A powder-supported nickel catalyst, its preparation method and application

Abstract

This application relates to the technical field of nickel-based catalysts, specifically disclosing a powder-supported nickel catalyst, its preparation method, and its application. The powder-supported nickel catalyst disclosed in this application is prepared from the following components in parts by weight: 1-3 parts of active component and 8-15 parts of porous aluminosilicate support; the active component comprises nickel, lanthanum, and cobalt; the active component is composed of nickel, lanthanum, and cobalt in a molar ratio of 1:0.2-0.5:0.03-0.1. Using the technical solution of this application, a powder-supported nickel catalyst with high catalytic activity and strong stability is provided; moreover, the preparation method of the catalyst provided in this application is simple and suitable for large-scale production.

Description

Technical Field

[0001] This application relates to the technical field of nickel catalysts, specifically to a powder-supported nickel catalyst, its preparation method, and its application. Background Technology

[0002] Supported nickel catalysts are widely used in hydrogenation, dehydrogenation, and reforming reactions in petrochemical and fine chemical industries due to their advantages such as high catalytic activity and relatively low cost. Powdered supports have the characteristics of large specific surface area and good dispersion performance. Loading nickel active components onto powdered supports can further improve the dispersion of active components and enhance the contact efficiency between the catalyst and reactants. However, existing powder-supported nickel catalysts still have many shortcomings. On the one hand, the active component nickel in traditional catalysts is prone to agglomeration, leading to a reduction in catalytic active sites and decreased catalytic efficiency. On the other hand, the catalysts have poor stability and are easily deactivated during the reaction process due to problems such as active component detachment and support structure collapse, resulting in a short service life. In addition, some preparation processes are complex and difficult to achieve large-scale industrial production.

[0003] Therefore, developing a powder-supported nickel catalyst with uniformly dispersed active components, high catalytic activity, strong stability, and simple preparation process is of great practical significance. Summary of the Invention

[0004] To address the aforementioned technical problems, this application provides a powder-supported nickel catalyst, its preparation method, and its application.

[0005] In a first aspect, this application provides a powder-supported nickel catalyst, which is prepared by comprising the following components in parts by weight: 1-3 parts of active component and 8-15 parts of porous aluminosilicate support; wherein the active component comprises nickel, lanthanum and cobalt; The active component consists of nickel, lanthanum, and cobalt in a molar ratio of 1:0.2-0.5:0.03-0.1.

[0006] The purpose of this application is to overcome the shortcomings of the prior art and provide a powder-supported nickel catalyst, which has the characteristics of uniform dispersion of active components, high catalytic activity and strong stability.

[0007] In this application, lanthanum and cobalt are used as active components of nickel as additives, and the molar ratio of each active component is controlled to promote high dispersion of the active component nickel, enhance the catalyst's resistance to sintering, and prevent its agglomeration during calcination and decomposition. Furthermore, the additives can alter the electronic structure of the active component nickel, improving its catalytic performance. Porous aluminosilicate powder is used as a support, and the active components nickel, lanthanum, and cobalt are uniformly distributed on the channels and surface of the aluminosilicate powder, thereby obtaining a catalyst with high catalytic activity.

[0008] It should be noted that in the composition representation of powder-supported nickel catalysts, the weight parts of the active components are measured by the total weight of Ni, La, and Co elements.

[0009] Preferably, the powder-supported nickel catalyst is prepared by comprising the following components in parts by weight: 1.5-2.5 parts of active component and 8-10 parts of porous aluminosilicate support.

[0010] Preferably, the active component consists of nickel, lanthanum and cobalt in a molar ratio of 1:0.3-0.4:0.05-0.07.

[0011] Secondly, this application provides a method for preparing the powder-supported nickel catalyst, comprising the following steps: Alumina was ultrasonically dispersed in an aqueous solution of 0.3-0.5 wt% surfactant, and then sodium silicate was added and mixed evenly. The pH was adjusted to 12.0-13.0 with an alkaline solution to obtain a slurry, which was reacted at 40-60℃ for 4-8 hours. The slurry was then dried at 90-110℃ for 5-10 hours, and then calcined at 500-600℃ for 3-5 hours. After cooling, porous aluminosilicate powder was obtained. The weight ratio of alumina, 0.3-0.5 wt% surfactant, and sodium silicate was 10-20:100:3-11.

[0012] The porous aluminosilicate powder was immersed in a mixed salt solution at a solid-liquid ratio of 1:8-12. Alkali solution was added dropwise under stirring at a water bath temperature of 70-90℃ until the pH reached 8.0. The mixture was then aged at this temperature for 2-6 hours. After aging, the mixture was filtered, and the filter cake was collected. The filter cake was then slurried with water and filtered repeatedly 3-5 times to obtain the precursor. The mixed salt solution consisted of nickel nitrate, lanthanum nitrate, and cobalt nitrate. The precursor was subjected to drying, calcination, reduction, and passivation treatments to obtain the powder-supported nickel catalyst.

[0013] The preparation principle of the porous aluminosilicate powder in this application is as follows: using alumina as the aluminum source and a surfactant as the dispersion liquid, the powder can self-assemble in the solution to form ordered structures such as micelles, vesicles, or microemulsions. These structures act as soft templates, guiding the directional assembly of inorganic precursors on their surface or inside, thus facilitating their use as pore-forming templates in subsequent processing. Then, sodium silicate, a silicon source, is added and the conditions are adjusted to a strongly alkaline environment. Under this environment, the aluminate ions dissolved from the alumina react with the silicate ions in the solution, precipitating and condensing to form an amorphous aluminosilicate gel layer. After drying and calcination, a composite powder carrier material with a regularly pore-rich aluminosilicate shell is formed.

[0014] Using the porous aluminosilicate powder prepared by the above scheme as a carrier is beneficial for the uniform distribution of active components and auxiliary components in the pores and surface of the aluminosilicate powder. Furthermore, the newly formed aluminosilicate layer may form a stronger chemical bond with the nickel species, which tightly fixes the nickel nanoparticles to the carrier surface and effectively prevents them from sintering at the reaction high temperature (small particles grow into inert large particles).

[0015] The method for preparing powder-supported nickel catalyst provided in this application employs an impregnation process to simultaneously load both the active nickel component and the auxiliary component. This ensures that each component is uniformly covered on the support surface, fully leveraging the synergistic effect of the auxiliary component. Furthermore, by precisely controlling process parameters such as drying and calcination, the structure and performance of the catalyst are further optimized.

[0016] Preferably, the mixed salt solution is a solution containing 0.1-0.3 mol / L nickel ions, 0.03-0.09 mol / L lanthanum ions, and 0.007-0.021 mol / L cobalt ions.

[0017] In one specific implementation, the content of nickel ions in the mixed salt solution can be 0.1 mol / L, 0.2 mol / L, or 0.3 mol / L; the content of lanthanum ions can be 0.03 mol / L, 0.06 mol / L, or 0.09 mol / L; and the content of cobalt ions can be 0.007 mol / L, 0.014 mol / L, or 0.021 mol / L.

[0018] Preferably, in the method for preparing the porous aluminosilicate powder, the weight ratio of alumina, 0.3-0.5 wt% surfactant aqueous solution, and sodium silicate is 13-17:100:5-8.

[0019] In one specific embodiment, the preparation method of the porous aluminosilicate powder involves the following weight ratios: alumina, 0.3-0.5 wt% surfactant aqueous solution, and sodium silicate, which are 10:100:3, 13:100:3, 15:100:3, 17:100:3, 20:100:5, 10:100:5, 13:100:5, 15:100:5, 17:100:5, 20 :100:5, 10:100:7, 13:100:7, 15:100:7, 17:100:7, 20:100:7, 10:100:8, 13:100:8, 15:100:8, 17:100:8, 20:100:8, 10:100:10, 13:100:10, 15:100:10, 17:100:10, 20:100:10.

[0020] Experimental analysis shows that, in the preparation method of porous aluminosilicate powder, controlling the weight ratio of alumina, 0.3-0.5 wt% surfactant aqueous solution, and sodium silicate within the above-mentioned range can further improve the performance of the catalyst.

[0021] Preferably, in the method for preparing porous aluminosilicate powder, the surfactant is selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether AEO-9, fatty alcohol polyoxyethylene ether AEO-7, Tween-80, and Triton X-100.

[0022] Preferably, the surfactant is composed of sodium dodecylbenzenesulfonate and Triton X-100 in a weight ratio of 10-15:1-3.

[0023] Experimental analysis shows that the surfactant composition of sodium dodecylbenzenesulfonate and Triton X-100 in the aforementioned weight ratio can further improve catalyst performance. Specifically, sodium dodecylbenzenesulfonate (anionic) and Triton X-100 (nonionic) used in this application can be used in combination to produce a synergistic effect, thereby controlling the pore structure, pore size, and distribution of the porous aluminosilicate powder material. In the subsequent catalyst preparation process, the various elements in the catalyst are uniformly distributed and composited on the pore walls of the porous aluminosilicate powder material, thereby improving the catalytic effect.

[0024] Preferably, the alkaline solution is selected from one or more of the following: sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, triethylamine, sodium carbonate, and sodium bicarbonate.

[0025] Preferably, the drying and calcining method is as follows: the precursor is dried at 100-120℃ for 8-14 hours; then, in an air atmosphere, the temperature is raised to 400-550℃ at a heating rate of 2-5℃ / min and calcined for 3-5 hours to obtain the calcined product.

[0026] Preferably, the reduction method is as follows: the calcined product is placed in a hydrogen-nitrogen mixed atmosphere and heated to 400-500℃ at a heating rate of 1-3℃ / min for reduction treatment for 3-6 hours; the passivation method is as follows: the reduced product is placed in a nitrogen-air mixed atmosphere at 20-30℃ for passivation treatment for 8-12 hours.

[0027] Thirdly, this application provides an application of the powder-supported nickel catalyst described above in olefin hydrogenation, nitro hydrogenation, and aldehyde / ketone hydrogenation.

[0028] Fourthly, this application provides a method for preparing 2-methoxy-4-methylphenol by hydrogenation of vanillin, wherein the method uses the powder-supported nickel catalyst described above, and the reaction conditions are as follows: the amount of the powder-supported nickel catalyst is 1-3% of the weight of vanillin; the reaction solvent is ethanol; the pressure is 1.0-2.0 MPa; and the temperature is 140-160℃.

[0029] The powder-supported nickel catalyst provided in this application is used in the hydrogenation reaction of vanillin to prepare 2-methoxy-4-methylphenol. The amount of catalyst used is small, the catalytic conversion rate of vanillin is high, the selectivity of the target product 2-methoxy-4-methylphenol is good, and the catalyst still has high catalytic activity after multiple cycles, that is, the catalyst has a long service life.

[0030] In summary, the technical solution of this application has the following effects: The powder-supported nickel catalyst of this application uses porous aluminosilicate powder as a carrier. By rationally combining active components and additives and using a specific impregnation-calcination process, the catalyst has the advantages of uniform dispersion of active components, high catalytic activity, and strong stability, and has broad application prospects in organic synthesis reactions such as hydrogenation.

[0031] The powder-supported nickel catalyst of this application has excellent application effects in the hydrogenation reaction of vanillin to prepare 2-methoxy-4-methylphenol, with high catalytic conversion rate, good product selectivity and long service life.

[0032] The method for preparing the powder-supported nickel catalyst provided in this application is simple, easy to operate, environmentally friendly, and low in cost, making it suitable for large-scale industrial production and showing good prospects for industrial application. Detailed Implementation

[0033] The present application will be further described in detail below with reference to embodiments, comparative examples and performance test results. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0034] Example

[0035] Example 1 Example 1 provides a powder-supported nickel catalyst and its preparation method.

[0036] The porous aluminosilicate powder in this embodiment is prepared as follows: 15g of alumina is ultrasonically dispersed in 100g of an aqueous solution of 0.4wt% surfactant (composed of sodium dodecylbenzenesulfonate and Triton X-100 in a weight ratio of 13:2), then 7g of sodium silicate is added and mixed evenly. The pH is adjusted to 12.5 with a 2mol / L sodium hydroxide alkaline solution to obtain a slurry, which is reacted at 50℃ for 6h. The slurry is then dried at 100℃ for 6h, and after drying, it is calcined at 550℃ for 4h. After cooling, porous aluminosilicate powder is obtained. The weight ratio of alumina, 0.4wt% sodium dodecylbenzenesulfonate aqueous solution, and sodium silicate is 15:100:7.

[0037] The preparation method of the powder-supported nickel catalyst in this embodiment includes the following steps: Preparation of mixed salt solution: Dissolve 0.1 mol nickel nitrate hexahydrate (Ni(NO3)2·6H2O), 0.03 mol lanthanum nitrate hexahydrate (La(NO3)3·6H2O), and 0.007 mol cobalt nitrate hexahydrate (Co(NO3)2·6H2O) in deionized water and bring the volume to 1000 mL to obtain a mixed salt solution containing 0.1 mol / L nickel ions, 0.03 mol / L lanthanum ions, and 0.007 mol / L cobalt ions.

[0038] Preparation of alkaline solution: Dissolve 1 mol of sodium carbonate and 1 mol of sodium hydroxide in deionized water, and bring the volume to 1000 mL to obtain a mixed alkaline solution.

[0039] Preparation of precursor: According to the solid-liquid ratio of 1:10, 10g of porous aluminosilicate powder was immersed in 100mL of mixed salt solution. Under stirring conditions and water bath temperature of 80℃, 0.2mol / L sodium hydroxide alkaline solution was added dropwise until the pH reached 8.0. The mixture was aged for 4h under the temperature holding condition. After aging, the mixture was filtered, and the filter cake was collected. The filter cake was then slurried with water and filtered. This process was repeated 3-5 times to obtain the precursor. Drying and calcining: The precursor was dried at 110℃ for 10h; then, in an air atmosphere, the temperature was increased to 500℃ at a heating rate of 3℃ / min and calcined for 4h to obtain the calcined product. Reduction and passivation: The calcined product was placed in a hydrogen-nitrogen mixed atmosphere and heated to 450℃ at a heating rate of 2℃ / min for 4 hours for reduction treatment; the reduced product was then placed in a nitrogen-air mixed atmosphere at 30℃ for passivation treatment for 10 hours, thus obtaining the powdered supported nickel catalyst. (In the final catalyst after reduction and passivation, 0.01 mol of Ni exists mostly in the particle core in a metallic state, with a mass of 0.01 mol × 58.69 g / mol (molar mass of Ni) = 0.587 g; La exists as lanthanum oxide (La₂O₃) and is not reduced.) The mass of a = 0.003 mol × 138.91 g / mol = 0.417 g; Co, similar to nickel, has a metallic core, and its mass = 0.0007 mol × 58.93 g / mol (molar mass of Co) = 0.041 g. Therefore, the composition of the powder-supported nickel catalyst is: 1.05 g of active component (based on metal elements, the total mass of the supported material = 0.5869 + 0.4167 + 0.0413 ≈ 1.05 g), 10 g of porous aluminosilicate support; the active component consists of nickel, lanthanum, and cobalt in a molar ratio of 1:0.3:0.07.

[0040] Examples 2-6 Examples 2-6 respectively provide a powder-supported nickel catalyst and its preparation method.

[0041] The difference between the above embodiments and Embodiment 1 is that the composition of the mixed salt solution is different, as shown below.

[0042] In Example 2, the mixed salt solution contained 0.2 mol / L nickel ions, 0.06 mol / L lanthanum ions, and 0.014 mol / L cobalt ions. The prepared powder-supported nickel catalyst consisted of 2.09 g of active component and 10 g of porous aluminosilicate support; the active component was composed of nickel, lanthanum, and cobalt in a molar ratio of 1:0.3:0.07.

[0043] In Example 3, the mixed salt solution contained 0.3 mol / L nickel ions, 0.09 mol / L lanthanum ions, and 0.021 mol / L cobalt ions. The prepared powder-supported nickel catalyst consisted of 3.13 g of active component and 10 g of porous aluminosilicate support; the active component was composed of nickel, lanthanum, and cobalt in a molar ratio of 1:0.3:0.07.

[0044] In Example 4, the mixed salt solution contained 0.2 mol / L nickel ions, 0.08 mol / L lanthanum ions, and 0.01 mol / L cobalt ions. The prepared powder-supported nickel catalyst consisted of 2.34 g of active component and 10 g of porous aluminosilicate support; the active component was composed of nickel, lanthanum, and cobalt in a molar ratio of 1:0.4:0.05.

[0045] In Example 5: the mixed salt solution was a mixed salt solution containing 0.2 mol / L nickel ions, 0.04 mol / L lanthanum ions, and 0.02 mol / L cobalt ions. The prepared powder-supported nickel catalyst consisted of 1.85 g of active component and 10 g of porous aluminosilicate support; the active component was composed of nickel, lanthanum, and cobalt in a molar ratio of 1:0.2:0.1.

[0046] In Example 6: the mixed salt solution was a mixed salt solution containing 0.2 mol / L nickel ions, 0.1 mol / L lanthanum ions, and 0.006 mol / L cobalt ions. The prepared powder-supported nickel catalyst consisted of 2.60 g of active component and 10 g of porous aluminosilicate support; the active component was composed of nickel, lanthanum, and cobalt in a molar ratio of 1:0.5:0.03.

[0047] All other process parameters in the above embodiments are the same as those in Embodiment 1.

[0048] Examples 7-10 Examples 7-10 respectively provide a powder-supported nickel catalyst and its preparation method.

[0049] The difference between the above embodiment and Embodiment 2 is that the preparation methods of the porous aluminosilicate powder are different, as shown below.

[0050] In Example 7: In the preparation method of porous aluminosilicate powder, the weight ratio of alumina, 0.4wt% sodium dodecylbenzenesulfonate aqueous solution, and sodium silicate is 10g:100g:10g.

[0051] In Example 8: In the preparation method of porous aluminosilicate powder, the weight ratio of alumina, 0.4wt% sodium dodecylbenzenesulfonate aqueous solution, and sodium silicate is 20g:100g:3g.

[0052] In Example 9: In the preparation method of porous aluminosilicate powder, the weight ratio of alumina, 0.4wt% sodium dodecylbenzenesulfonate aqueous solution, and sodium silicate is 13g:100g:8g.

[0053] In Example 10: In the preparation method of porous aluminosilicate powder, the weight ratio of alumina, 0.4wt% sodium dodecylbenzenesulfonate aqueous solution, and sodium silicate is 17g:100g:5g.

[0054] All other process parameters in the above embodiments are the same as those in Embodiment 2.

[0055] Examples 11-14 Examples 11-14 respectively provide a powder-supported nickel catalyst and its preparation method.

[0056] The difference between the above embodiment and Embodiment 2 is that the composition of the surfactant in the preparation method of porous aluminosilicate powder is different, as shown below.

[0057] In Example 11: The surfactant is composed of sodium dodecylbenzenesulfonate and Tween-80 in a weight ratio of 13:2.

[0058] In Example 12: The surfactant was composed of sodium dodecylbenzenesulfonate and Triton X-100 in a weight ratio of 2:13.

[0059] In Example 13: The surfactant was composed of sodium dodecylbenzenesulfonate and Triton X-100 in a weight ratio of 10:3.

[0060] In Example 14: The surfactant was composed of sodium dodecylbenzenesulfonate and Triton X-100 in a weight ratio of 15:1.

[0061] All other process parameters in the above embodiments are the same as those in Embodiment 2.

[0062] Comparative Example Comparative Examples 1-3 Comparative Examples 1-3 provide a powder-supported nickel catalyst and its preparation method, respectively.

[0063] The difference between the above comparative example and Example 2 is that the composition of the mixed salt solution is different, as shown below.

[0064] In Comparative Example 1: the mixed salt solution contained 0.2 mol / L nickel ions, 0.014 mol / L lanthanum ions, and 0.06 mol / L cobalt ions. The prepared powder-supported nickel catalyst consisted of 1.72 g of active component and 10 g of porous aluminosilicate support; the active component was composed of nickel, lanthanum, and cobalt in a molar ratio of 1:0.07:0.3.

[0065] In Comparative Example 2: the mixed salt solution was a mixed salt solution containing 0.2 mol of nickel ions, 0.12 mol / L of lanthanum ions, and 0.004 mol / L of cobalt ions. The prepared powder-supported nickel catalyst had the following composition: 2.86 g of active component and 10 g of porous aluminosilicate support; the active component consisted of nickel, lanthanum, and cobalt in a molar ratio of 1:0.6:0.02.

[0066] In Comparative Example 3: the mixed salt solution contained 0.2 mol / L nickel ions, 0.06 mol / L zinc ions, and 0.014 mol / L cobalt ions. The prepared powder-supported nickel catalyst had the following composition: 1.65 g of active component and 10 g of porous aluminosilicate support; the active component consisted of nickel, lanthanum, and zinc in a molar ratio of 1:0.3:0.07.

[0067] All other process parameters in the above comparative examples are the same as those in Example 2.

[0068] Comparative Examples 4-6 Comparative Examples 4-6 each provide a powder-supported nickel catalyst and its preparation method.

[0069] The difference between the above comparative example and Example 2 is as follows:

[0070] In Comparative Example 4: In the preparation method of porous aluminosilicate powder: an equal amount of aqueous solution was used to replace 0.4 wt% of surfactant aqueous solution.

[0071] In Comparative Example 5: In the preparation method of porous aluminosilicate powder: an equal amount of 0.1 wt% surfactant aqueous solution was used instead of 0.4 wt% sodium dodecylbenzenesulfonate aqueous solution.

[0072] In Comparative Example 6: In the preparation method of porous aluminosilicate powder, the weight ratio of alumina, 0.4wt% surfactant aqueous solution, and sodium silicate is 5g:100g:17g.

[0073] All other process parameters in the above comparative examples are the same as those in Example 2.

[0074] Performance testing Catalytic performance: The catalysts used in the examples and comparative examples were tested for catalytic performance. The specific steps were as follows: 10 mL of ethanol, 1 g of vanillin, and 0.01 g of catalyst were placed in a high-pressure reactor. The reactor was purged with hydrogen five times to remove air, and then hydrogen was introduced to bring the pressure inside the reactor to 2.0 MPa. The reactor was then heated to 150 °C, and the rotation speed was adjusted to 400 rpm for 3 h. After the reaction was completed, the liquid product was collected and analyzed by chromatography. The conversion rate of vanillin and the selectivity of the target product (2-methoxy-4-methylphenol) were calculated.

[0075] Stability: The catalyst was separated from the reaction system, dried, and its catalytic activity was tested again after 5 cycles. The conversion rate of vanillin and the selectivity of the target product (2-methoxy-4-methylphenol) were calculated to evaluate the stability of the catalyst. Vanillin conversion stability = (Vanillin conversion rate after 5 cycles / Vanillin conversion rate of the initial catalyst) × 100%; 2-Methoxy-4-methylphenol selectivity stability = (2-Methoxy-4-methylphenol selectivity after 5 cycles / 2-Methoxy-4-methylphenol selectivity of the initial catalyst) × 100%.

[0076] Test results are shown in Table 1.

[0077] Table 1. Performance test results of the catalysts in the examples and comparative examples.

[0078] As can be seen from the test results in Table 1 above, the powder-supported nickel catalyst prepared in this application has good performance. Specifically, in the application of vanillin hydrogenation to prepare 2-methoxy-4-methylphenol, the conversion rate of vanillin raw material is above 99.0%, and the selectivity of the target product 2-methoxy-4-methylphenol is above 95.6%. Moreover, after five catalyst cycles, the conversion stability of vanillin and the selectivity stability of 2-methoxy-4-methylphenol are higher than 95.2%, indicating that the powder-supported nickel catalyst prepared in this application has good catalytic stability.

[0079] Comparing the test results of Examples 1-6 and Comparative Examples 1-3, it can be seen that the composition of the active component has a significant impact on the performance of the powder-supported nickel catalyst. In Comparative Example 1, the active component consisted of nickel, lanthanum, and cobalt in a molar ratio of 1:0.07:0.3; in Comparative Example 2, the active component consisted of nickel, lanthanum, and cobalt in a molar ratio of 1:0.6:0.02; and in Comparative Example 3, the active component consisted of nickel, lanthanum, and zinc in a molar ratio of 1:0.3:0.07. The catalyst materials prepared in these examples exhibited poor performance. In contrast, the catalyst material prepared in this application, using an active component composed of nickel, lanthanum, and cobalt in a molar ratio of 1:0.2-0.5:0.03-0.1, demonstrates superior performance.

[0080] Comparing the test results of Examples 2, 7-10, and Comparative Examples 4-6, it can be seen that the preparation method of porous aluminosilicate powder has a significant impact on the performance of the catalyst material. In the preparation methods of porous aluminosilicate powder, in Comparative Example 4, an equal amount of aqueous solution was used instead of the 0.4 wt% surfactant aqueous solution; in Comparative Example 5, an equal amount of 0.1 wt% surfactant aqueous solution was used instead of the 0.4 wt% surfactant aqueous solution, resulting in catalyst materials with poor stability. In Comparative Example 6, the weight ratio of alumina, 0.4 wt% surfactant aqueous solution, and sodium silicate was 5 g:100 g:17 g, resulting in catalyst materials with poor catalytic performance and stability. In contrast, this application uses 0.3-0.5 wt% surfactant aqueous solution as the dispersion and controls the weight ratio of alumina, 0.3-0.5 wt% surfactant aqueous solution, and sodium silicate to be 10-20:100:3-10, thus preparing a powder-supported nickel catalyst material with excellent catalytic performance and stability.

[0081] By comparing the test results of Examples 1 and 11-14, it can be seen that the type of surfactant in the preparation method of porous aluminosilicate powder has a significant impact on the performance of the catalyst material. Through multiple experiments, this application selected a surfactant composed of sodium dodecylbenzenesulfonate and Triton X-100 in a weight ratio of 10-15:1-3, which can further improve the catalytic performance and stability of the catalyst.

[0082] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A powder-supported nickel catalyst, characterized in that, It is prepared by comprising the following components in parts by weight: 1-3.2 parts of active component and 8-15 parts of porous aluminosilicate support; wherein the active component comprises nickel, lanthanum and cobalt; The active component consists of nickel, lanthanum, and cobalt in a molar ratio of 1:0.2-0.5:0.03-0.

1.

2. The powder-supported nickel catalyst according to claim 1, characterized in that, It is prepared by comprising the following components in parts by weight: 1.5-2.5 parts of active component and 8-10 parts of porous aluminosilicate support.

3. The powder-supported nickel catalyst according to claim 1, characterized in that, The active component consists of nickel, lanthanum, and cobalt in a molar ratio of 1:0.3-0.4:0.05-0.

07.

4. The method for preparing the powder-supported nickel catalyst according to any one of claims 1-3, characterized in that, Includes the following steps: Alumina was ultrasonically dispersed in an aqueous solution of 0.3-0.5 wt% surfactant, and then sodium silicate was added and mixed evenly. The pH was adjusted to 12.0-13.0 with an alkaline solution to obtain a slurry, which was reacted at 40-60℃ for 4-8 hours. The slurry was then dried at 90-110℃ for 5-10 hours, and then calcined at 500-600℃ for 3-5 hours. After cooling, porous aluminosilicate powder was obtained. The weight ratio of alumina, 0.3-0.5 wt% surfactant, and sodium silicate was 10-20:100:3-11. The porous aluminosilicate powder was immersed in a mixed salt solution at a solid-liquid ratio of 1:8-12. Alkali solution was added dropwise under stirring at a water bath temperature of 70-90℃ until the pH reached 8.

0. The mixture was then aged at this temperature for 2-6 hours. After aging, the mixture was filtered, and the filter cake was collected. The filter cake was then slurried with water and filtered repeatedly 3-5 times to obtain the precursor. The mixed salt solution consisted of nickel nitrate, lanthanum nitrate, and cobalt nitrate. The precursor was subjected to drying, calcination, reduction, and passivation treatments to obtain the powder-supported nickel catalyst.

5. The method for preparing the powder-supported nickel catalyst according to claim 4, characterized in that, In the method for preparing porous aluminosilicate powder, the surfactant is selected from one or more of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether AEO-9, fatty alcohol polyoxyethylene ether AEO-7, Tween-80, and Triton X-100.

6. The method for preparing the powder-supported nickel catalyst according to claim 5, characterized in that, The surfactant is composed of sodium dodecylbenzenesulfonate and Triton X-100 in a weight ratio of 10-15:1-3.

7. The method for preparing the powder-supported nickel catalyst according to claim 4, characterized in that, The alkaline solution is selected from one or more of the following: sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, triethylamine, sodium carbonate, and sodium bicarbonate.

8. The method for preparing the powder-supported nickel catalyst according to claim 4, characterized in that, The drying and calcination method is as follows: the precursor is dried at 100-120℃ for 8-14 hours; then, in an air atmosphere, the temperature is raised to 400-550℃ at a heating rate of 2-5℃ / min and calcined for 3-5 hours to obtain the calcined product.

9. The application of a powder-supported nickel catalyst as described in any one of claims 1-3 in olefin hydrogenation, nitro hydrogenation, and aldehyde / ketone hydrogenation.

10. A method for preparing 2-methoxy-4-methylphenol by hydrogenation of vanillin, characterized in that, The method uses the powder-supported nickel catalyst according to any one of claims 1-3, and the reaction conditions are as follows: the amount of the powder-supported nickel catalyst is 1-3% of the weight of vanillin; the reaction solvent is ethanol; the pressure is 1.0-2.0 MPa; and the temperature is 140-160℃.

Images