Metal element doped zinc-aluminum spinel catalyst as well as preparation method and application thereof

Abstract

The invention provides a metal element doped zinc-aluminum spinel catalyst as well as a preparation method and application thereof. Lattice sites on the surface of the zinc-aluminum spinel are accurately anchored by metal elements in a monatomic form, a lattice atom substitution or gap doping strategy is realized, and the technical problem of preparation of the metal element doped zinc-aluminum spinel in the prior art is mainly solved. The preparation method of the metal element doped zinc-aluminum spinel comprises the following steps: dissolving a zinc source, an aluminum source, a metal M (Ni / Cu / Pt / Pd) precursor and a precipitator in water, stirring and mixing, carrying out hydrothermal treatment, separating solids, filtering, drying, and calcining to obtain the metal element doped zinc-aluminum spinel catalyst (M-ZnAl2O4). Wherein the nickel metal element is doped with the zinc-aluminum spinel catalyst, so that larger nickel particles are more favorably formed, the particle size distribution is uniform, and the catalytic activity and the stability are greatly improved in the reaction of preparing ethylene through acetylene hydrogenation; the copper-nickel metal element doped zinc-aluminum spinel catalyst also shows good catalytic activity and stability in a methanol reforming hydrogen production reaction.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalyst preparation and application, and specifically relates to a metal element (one or more of Ni, Cu, Pt, and Pd)-doped catalyst with zinc aluminum spinel (ZnAl2O4) as a carrier, and a process for preparing the catalyst by a hydrothermal method. It also relates to the industrial application of the catalyst in acetylene hydrogenation to ethylene and methanol reforming to produce hydrogen. Background Art

[0002] The ethylene industry is the core of the petrochemical industry. Its products account for over 75% of petrochemical output, making it one of the world's most produced chemical products and a key raw material for the plastics industry. It holds a crucial role in the national economy. Given my country's abundant coal and limited oil resources, the development of an efficient acetylene hydrogenation process to produce ethylene using coal-based acetylene as a feedstock is of strategic importance. Widespread deployment of this technology will effectively reduce my country's ethylene dependence on foreign imports, thereby alleviating pressure on the naphtha cracking industry to produce olefins. This holds strategic significance for ensuring the healthy development of my country's economy and safeguarding national energy security.

[0003] Currently, acetylene hydrogenation to ethylene technology primarily uses alumina as a catalyst support. Patent CN1854670A discloses a ruthenium-based catalyst supported on modified alumina. Under normal pressure and 140°C, it achieves efficient ethylene production and significantly improves the catalyst's hydrogenation stability. The literature (Fan Xue, Qiang Li, Mingxin Lv, et al. Atomic Three-Dimensional Investigations of Pdanocatalysts for Acetylene Semi-hydrogenation[J]. J. Am. Chem. Soc. 2023:145, 26728−26735.) compares three different shaped Pd nanocatalysts in the acetylene semi-hydrogenation reaction. The results show that when acetylene is fully converted, the Pd nanocatalyst is more stable than the Pd nanocatalyst. sph The selectivity of the / Al2O3 catalyst is as high as 88%, much higher than that of Pd cub / Al2O3 and Pd oct Although this series of catalysts has good catalytic activity, over-hydrogenation still occurs. In addition, the use of expensive precious metal Pd as the active center not only increases the cost but also leaves room for improvement in the actual acetylene conversion rate and ethylene selectivity in the acetylene hydrogenation to ethylene operation.

[0004] The general formula of spinel structure is AB2O4, Fd3 m space group, where A represents divalent cation, B represents trivalent cation, O 2–Cubic close packing arrangement, A ions occupy tetrahedral voids, B ions occupy octahedral voids, in zinc aluminum spinel, A is Zn 2+ , B is Al 3+ . Zinc-aluminum spinel has the advantages of high melting point, low thermal expansion coefficient and high thermal stability, and can be used as ceramic materials, catalysts, optical materials, electronic coatings, etc. The literature (Zijian Yuan, Anuj Kumar,Daojin Zhou, et al. Highly efficient semi-hydrogenation of acetylene over Nisupported mesoporous MgAl2O4spinel derived from aluminate-intercalated layereddouble hydroxide[J]. J. Catal. 2022: 414, 374–384.) reported that aluminate intercalated layered double hydroxide (Al-LDH) was used as a precursor to prepare a high surface area (309 m2) at a relatively low temperature (500 °C). 2 / g) and mesoporous Ni-supported pure-phase spinel achieved an acetylene conversion of over 99% at a reaction temperature of 140°C, with an ethylene selectivity exceeding 80%. This provides insights into the development of supports for acetylene hydrogenation to ethylene.

[0005] Furthermore, as a clean energy carrier, hydrogen holds enormous potential for achieving sustainable energy development and addressing climate change, making its commercial development particularly crucial. Liquid methanol, due to its numerous advantages (high H / C ratio, lack of C-C bonds, and ease of storage and transportation), can be used as a hydrogen carrier for real-time hydrogen production. Methanol reforming offers relatively mild reaction conditions, high hydrogen yields, simple process control, and ease of industrial operation, making it an effective solution for addressing current hydrogen storage and transportation challenges. Spinel has been extensively studied as a methanol reforming catalyst and offers valuable insights into the long-term stability of catalysts.

[0006] The presence of oxygen vacancies on zinc-aluminum spinel contributes to the formation of active sites and energy barriers for hydrogen adsorption and dissociation. Therefore, by using zinc-aluminum spinel as a support for doping with metal active species, a doping-separation strategy has been successfully implemented to achieve the stable presence of subnanometer-sized metal particles at high temperatures. This avoids the degradation of metal particles due to high-temperature sintering in traditional methods, effectively improving the activity and stability of the spinel catalyst. This has laid the foundation for the development of spinel-supported catalysts for the hydrogenation of acetylene to produce ethylene, and has also yielded promising results in methanol reforming to produce hydrogen. Summary of the Invention

[0007] One of the technical problems to be solved by the present invention is to provide a metal element doped zinc aluminum spinel catalyst to solve the technical problems of active metal element particle size and active species distribution in existing catalysts.

[0008] The second technical problem to be solved by the present invention is to provide a preparation method of a metal element-doped zinc-aluminum spinel catalyst corresponding to the first technical problem to be solved, which can solve the problem of uneven particle size of active metal species particles.

[0009] The third technical problem to be solved by the present invention is to provide a method for preparing ethylene from acetylene by hydrogenation, which is corresponding to the first technical problem to be solved. The method has the characteristics of high acetylene conversion, high ethylene selectivity, and high ethylene yield; and overcomes the shortcomings of the current ethylene preparation process such as catalyst carbon deposition and a large amount of green oil by-products.

[0010] The fourth technical problem to be solved by the present invention is to provide a method for producing a catalyst for hydrogen production from methanol reforming corresponding to the first technical problem to be solved, which has the characteristics of high methanol conversion rate, low CO selectivity and high H2 yield; and improves the shortcomings of the catalyst in the current methanol reforming hydrogen production process, such as easy sintering and poor long-term stability.

[0011] In order to solve the above-mentioned technical problem 1, the technical solution adopted by the present invention is as follows: a metal element doped zinc aluminum spinel catalyst, calculated by mass percentage.

[0012] The zinc-aluminum spinel comprises a percentage of greater than or equal to 60% and less than 99% of the total catalyst weight, and the metal element comprises a percentage of greater than 1 and less than or equal to 40% of the total catalyst weight. The zinc and aluminum sources in the zinc-aluminum spinel are prepared in an atomic ratio of zinc to aluminum within a range of 1:2 to 4.

[0013] In the above technical solution, the metal element doped into the zinc-aluminum spinel is one or more of Ni, Cu, Pt and Pd. The specific surface area of ​​the catalyst is 5 to 400 m 2 / g, pore volume is 0.11~0.57 cm 3 / g.

[0014] To solve the above technical problem 2, a method for preparing a metal element-doped zinc-aluminum spinel catalyst for high-selective hydrogenation of acetylene is provided by a hydrothermal method, comprising the following steps: S01: dissolving the zinc source, aluminum source, metal M precursor, and precipitant in water, and stirring at 20-80°C for 0.5-8h to obtain a mixed solution A; S02: subjecting the mixed solution A to a hydrothermal reaction, controlling the reaction time to 12 to 72 h and the reaction temperature to 100 to 300° C., to obtain a mixed solution B; S03: Cooling the mixed solution B to room temperature, washing multiple times and collecting the precipitate; S04: drying the collected precipitate at 40-120° C. for 6-18 h, and calcining at 400-1200° C. for 2-20 h to obtain a metal element-doped zinc aluminum spinel catalyst.

[0015] Preferably, the atomic ratio of zinc to aluminum is in the range of 1:2 to 4, and most preferably 1:2.

[0016] Preferably, the metal element M is one or more of Ni, Cu, Pt and Pd, most preferably Ni, with a loading amount of 0 to 40%, further optimized to 2 to 10%.

[0017] Preferably, the zinc source is one of zinc nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc phosphate, and zinc oxalate, and most preferably zinc nitrate.

[0018] Preferably, the aluminum source is one of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum carbonate, potassium aluminum sulfate, and aluminum bromide, and most preferably aluminum nitrate.

[0019] Preferably, the precipitant is one of ammonium carbonate, sodium hydroxide, sodium carbonate, and urea, or a combination of multiple thereof, and urea is most preferred.

[0020] Preferably, the amount of the precipitant used is generally 1 to 10 times the molar amount of the total metal ions, preferably 1 to 3 times.

[0021] Preferably, the stirring temperature is 25 to 70 °C, and the stirring time is 0.5 to 2 h; Preferably, the reaction time is 12 to 48 h, and the reaction temperature is 100 to 200 °C. More preferably, the reaction time is 24 h, and the reaction temperature is 180 °C.

[0022] Preferably, the calcination temperature is 900-1100° C., and the calcination time is 5-8 h.

[0023] To solve the above technical problem 3, acetylene and hydrogen are used as raw materials, the reduction temperature is 200-600 °C, the reaction temperature is 50-250 °C, the reaction pressure is 0.1-4 MPa, and the space velocity is 15000 mL×g cat -1 ×h -1 The ethylene oxide is brought into contact with the catalyst bed under the conditions of ethylene oxide and reacts to generate products containing ethylene.

[0024] In the production of ethylene by hydrogenation of acetylene, the reaction temperature is 100-200°C, the acetylene conversion rate is ≥97%, and the ethylene selectivity is ≥85%.

[0025] In order to solve the above technical problem 4, a substance containing methanol is used as a raw material, the reaction temperature is 120-400 ℃, the reaction pressure is 0.1-10.0 MPa, and the mass space velocity of methanol is 1-30 h -1 In the methanol reforming hydrogen production, the reaction temperature is 250-350℃, the methanol conversion rate is ≥90%, and the CO selectivity is ≤1%. Compared with the prior art, the advantages of the present invention are: (1) The present invention uses the prepared metal element doped zinc aluminum spinel catalyst to precisely control the dispersion of metal particles in the catalyst, thus overcoming the instability problems of the catalyst such as agglomeration and sintering of metal active sites at high temperatures.

[0026] (2) The present invention provides a method for preparing a metal element-doped zinc aluminum spinel catalyst. This method can be used to produce a metal element-doped zinc aluminum spinel catalyst. The preparation is simple and easy to operate, which improves the problem of the cumbersome process of the existing production technology.

[0027] (3) The catalyst prepared by the present invention has low-cost catalyst raw materials and is simple to prepare and easy to operate. In the reaction of acetylene to ethylene, it has a high conversion rate and excellent selectivity, a high ethylene yield, and high stability. In the reaction of methanol reforming to hydrogen, it has a high conversion rate and hydrogen yield, and its good anti-sintering ability effectively extends the service life of the catalyst, and has very good industrial application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The XRD patterns of the zinc-aluminum spinel catalysts prepared in the present invention with different nickel loadings are shown. DETAILED DESCRIPTION

[0029] The present invention is described below by means of specific examples, but the present invention is not limited thereto.

[0030] Unless otherwise specified, the preparation methods and operating conditions used in the following examples are conventional methods; the reagents and materials used in the following examples are all commercially available unless otherwise specified.

[0031] [Example 1] (1) Synthesis of nickel-doped zinc-aluminum spinel: First, 2.11 g zinc nitrate hexahydrate, 5.54 g aluminum nitrate nonahydrate, 0.10 g nickel nitrate nonahydrate, and 1.97 g urea were weighed and dissolved in 60 ml deionized water. The mixture was stirred at room temperature for 0.5 h, and then transferred to a reactor and reacted at 180 °C for 24 h. The mixture was then cooled to room temperature, centrifuged and washed until the supernatant was neutral, and dried at 80 °C for 12 h. Finally, it was calcined at 900 °C for 5 h to obtain the desired 2% Ni-ZnAl2O4-2.

[0032] (2) The prepared 2% Ni-ZnAl2O4-2 spinel catalyst contains 2% Ni by mass, 98% ZnAl2O4 by mass, and a Zn:Al ratio of 1:2. The specific surface area of ​​the catalyst is 96 m 2 / g, pore volume at 0.31 cm 3 / g.

[0033] [Example 2] (1) Weigh 3.17 g of zinc nitrate hexahydrate, 3.69 g of aluminum nitrate nonahydrate, 0.10 g of nickel nitrate nonahydrate, and 2.13 g of urea. The rest of the preparation process is the same as in Example 1 to obtain 2% Ni-ZnAl2O4-3.

[0034] (2) The prepared 2% Ni-ZnAl2O4-3 spinel catalyst contains 2% Ni by mass, 98% ZnAl2O4 by mass, and a Zn:Al ratio of 1:3. The specific surface area of ​​the catalyst is 105 m 2 / g, pore volume at 0.35 cm 3 / g.

[0035] [Example 3] (1) Weigh 2.11 g of zinc nitrate hexahydrate, 5.54 g of aluminum nitrate nonahydrate, 0.25 g of nickel nitrate nonahydrate, and 1.97 g of urea. The rest of the preparation process is the same as in Example 1 to obtain 4% Ni-ZnAl2O4-2.

[0036] (2) The prepared 4% Ni-ZnAl2O4-2 spinel catalyst contains 4% Ni by mass, 96% ZnAl2O4 by mass, and a Zn:Al ratio of 1:2. The specific surface area of ​​the catalyst is 77 m 2 / g, pore volume at 0.29 cm 3 / g.

[0037] [Example 4] (1) Weigh 3.17 g of zinc nitrate hexahydrate, 3.69 g of aluminum nitrate nonahydrate, 0.25 g of nickel nitrate nonahydrate, and 2.13 g of urea. The rest of the preparation process is the same as in Example 1 to obtain 4% Ni-ZnAl2O4-3.

[0038] (2) The prepared 4% Ni-ZnAl2O4-3 spinel catalyst contains 4% Ni by mass, 96% ZnAl2O4 by mass, and a Zn:Al ratio of 1:3. The specific surface area of ​​the catalyst is 89 m 2 / g, pore volume at 0.33 cm 3 / g.

[0039] [Example 5] (1) Weigh 2.11 g of zinc nitrate hexahydrate, 5.54 g of aluminum nitrate nonahydrate, 0.31 g of nickel nitrate nonahydrate, and 1.97 g of urea. The rest of the preparation process is the same as in Example 1 to obtain 6% Ni-ZnAl2O4-2.

[0040] (2) The prepared 6%Ni-ZnAl2O4-2 spinel catalyst contains 6% Ni by mass, 94% ZnAl2O4 by mass, and a Zn:Al ratio of 1:2. The specific surface area of ​​the catalyst is 59 m 2 / g, pore volume at 0.28 cm 3 / g.

[0041] [Example 6] (1) Weigh 3.17 g of zinc nitrate hexahydrate, 3.69 g of aluminum nitrate nonahydrate, 0.31 g of nickel nitrate nonahydrate, and 2.13 g of urea. The rest of the preparation process is the same as in Example 1 to obtain 6% Ni-ZnAl2O4-3.

[0042] (2) The prepared 6%Ni-ZnAl2O4-3 spinel catalyst contains 6% Ni by mass, 94% ZnAl2O4 by mass, and a Zn:Al ratio of 1:3. The specific surface area of ​​the catalyst is 64 m 2 / g, pore volume at 0.32 cm 3 / g.

[0043] [Example 7] (1) Weigh 2.11 g of zinc nitrate hexahydrate, 5.54 g of aluminum nitrate nonahydrate, 0.39 g of nickel nitrate nonahydrate, and 1.97 g of urea. The rest of the preparation process is the same as in Example 1 to obtain 8% Ni-ZnAl2O4-2.

[0044] (2) The prepared 8%Ni-ZnAl2O4-2 spinel catalyst contains 8% Ni by mass, 92% ZnAl2O4 by mass, and a Zn:Al ratio of 1:2. The specific surface area of ​​the catalyst is 46 m 2 / g, pore volume at 0.28 cm 3 / g.

[0045] [Example 8] (1) Synthesis of copper-nickel doped zinc-aluminum spinel: 2.11 g zinc nitrate hexahydrate, 5.54 g aluminum nitrate nonahydrate, 0.38 g copper nitrate hexahydrate, 0.10 g nickel nitrate nonahydrate, and 1.97 g urea were weighed and dissolved in 60 ml deionized water. The mixture was stirred at room temperature for 0.5 h. The mixture was transferred to a reactor and reacted at 180 °C for 24 h. The mixture was then cooled to room temperature, centrifuged and washed until the supernatant was neutral, and dried at 80 °C for 12 h. Finally, the desired Cu was obtained by calcining at 800 °C for 5 h. 10 Ni2-ZnAl2O4-2.

[0046] (2) The prepared Cu 10 Ni2-ZnAl2O4-2 spinel catalyst contains 10% Cu by mass, 2% Ni by mass, 88% ZnAl2O4 by mass, and a Zn:Al ratio of 1:2. The specific surface area of ​​the catalyst is 67m 2 / g, pore volume at 0.26 cm 3 / g.

[0047] [Comparative Example 1] The difference between the preparation method described in this comparative example and that in Example 3 is that the active metal content loaded in Comparative Example 1 is 0%.

[0048] ZnAl2O4 was prepared by a hydrothermal method: 5.54 g of aluminum nitrate hexahydrate, 2.06 g of zinc nitrate hexahydrate, and 1.97 g of urea were weighed and dissolved in 60 ml of deionized water and stirred at low temperature for 0.5 h. The mixture was transferred to a reactor and reacted at 180 °C for 24 h. The mixture was then cooled to room temperature, centrifuged and washed until the supernatant was neutral, and dried at 80 °C for 12 h. The desired ZnAl2O4 was then calcined at 900 °C for 5 h.

[0049] The obtained zinc-aluminum spinel catalyst has a mass fraction of ZnAl2O4 of 100%, a Zn:Al ratio of 1:2, and a specific surface area of ​​99 m 2 / g, pore volume at 0.32 cm 3 / g.

[0050] [Comparative Example 2] The difference between the catalyst prepared in this comparative example and the catalyst prepared in Example 3 is that the catalyst preparation methods are different.

[0051] 4% Ni-ZnAl2O4 was prepared by co-precipitation method: 0.19 g nickel nitrate hexahydrate, 2.06 g zinc nitrate hexahydrate and 5.5 g aluminum nitrate nonahydrate were dissolved in 40 ml deionized water as solution A; 12.7 g sodium carbonate was dissolved in 80 ml deionized water as solution B; solution B was slowly added dropwise to solution A with stirring at 70°C until the pH reached 9; after stirring for 12 h, the precipitate was filtered and washed until the filtrate was neutral, the precipitate was dried at 80°C for 12 h, and then calcined at 900°C for 5 h to obtain the product.

[0052] The prepared 4% Ni-ZnAl2O4 spinel catalyst contains 4% Ni by mass, 96% ZnAl2O4 by mass, and a Zn:Al ratio of 1:2. The specific surface area of ​​the catalyst is 53 m 2 / g, pore volume at 0.25 cm 3 / g.

[0053] [Comparative Example 3] The difference between the catalyst prepared in this comparative example and the catalyst prepared in Example 3 is that the catalyst preparation methods are different.

[0054] 4% Ni-ZnAl2O4 was prepared by the sol-gel method: 0.19 g nickel nitrate hexahydrate, 2.06 g zinc nitrate hexahydrate, and 5.42 g aluminum nitrate nonahydrate were dissolved in 60 ml deionized water and stirred for 0.5 h to form solution A; 7.85 g anhydrous citric acid was dissolved in 15 ml deionized water to form solution B; solution B was slowly added dropwise to solution A with stirring at 60 °C; ammonia was continuously added to adjust the pH of the solution until it reached 9.5-10; after stirring for 1 h, the temperature was raised to 120 °C, and the water was slowly evaporated to form a highly viscous gel, which was continued to be heated for 1 h; black fluffy ash was obtained at 170 °C; and the product was then calcined at 900 °C for 5 h.

[0055] The prepared 4% Ni-ZnAl2O4 spinel catalyst contains 4% Ni by mass, 96% ZnAl2O4 by mass, and a Zn:Al ratio of 1:2. The specific surface area of ​​the catalyst is 102 m 2 / g, pore volume at 0.33 cm 3 / g.

[0056] Examples 9-35 M-ZnAl2O4 was prepared according to the conditions in Table 1. Except for the design parameters, other parameters were the same as those in the embodiment, thus obtaining the zinc-aluminum spinel catalyst doped with different metal elements as described in Table 2.

[0057] Table 1

[0058] Table 2

[0059] The catalysts prepared in Examples 1-32 and Comparative Examples 1-3 were used in the acetylene hydrogenation reaction to produce ethylene. Catalytic performance was evaluated according to the reaction conditions in Table 3, yielding ethylene-rich products. The catalysts used in Examples 1-32 in Table 3 correspond to the catalysts used in Examples 1-32 in Table 1.

[0060] Table 3

[0061] The catalysts prepared in Examples 8, 15, and 33-35 were used in methanol reforming to produce hydrogen. Catalytic performance was evaluated according to the reaction conditions in Table 4, yielding hydrogen-rich products. The catalysts used in Examples 1-5 mentioned in Table 4 correspond to the catalyst in Example 8 above. The catalysts used in Examples 6-9 correspond to the catalyst in Example 15 in Table 1. The catalysts used in Examples 10-12 correspond to the catalysts described in Examples 33-35 in Table 1, respectively.

[0062] Table 4

[0063] The foregoing merely represents preferred embodiments of the present invention, and while the description is relatively specific and detailed, it should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make various modifications, improvements, and substitutions without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A metal element-doped zinc-aluminum spinel catalyst, characterized in that: The zinc aluminum spinel accounts for 60% to 99% of the total weight of the catalyst; The metal element is doped in the form of single atoms, accounting for 1% to 40% of the total weight of the catalyst; Wherein, the metal element is selected from one or more of Ni, Cu, Pt, and Pd.

2. The catalyst according to claim 1, characterized in that: The chemical formula of the metal element doped zinc aluminum spinel catalyst is M-ZnAl2O4; The metal M includes one or a combination of two or more metals selected from the group consisting of Ni, Cu, Pt and Pd.

3. The catalyst according to claim 1, characterized in that: The zinc source and the aluminum source in the zinc-aluminum spinel are prepared according to the atomic ratio of zinc to aluminum in the range of 1:2 to 4.

4. The catalyst according to claim 1, characterized in that: The specific surface area of ​​the catalyst is 5 to 400 m 2 / g, pore volume is 0.11~0.57 cm 3 / g.

5. A method for preparing a metal element-doped zinc-aluminum spinel catalyst, comprising the following steps: S01: dissolving the zinc source, aluminum source, metal M precursor, and precipitant in water, and stirring at 20-80 °C for 0.5-8 h to obtain a mixed solution A; S02: subjecting the mixed solution A to a hydrothermal reaction, controlling the reaction time to 12 to 72 h and the reaction temperature to 100 to 300° C., to obtain a mixed solution B; S03: Cooling the mixed solution B to room temperature, washing multiple times and collecting the precipitate; S04: Dry the collected precipitate at 40-120°C for 6-18 h, and calcine at 400-1200°C for 2-20 h to obtain a metal element-doped zinc aluminum spinel catalyst.

6. The preparation method according to claim 5, characterized in that: The metal M precursor is a salt of metal M; Wherein, the metal Ni precursor is one of nickel nitrate, nickel sulfate, nickel chloride, and nickel acetate; Wherein, the metal Cu precursor is one of copper sulfate, copper nitrate, copper acetate and copper chloride; Wherein, the metal Pt precursor is one of platinum sulfate and platinum nitrate; Wherein, the metal Pd precursor is one of palladium chloride, palladium acetate and palladium nitrate.

7. The preparation method according to claim 5, characterized in that: In the precursor solution for preparing zinc aluminum spinel, the zinc source is one of zinc nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc phosphate, and zinc oxalate, and the aluminum source is one of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum carbonate, potassium aluminum sulfate, and aluminum bromide.

8. The preparation method according to claim 5, characterized in that: The precipitant is one or a combination of ammonium carbonate, sodium hydroxide, sodium carbonate, and urea. The amount of the precipitant is generally 1 to 10 times the molar amount of the total metal ions.

9. Use of a metal element-doped zinc aluminum spinel catalyst in acetylene hydrogenation to ethylene, using any one of the catalysts of claims 1 to 4, acetylene and hydrogen as raw materials, a reduction temperature of 200 to 600°C, a reaction temperature of 50 to 250°C, a reaction pressure of 0.1 to 4 MPa, and a space velocity of 1500 to 15000 mL×gcat -1 ×h -1 The ethylene oxide is brought into contact with the catalyst bed under the conditions of ethylene oxide and reacts to generate products containing ethylene.

10. The use according to claim 9, characterized in that: In the production of ethylene by hydrogenation of acetylene, the reaction temperature is 100-200°C, the acetylene conversion rate is ≥97%, and the ethylene selectivity is ≥85%.

11. A metal element doped zinc aluminum spinel catalyst for hydrogen production from methanol reforming, using any one of the catalysts of claims 1 to 4, a substance containing methanol as a raw material, a reaction temperature of 120-400 ° C, a reaction pressure of 0.1-10.0 MPa, and a methanol mass space velocity of 1-30 h -1 The product contacts the catalyst bed under the conditions of , and reacts to generate products containing hydrogen.

12. The application according to claim 11, characterized in that: In methanol reforming to produce hydrogen, the reaction temperature is 250-350°C, the methanol conversion rate is ≥90%, and the CO selectivity is ≤1%.

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