Preparation method and application of a foamed nickel supported Pd / gamma-Al2O3 catalyst for anthraquinone hydrogenation

Abstract

The application discloses a preparation method of a foam nickel supported Pd / gamma-Al2O3 catalyst for anthraquinone hydrogenation and application thereof, and belongs to the technical field of catalysts and hydrogen peroxide preparation. The preparation method comprises the following steps: dissolving an aluminum source and terephthalic acid in an organic solvent, placing the foam nickel and the organic solvent in a high-pressure reaction kettle, sealing the high-pressure reaction kettle and performing heat reaction for 10-36 hours, cooling, drying and calcining to obtain gamma-Al2O3 with foam nickel as a substrate; and then adding the gamma-Al2O3 into a palladium source solution to perform impregnation and calcination, thereby obtaining the foam nickel supported Pd / gamma-Al2O3 catalyst. In the application, the foam nickel is used as a substrate and cooperates with a structure directing agent and terephthalic acid, so that the gamma-Al2O3 forms a structure with regular micro-morphology and uniform distribution and grows on the surface of the foam nickel; the loading amount of palladium in the obtained catalyst is 0.1%-1.0%, and the hydrogenation efficiency can reach 12.48 g·L ‑1 at the highest, which is significantly better than the level of existing commercial catalysts and can be applied to the preparation of hydrogen peroxide by the anthraquinone method, thereby significantly improving the hydrogenation efficiency in the anthraquinone hydrogenation reaction.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology and hydrogen peroxide preparation technology, specifically relating to a method for preparing a nickel foam-supported Pd / γ-Al2O3 catalyst for anthraquinone hydrogenation and its application in the anthraquinone method for preparing hydrogen peroxide. Background Technology

[0002] Hydrogen peroxide (H2O2) is an important green chemical product, widely used in papermaking, textiles, chemical synthesis, environmental protection, and the electronics industry. Currently, the mainstream method for industrial production of hydrogen peroxide is the anthraquinone process, which has advantages such as low energy consumption, high safety, and suitability for large-scale continuous production.

[0003] The core principle of hydrogen peroxide production via the anthraquinone process is that alkyl anthraquinones (such as 2-ethylanthraquinone) react with hydrogen in the presence of a hydrogenation catalyst to produce hydrogen anthraquinone. The hydrogen anthraquinone is then oxidized by air to produce hydrogen peroxide, while the anthraquinone is regenerated and recycled. The hydrogenation step is the key component of the entire process, and the performance of the hydrogenation catalyst is closely related to the hydrogenation efficiency, the quality of the hydrogen peroxide product, and the production cost.

[0004] The performance of the catalytic system is crucial for regulating the efficiency of anthraquinone hydrogenation. Palladium (Pd) has become the most widely used active metal component in this reaction due to its excellent hydrogenation activity and product selectivity. However, as a noble metal, the utilization rate, dispersibility, stability, and catalytic lifetime of palladium largely depend on the structure and surface properties of the support material. Therefore, the precise design and optimization of the support has become a core research direction for improving the overall performance of the catalytic system. Alumina (Al2O3), with its good chemical stability, suitable surface acidity, and interaction with the active metal, has become the mainstream support for palladium-based anthraquinone hydrogenation catalysts. Notably, the pore structure of the support has a significant impact on catalytic performance—specific surface area, pore size distribution, and pore volume not only directly determine the dispersion of palladium nanoparticles but also affect the mass transfer efficiency of anthraquinone molecules and their sufficient contact with active sites.

[0005] Currently, the anthraquinone hydrogenation catalysts widely used in industry are mainly supported palladium catalysts, and their supports are mostly γ-Al2O3. However, the existing technology still has the following shortcomings: (1) Low utilization rate of precious metals: In catalysts prepared by the traditional impregnation method, the palladium active component is often distributed on the inner and outer surfaces of the entire alumina support. For diffusion-controlled reactions such as anthraquinone hydrogenation, the mass transfer path of the active sites located in the deep pores of the support is long, and the reactant molecules are difficult to contact effectively, which limits the actual utilization rate of precious metals. (2) Limited hydrogenation efficiency: The hydrogenation efficiency of existing industrial catalysts is generally between 6 and 9 g·L. -1There is still considerable room for improvement in the range. The pore structure and active site distribution of the catalyst directly affect the mass transfer rate between reactants and products, and thus affect the overall reaction efficiency. (3) Poor matching between support particle size and diffusion: Existing technologies mostly use millimeter-sized alumina spheres (such as 1–5 mm in diameter), which have a long internal diffusion path and are prone to over-hydrogenation side reactions, increasing the degree of anthraquinone degradation, thereby affecting the service life of the catalyst.

[0006] Based on the above technical background, developing a novel anthraquinone hydrogenation catalyst with high activity, high selectivity and high stability is of great practical significance. Summary of the Invention

[0007] The technical problem solved by this invention is to overcome the low hydrogenation efficiency and insufficient palladium utilization of existing γ-Al₂O₃ supported palladium catalysts in the anthraquinone hydrogenation reaction, and to provide a method for preparing a nickel foam-supported Pd / γ-Al₂O₃ catalyst for anthraquinone hydrogenation and its application. This catalyst exhibits excellent hydrogenation efficiency in the anthraquinone hydrogenation reaction.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] The first aspect of this invention provides a method for preparing a nickel foam-supported Pd / γ-Al2O3 catalyst for anthraquinone hydrogenation, comprising the following steps:

[0010] (1) Dissolve the aluminum source and terephthalic acid in an organic solvent to obtain a mixed solution;

[0011] (2) Place the nickel foam in a high-pressure reactor, add the mixed solution obtained in step (1), seal it, and heat it at 180~260°C for 10~36h. After cooling, collect the product, wash and dry it to obtain the precursor.

[0012] (3) The precursor obtained in step (2) is calcined at a temperature of 400~520°C for 1~5h to obtain γ-Al2O3 with nickel foam as the substrate.

[0013] (4) Prepare a palladium source solution, add the γ-Al2O3 with nickel foam as the substrate obtained in step (3) into the palladium source solution for impregnation, separate the solid and liquid, and calcine. The calcine temperature is 400~520°C and the time is 1~5h to obtain the Pd / γ-Al2O3 catalyst supported on nickel foam.

[0014] In step (3), γ-Al2O3 with nickel foam as the base is nickel foam with white powder attached to its surface.

[0015] Preferably, the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, and aluminum isopropoxide;

[0016] And / or, the palladium source is one or a mixture of two or more of palladium chloride, palladium acetate, sodium chloropalladium, and palladium nitrate.

[0017] Preferably, the organic solvent is one or more of N,N-dimethylformamide, N,N-diethylformamide and N,N-dimethylacetamide.

[0018] Preferably, the molar ratio of Al to phthalic acid in the aluminum source is 1~3:1~2;

[0019] And / or, the ratio of Al in the aluminum source to the nickel foam is (0.001~0.1) mol / cm³. 2 .

[0020] Preferably, the ratio of the nickel foam to the organic solvent is (0.01~0.03) cm⁻¹. 2 / mL. More preferably,

[0021] Preferably, in step (3), the heating rate of calcination is 1~5°C / min, and the holding time after heating to the calcination temperature is 1.5~3h.

[0022] Preferably, in step (4), the immersion time is 2 to 10 hours, and the pH of the palladium source solution used for immersion is adjusted to 3 to 4 beforehand;

[0023] And / or, in step (4), the heating rate of the calcination is 1-5°C / min, and the holding time after heating to the calcination temperature is 1.5-3h.

[0024] Preferably, in step (4), the amount of palladium source added is calculated as the mass percentage of palladium in the final catalyst, and the weight of palladium is 0.1% to 1.0% of the mass of the nickel foam-supported Pd / γ-Al2O3 catalyst. More preferably, the weight of palladium is 0.3% of the mass of the nickel foam-supported Pd / γ-Al2O3 catalyst.

[0025] Preferably, in step (2), the washing process involves alternating between deionized water and anhydrous ethanol at least twice.

[0026] Preferably, in step (2), the drying temperature is 80~200℃ and the time is 0.5~10h.

[0027] More preferably, in step (4), the pH is adjusted using a dilute acid solution; the dilute acid solution includes, but is not limited to, hydrochloric acid, sulfuric acid, and nitric acid with a concentration of 0.01~0.5 mol / L.

[0028] The second aspect of the present invention provides a nickel foam-supported Pd / γ-Al2O3 catalyst prepared by the above-described preparation method.

[0029] The third aspect of this invention provides the application of the above-described nickel-supported Pd / γ-Al2O3 catalyst in the anthraquinone process for the preparation of hydrogen peroxide.

[0030] The key technical features of this invention, compared to existing technologies, are as follows:

[0031] (1) The simultaneous introduction of terephthalic acid and nickel foam in the solvothermal reaction: the two work synergistically to promote the formation of a well-shaped and uniformly distributed precursor structure and its growth on the surface of nickel foam. Terephthalic acid acts as an organic ligand to coordinate with aluminum ions, while nickel foam acts as a substrate and structure directing agent; both are indispensable. Comparative results show that the hydrogenation efficiency of the catalyst prepared on the resulting support decreases significantly when either terephthalic acid or nickel foam is absent.

[0032] (2) Low-temperature calcination process: The present invention uses aluminum-based coordination polymer as a precursor. After low-temperature calcination at no more than 525°C, the γ crystal phase can be expected to be formed, which reduces the production cost and avoids the morphological collapse and increased energy consumption caused by high-temperature calcination.

[0033] (3) Optimization of palladium loading: By adjusting the palladium loading to 0.1%~1%, the active component is highly dispersed on the surface of the support, thereby making efficient use of the palladium active component; when the palladium loading is 0.3 wt%, the catalytic activity reaches the optimal level.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) This invention uses terephthalic acid as an organic ligand and nickel foam as a substrate and structure directing agent. A precursor with a regular and uniformly distributed structure is first prepared by a solvothermal method. A white powder is grown on the surface of the nickel foam, and then calcined to obtain γ-Al2O3 based on nickel foam. The γ-Al2O3 prepared by this method has a regular morphology and uniform growth, which is conducive to providing a high specific surface area and a suitable pore structure, providing an ideal dispersion carrier for the active component. Moreover, since the γ-Al2O3 grows on the surface of the nickel foam to form an open thin-layer structure, the open γ-Al2O3 layer makes the mass transfer path of the catalyst extremely short, and the anthraquinone reactants can more easily contact the Pd active sites. Compared with the traditional impregnation method, the Pd active component is distributed on the inner and outer surfaces of the millimeter-sized γ-Al2O3 particles, and the mass transfer path of the Pd active component inside the carrier is longer. Therefore, under the same Pd loading, the dispersion carrier of this invention can more effectively improve the Pd utilization rate.

[0036] (2) By combining a dispersion support with a suitable specific surface area and a suitable pore structure with a suitable palladium loading, the present invention can significantly improve the utilization rate of noble metals, so that they exhibit excellent catalytic activity in the anthraquinone hydrogenation reaction.

[0037] (3) The nickel foam-supported Pd / γ-Al2O3 catalyst prepared in this invention exhibits excellent catalytic performance in the anthraquinone hydrogenation reaction, with a hydrogenation efficiency of up to 12.48 g·L. -1 It is significantly superior to commercially available industrial anthraquinone hydrogenation palladium catalyst (Sinopec Changling Branch EK-Ⅲ type).

[0038] (4) The method of the present invention is simple, easy to operate, uses readily available raw materials, and has good repeatability, making it suitable for industrial production. Detailed Implementation

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. However, the following embodiments are only some embodiments of the present invention, and not all embodiments.

[0040] Unless otherwise specified, all raw materials used in the following examples and comparative examples can be obtained commercially or prepared, and all percentages used are by mass unless otherwise specified.

[0041] Example 1

[0042] A method for preparing γ-Al2O3 based on nickel foam, comprising the following steps:

[0043] (1) Take 15 g of aluminum nitrate nonahydrate (Al(NO3)3·9H2O) and 6.65 g of terephthalic acid (H2BDC) (molar ratio 1:1) and dissolve them in 150 mL of N,N-dimethylformamide (DMF). Stir thoroughly until completely dissolved to obtain a mixed solution.

[0044] (2) Cut a 4cm piece 2 Nickel foam was placed in a high-pressure reactor with a polytetrafluoroethylene liner, and the mixed solution obtained in step (1) was added and sealed. The reactor was placed in an oven and reacted at 200 °C for 24 h. After naturally cooling to room temperature, the nickel foam and the white product grown on its surface were taken out and washed repeatedly with deionized water and anhydrous ethanol more than 3 times to remove unreacted raw materials and residual DMF. The product was dried in a vacuum oven at 120 °C for 2 h to obtain the precursor.

[0045] (3) The precursor was placed in a muffle furnace for calcination. The temperature was first increased to 500 °C at a rate of 5 °C / min, and then kept at 500 °C for 3 hours to obtain γ-Al2O3 based on nickel foam, denoted as P1.

[0046] (4) Based on the Pd content of 0.1 wt% in the final catalyst, accurately weigh 0.017 g of palladium chloride (PdCl2), dissolve it in 10 mL of distilled water, and add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 3~4 to obtain the palladium source solution. Under these conditions, it is beneficial for the palladium precursor to be uniformly adsorbed on the surface of γ-Al2O3. If the pH is too low, the active component will be lost, and if it is too high, palladium hydroxide precipitate will be easily formed, affecting the dispersion. Add 10 g of γ-Al2O3 (containing the foamed nickel substrate) prepared in step (3) and impregnate for 5 h. Filter, place the filtered sample in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at 500°C for 2 h, and let it cool naturally to room temperature to obtain the foamed nickel supported Pd / γ-Al2O3 catalyst, which is denoted as S1.

[0047] Example 2

[0048] A method for preparing γ-Al2O3 based on nickel foam, comprising the following steps:

[0049] Steps (1)-(3) are the same as in Example 1.

[0050] (4) Based on the Pd content of 0.1 wt% in the final catalyst, accurately weigh 0.05 g of palladium chloride (PdCl2), dissolve it in 10 mL of distilled water, and add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 3~4 to obtain the palladium source solution. Under these conditions, it is beneficial for the palladium precursor to be uniformly adsorbed on the surface of γ-Al2O3. If the pH is too low, the active component will be lost, and if it is too high, palladium hydroxide precipitate will be easily formed, affecting the dispersion. Add 10 g of γ-Al2O3 (containing the nickel foam substrate) prepared in step (3) and impregnate for 5 h. Filter, place the filtered sample in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at 500°C for 2 h, and let it cool naturally to room temperature to obtain the nickel foam-supported Pd / γ-Al2O3 catalyst, which is denoted as S2.

[0051] Example 3

[0052] A method for preparing γ-Al2O3 based on nickel foam, comprising the following steps:

[0053] Steps (1)-(3) are the same as in Example 1.

[0054] (4) Based on the final catalyst having a Pd content of 0.5wt%, accurately weigh 0.083g of palladium chloride (PdCl2), dissolve it in 10mL of distilled water, and add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 3~4 to obtain a palladium source solution. Under these conditions, it is beneficial for the palladium precursor to be uniformly adsorbed on the surface of γ-Al2O3. If the pH is too low, the active component will be lost, and if it is too high, palladium hydroxide precipitate will be easily formed, affecting the dispersion. Add 10g of γ-Al2O3 (containing the nickel foam substrate) prepared in step (3) and impregnate for 5h. Filter, place the filtered sample in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at 500°C for 2h, and let it cool naturally to room temperature to obtain the nickel foam-supported Pd / γ-Al2O3 catalyst, which is denoted as S3.

[0055] Example 4

[0056] A method for preparing γ-Al2O3 based on nickel foam, comprising the following steps:

[0057] Steps (1)-(3) are the same as in Example 1.

[0058] (4) Based on the final catalyst having a Pd content of 1.0 wt%, accurately weigh 0.167 g of palladium chloride (PdCl2), dissolve it in 10 mL of distilled water, and add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 3~4 to obtain a palladium source solution. Under these conditions, it is beneficial for the palladium precursor to be uniformly adsorbed on the surface of γ-Al2O3. If the pH is too low, the active component will be lost, and if it is too high, palladium hydroxide precipitate will be easily formed, affecting the dispersion. Add 10 g of γ-Al2O3 (containing the nickel foam substrate) prepared in step (3) and impregnate for 5 h. Filter, place the filtered sample in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at 500°C for 2 h, and let it cool naturally to room temperature to obtain the nickel foam-supported Pd / γ-Al2O3 catalyst, which is denoted as S4.

[0059] Comparative Example 1

[0060] The process is basically the same as in Example 2, except that in step (1), 15 g of aluminum nitrate nonahydrate (Al(NO3)3·9H2O) is dissolved in 150 mL of N,N-dimethylformamide (DMF) and stirred thoroughly until completely dissolved to obtain an aluminum source solution. The aluminum source solution replaces the mixed solution to continue the operation in the subsequent step (2), and the resulting catalyst is denoted as S5.

[0061] Comparative Example 2

[0062] The process is basically the same as in Example 2, except that in step (2), no nickel foam is added. The mixed solution is added to a high-pressure reactor with a polytetrafluoroethylene liner and sealed for reaction. The subsequent operations are the same. After calcination, the carrier is obtained as powdered γ-Al2O3.

[0063] In step (4), during impregnation, a powder sample (about 10g, excluding nickel foam) with the same mass as γ-Al2O3 in Example 2 is weighed and impregnated and calcined under the same conditions. The resulting catalyst is denoted as S6.

[0064] Comparative Example 3

[0065] The process is basically the same as in Example 2, except that terephthalic acid is not added in step (1) and nickel foam is not added in step (2). The resulting product is a powdered γ-Al2O3 precursor, which is then calcined to obtain powdered γ-Al2O3.

[0066] In step (4), during impregnation, a powder sample (about 10 g, excluding nickel foam) with the same mass as γ-Al2O3 in Example 2 is weighed and impregnated and calcined under the same conditions. The resulting catalyst is denoted as S7.

[0067] Comparative Example 4

[0068] The catalyst used was a commercially available industrial anthraquinone hydrogenation palladium catalyst (Sinopec Changling Branch EK-Ⅲ type), and the resulting catalyst was designated as S8.

[0069] Performance Test Examples

[0070] Take 0.2 g of catalysts S1-S8 respectively, pretreat them with hydrogen at 120 °C for 3 h, and then load them into the anthraquinone hydrogenation evaluation device. Add 50 mL of ethyl anthraquinone working solution (aromatics, trioctyl phosphate, tetrabutylurea volume ratio 75%:15%:10%, 2-ethyl anthraquinone concentration 160 g·L⁻¹). -1 After hydrogen purging, the apparatus was reacted at 0.3 MPa and 55 °C for 30 min. The catalyst was recovered by centrifugation, and the hydrogenated liquid was retained. 5 mL of the hydrogenated liquid was taken and high-purity oxygen was bubbled into 2 mL of dilute phosphoric acid (2 mol / L) and 20 mL of deionized water until a bright yellow color was obtained. Hydrogen peroxide was then extracted three times with deionized water. The aqueous phases were combined, and 20 mL of 20% sulfuric acid was added. The solution was titrated with 0.03 mol / L potassium permanganate to calculate the hydrogenation efficiency.

[0071] The test results are summarized in Table 1.

[0072]

[0073] Note: " / " indicates that it is not applicable. This sample is a commercially available finished catalyst and was not prepared according to the method of this invention.

[0074] Examples 1-4 compared the catalytic performance under different palladium loadings. Table 1 shows that when the Pd loading is 0.1%, the hydrogenation efficiency is 8.43 g·L⁻¹. -1 When the Pd loading increases to 0.3%, the hydrogenation efficiency reaches its highest value of 12.48 g·L⁻¹. -1 When the concentration is further increased to 0.5%, the hydrogenation efficiency decreases to 10.80 g·L⁻¹. -1 When the concentration is further increased to 1.0%, the hydrogenation efficiency decreases to 9.25 g·L⁻¹. -1 The above results indicate that the nickel foam-supported Pd / γ-Al2O3 catalyst prepared using the method of this embodiment exhibits the best catalytic activity when the palladium loading is 0.3%. Below this value, there are insufficient active sites, while above this value, palladium particles may agglomerate, reducing dispersion and specific activity.

[0075] The results of Comparative Examples 1-3 confirm that, as shown in the test results of Example 2, the hydrogenation efficiency can reach 12.48 g·L⁻¹ when terephthalic acid and nickel foam are added simultaneously. -1 In the absence of terephthalic acid (Comparative Example 1), the hydrogenation efficiency decreased to 8.19 g·L⁻¹. -1 In the absence of nickel foam (Comparative Example 2), the hydrogenation efficiency decreased to 7.36 g·L⁻¹. -1 When both are absent (Comparative Example 3), the hydrogenation efficiency further decreases to 5.01 g·L⁻¹. -1 The above results indicate that the synergistic effect of terephthalic acid and nickel foam is a key factor in forming a regular, uniformly distributed γ-Al2O3 morphology on the surface of nickel foam, and is also crucial for improving Tsinghua efficiency.

[0076] The optimal catalyst of this invention (S2, Pd loading 0.3%, hydrogenation efficiency 12.48 g·L) -1 ) and existing commercial palladium catalysts (hydrogenation efficiency 8.10 g·L) -1 Compared with [previous invention], the hydrogenation efficiency of this invention is improved by approximately 54%. This achieves the technical goal of "low palladium, high activity".

[0077] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a nickel foam-supported Pd / γ-Al2O3 catalyst for anthraquinone hydrogenation, characterized in that, Includes the following steps: (1) Dissolve the aluminum source and terephthalic acid in an organic solvent to obtain a mixed solution; (2) Place the nickel foam in a high-pressure reactor, add the mixed solution obtained in step (1), seal it, and heat it at 180~260°C for 10~36h. After cooling, collect the product, wash and dry it to obtain the precursor. (3) The precursor obtained in step (2) is calcined at a temperature of 400~520°C for 1~5h to obtain γ-Al2O3 with nickel foam as the substrate. (4) Prepare a palladium source solution, add the γ-Al2O3 with nickel foam as the substrate obtained in step (3) into the palladium source solution for impregnation, separate the solid and liquid, and calcine. The calcine temperature is 400~520°C and the time is 1~5h to obtain the Pd / γ-Al2O3 catalyst supported on nickel foam.

2. The preparation method according to claim 1, characterized in that, The aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, and aluminum isopropoxide; And / or, the palladium source is one or a mixture of two or more of palladium chloride, palladium acetate, sodium chloropalladium, and palladium nitrate.

3. The preparation method according to claim 1, characterized in that, The organic solvent is one or more of N,N-dimethylformamide, N,N-diethylformamide and N,N-dimethylacetamide.

4. The preparation method according to claim 1, characterized in that, The molar ratio of Al to phthalic acid in the aluminum source is 1~3:1~2; And / or, the ratio of Al in the aluminum source to the nickel foam is (0.001~0.1) mol / cm³. 2 .

5. The preparation method according to claim 1, characterized in that, The ratio of the nickel foam to the organic solvent is (0.01~0.03) cm³. 2 / mL.

6. The preparation method according to claim 1, characterized in that, In step (3), the heating rate of calcination is 1~5°C / min, and the holding time after heating to the calcination temperature is 1.5~3h.

7. The preparation method according to claim 1, characterized in that, In step (4), the immersion time is 2 to 10 hours, and the pH of the palladium source solution used for immersion is adjusted to 3 to 4 beforehand; And / or, in step (4), the heating rate of the calcination is 1-5°C / min, and the holding time after heating to the calcination temperature is 1.5-3h.

8. The preparation method according to claim 1, characterized in that, In step (4), the amount of palladium source added is calculated based on the mass percentage of palladium in the final catalyst, and the weight of palladium is 0.1% to 1.0% of the mass of the nickel foam-supported Pd / γ-Al2O3 catalyst.

9. The nickel foam-supported Pd / γ-Al2O3 catalyst prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the nickel-supported Pd / γ-Al2O3 catalyst of claim 9 in the anthraquinone process for the preparation of hydrogen peroxide.

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