Catalyst for hydrogen production based on organic solid waste and sewage and preparation method thereof
By using organic solid waste and wastewater preparation methods in water vapor cracking hydrogen production catalyst, combined with the mixed treatment of polyethylene glycol, metal salt and stabilizer, the problems of decreasing activity and low efficiency of traditional catalysts are solved, and efficient and stable hydrogen production effect is achieved.
Patent Information
- Application Number
- CN202510247904.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-04
- Publication Date
- 2025-05-27
AI Technical Summary
Traditional water vapor cracking hydrogen production catalysts have problems such as oxide film formation, decreased catalytic activity, large metal particle size, and limited contact area. The composite metal catalyst has poor reaction selectivity and low hydrogen production efficiency.
The catalyst preparation method based on organic solid waste and wastewater is adopted to improve catalytic activity and stability by mixing polyethylene glycol, metal salt and stabilizer trisodium citrate with vinyl carbonate, and then rotary vaporization, drying, heat treatment and sieving.
The hydrogen production rate and hydrogen production volume of the catalyst are improved, the energy barriers of the hydrogen production reaction are reduced, and hydrogen is more easily generated at lower temperatures and pressures, which enhances the structural stability and selectivity of the catalyst.
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Abstract
Description
Technical Field
[0001] This application relates to the technical field of catalysts, and specifically relates to a catalyst for hydrogen production based on organic solid waste and sewage and a preparation method thereof. Background Art
[0002] At present, hydrogen production technologies mainly include various methods such as water electrolysis method, natural gas reforming method, biomass conversion method, etc. Among them, hydrogen production by steam cracking has received extensive attention due to its environmental friendliness and high theoretical hydrogen production rate. Moreover, the heat source (raw material) for burning steam can preferably use domestic waste, and the water source uses reclaimed water and sewage generated in industrial production or daily life, with higher energy utilization efficiency and significantly improving the levels of harmlessness, reduction, and resource utilization. However, traditional steam cracking hydrogen production catalysts have many limitations. For example, an oxide film is easily formed on the surface of a single metal, resulting in a decrease in catalytic activity, and the particle size of the metal is usually large, with a limited contact area, which restricts the hydrogen production rate. In addition, although some highly active metals (such as aluminum powder) exhibit good catalytic performance under low-temperature conditions, the reaction rate is too fast in a high-temperature steam environment and is difficult to effectively control, which further limits their practical applications.
[0003] In order to overcome the limitations of single metals, researchers have developed some composite metal catalysts, such as Fe-Ni, Ni-Al, etc. These composite metal catalysts can improve catalytic activity and stability to a certain extent by optimizing the electronic structure and spatial arrangement between metals. However, existing composite metal catalysts still have problems of poor reaction selectivity and low hydrogen production efficiency. Summary of the Invention
[0004] To solve the above technical problems, this application provides a catalyst for hydrogen production based on organic solid waste and sewage and a preparation method thereof.
[0005] In the first aspect, this application provides a preparation method of a catalyst for hydrogen production based on organic solid waste and sewage, which specifically includes the following steps carried out in sequence: Dissolve 6 - 12 parts by weight of polyethylene glycol and 2 - 4 parts by weight of a stabilizer in 100 parts by weight of water at a temperature of 60 - 80°C, stir for 40 - 80 min, add 16 - 22 parts by weight of a metal salt, stir for 6 - 8 h, and after cooling to room temperature, obtain a precursor solution; Spin - evaporate the solvent from the precursor solution, dry it at 100 - 140°C for 2 - 4 h, then carry out heat treatment and sieving to obtain the catalyst for hydrogen production based on organic solid waste and sewage; The stabilizer is composed of a mixture of trisodium citrate and vinylene carbonate with a weight ratio of 9:1 - 7.
[0006] In the technical solution provided by this application, the heat treatment reaction causes a chemical reaction between polyethylene glycol and metal salts to generate substances with high catalytic activity; it can reduce the energy barrier of the hydrogen production reaction, making it easier for hydrogen to be generated at lower temperatures and pressures, thereby greatly improving the hydrogen production efficiency. The addition of trisodium citrate and vinylene carbonate as stabilizers can effectively prevent the metal salts from agglomerating or decomposing during the reaction, thus ensuring that the metal salts can be evenly dispersed in polyethylene glycol; this uniform dispersion is crucial for increasing the active sites and reaction efficiency of the catalyst. Secondly, these two stabilizers can also form stable chemical bonds with the metal salts, further enhancing the structural stability of the catalyst. This stability can not only extend the service life of the catalyst but also ensure its high catalytic activity during the reaction. In addition, the specific chemical properties of trisodium citrate and vinylene carbonate can also regulate the surface properties of the catalyst, making it easier to contact and react with the reactants; this optimization of the surface properties helps to improve the selectivity and reaction rate of the catalyst.
[0007] In addition, the preparation method of the catalyst provided by this application also has the characteristics of environmental protection and sustainable development: the raw materials used are all common chemical substances, which are widely sourced and easily obtainable. At the same time, less waste is generated during the preparation process, and it can be treated and recycled through appropriate methods, thereby reducing environmental pollution.
[0008] Preferably, the metal salt is selected from one or more of iron salts, cobalt salts, nickel salts, and palladium salts.
[0009] Preferably, the metal salt is composed of nickel nitrate hexahydrate and cobalt nitrate hexahydrate with a weight ratio of 0.5 - 1.5:3 - 7.
[0010] Preferably, the metal salt is composed of nickel nitrate hexahydrate and cobalt nitrate hexahydrate with a weight ratio of 0.8 - 1.2:4 - 6.
[0011] In a specific embodiment, the weight ratio of nickel nitrate hexahydrate to cobalt nitrate hexahydrate can be: 0.5:3, 0.5:4, 0.5:5, 0.5:6, 0.5:7, 0.8:3, 0.8:4, 0.8:5, 0.8:6, 0.8:7, 1:3, 1:4, 1:5, 1:6, 1:7, 1.2:3, 1.2:4, 1.2:5, 1.2:6, 1.2:7, 1.5:3, 1.5:4, 1.5:5, 1.5:6, 1.5:7.
[0012] Through experimental analysis, it can be known that using metal salts composed of nickel nitrate hexahydrate and cobalt nitrate hexahydrate with the above weight ratio in this application can further improve the hydrogen production performance of the catalyst.
[0013] Preferably, the stabilizer is composed of sodium citrate and vinylene carbonate mixed in a weight ratio of 9:3-5.
[0014] In a specific embodiment, the weight ratio of sodium citrate to vinylene carbonate can be 9:1, 9:3, 9:4, 9:5, 9:7.
[0015] Through experimental analysis, it can be known that in this application, using the above weight ratio of sodium citrate and vinylene carbonate to form a stabilizer can further improve the hydrogen production performance of the catalyst.
[0016] Preferably, the molecular weight of the polyethylene glycol is 600-1000.
[0017] Preferably, the specific steps of the heat treatment are: heat treatment and insulation at a temperature of 400-500 °C for 2-4 h, and then heat treatment and insulation at a temperature of 550-750 °C for 3-5 h.
[0018] Preferably, the specific steps of the heat treatment are: heat treatment and insulation at a temperature of 420-480 °C for 2-4 h, and then heat treatment and insulation at a temperature of 600-700 °C for 3-5 h.
[0019] In a second aspect, this application provides the above-mentioned catalyst for hydrogen production based on organic solid waste and sewage, which is prepared by the above-mentioned preparation method.
[0020] In a third aspect, this application provides the application of the above-mentioned catalyst for hydrogen production based on organic solid waste and sewage in the field of hydrogen supply.
[0021] In summary, the technical solution of this application has the following effects: In this application, by using sodium citrate and vinylene carbonate as stabilizers and polyethylene glycol and metal salts as reaction raw materials, a catalyst is prepared and applied to the scenario of catalytic hydrogen production, which can effectively improve the hydrogen production rate and hydrogen production amount of the catalyst.
[0022] The catalyst preparation method provided by this application has the characteristics of environmental protection and sustainable development. The raw materials used are all common chemical substances, which are widely sourced and easily obtainable. At the same time, less waste is generated during the preparation process, and it can be treated and recycled through appropriate methods, thereby reducing environmental pollution. Specific Embodiments
[0023] The following further describes this application in detail in combination with examples, comparative examples, and performance detection tests. These examples should not be construed as limiting the scope claimed by this application.
[0024] The sources of the reagents used in this application are specifically as follows: Polyvinyl alcohol (product number: V30211, degree of alcoholysis: 87.0 - 89.0 mol%, viscosity: 40.0 - 48.0 mPa·s), polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, and polyethylene glycol 1500 were purchased from Shanghai Yuanye Bio-Technology Co., Ltd. Example Examples 1 - 5
[0025] Examples 1 - 5 respectively provide a catalyst for hydrogen production based on organic solid waste and sewage and its preparation method.
[0026] The differences between the above examples are as follows: The dosages of each component are different, as shown in Table 1 specifically.
[0027] The preparation method of the catalyst in the above examples is as follows: Weigh the corresponding raw material components according to Table 1 and set aside; Dissolve polyethylene glycol 800 and the stabilizer (the stabilizer is composed of sodium citrate and vinylene carbonate mixed in a weight ratio of 9:4) in 100 g of water at 70 °C, stir for 60 min, add the metal salt (composed of nickel nitrate hexahydrate and cobalt nitrate hexahydrate in a weight ratio of 1:5), stir at a rotation speed of 1200 rpm for 7 h, and after cooling to room temperature, obtain the precursor solution; Evaporate the solvent from the precursor solution by rotary evaporation, dry it at 120 °C for 3 h, then perform heat treatment and pass through a 500 - mesh sieve to obtain the catalyst for hydrogen production based on organic solid waste and sewage; The specific steps of the heat treatment are as follows: Heat treatment is carried out at 450 °C for 3 h of heat preservation, and then at 650 °C for 4 h of heat preservation.
[0028] Table 1 Dosages of each component in Examples 1 - 5 and Comparative Examples 1 - 2 Examples 6 - 9
[0029] Examples 6 - 9 respectively provide a catalyst for hydrogen production based on organic solid waste and sewage and its preparation method.
[0030] The differences between the above examples and Example 3 are specifically as follows: The types of metal salts are different, as shown below.
[0031] In Example 6: The metal salt is composed of nickel nitrate hexahydrate and iron nitrate in a weight ratio of 1:5.
[0032] In Example 7: The metal salt is composed of nickel nitrate hexahydrate and cobalt nitrate hexahydrate in a weight ratio of 5:1.
[0033] In Example 8: The metal salt consists of nickel nitrate hexahydrate and cobalt nitrate hexahydrate with a weight ratio of 0.5:7.
[0034] In Example 9: The metal salt consists of nickel nitrate hexahydrate and cobalt nitrate hexahydrate with a weight ratio of 1.5:3.
[0035] In the above examples, other process parameters are the same as those in Example 3. Examples 10 - 13
[0036] Examples 10 - 13 respectively provide a catalyst for hydrogen production based on organic solid waste and sewage and its preparation method.
[0037] The differences between the above examples and Example 3 are specifically as follows: The types of stabilizers are different, as shown below.
[0038] In Example 10: The stabilizer is composed of a mixture of trisodium citrate and vinylene carbonate with a weight ratio of 9:1.
[0039] In Example 11: The stabilizer is composed of a mixture of trisodium citrate and vinylene carbonate with a weight ratio of 9:7.
[0040] In Example 12: The stabilizer is composed of a mixture of trisodium citrate and vinylene carbonate with a weight ratio of 9:3.
[0041] In Example 13: The stabilizer is composed of a mixture of trisodium citrate and vinylene carbonate with a weight ratio of 9:5.
[0042] In the above examples, other process parameters are the same as those in Example 3. Examples 14 - 17
[0043] Examples 14 - 17 respectively provide a catalyst for hydrogen production based on organic solid waste and sewage and its preparation method.
[0044] The differences between the above examples and Example 3 are specifically as follows: The types of polyethylene glycol are different, as shown below.
[0045] In Example 14: Polyethylene glycol 400 is used to replace polyethylene glycol 800 in equal amounts.
[0046] In Example 15: Polyethylene glycol 600 is used to replace polyethylene glycol 800 in equal amounts.
[0047] In Example 16: Polyethylene glycol 1000 is used to replace polyethylene glycol 800 in equal amounts.
[0048] In Example 17: Polyethylene glycol 1500 is used to replace polyethylene glycol 800 in equal amounts.
[0049] In the above examples, other process parameters are the same as those in Example 3. Comparative Example
[0050] Comparative Examples 1-2
[0051] Comparative Examples 1-2 respectively provide a catalyst for hydrogen production based on organic solid waste and sewage and a preparation method thereof.
[0052] The difference between the above-mentioned comparative examples and Example 3 lies in: the dosages of each component are different, as specifically shown in Table 1.
[0053] Other process parameters in the above-mentioned comparative examples are the same as those in Example 3. Comparative Examples 3-4
[0054] Comparative Examples 3-4 respectively provide a catalyst for hydrogen production based on organic solid waste and sewage and a preparation method thereof.
[0055] The differences between the above-mentioned comparative examples and Example 3 are specifically as follows.
[0056] In Comparative Example 3: The stabilizer is composed of a mixture of disodium ethylenediaminetetraacetate and vinylene carbonate with a weight ratio of 9:4.
[0057] In Comparative Example 4: Polyvinyl alcohol is used to replace polyethylene glycol 800 in equal amounts.
[0058] Other process parameters in the above-mentioned comparative examples are the same as those in Example 3. Performance Detection Test
[0059] Catalytic Hydrogen Production Performance Detection: (1) MgCl 2 Solution: At 45 °C, in 0.05 mol / L MgCl 2 Solution, the catalytic hydrogen production performance is tested within 15 min.
[0060] (2) Organic Sewage: Using plexiglass as the reactor material, 500 mL of organic sewage (COD 4521 mg / L, ammonia nitrogen concentration 303 mg / L, SS concentration 1126 mg / L, TDS 3128 mg / L) is added to the reactor. Under anaerobic environment and normal temperature and pressure conditions, an external voltage of 0.8 V is applied, and the hydrogen production rate and hydrogen content are respectively tested using a 200-1.5B type soap bubble flowmeter and a 7890 gas chromatograph.
[0061] Detection Results: As shown in Table 2.
[0062] Table 2 Detection Results of the Application Performance of the Catalysts in Examples and Comparative Examples
[0063] Combined with Table 2, by comparing the detection results of the examples and the comparative examples, it can be seen that the catalyst prepared by using the technical solution of the present application can effectively reduce the activation energy of the catalytic hydrogen production reaction during the actual application process, and improve the overall performance of catalytic hydrogen production.
[0064] By comparing the detection results of Examples 1-5 and Comparative Examples 1-2, it can be seen that the dosage ratio of each raw material component has a great influence on the performance of the catalyst. Through reasonable screening and matching of the dosages of each raw material component, the present application has obtained a catalyst with excellent performance.
[0065] By comparing the detection results of Example 3 and Examples 6-9, it can be seen that the present application uses nickel nitrate hexahydrate and cobalt nitrate hexahydrate with a specific weight ratio of 0.5-1.5:3-7 to form a metal salt, which can further improve the hydrogen production performance of the catalyst.
[0066] By comparing the detection results of Example 3, Examples 10-13 and Comparative Example 3, it can be seen that through experimental analysis, the present application uses trisodium citrate and vinylene carbonate with a weight ratio of 9:1-7 to form a stabilizer, which can further improve the hydrogen production performance of the catalyst.
[0067] By comparing the detection results of Example 3, Examples 14-17 and Comparative Example 4, it can be seen that the present application uses polyethylene glycol with a molecular weight of 600-1000 as a raw material reagent, which can further improve the hydrogen production performance of the catalyst.
[0068] Although the present invention has been described in detail with general descriptions and specific embodiments above, based on the present invention, some modifications or improvements can be made, which are obvious to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection required by the present invention.
Claims
1. A method for preparing a catalyst for hydrogen production from organic solid waste and sewage, characterized in that: Specifically, the following steps are performed in sequence: Dissolve 6-12 parts by weight of polyethylene glycol and 2-4 parts by weight of a stabilizer in 100 parts by weight of water at a temperature of 60-80° C., stir for 40-80 minutes, add 16-22 parts by weight of a metal salt, stir for 6-8 hours, and cool to room temperature to obtain a precursor solution; The precursor solution is subjected to rotary evaporation to remove the solvent, dried at 100-140° C. for 2-4 hours, and then subjected to heat treatment and screening to obtain the catalyst for hydrogen production based on organic solid waste and sewage; The stabilizer is composed of a mixture of trisodium citrate and vinylene carbonate in a weight ratio of 9:1-7.
2. The catalyst for producing hydrogen from organic solid waste and sewage according to claim 1, characterized in that: The metal salt is selected from one or more of iron salts, cobalt salts, nickel salts and palladium salts.
3. The catalyst for producing hydrogen from organic solid waste and sewage according to claim 2, characterized in that: The metal salt consists of nickel nitrate hexahydrate and cobalt nitrate hexahydrate in a weight ratio of 0.5-1.5:3-7.
4. The catalyst for producing hydrogen from organic solid waste and sewage according to claim 3, characterized in that: The metal salt consists of nickel nitrate hexahydrate and cobalt nitrate hexahydrate in a weight ratio of 0.8-1.2:4-6.
5. The catalyst for producing hydrogen from organic solid waste and sewage according to claim 1, characterized in that: The stabilizer is composed of a mixture of trisodium citrate and vinylene carbonate in a weight ratio of 9:3-5.
6. The catalyst for producing hydrogen from organic solid waste and sewage according to claim 1, characterized in that: The molecular weight of the polyethylene glycol is 600-1000.
7. The catalyst for producing hydrogen from organic solid waste and sewage according to claim 1, characterized in that: The specific steps of the heat treatment are: heat treatment at a temperature of 400-500° C. for 2-4 hours, and then heat treatment at a temperature of 550-750° C. for 3-5 hours.
8. The catalyst for producing hydrogen from organic solid waste and sewage according to claim 7, characterized in that: The specific steps of the heat treatment are: heat treatment at a temperature of 420-480° C. for 2-4 hours, and then heat treatment at a temperature of 600-700° C. for 3-5 hours.
9. A catalyst for producing hydrogen from organic solid waste and sewage, characterized in that: The method is prepared according to any one of claims 1 to 8.
10. Use of the catalyst for producing hydrogen from organic solid waste and sewage according to claim 9 in the field of hydrogen supply.