active sites are formed, thereby improving the catalytic activity and selectivity of the catalyst.

[0038] 2. The present application loads nano-inorganic polymers formed by molybdenum / cobalt composite salts on the carrier. These nano-inorganic polymers can play a protective role on the catalyst support surface, regulate the catalyst structure and surface microenvironment, inhibit the leaching of active metals, and improve the stability of the catalyst. In addition, the doping of molybdenum / cobalt elements provides more catalytic active sites, while also introducing P, N, and O vacancies, enhancing the adsorption of reactants, increasing the number of acidic sites, and further improving the selectivity and activity of the catalyst. In addition, the nano-inorganic polymers formed by molybdenum / cobalt composite salts can inhibit the agglomeration of metal atoms, thereby improving the reaction rate and stability of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 Schematic diagram of the catalyst hydrodeoxygenation performance test data of Examples 1-2 and Control Groups 1-2 of the present application.

[0040] Figure 2 This is a TEM image of the catalyst of Example 2 of the present application.

[0041] Figure 3 This is the TEM image of the catalyst of control group 2 of this application.

[0042] Figure 4 This is a TEM image of the nano-inorganic polymer of Example 2 of the present application. DETAILED DESCRIPTION

[0043] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0044] Example 1

[0045] The preparation method of the highly stable nickel-based catalyst of this embodiment comprises the following steps:

[0046] 1) Accurately weigh 1 mL of tetrabutyl titanate, 0.25 g of polyvinyl pyrrolidone, and 55 mL of glacial acetic acid into a sealed beaker and vigorously stir to mix. The resulting mixture is then transferred to a polytetrafluoroethylene-lined autoclave and aged at 150°C for 24 h. The precipitate is filtered to obtain a precipitate, which is washed three times with anhydrous ethanol and then dried in a vacuum drying oven at 65°C for 3.5 h. The precipitate is then transferred to a muffle furnace and calcined at 550°C for 4 h in an air atmosphere to obtain a support.

[0047] 2) Add 100 mL of ethanol to a beaker, add 0.35 g of a molybdenum / cobalt complex salt to the beaker, dissolve the molybdenum / cobalt complex salt in the 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 5 mL of a phosphoric acid / ethanol mixed solution dropwise, wherein the volume ratio of phosphoric acid to ethanol in the phosphoric acid / ethanol mixed solution is 1:48, stir the reaction, centrifuge, wash with ultrapure water, and then remove the supernatant by decantation with ethanol to obtain a colloid, then take 30 mL of anhydrous ethanol and 0.5 mL of triethanolamine and vigorously stir the colloid 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 a carboxyl complex (1,4-benzenedicarboxylic acid) in 10 mL of deionized water to obtain a second precursor solution;

[0048] 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 carrier and continue mixing, then age and react at room temperature for 12 h, then dry at 50 ° C for 12 h, then transfer to a muffle furnace, and in a nitrogen atmosphere, heat the temperature to 400 ° C at a rate of 2.5 ° C / min, calcine for 5 h, cool to room temperature, and then reduce the resulting product to 500 ° C at a rate of 2 ° C / min in a hydrogen flow of 60 mL / min for 3 h, and cool to room temperature.

[0049] Example 2

[0050] The preparation method of the highly stable nickel-based catalyst of this embodiment comprises the following steps:

[0051] 1) Accurately weigh 1 mL of tetrabutyl titanate, 0.25 g of polyvinyl pyrrolidone, and 55 mL of glacial acetic acid into a sealed beaker and vigorously stir to mix. The resulting mixture is then transferred to a polytetrafluoroethylene-lined autoclave and aged at 150°C for 24 h. The precipitate is filtered to obtain a precipitate, which is washed three times with anhydrous ethanol and then dried in a vacuum drying oven at 65°C for 3.5 h. The precipitate is then transferred to a muffle furnace and calcined at 550°C for 4 h in an air atmosphere to obtain a support.

[0052] 2) Add 100 mL of ethanol to a beaker, add 0.35 g of a molybdenum / cobalt complex salt to the beaker, dissolve the molybdenum / cobalt complex salt in the 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 5 mL of a phosphoric acid / ethanol mixed solution dropwise, wherein the volume ratio of phosphoric acid to ethanol in the phosphoric acid / ethanol mixed solution is 1:48, stir the reaction, centrifuge, wash with ultrapure water, and then remove the supernatant by decantation with ethanol to obtain a colloid, then take 30 mL of anhydrous ethanol and 0.5 mL of triethanolamine and vigorously stir the colloid 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 a carboxyl complex (1,4-benzenedicarboxylic acid) in 10 mL of deionized water to obtain a second precursor solution;

[0053] 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 carrier and 0.015 g of 5-hydroxy-1-indanone and continue mixing, then age at room temperature for 12 h, then dry at 50 ° C for 12 h, then transfer to a muffle furnace, and in a nitrogen atmosphere, heat to 400 ° C at a heating rate of 2.5 ° C / min, calcine for 5 h, cool to room temperature, and then reduce the resulting product in a hydrogen flow of 60 mL / min at a rate of 2 ° C / min to 500 ° C for 3 h, and cool to room temperature.

[0054] Control group 1

[0055] The preparation method of the catalyst of this control group comprises the following steps:

[0056] 1) Accurately weigh 1 mL of tetrabutyl titanate, 0.25 g of polyvinyl pyrrolidone, and 55 mL of glacial acetic acid into a sealed beaker and vigorously stir to mix. The resulting mixture is then transferred to a polytetrafluoroethylene-lined autoclave and aged at 150°C for 24 h. The precipitate is filtered to obtain a precipitate, which is washed three times with anhydrous ethanol and then dried in a vacuum drying oven at 65°C for 3.5 h. The precipitate is then transferred to a muffle furnace and calcined at 550°C for 4 h in an air atmosphere to obtain a support.

[0057] 2) Dissolve 0.29 g of nickel nitrate hexahydrate, 0.434 g of cerium nitrate hexahydrate, and 0.05 g of the carboxyl complex (1,4-benzenedicarboxylic acid) in 10 mL of deionized water to obtain a loading solution;

[0058] 3) Take 10 mL of the load liquid, add 0.5 g of the carrier and continue mixing. 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 to 400°C at a heating rate of 2.5°C / min under a nitrogen atmosphere. Calcinate it for 5 h and cool it to room temperature. Then, reduce the resulting product to 500°C at a rate of 2°C / min in a hydrogen flow of 60 mL / min for 3 h and cool it to room temperature.

[0059] Control group 2

[0060] The preparation method of the catalyst of this control group comprises the following steps:

[0061] 1) Accurately weigh 1 mL of tetrabutyl titanate, 0.25 g of polyvinyl pyrrolidone, and 55 mL of glacial acetic acid into a sealed beaker and vigorously stir to mix. The resulting mixture is then transferred to a polytetrafluoroethylene-lined autoclave and aged at 150°C for 24 h. The precipitate is filtered to obtain a precipitate, which is washed three times with anhydrous ethanol and then dried in a vacuum drying oven at 65°C for 3.5 h. The precipitate is then transferred to a muffle furnace and calcined at 550°C for 4 h in an air atmosphere to obtain a support.

[0062] 2) Mix 0.35 g of a molybdenum / cobalt complex salt and 30 mL of anhydrous ethanol to obtain a first precursor solution, wherein the molar ratio of molybdenum to cobalt in the molybdenum / cobalt complex salt is controlled 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 a carboxyl complex (1,4-benzenedicarboxylic acid) in 10 mL of deionized water to obtain a second precursor solution;

[0063] 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 carrier and continue mixing, then age and react at room temperature for 12 h, then dry at 50 ° C for 12 h, then transfer to a muffle furnace, and in a nitrogen atmosphere, heat the temperature to 400 ° C at a rate of 2.5 ° C / min, calcine for 5 h, cool to room temperature, and then reduce the resulting product to 500 ° C at a rate of 2 ° C / min in a hydrogen flow of 60 mL / min for 3 h, and cool to room temperature.

[0064] Performance testing

[0065] 1. The catalysts of Examples 1-2 and Control Groups 1-2 were tested for catalytic performance. Vanillin was used as a model reaction, and the hydrodeoxygenation performance test was carried out in a 30 mL quadruple parallel reactor. The specific steps are as follows: First, 0.50 g of vanillin, 0.05 g of catalyst, and 5.0 mL of ethanol were placed in a high-pressure reactor. The air was purged with hydrogen 5 times, and then hydrogen was introduced to make the pressure in the reactor reach 2.0 MPa, and then heated to 150°C. Subsequently, the reaction was maintained under magnetic stirring at 500 rpm for 4 hours. After the reaction was completed, the liquid product was taken and quantitative and qualitative analysis was performed by gas chromatography (Agilent Technologies 7890B, FID detector and SE-30 capillary column) and gas chromatography-mass spectrometry. The results are as follows: Figure 1 The conversion rate of vanillin and the selectivity of the target product (2-methoxy-4-methylphenol) were calculated according to the following formula:

[0066] , is the amount of substance converted to vanillin, is the amount of material originally added to the vanillin.

[0067] , is the amount of the substance that has generated the target product, is the amount of substance that has been converted to vanillin.

[0068] Combine Figure 1 It can be seen that the conversion rate of vanillin of the catalyst of Example 1-2 is close to 100%, and the selectivity of the target product is also very high, while the selectivity of the catalyst of Control Group 1-2 is worse than that of Example 1 and Example 2.

[0069] 2. The catalysts of Example 2 and Control Group 2 were tested by transmission electron microscopy. The results are as follows: Figure 2 and Figure 3 Take the first precursor solution of Example 2 for transmission electron microscopy test to observe the morphology of the nano-inorganic polymer, as shown Figure 4 As shown in Figure 2, the pores of the catalyst of Example 2 are supported to a certain extent by the nano-inorganic polymer, thereby improving the catalytic activity and selectivity of the catalyst. Furthermore, the addition of the carboxyl complex and hydroxyindanone further improves the catalyst's microstructure, enhancing its stability and catalytic activity.

[0070] Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments, or make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a highly stable nickel-based catalyst, characterized in that: The steps include: 1) Accurately weigh 1 mL of tetrabutyl titanate, 0.25 g of polyvinyl pyrrolidone, and 55 mL of glacial acetic acid into a sealed beaker and vigorously stir to mix. The resulting mixture is then transferred to a polytetrafluoroethylene-lined autoclave and aged at 150°C for 24 h. The precipitate is filtered to obtain a precipitate, which is washed three times with anhydrous ethanol and then dried in a vacuum drying oven at 65°C for 3.5 h. The precipitate is then transferred to a muffle furnace and calcined 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 a molybdenum / cobalt complex salt to the beaker, dissolve the molybdenum / cobalt complex salt in the ethanol at a stirring speed of 600 r / min, and control the molybdenum to cobalt molybdenum complex salt 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 5 mL of a phosphoric acid / ethanol mixed solution dropwise, wherein the volume ratio of phosphoric acid to ethanol in the phosphoric acid / ethanol mixed solution is 1:48, stir the reaction, centrifuge, wash with ultrapure water, and then remove the supernatant by decantation with ethanol to obtain a colloid, then take 30 mL of anhydrous ethanol, 0.5 mL of triethanolamine and the colloid and stir vigorously to obtain a first precursor solution; 0.29 g of nickel nitrate hexahydrate, 0.434 g of cerium nitrate hexahydrate, and 0.05 g of 1,4-benzenedicarboxylic acid are dissolved 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 carrier and continue mixing, then age and react at room temperature for 12 h, then dry at 50 ° C for 12 h, then transfer to a muffle furnace, and in a nitrogen atmosphere, heat the temperature to 400 ° C at a rate of 2.5 ° C / min, calcine for 5 h, cool to room temperature, and then reduce the resulting product to 500 ° C at a rate of 2 ° C / min in a hydrogen flow of 60 mL / min for 3 h, and cool to room temperature.

2. A method for preparing a highly stable nickel-based catalyst, characterized in that: The steps include: 1) Accurately weigh 1 mL of tetrabutyl titanate, 0.25 g of polyvinyl pyrrolidone, and 55 mL of glacial acetic acid into a sealed beaker and vigorously stir to mix. The resulting mixture is then transferred to a polytetrafluoroethylene-lined autoclave and aged at 150°C for 24 h. The precipitate is filtered to obtain a precipitate, which is washed three times with anhydrous ethanol and then dried in a vacuum drying oven at 65°C for 3.5 h. The precipitate is then transferred to a muffle furnace and calcined 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 a molybdenum / cobalt complex salt to the beaker, dissolve the molybdenum / cobalt complex salt in the ethanol at a stirring speed of 600 r / min, and control the molybdenum to cobalt molybdenum complex salt 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 5 mL of a phosphoric acid / ethanol mixed solution dropwise, wherein the volume ratio of phosphoric acid to ethanol in the phosphoric acid / ethanol mixed solution is 1:48, stir the reaction, centrifuge, wash with ultrapure water, and then remove the supernatant by decantation with ethanol to obtain a colloid, then take 30 mL of anhydrous ethanol, 0.5 mL of triethanolamine and the colloid and stir vigorously to obtain a first precursor solution; 0.29 g of nickel nitrate hexahydrate, 0.434 g of cerium nitrate hexahydrate, and 0.05 g of 1,4-benzenedicarboxylic acid are dissolved 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 carrier and 0.015 g of 5-hydroxy-1-indanone and continue mixing, then age at room temperature for 12 h, then dry at 50 ° C for 12 h, then transfer to a muffle furnace, and in a nitrogen atmosphere, heat to 400 ° C at a heating rate of 2.5 ° C / min, calcine for 5 h, cool to room temperature, and then reduce the resulting product in a hydrogen flow of 60 mL / min at a rate of 2 ° C / min to 500 ° C for 3 h, and cool to room temperature.

3. A highly stable nickel-based catalyst, characterized in that: The method is as described in claim 1 or 2.

Images