Precious metal catalyst as well as preparation method and application thereof

Abstract

The invention provides a noble metal catalyst and a manufacturing method and application thereof, the noble metal catalyst comprises a Pt-In-Ga / Al2O3 catalyst, the Pt-In-Ga / Al2O3 catalyst comprises an Al2O3 carrier and Pt-In2O3-Ga2O3 active components loaded on the Al2O3 carrier, and the total mass of the Pt-In2O3-Ga2O3 active components accounts for 5-50% of the total mass of the catalyst; according to the present invention, under the high temperature reaction condition, the catalyst still has the high methanol conversion rate and the high hydrogen production rate at the high space velocity, the CO selectivity is low, the CO content in the product is low, the methanol conversion rate, the CO content in the reformed gas, the hydrogen production rate and other properties are excellent under the long operation time working condition, and the long-term stability of the catalyst in use is improved.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a noble metal catalyst, its manufacturing method, and its application. Background Technology

[0002] With the rapid development of the hydrogen energy industry, methanol steam reforming (MSR) has become an important technology for distributed hydrogen supply due to its readily available raw materials and mild reaction conditions. In this reaction, the performance of the catalyst directly determines the hydrogen yield, CO byproduct control, and the operating cycle of the unit. Noble metal-based catalysts have been extensively studied due to their excellent CH bond activation ability. However, existing catalysts have the following limitations: 1) The contradiction between activity and selectivity: While traditional Pt / γ-Al₂O₃ catalysts possess advantages such as high activity and mild reaction conditions, they are prone to problems like Pt particle sintering and carbon deposition under high temperature (>300℃) and high space velocity conditions, leading to decreased activity and an increased proportion of CO byproducts. Studies have shown that the methanol conversion rate of single-metal Pt catalysts is typically below 70%, and the CO selectivity generally exceeds 5%, severely limiting the purity of hydrogen products and catalyst lifespan. Introducing In₂O₃ can suppress CO formation, but it sacrifices approximately 15%-20% of the methanol conversion efficiency.

[0003] 2) Insufficient stability in long-term use: For example (Pt-Sn / Al2O3): CO generation is suppressed by SnO2, but the conversion rate still declines during long-term operation (e.g., a 35% decrease after 100h). In addition, existing technologies disclose that the hydrogen production rate declines to below 0.05 mmol / (gcat·s) after 500h of catalyst use.

[0004] 3) Insufficient synergistic regulation of multiple components; few reports on multi-metal systems; and existing preparation methods struggle to achieve atomically uniform dispersion of active components. For example, existing techniques employ a stepwise impregnation method, resulting in significant phase separation between metals. Ga2O3 covers some Pt ​​active sites, leading to a hydrogen production rate below 0.05 mmol / (gcat·s).

[0005] The above background information is disclosed only to assist in understanding the inventive concept and technical solution of this invention. It does not necessarily belong to the prior art of this patent application, nor does it necessarily provide technical teachings. In the absence of clear evidence, the novelty and inventiveness of the above application shall be deemed to be incomplete. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a noble metal catalyst, its manufacturing method, and its application. Under high-temperature reaction conditions, it achieves high methanol conversion and hydrogen production rates even at high space velocities. It not only exhibits low CO selectivity and low CO content in the products, but also demonstrates excellent performance in methanol conversion, CO content in the reformate, and hydrogen production rate over extended operating times, thereby improving the long-term stability of the catalyst.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows: On one hand, the present invention provides a noble metal catalyst, comprising: a Pt-In-Ga / Al2O3 catalyst, wherein the Pt-In-Ga / Al2O3 catalyst comprises an Al2O3 support and a Pt-In2O3-Ga2O3 active component supported on the Al2O3 support, wherein the total mass of the Pt-In2O3-Ga2O3 active component accounts for 5 to 50% of the total mass of the catalyst.

[0008] This invention provides a precious metal catalyst, its manufacturing method, and its application. Under high-temperature reaction conditions, it achieves high methanol conversion and hydrogen production rates even at high space velocities. It not only exhibits low selectivity for CO and low CO content in the product, but also demonstrates excellent performance in methanol conversion, CO content in the reformate, and hydrogen production rate over extended operating times, thereby improving the long-term stability of the catalyst.

[0009] As a preferred technical solution, the molar ratio of Pt:In2O3 in the Pt-In-Ga / Al2O3 catalyst is (0.8-1.2):1, and the molar ratio of Pt:Ga2O3 is (2-10):1.

[0010] As a preferred technical solution, it includes: Ce x Zr 1-x O2 cerium zirconium solid solution, wherein the Ce:Zr molar ratio is 4:1.

[0011] As a preferred technical solution, it includes: a support body, the surface of which is alternately coated with a substance containing Ce. x Zr 1-x The coating layer of O2 cerium zirconium solid solution and the coating layer containing Pt-In-Ga / Al2O3 catalyst.

[0012] As a preferred technical solution, the coating layer containing the Pt-In-Ga / Al2O3 catalyst comprises the following components by mass percentage: Pt-In-Ga / Al2O3 catalyst 10%-35%; 3-5% polyol rheology modifier; The remainder is a polymer dispersion; The polyol rheology modifier comprises at least one of glycerol, propylene glycol, and polyethylene glycol 400.

[0013] As a preferred technical solution, the one comprising the Ce x Zr 1-x The O2 cerium zirconium solid solution coating contains the following components by mass percentage: Ce x Zr 1-x O2 cerium zirconium solid solution 15-25%; Pore-forming agent 5-8%; 3-5% polyol rheology modifier; The remainder is a polymer dispersion; The pore-forming agent includes: ammonium nitrate; The polyol rheology modifier comprises at least one of glycerol, propylene glycol, and polyethylene glycol 400.

[0014] On the other hand, the present invention provides a method for manufacturing a noble metal catalyst, which, in order to obtain the noble metal catalyst as described above, includes: a method for manufacturing a Pt-In-Ga / Al2O3 catalyst, comprising the following steps: S1 prepares a solution containing Al(NO3)3 as a carrier precursor solution; S2. Pt nitrate, In nitrate, Ga nitrate and a polymeric dispersant are added to the solution in step S1 to form a mixed metal salt solution; S3 undergoes a reduction reaction by adding NaBH4 solution to a mixed metal salt solution under ice bath conditions; S4 was subjected to ice bath conditions, and ammonium carbonate solution was added dropwise to the reduced solution until the pH reached 8-9. After aging, separation, and washing, the precipitate was obtained. S5 dried the precipitate sequentially and calcined it at a programmed temperature to obtain the Pt-In-Ga / Al2O3 catalyst.

[0015] As a preferred technical solution, the polymeric dispersant in step S2 is polyethylene glycol 2000, and the amount added is 0.1-2 wt% of the total mass of the solution. In step S3, the concentration of the NaBH4 solution is 0.01-1 mol / L, and the ratio of the total molar amount of NaBH4 to the metal salt is (1-10):1. In step S3, the reduction reaction is carried out under ice bath conditions, and the NaBH4 solution is added at a rate of 1-2 mL / s for 1-30 seconds. In step S4, the dropping rate of the ammonium carbonate solution is 1-3 mL / min, the aging temperature is 60-80℃, and the aging time is 4-12 hours. The programmed temperature rise calcination in step S5 includes: (a) raising the temperature from room temperature to 400°C at a rate of 2-5°C / min and holding for 2-4 hours; (b) raising the temperature from 400°C to 550-650°C at a rate of 5-15°C / min and holding for 2-4 hours.

[0016] As a preferred technical solution, it includes: Ce x Zr 1-x The method for manufacturing O2 cerium zirconium solid solution includes the following steps: Weigh out soluble cerium and zirconium salts according to the target Ce and Zr molar ratio, and dissolve them in deionized water to form a mixed salt solution; Slowly add ammonia to the mixed salt solution to control the OH content. - For concentrations in the range of 0.1~1.5M, adjust the pH to 8.5-9.5; The reaction was carried out under continuous stirring at a temperature of 20-50℃ for 1-3 hours. Stirring at room temperature, and after aging for 8-24 hours, perform solid-liquid separation. The precipitate was washed alternately with water and alcohol-based detergents; After vacuum drying, Ce is calcined at 350-450℃ for 3-5 hours to obtain Ce. x Zr 1-x O2 cerium zirconium solid solution; The soluble cerium salt includes at least one of cerium nitrate or cerium acetate; The soluble zirconium salt includes at least one of Zr(NO3)4·5H2O, zirconium oxynitrate, or zirconium acetate; The alcohol-based detergents include: ethanol.

[0017] As a preferred technical solution, a method for manufacturing a coating slurry containing a Pt-In-Ga / Al2O3 catalyst is included, comprising the following steps: First, prepare a saturated solution of PVA dispersant, then dilute it with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. Add 0.2-0.8% by mass of PEG2000 to obtain a polymer dispersion. After adding the Pt-In-Ga / Al2O3 catalyst, adjust the pH value to 2.5-4.5 with HNO3 solution and stir thoroughly. A polyol rheology modifier was added to obtain a coating slurry containing a Pt-In-Ga / Al2O3 catalyst.

[0018] As a preferred technical solution, it includes: comprising the Ce x Zr 1-x A method for manufacturing a coating slurry of O2 cerium-zirconium solid solution includes the following steps: First, prepare a saturated solution of PVA dispersant, then dilute it with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. Add 0.2-0.8% by mass of PEG2000 to obtain a polymer dispersion. The pore-forming agent is dissolved in a polymer dispersion to obtain a mixed solution; Add Ce to the mixed solution x Zr 1-x O2 cerium zirconium solid solution, mix thoroughly, adjust the pH value to 2.5-4.5 with HNO3 solution, and stir thoroughly; Adding a polyol rheology modifier yields a product containing the Ce. x Zr 1-x Coating slurry for O2 cerium zirconium solid solution; Immerse the support in Ce x Zr 1-x The coating slurry of O2 cerium zirconium solid solution is dried and pre-calcined to obtain a coating containing Ce. x Zr 1-x The support for the coating layer of O2 cerium zirconium solid solution will be coated with Ce x Zr 1-x The support for the O2 cerium-zirconium solid solution coating is immersed in a slurry containing a Pt-In-Ga / Al2O3 catalyst. After drying, the above coating steps are repeated several times in a cycle. Following calcination and furnace cooling, a Ce2-zirconium solid solution is formed on the surface of the support. x Zr 1-x The coating layer of O2 cerium zirconium solid solution and the coating layer containing Pt-In-Ga / Al2O3 catalyst.

[0019] On the other hand, the application of precious metal catalysts as described in any of the above-mentioned items in methanol-to-hydrogen units.

[0020] The present invention provides a noble metal catalyst, its manufacturing method, and its application, which have the following beneficial effects: Under high-temperature reaction conditions, the catalyst exhibits high methanol conversion and hydrogen production rates even at high space velocities. It not only has low CO selectivity and low CO content in the product, but also demonstrates excellent performance in methanol conversion, CO content in the reformate, and hydrogen production rate over extended operating times, thus improving the long-term stability of the catalyst. Attached Figure Description

[0021] Figure 1 This is a SEM image of the noble metal catalyst provided in Example 2 of the present invention; Figure 2 SEM image of the noble metal catalyst provided for Comparative Example 1; Figure 3The methanol conversion spectral data of the noble metal catalysts provided in Example 2 and Comparative Example 1 of this invention are shown. Figure 4 The CO content spectra of the noble metal catalysts provided in Example 2 and Comparative Example 1 of this invention are shown. Figure 5 The hydrogen production rate spectra of the noble metal catalysts provided in Example 2 and Comparative Example 1 of this invention; Figure 6 Example 2 of the present invention provides a long-term stability test spectrum of a noble metal catalyst (the relationship between cumulative duration and methanol conversion rate and CO content under test conditions of start-stop). Figure 7 Example 2 of this invention provides a long-term stability test spectrum of a noble metal catalyst (the relationship between cumulative duration and hydrogen production rate under test conditions of start-stop). Detailed Implementation

[0022] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0023] This invention provides a noble metal catalyst, comprising: a Pt-In-Ga / Al2O3 catalyst, wherein the Pt-In-Ga / Al2O3 catalyst comprises an Al2O3 support and a Pt-In2O3-Ga2O3 active component supported on the Al2O3 support, wherein the total mass of the Pt-In2O3-Ga2O3 active component accounts for 5 to 50% of the total mass of the catalyst.

[0024] This invention provides a precious metal catalyst, its manufacturing method, and its application. Under high-temperature reaction conditions, it achieves high methanol conversion and hydrogen production rates even at high space velocities. It not only exhibits low selectivity for CO and low CO content in the product, but also demonstrates excellent performance in methanol conversion, CO content in the reformate, and hydrogen production rate over extended operating times, thereby improving the long-term stability of the catalyst.

[0025] Preferably, the molar ratio of Pt:In2O3 in the Pt-In-Ga / Al2O3 catalyst is (0.8-1.2):1, and the molar ratio of Pt:Ga2O3 is (2-10):1.

[0026] Preferably, it includes: Ce x Zr 1-x O2 cerium zirconium solid solution, wherein the Ce:Zr molar ratio is 4:1.

[0027] Preferably, it includes: a support body, the surface of which is alternately coated with a substance containing Ce. x Zr 1-x The coating layer of O2 cerium zirconium solid solution and the coating layer containing Pt-In-Ga / Al2O3 catalyst.

[0028] Preferably, the coating containing the Pt-In-Ga / Al2O3 catalyst comprises the following components by mass percentage: Pt-In-Ga / Al2O3 catalyst 10%-35%; 3-5% polyol rheology modifier; The remainder is a polymer dispersion; The polyol rheology modifier comprises at least one of glycerol, propylene glycol, and polyethylene glycol 400.

[0029] Preferably, the one containing the Ce x Zr 1-x The O2 cerium zirconium solid solution coating contains the following components by mass percentage: Ce x Zr 1-x O2 cerium zirconium solid solution 15-25%; Pore-forming agent 5-8%; 3-5% polyol rheology modifier; The remainder is a polymer dispersion; The pore-forming agent includes: ammonium nitrate; The polyol rheology modifier comprises at least one of glycerol, propylene glycol, and polyethylene glycol 400.

[0030] On the other hand, the present invention provides a method for manufacturing a noble metal catalyst, which, in order to obtain the noble metal catalyst as described above, includes: a method for manufacturing a Pt-In-Ga / Al2O3 catalyst, comprising the following steps: S1 prepares a solution containing Al(NO3)3 as a carrier precursor solution; S2. Pt nitrate, In nitrate, Ga nitrate and a polymeric dispersant are added to the solution in step S1 to form a mixed metal salt solution; S3 undergoes a reduction reaction by adding NaBH4 solution to a mixed metal salt solution under ice bath conditions; S4 was subjected to ice bath conditions, and ammonium carbonate solution was added dropwise to the reduced solution until the pH reached 8-9. After aging, separation, and washing, the precipitate was obtained. S5 dried the precipitate sequentially and calcined it at a programmed temperature to obtain the Pt-In-Ga / Al2O3 catalyst.

[0031] Preferably, the polymeric dispersant in step S2 is polyethylene glycol 2000, and the amount added is 0.1-2 wt% of the total mass of the solution. In step S3, the concentration of the NaBH4 solution is 0.01-1 mol / L, and the ratio of the total molar amount of NaBH4 to the metal salt is (1-10):1. In step S3, the reduction reaction is carried out under ice bath conditions, and the NaBH4 solution is added at a rate of 1-2 mL / s for 1-30 seconds. In step S4, the dropping rate of the ammonium carbonate solution is 1-3 mL / min, the aging temperature is 60-80℃, and the aging time is 4-12 hours. The programmed temperature rise calcination in step S5 includes: (a) raising the temperature from room temperature to 400°C at a rate of 2-5°C / min and holding for 2-4 hours; (b) raising the temperature from 400°C to 550-650°C at a rate of 5-15°C / min and holding for 2-4 hours.

[0032] Preferably, it includes: Ce x Zr 1-x The method for manufacturing O2 cerium zirconium solid solution includes the following steps: Weigh out soluble cerium and zirconium salts according to the target Ce and Zr molar ratio, and dissolve them in deionized water to form a mixed salt solution; Slowly add ammonia to the mixed salt solution to control the OH content. - For concentrations in the range of 0.1~1.5M, adjust the pH to 8.5-9.5; The reaction was carried out under continuous stirring at a temperature of 20-50℃ for 1-3 hours. Stirring at room temperature, and after aging for 8-24 hours, perform solid-liquid separation. The precipitate was washed alternately with water and alcohol-based detergents; After vacuum drying, Ce is calcined at 350-450℃ for 3-5 hours to obtain Ce. x Zr 1-x O2 cerium zirconium solid solution; The soluble cerium salt includes at least one of cerium nitrate or cerium acetate; The soluble zirconium salt includes at least one of Zr(NO3)4·5H2O, zirconium oxynitrate, or zirconium acetate; The alcohol-based detergents include: ethanol.

[0033] Preferably, it includes: a method for manufacturing a coating slurry containing a Pt-In-Ga / Al2O3 catalyst, comprising the following steps: First, prepare a saturated solution of PVA dispersant, then dilute it with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. Add 0.2-0.8% by mass of PEG2000 to obtain a polymer dispersion. After adding the Pt-In-Ga / Al2O3 catalyst, adjust the pH value to 2.5-4.5 with HNO3 solution and stir thoroughly. A polyol rheology modifier was added to obtain a coating slurry containing a Pt-In-Ga / Al2O3 catalyst.

[0034] Preferably, it includes: containing the Ce x Zr 1-x A method for manufacturing a coating slurry of O2 cerium-zirconium solid solution includes the following steps: First, prepare a saturated solution of PVA dispersant, then dilute it with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. Add 0.2-0.8% by mass of PEG2000 to obtain a polymer dispersion. The pore-forming agent is dissolved in a polymer dispersion to obtain a mixed solution; Add Ce to the mixed solution x Zr 1-x O2 cerium zirconium solid solution, mix thoroughly, adjust the pH value to 2.5-4.5 with HNO3 solution, and stir thoroughly; Adding a polyol rheology modifier yields a product containing the Ce. x Zr 1-x Coating slurry for O2 cerium zirconium solid solution; Immerse the support in Ce x Zr 1-x The coating slurry of O2 cerium zirconium solid solution is dried and pre-calcined to obtain a coating containing Ce. x Zr 1-x The support for the coating layer of O2 cerium zirconium solid solution will be coated with Ce x Zr 1-x The support for the O2 cerium-zirconium solid solution coating is immersed in a slurry containing a Pt-In-Ga / Al2O3 catalyst. After drying, the above coating steps are repeated several times in a cycle. Following calcination and furnace cooling, a Ce2-zirconium solid solution is formed on the surface of the support. x Zr 1-x The coating layer of O2 cerium zirconium solid solution and the coating layer containing Pt-In-Ga / Al2O3 catalyst; Pre-baking: Baking at 550-650℃ for 1-3 hours, with the pre-baking temperature increasing as the number of coating layers increases; The roasting process involves raising the temperature from room temperature to 300℃ at a rate of 1℃ / min, holding it at 300℃ for 1-2 hours, raising it from 300℃ to 500℃ at a rate of 2℃ / min, holding it at 500℃ for 2-4 hours, raising it from 500℃ to 650℃ at a rate of 5℃ / min, and holding it at 650℃ for 2-4 hours. Preferably, the support is cleaned and heat-treated before being immersed in the slurry to ensure the coating effect.

[0035] Preferably, the present invention employs a two-step method for preparing a Pt-In-Ga / Al2O3 catalyst slurry, comprising the following steps: preparing a Pt-In-Ga / Al2O3 catalyst, then preparing a Pt-In-Ga / Al2O3 catalyst slurry using the Pt-In-Ga / Al2O3 catalyst; and alternately coating a cleaned and heat-treated support with Ce. x Zr 1-x A noble metal catalyst (catalyst I) is obtained by coating a slurry of O2 cerium-zirconium solid solution and a slurry of Pt-In-Ga / Al2O3 catalyst. This catalyst exhibits high methanol conversion and hydrogen production rates under high temperature and high space velocity conditions, but low selectivity for CO and low CO content in the product.

[0036] On the other hand, the application of precious metal catalysts as described in any of the above-mentioned items in methanol-to-hydrogen units.

[0037] Example 1 Example 1 provides a method for manufacturing a noble metal catalyst, comprising: The method for manufacturing Pt-In-Ga / Al2O3 catalyst includes the following steps: S1 prepared a solution containing Al(NO3)3 as a carrier precursor solution. 22.74 g (AR) of Al(NO3)3·9H2O was added to 100 mL of deionized water and stirred to dissolve, thus obtaining a solution containing Al(NO3)3. S2. Add 1.546g Pt(NO3)2, 0.604g indium nitrate hydrate, 0.100g gallium nitrate hydrate and 1g polyethylene glycol 2000 to the solution in step S1 to form a mixed metal salt solution; S3 was subjected to a reduction reaction by adding 0.5 mol / L NaBH4 solution to a mixed metal salt solution under ice bath conditions and stirring. The reduction reaction was carried out under ice bath conditions, with 12.6 mL of NaBH4 solution added at a rate of 1 mL / s for 13 seconds. S4 was added dropwise to the reduced solution at a rate of 1 mL / min under ice bath conditions until the pH reached 8. The temperature was then raised to 60°C and stirred for 6 hours. After separation, the precipitate was washed repeatedly with a large amount of warm water (50°C) until neutral, and then washed alternately with ethanol and deionized water to obtain the precipitate. S5 The precipitate was successively dried under vacuum overnight at 40℃, then calcined by heating from room temperature to 400℃ at 2℃ / min and holding for 3 hours; then calcined by heating from 400℃ to 550℃ at 5℃ / min and holding for 4 hours; thus obtaining the 7.5Pt-7.5In2O3-1Ga2O3 / Al2O3 catalyst. Includes: Ce x Zr1-x The method for manufacturing O2 cerium zirconium solid solution includes the following steps: Weigh out soluble Ce(NO3)3·6H2O and Zr(NO3)4·5H2O according to the target Ce and Zr molar ratio of 4:1, and dissolve them in deionized water to form a mixed salt solution. Slowly add 0.5M ammonia solution to the mixed salt solution, controlling the OH content. - For concentrations within the 0.1M range, adjust the pH to 8.5; The reaction was continuously stirred at 30°C for 2 hours. Stirring at room temperature, and after aging for 12 hours, perform solid-liquid separation. The precipitate was washed with water and ethanol detergent alternately. After vacuum drying, Ce was calcined at 350°C for 5 hours to obtain Ce. x Zr 1-x O2 cerium zirconium solid solution; A method for manufacturing a coating containing a Pt-In-Ga / Al2O3 catalyst includes the following steps: A saturated solution of PVA dispersant was first prepared and then diluted with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. 0.5% by mass of PEG2000 was added as a dispersant to obtain a polymer dispersion. After adding 35% by mass of Pt-In-Ga / Al2O3 catalyst, the pH value was adjusted to 3 with HNO3 solution and stirred thoroughly. Finally, 5% by mass of glycerol is added to make the viscosity between 500-1000 mPa·s, thus obtaining a slurry containing the Pt-In-Ga / Al2O3 catalyst. Contains the Ce x Zr 1-x The method for manufacturing a coating layer of O2 cerium zirconium solid solution includes the following steps: A saturated solution of PVA dispersant was first prepared and then diluted with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. 0.5% by mass of PEG2000 was added as a dispersant to obtain a polymer dispersion. A mixed solution is obtained by dissolving 10% by mass of the pore-forming agent in a polymer dispersion; Add 25% by mass of Ce to the mixed solution x Zr 1-x O2 cerium zirconium solid solution, mix evenly, adjust the pH value to 3 with HNO3 solution, and stir thoroughly; Finally, 5% by mass of glycerol is added to achieve a viscosity between 500-1000 mPa·s, yielding the product containing Ce. x Zr1-x Coating slurry for O2 cerium zirconium solid solution; The cleaned and heat-treated support is immersed in Ce. x Zr 1-x The coating slurry of O2 cerium zirconium solid solution is dried and pre-calcined to obtain a coating containing Ce. x Zr 1-x The support for the coating layer of O2 cerium zirconium solid solution will be coated with Ce x Zr 1-x The support for the O2 cerium-zirconium solid solution coating is immersed in a slurry containing a Pt-In-Ga / Al2O3 catalyst. After drying, the above coating steps are repeated several times. Finally, after calcination and furnace cooling, a Ce-containing coating is formed on the surface of the support. x Zr 1-x The coating layers consist of O2 cerium-zirconium solid solution and Pt-In-Ga / Al2O3 catalyst. The initial pre-calcination was performed at 550℃ for 2 hours, the second pre-calcination was performed at 575℃ for 2 hours, and so on. The calcination process included the following steps: increasing the temperature from room temperature to 300℃ at a rate of 1℃ / min, holding at 300℃ for 1 hour, increasing the temperature from 300℃ to 500℃ at a rate of 2℃ / min, holding at 500℃ for 2 hours, increasing the temperature from 500℃ to 650℃ at a rate of 5℃ / min, and holding at 650℃ for 2 hours.

[0038] Example 1 provides a noble metal catalyst, which is manufactured according to the above-described method for manufacturing noble metal catalysts.

[0039] Example 2 Example 2 provides a method for manufacturing a noble metal catalyst, comprising: The method for manufacturing Pt-In-Ga / Al2O3 catalyst includes the following steps: S1 prepared a solution containing Al(NO3)3 as a carrier precursor solution. 22.74 g (AR) of Al(NO3)3·9H2O was added to 100 mL of deionized water and stirred to dissolve, thus obtaining a solution containing Al(NO3)3. S2. Add 3.818g Pt(NO3)2, 1.491g indium nitrate hydrate, 0.248g gallium nitrate hydrate and 1g polyethylene glycol 2000 to the solution in step S1 to form a mixed metal salt solution; S3 was subjected to a reduction reaction by adding 0.5 mol / L NaBH4 solution to a mixed metal salt solution under ice bath conditions and stirring. The reduction reaction was carried out under ice bath conditions, with 31.1 mL of NaBH4 solution added at a rate of 1.5 mL / s for 21 seconds. S4 was added dropwise to the reduced solution at a rate of 2 mL / min under ice bath conditions until the pH reached 8.5. The temperature was raised to 70°C and stirring was continued. The mixture was aged for 8 hours. After separation, the precipitate was washed repeatedly with a large amount of warm water (60°C) until neutral, and then washed alternately with ethanol and deionized water to obtain the precipitate. S5 sequentially dried the precipitate under vacuum overnight at 40℃, then calcined it by heating it to 400℃ at 3℃ / min and holding it at that temperature for 3 hours; then calcined it by heating it from 400℃ to 600℃ at 10℃ / min and holding it at that temperature for 3 hours; thus obtaining the 15Pt-15In-2Ga / Al2O3 catalyst. Ce x Zr 1-x The method for manufacturing O2 cerium zirconium solid solution includes the following steps: Weigh out soluble Ce(NO3)3·6H2O and Zr(NO3)4·5H2O according to the target Ce and Zr molar ratio of 4:1, and dissolve them in deionized water to form a mixed salt solution. Slowly add 0.5M ammonia solution to the mixed salt solution, controlling the OH content. - For concentrations within the 1M range, adjust the pH to 9.0; The reaction was continuously stirred at 40°C for 2 hours. Stirring at room temperature, and after aging for 18 hours, perform solid-liquid separation. The precipitate was washed with water and ethanol detergent alternately. After vacuum drying, Ce was calcined at 400℃ for 3 hours to obtain Ce. x Zr 1-x O2 cerium zirconium solid solution; A method for manufacturing a coating containing a Pt-In-Ga / Al2O3 catalyst includes the following steps: A saturated solution of PVA dispersant was first prepared and then diluted with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. 0.5% by mass of PEG2000 was added as a dispersant to obtain a polymer dispersion. After adding 35% by mass of Pt-In-Ga / Al2O3 catalyst, adjust the pH to 3.5 with HNO3 solution and stir thoroughly. Finally, 5% by mass of glycerol is added to make the viscosity between 500-1000 mPa·s, thus obtaining a slurry containing the Pt-In-Ga / Al2O3 catalyst. Contains the Ce x Zr 1-x The method for manufacturing a coating layer of O2 cerium zirconium solid solution includes the following steps: A saturated solution of PVA dispersant was first prepared and then diluted with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. 0.5% by mass of PEG2000 was added as a dispersant to obtain a polymer dispersion. A mixed solution is obtained by dissolving 10% by mass of the pore-forming agent in a polymer dispersion; Add 25% by mass of Ce to the mixed solution x Zr 1-x O2 cerium zirconium solid solution, mixed evenly, pH adjusted to 3.5 with HNO3 solution, and stirred thoroughly; Finally, 5% by mass of glycerol is added to achieve a viscosity between 500-1000 mPa·s, yielding the product containing Ce. x Zr 1-x Coating slurry for O2 cerium zirconium solid solution; The cleaned and heat-treated support is immersed in Ce. x Zr 1-x The coating slurry of O2 cerium zirconium solid solution is dried and pre-calcined to obtain a coating containing Ce. x Zr 1-x The support for the coating layer of O2 cerium zirconium solid solution will be coated with Ce x Zr 1-x The support for the O2 cerium-zirconium solid solution coating is immersed in a slurry containing a Pt-In-Ga / Al2O3 catalyst. After drying, the above coating steps are repeated several times. Finally, after calcination and furnace cooling, a Ce-containing coating is formed on the surface of the support. x Zr 1-x The coating layers consist of O2 cerium-zirconium solid solution and Pt-In-Ga / Al2O3 catalyst. The initial pre-calcination was performed at 550℃ for 2 hours, the second pre-calcination was performed at 575℃ for 2 hours, and so on. The calcination process included the following steps: increasing the temperature from room temperature to 300℃ at a rate of 1℃ / min, holding at 300℃ for 1.5 hours, increasing the temperature from 300℃ to 500℃ at a rate of 2℃ / min, holding at 500℃ for 3 hours, increasing the temperature from 500℃ to 650℃ at a rate of 5℃ / min, and holding at 650℃ for 3 hours.

[0040] Example 2 provides a noble metal catalyst, which is manufactured according to the above method for manufacturing noble metal catalysts.

[0041] Example 3 Example 3 provides a method for manufacturing a noble metal catalyst, comprising: The method for manufacturing Pt-In-Ga / Al2O3 catalyst includes the following steps: S1 prepared a solution containing Al(NO3)3 as a carrier precursor solution. 22.74 g (AR) of Al(NO3)3·9H2O was added to 100 mL of deionized water and stirred to dissolve, thus obtaining a solution containing Al(NO3)3. S2. Add 6.074g Pt(NO3)2, 2.372g indium nitrate hydrate, 0.443g gallium nitrate hydrate and 1g polyethylene glycol 2000 to the solution in step S1 to form a mixed metal salt solution; S3 was subjected to a reduction reaction by adding 0.5 mol / L NaBH4 solution to a mixed metal salt solution under ice bath conditions and stirring. The reduction reaction was carried out under ice bath conditions, with 50.1 mL of NaBH4 solution added at a rate of 2 mL / s for 25 seconds. S4 added 0.5M ammonium carbonate solution dropwise to the reduced solution at a rate of 3 mL / min until pH 9, heated to 80℃ and continued stirring, aged for 12 h, the precipitate was separated and washed repeatedly with a large amount of warm water (70℃) until neutral, and then washed alternately with ethanol and deionized water to obtain the precipitate. S5 sequentially dried the precipitate under vacuum overnight at 40℃, then calcined it by heating it to 400℃ at 3℃ / min and holding it at that temperature for 3 hours; then calcined it by heating it from 400℃ to 650℃ at 10℃ / min and holding it at that temperature for 3 hours; thus obtaining the 20Pt-20In-3Ga / Al2O3 catalyst. Ce x Zr 1-x The method for manufacturing O2 cerium zirconium solid solution includes the following steps: Weigh out soluble Ce(NO3)3·6H2O and Zr(NO3)4·5H2O according to the target Ce and Zr molar ratio of 4:1, and dissolve them in deionized water to form a mixed salt solution. Slowly add 0.5M ammonia solution to the mixed salt solution, controlling the OH content. - For concentrations within the 1.5M range, adjust the pH to 9.5; The reaction was continuously stirred at 50°C for 1 hour. Stirring at room temperature, and after aging for 24 hours, perform solid-liquid separation. The precipitate was washed with water and ethanol detergent alternately. After vacuum drying, Ce was calcined at 450°C for 3 hours to obtain Ce. x Zr 1-x O2 cerium zirconium solid solution; A method for manufacturing a coating containing a Pt-In-Ga / Al2O3 catalyst includes the following steps: A saturated solution of PVA dispersant was first prepared and then diluted with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. 0.5% by mass of PEG2000 was added as a dispersant to obtain a polymer dispersion. After adding 35% by mass of Pt-In-Ga / Al2O3 catalyst, the pH value was adjusted to 4 with HNO3 solution and stirred thoroughly. Finally, 5% by mass of glycerol is added to make the viscosity between 500-1000 mPa·s, thus obtaining a slurry containing the Pt-In-Ga / Al2O3 catalyst. Contains the Ce x Zr 1-x The method for manufacturing a coating layer of O2 cerium zirconium solid solution includes the following steps: A saturated solution of PVA dispersant was first prepared and then diluted with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. 0.5% by mass of PEG2000 was added as a dispersant to obtain a polymer dispersion. A mixed solution is obtained by dissolving 10% by mass of the pore-forming agent in a polymer dispersion; Add 25% by mass of Ce to the mixed solution x Zr 1-x O2 cerium zirconium solid solution, mixed evenly, pH adjusted to 4 with HNO3 solution, and stirred thoroughly; Finally, 5% by mass of glycerol is added to achieve a viscosity between 500-1000 mPa·s, yielding the product containing Ce. x Zr 1-x Coating slurry for O2 cerium zirconium solid solution; The cleaned and heat-treated support is immersed in Ce. x Zr 1-x The coating slurry of O2 cerium zirconium solid solution is dried and pre-calcined to obtain a coating containing Ce. x Zr 1-x The support for the coating layer of O2 cerium zirconium solid solution will be coated with Ce x Zr 1-x The support for the O2 cerium-zirconium solid solution coating is immersed in a slurry containing a Pt-In-Ga / Al2O3 catalyst. After drying, the above coating steps are repeated several times. Finally, after calcination and furnace cooling, a Ce-containing coating is formed on the surface of the support. x Zr 1-xThe coating layers consist of O2 cerium-zirconium solid solution and Pt-In-Ga / Al2O3 catalyst. The initial pre-calcination was performed at 550℃ for 2 hours, the second pre-calcination was performed at 575℃ for 2 hours, and so on. The calcination process included the following steps: increasing the temperature from room temperature to 300℃ at a rate of 1℃ / min, holding at 300℃ for 2 hours, increasing the temperature from 300℃ to 500℃ at a rate of 2℃ / min, holding at 500℃ for 4 hours, increasing the temperature from 500℃ to 650℃ at a rate of 5℃ / min, and holding at 650℃ for 4 hours.

[0042] Example 3 provides a noble metal catalyst, which is manufactured according to the above method for manufacturing noble metal catalysts.

[0043] Comparative Example 1 Comparative Example 1 provides a method for manufacturing a noble metal catalyst, comprising: Ce x Zr 1-x The method for manufacturing O2 cerium zirconium solid solution includes the following steps: Weigh out soluble Ce(NO3)3·6H2O and Zr(NO3)4·5H2O according to the target Ce and Zr molar ratio of 4:1, and dissolve them in deionized water to form a mixed salt solution. Slowly add 0.5M ammonia solution to the mixed salt solution, controlling the OH content. - For concentrations within the 1M range, adjust the pH to 9.0; The reaction was continuously stirred at 40°C for 2 hours. Stirring at room temperature, and after aging for 18 hours, perform solid-liquid separation. The precipitate was washed with water and ethanol detergent alternately. After vacuum drying, Ce was calcined at 400℃ for 3 hours to obtain Ce. x Zr 1-x O2 cerium zirconium solid solution; Contains the Ce x Zr 1-x The method for manufacturing a coating layer of O2 cerium zirconium solid solution includes the following steps: A saturated solution of PVA dispersant was first prepared and then diluted with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. 0.5% by mass of PEG2000 was added as a dispersant to obtain a polymer dispersion. A mixed solution is obtained by dissolving 10% by mass of the pore-forming agent in a polymer dispersion; Add 25% by mass of Ce to the mixed solution x Zr 1-x O2 cerium zirconium solid solution, mixed evenly, pH adjusted to 3.5 with HNO3 solution, and stirred thoroughly; Finally, 5% by mass of glycerol is added to achieve a viscosity between 500-1000 mPa·s, yielding the product containing Ce. x Zr 1-x Coating slurry for O2 cerium zirconium solid solution; A method for manufacturing a coating slurry containing an active component includes the following steps: A saturated solution of PVA dispersant was first prepared and then diluted with deionized water to a mass ratio of PVA dispersant to deionized water of 1:4. 0.5% by mass of PEG2000 was added as a dispersant to obtain a polymer dispersion. 3.818g Pt(NO3)2, 1.491g In(NO3)3, 0.248g Ga(NO3)3, and 3.119g Al2O3 were added sequentially to the polymer dispersion and stirred evenly. Then, 1g of polyethylene glycol 2000 was added and stirred thoroughly. Finally, 5% by mass of glycerol was added to make the viscosity between 500-1000 mPa·s to obtain the coating slurry. The cleaned and heat-treated support is immersed in Ce. x Zr 1-x The coating slurry of O2 cerium zirconium solid solution is dried and pre-calcined to obtain a coating containing Ce. x Zr 1-x The support for the coating layer of O2 cerium zirconium solid solution will be coated with Ce x Zr 1-x The support for the O2 cerium-zirconium solid solution coating is immersed in the coating slurry. After drying, the above coating steps are repeated several times. Finally, after calcination and furnace cooling, a Ce-containing layer is formed on the surface of the support. x Zr 1-x The coating layers consist of O2 cerium-zirconium solid solution and a coating slurry. The initial pre-calcination is performed at 550℃ for 2 hours, the second pre-calcination is performed at 575℃ for 2 hours, and so on. The calcination process includes the following steps: increasing the temperature from room temperature to 300℃ at a rate of 1℃ / min, holding at 300℃ for 1.5 hours, increasing the temperature from 300℃ to 500℃ at a rate of 2℃ / min, holding at 500℃ for 3 hours, increasing the temperature from 500℃ to 650℃ at a rate of 5℃ / min, and holding at 650℃ for 3 hours.

[0044] Comparative Example 1 provides a noble metal catalyst, which is manufactured according to the above-described method for manufacturing noble metal catalysts.

[0045] Experimental methods The performance of the noble metal catalysts in Examples 1-3 and Comparative Example 1 was tested using the following experimental methods: Catalyst performance testing was conducted on a self-built single-tube reactor test rig, using segmented electric heating to provide heat for the reaction. The catalyst was packed inside the reaction tube, and the methanol-water solution was vaporized and preheated to the reaction temperature before entering the reaction tube. Thermocouples were installed in segments to monitor the temperature in real time and adjust the electric heating status to ensure the catalyst remained at a suitable reaction temperature. A peristaltic pump was used for liquid injection, and an electronic balance was used to record the injection volume in real time for calculating the WHSV. The reaction products were condensed and the condensate was collected. The flow rate of insoluble gases was measured using a soap film flow meter. Gas chromatography (Furi GC9790II (dual TCD detector)) was used to determine the methanol content in the condensate and the CO (CO content), CO2, and H2 content in the product gases, and the methanol conversion rate (X) was calculated. MeOH ), hydrogen production rate.

[0046] The performance data of the noble metal catalysts in Examples 1-3, tested using the above-mentioned experimental methods at reaction temperatures of 325-400℃, are shown in Table 1 below: Table 1. Performance experimental data of the noble metal catalysts in Examples 1-3 As can be seen from Table 1, the noble metal catalysts provided in Examples 1-3, under high temperature reaction conditions, still have high methanol conversion and hydrogen production rates at high space velocities, and not only have low selectivity for CO, but also low CO content in the products.

[0047] like Figure 1-2 From the SEM images of the noble metal catalysts provided in Example 2 and Comparative Example 1 of this invention, we can observe that... Figure 1 The surface of the noble metal catalyst (catalyst I) prepared in Example 2 of this invention is uniformly sized particles. Figure 2 Comparative Example 1 yielded a noble metal catalyst (Catalyst II) with a gel-like surface and obvious cracks, and the cracks exhibited similar characteristics. Figure 1 The precious metal catalyst (catalyst I) was produced in particulate form. It can be considered that the precious metal catalyst produced in Example 2 of the present invention was prepared by a two-step coating method of first synthesizing the catalyst and then dispersing it into a slurry, forming a uniform coating on the surface of the support. In contrast, the precious metal catalyst prepared in Comparative Example 1 was prepared by a one-step synthesis and coating method, which formed a denser coating on the surface. Moreover, after fine calcination, more cracks were still generated on the surface, and more particles were generated at the cracks.

[0048] like Figure 3 As shown, with the increase of liquid feed, the methanol conversion rate of the noble metal catalyst (catalyst I) prepared in Example 2 of the present invention decreases slowly, while the methanol conversion rate of the noble metal catalyst (catalyst II) prepared in Comparative Example 1 decreases rapidly, making it unsuitable for high space velocity environments.

[0049] like Figure 4 As shown, the CO content in the product of the noble metal catalyst (catalyst I) prepared in Example 2 of the present invention is significantly lower than the CO content in the product of the noble metal catalyst (catalyst II) prepared in Comparative Example 1.

[0050] like Figure 5 As shown, under the condition of similar liquid feed volume, the hydrogen production rates of the noble metal catalyst (catalyst I) prepared in Example 2 of the present invention and the noble metal catalyst (catalyst II) prepared in Comparative Example 1 are relatively consistent at low space velocities. However, at higher space velocities, the hydrogen production rate of the noble metal catalyst (catalyst I) prepared in Example 2 of the present invention is higher than that of the noble metal catalyst (catalyst II) prepared in Comparative Example 1.

[0051] The characterization and testing results above indicate that, under the condition of consistent material composition, catalysts obtained by different coating methods exhibit significant differences in surface morphology and catalytic performance. This is because the methanol-to-hydrogen process is highly sensitive to surface structure.

[0052] The noble metal catalyst (catalyst I) prepared in Example 2 of this invention has a uniform particle surface with relatively consistent physicochemical properties, which makes the active sites evenly distributed and methanol molecules can effectively and evenly contact the active sites. This results in a high methanol conversion rate and hydrogen production rate even at high space velocities. At the same time, the uniform particle surface provides relatively consistent control of the reaction path and has low selectivity for CO. At high space velocities, the CO content in the product increases at a relatively low rate within a low range. The dense outer surface of the noble metal catalyst (Catalyst II) prepared in Comparative Example 1 not only reduces the specific surface area but may also restrict the diffusion and adsorption of methanol molecules. Methanol molecules struggle to penetrate the active sites within the catalyst, resulting in a significant decrease in methanol conversion rate with increasing feed volume. Simultaneously, the outer surface contains both dense morphology and particulate matter within cracks. The dense morphology is detrimental to heat transfer, leading to significant differences in reaction pathways. Defect sites may promote CO desorption, causing a sharp increase in CO content with increasing feed volume. The presence of particulate matter within cracks may have created a particle structure similar to that of the noble metal catalyst (Catalyst I) prepared in Example 2 of this invention. With identical material composition, the similarity in the external surface particle structure and composition of the two catalysts may be maintained. Therefore, with increasing feed volume, the hydrogen production rates of the two catalysts show little difference at lower space velocities.

[0053] like Figure 6-7The image shows the long-term stability test spectrum of the noble metal catalyst (catalyst I) prepared in Example 2 of this invention. The noble metal catalyst (catalyst I) prepared in Example 2 of this invention was subjected to a long-term stability test for 800 hours, with switching on and off every 8 hours, and samples were taken for analysis of each catalytic performance parameter. WHSV = 7.5 ± 0.3 h -1 The reaction temperature was controlled at 350±25℃. After a cumulative 800h on / off test, the performance indicators changed over time. As shown in the figure, after the initial 50h stabilization period, under conditions of frequent on / off cycles and high / low temperature shocks, the methanol conversion rate of the noble metal catalyst (catalyst I) prepared in Example 2 of this invention remained above 90% for 800h, with the CO content in the product between 4% and 5.5%. During the 800h test period, the hydrogen production rate remained stable at 0.0954-0.102 mmol / (gcat·s), indicating that the catalyst possesses long-term stability under regular on / off conditions.

[0054] It is understood that this invention has been described through some embodiments, and those skilled in the art will recognize that various changes or equivalent substitutions can be made to these features and embodiments without departing from the spirit and scope of this invention. Furthermore, under the teachings of this invention, these features and embodiments can be modified to adapt to specific situations and materials without departing from the spirit and scope of this invention. Therefore, this invention is not limited to the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application are protected by this invention. Furthermore, under the teachings of this invention, these features and embodiments can be modified to adapt to specific situations and materials without departing from the spirit and scope of this invention. Therefore, this invention is not limited to the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application are within the scope of protection of this invention.

Claims

1. A noble metal catalyst, characterized in that, include: The Pt-In-Ga / Al2O3 catalyst comprises an Al2O3 support and a Pt-In2O3-Ga2O3 active component supported on the Al2O3 support, wherein the total mass of the Pt-In2O3-Ga2O3 active component accounts for 5 to 50% of the total mass of the catalyst.

2. The noble metal catalyst according to claim 1, characterized in that, The Pt:In2O3 molar ratio of the Pt-In-Ga / Al2O3 catalyst is (0.8-1.2):1, and the Pt:Ga2O3 molar ratio is (2-10):

1.

3. The noble metal catalyst according to claim 1 or 2, characterized in that, include: Ce x Zr 1-x O2 cerium-zirconium solid solution, wherein the Ce:Zr molar ratio is 4:

1.

4. The noble metal catalyst according to claim 3, characterized in that, include: a support whose surface is alternately coated with Ce x Zr 1-x a coating layer of O2 cerium zirconium solid solution and a coating layer comprising a Pt-In-Ga / Al2O3 catalyst.

5. The noble metal catalyst according to claim 4, characterized in that, The coating containing the Pt-In-Ga / Al2O3 catalyst comprises the following components by mass percentage: Pt-In-Ga / Al2O3 catalyst 10%-35%; 3-5% polyol rheology modifier; The remainder is a polymer dispersion; The polyol rheology modifier comprises at least one of glycerol, propylene glycol, and polyethylene glycol 400.

6. The noble metal catalyst according to claim 4, characterized in that, The coating layer comprising the Ce x Zr 1-x The coating layer of the O2 cerium-zirconium solid solution comprises the following components in mass percentage: Ce x Zr 1-x O2 ceria 5-15% Pore-forming agent 5-8%; 3-5% polyol rheology modifier; The remainder is a polymer dispersion; The pore-forming agent includes: ammonium nitrate; The polyol rheology modifier comprises at least one of glycerol, propylene glycol, and polyethylene glycol 400.

7. A method for manufacturing a noble metal catalyst, characterized in that, Manufacturing a noble metal catalyst as described in any one of claims 1-6 comprises: a method for manufacturing a Pt-In-Ga / Al2O3 catalyst, comprising the following steps: S1 prepares a solution containing Al(NO3)3 as a carrier precursor solution; S2. Pt nitrate, In nitrate, Ga nitrate and a polymeric dispersant are added to the solution in step S1 to form a mixed metal salt solution; S3 undergoes a reduction reaction by adding NaBH4 solution to a mixed metal salt solution under ice bath conditions; S4 was subjected to ice bath conditions, and ammonium carbonate solution was added dropwise to the reduced solution until the pH reached 8-9. After aging, separation, and washing, the precipitate was obtained. S5 dried the precipitate sequentially and calcined it at a programmed temperature to obtain the Pt-In-Ga / Al2O3 catalyst.

8. The method for manufacturing the noble metal catalyst according to claim 7, characterized in that, The polymeric dispersant mentioned in step S2 is polyethylene glycol 2000, and the amount added is 0.1-2 wt% of the total mass of the solution. In step S3, the concentration of the NaBH4 solution is 0.01-1 mol / L, and the ratio of the total molar amount of NaBH4 to the metal salt is (1-10):

1. In step S3, the reduction reaction is carried out under ice bath conditions, and the NaBH4 solution is added at a rate of 1-2 mL / s for 1-30 seconds. In step S4, the dropping rate of the ammonium carbonate solution is 1-3 mL / min, the aging temperature is 60-80℃, and the aging time is 4-12 hours. The programmed temperature rise calcination in step S5 includes: (a) raising the temperature from room temperature to 400°C at a rate of 2-5°C / min and holding it at that temperature for 2-4 hours; (b) Increase the temperature from 400℃ to 550-650℃ at a rate of 5-15℃ / min and hold for 2-4 hours.

9. The method for manufacturing the noble metal catalyst according to claim 7, characterized in that, include: Ce x Zr 1-x The method for manufacturing O2 cerium zirconium solid solution includes the following steps: Weigh out soluble cerium and zirconium salts according to the target Ce and Zr molar ratio, and dissolve them in deionized water to form a mixed salt solution; Slowly add ammonia to the mixed salt solution to control the OH content. - For concentrations in the range of 0.1~1.5M, adjust the pH to 8.5-9.5; The reaction was carried out under continuous stirring at a temperature of 20-50℃ for 1-3 hours. Stirring at room temperature, and after aging for 8-24 hours, perform solid-liquid separation. The precipitate was washed alternately with water and alcohol-based detergents; After vacuum drying, Ce is calcined at 350-450℃ for 3-5 hours to obtain Ce. x Zr 1-x O2 cerium zirconium solid solution; The soluble cerium salt includes at least one of cerium nitrate or cerium acetate; The soluble zirconium salt includes at least one of Zr(NO3)4·5H2O, zirconium oxynitrate, or zirconium acetate; The alcohol-based detergents include: ethanol.

10. The method for manufacturing a noble metal catalyst according to any one of claims 7-9, characterized in that, include: A method for manufacturing a coating slurry containing a Pt-In-Ga / Al2O3 catalyst includes the following steps: First, prepare a saturated solution of PVA dispersant, then dilute it with deionized water to a mass ratio of PVA dispersant to deionized water of 1:

4. Add 0.2-0.8% by mass of PEG2000 to obtain a polymer dispersion. After adding the Pt-In-Ga / Al2O3 catalyst, adjust the pH value to 2.5-4.5 with HNO3 solution and stir thoroughly. A polyol rheology modifier was added to obtain a coating slurry containing a Pt-In-Ga / Al2O3 catalyst; Contains the Ce x Zr 1-x A method for manufacturing a coating slurry of O2 cerium-zirconium solid solution includes the following steps: First, prepare a saturated solution of PVA dispersant, then dilute it with deionized water to a mass ratio of PVA dispersant to deionized water of 1:

4. Add 0.2-0.8% by mass of PEG2000 to obtain a polymer dispersion. The pore-forming agent is dissolved in a polymer dispersion to obtain a mixed solution; Add Ce to the mixed solution x Zr 1-x O2 cerium zirconium solid solution, mix thoroughly, adjust the pH value to 2.5-4.5 with HNO3 solution, and stir thoroughly; Adding a polyol rheology modifier yields a product containing the Ce. x Zr 1-x Coating slurry for O2 cerium zirconium solid solution.

11. The method for manufacturing the noble metal catalyst according to claim 10, characterized in that, Includes the following steps: Immerse the support in the Ce-containing x Zr 1-x The coating slurry of O2 cerium zirconium solid solution is dried and pre-calcined to obtain a coating containing Ce. x Zr 1-x The support for the coating layer of O2 cerium zirconium solid solution will be coated with Ce x Zr 1-x The support for the O2 cerium-zirconium solid solution coating is immersed in the slurry containing the Pt-In-Ga / Al2O3 catalyst. After drying, the above coating steps are repeated several times in a cycle. After calcination and furnace cooling, a Ce-containing coating is formed on the surface of the support. x Zr 1-x The coating layer of O2 cerium zirconium solid solution and the coating layer containing Pt-In-Ga / Al2O3 catalyst.

12. The application of the noble metal catalyst according to any one of claims 1-6 in a methanol-to-hydrogen plant.

Images