Nickel-doped yttrium hydride oxide catalyst as well as preparation method and application thereof
By preparing the nickel-doped yttrium hydride catalyst, the problem of insufficient activity and stability of the carbon dioxide methanation catalyst is solved, and efficient carbon dioxide reduction and catalyst air stability are achieved.
Patent Information
- Application Number
- CN202510587517.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-08
- Publication Date
- 2025-08-08
AI Technical Summary
The existing carbon dioxide methanation catalysts are insufficient in activity and stability, making it difficult to efficiently reduce carbon dioxide.
By mixing the yttrium salt and nickel salt into a gel, mixing it with the metal hydride after drying, calcining, annealing, grinding, tableting and calcining again, a nickel-doped yttrium hydride catalyst is prepared, which improves the lattice H content and carbon deposit resistance of the catalyst.
It improves the activity and stability of the catalyst, can efficiently reduce carbon dioxide, and has a simple preparation process and good stability in air.
Smart Images
Figure CN120438020A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of carbon dioxide methanation catalysts, and in particular to a nickel-doped yttrium oxyhydride catalyst, a preparation method thereof, and applications thereof. Background Art
[0002] Since the Industrial Revolution, the prosperity of human society has been accompanied by the massive consumption of fossil fuels, leading to a sharp increase in greenhouse gas emissions, primarily carbon dioxide. This excess carbon dioxide released into the atmosphere has triggered a series of environmental problems, including global warming and sea level rise. Reducing atmospheric carbon dioxide concentrations and finding effective ways to recycle carbon dioxide as a resource have become important global research topics. Carbon dioxide methanation, a chemical reaction that converts carbon dioxide into methane, not only helps reduce atmospheric carbon dioxide concentrations and mitigate the greenhouse effect, but also generates clean methane energy to meet human energy needs. This reaction has important environmental implications and practical applications, making it a hot topic of current research.
[0003] Despite significant progress in CO2 methanation technology, numerous challenges remain. Further research and solutions are needed to address issues such as catalyst activity and stability, as well as the energy efficiency and environmental friendliness of the reaction process. Therefore, developing a catalyst with high activity, low energy consumption, and good stability is crucial. Summary of the Invention
[0004] The purpose of the present invention is to provide a nickel-doped yttrium oxyhydride catalyst and its preparation method and application, so as to solve the problems of low activity and poor stability of carbon dioxide methanation catalysts in the prior art.
[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0006] The present invention provides a method for preparing a nickel-doped yttrium oxyhydride catalyst, comprising the following steps:
[0007] (1) Yttrium salt and nickel salt are mixed in water and heated to evaporate to form a gel;
[0008] (2) drying, calcining and annealing the gel of step (1) to obtain Y 2-x Ni x O3;
[0009] (3) Y 2-x Ni x O3 and metal hydride are mixed, and then ground, pressed and calcined in sequence to prepare nickel-doped yttrium oxyhydride catalyst.
[0010] Preferably, in step (2), the drying temperature is 300-400° C. and the drying time is 1-3 hours.
[0011] Preferably, in step (2), the calcination temperature is 700-900° C. and the calcination time is 4-8 hours.
[0012] Preferably, in step (2), the annealing temperature is 1000-1200° C., and the time is 4-8 hours.
[0013] Preferably, in step (2), the Y 2-x Ni x In O3, 0<x≤0.1.
[0014] Preferably, in step (3), the Y 2-x Ni x The molar ratio of O3 to metal hydride is 1:3-4; the metal hydride comprises calcium hydride, magnesium hydride or barium hydride.
[0015] Preferably, in step (3), the grinding is carried out in an inert atmosphere for 30 to 40 minutes; the calcination temperature is 800 to 900° C. for 40 to 48 hours.
[0016] Preferably, in step (3), washing is performed with an ammonium chloride methanol solution after calcination; the concentration of the ammonium chloride methanol solution is 0.05 to 0.2 mol / L.
[0017] The present invention also provides a nickel-doped yttrium oxyhydride catalyst prepared by the above-mentioned preparation method of the nickel-doped yttrium oxyhydride catalyst.
[0018] The present invention also provides a use of the nickel-doped yttrium oxyhydride catalyst in carbon dioxide methanation.
[0019] Beneficial effects of the present invention:
[0020] The present invention enables the lattice H content in the yttrium oxyhydride catalyst to be higher by doping nickel, and can improve the catalyst's ability to resist carbon deposition, thereby enabling efficient reduction of carbon dioxide.
[0021] The process for preparing the nickel-doped yttrium oxyhydride catalyst is simple, and the prepared nickel-doped yttrium oxyhydride catalyst has good stability in the air. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 Y 1.98 Ni 0.02 O3, Y 1.96 Ni 0.04 O3, Y 1.9 Ni 0.1 XRD patterns of O3 and Y2O3 powders;
[0023] Figure 2 Y 1.98 Ni 0.02 SEM image of O3 powder;
[0024] Figure 3 Y 1.96 Ni 0.04 SEM image of O3 powder;
[0025] Figure 4 Y 1.9 Ni 0.1 SEM image of O3 powder;
[0026] Figure 5 Y 1.94 Ni 0.06 EDS pattern of O3 powder;
[0027] Figure 6 Y 1.9 Ni 0.1 EDS pattern of O3 powder;
[0028] Figure 7 Y 1.94 Ni 0.06 O3 powder, Y 0.97 Ni 0.03 XRD patterns of HO catalyst, Y2O3 powder and YHO catalyst;
[0029] Figure 8 Y 0.97 Ni 0.03 TG-MS curve of HO catalyst. DETAILED DESCRIPTION
[0030] The present invention provides a method for preparing a nickel-doped yttrium oxyhydride catalyst, comprising the following steps:
[0031] (1) Yttrium salt and nickel salt are mixed in water and heated to evaporate to form a gel;
[0032] (2) drying, calcining and annealing the gel of step (1) to obtain Y 2-x Ni x O3;
[0033] (3) Y 2-x Ni x O3 and metal hydride are mixed, and then ground, pressed and calcined in sequence to prepare nickel-doped yttrium oxyhydride catalyst.
[0034] In the present invention, the yttrium salt is preferably yttrium nitrate; and the nickel salt is preferably nickel acetate.
[0035] In the present invention, in step (2), the drying temperature is 300-400°C, preferably 300°C, 350°C, or 400°C, and the drying time is 1-3h, preferably 1.5-2.5h, and more preferably 2h.
[0036] In the present invention, in step (2), the calcination temperature is 700-900°C, preferably 750-850°C, more preferably 800°C; the calcination time is 4-8h, preferably 5-7h, more preferably 6h.
[0037] In the present invention, in step (2), the annealing temperature is 1000-1200°C, preferably 1000°C, 1050°C, 1100°C, 1150°C, 1200°C; the time is 4-8h, preferably 5-7h, and more preferably 6h.
[0038] In the present invention, in step (2), the Y 2-x Ni x In O3, 0<x≤0.1, preferably 0.01, 0.02, 0.03, 0.04, 0.06, 0.08, 0.1.
[0039] In the present invention, in step (3), the Y 2-x Ni x The molar ratio of O3 to metal hydride is 1:3-4, preferably 1:3.5-4; the metal hydride comprises calcium hydride, magnesium hydride or barium hydride, preferably calcium hydride.
[0040] In the present invention, in step (3), the grinding is carried out in an inert atmosphere, and the grinding time is 30 to 40 minutes, preferably 30 minutes, 35 minutes, or 40 minutes; the calcination temperature is 800 to 900°C, preferably 800°C, 850°C, or 900°C, and the calcination time is 40 to 48 hours, preferably 40 hours, 42 hours, 44 hours, 46 hours, or 48 hours.
[0041] In the present invention, in step (3), washing is performed with an ammonium chloride methanol solution after calcination; the concentration of the ammonium chloride methanol solution is 0.05 to 0.2 mol / L, preferably 0.1 mol / L.
[0042] In the present invention, the washing time Y 2-x Ni x The mass volume ratio of O3 and ammonium chloride methanol solution is 0.5~1.5g:300~500mL.
[0043] The invention first introduces nickel into the Y2O3 lattice, and then reduces it with metal hydride to prepare the nickel-doped yttrium oxyhydride catalyst.
[0044] The present invention also provides a nickel-doped yttrium oxyhydride catalyst prepared by the above-mentioned preparation method of the nickel-doped yttrium oxyhydride catalyst.
[0045] The present invention also provides a use of the nickel-doped yttrium oxyhydride catalyst in carbon dioxide methanation.
[0046] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0047] Example 1
[0048] Weigh 5g of Y(NO3)3·6H2O and 32.5mg of Ni(CH3COO)2·4H2O, dissolve the above raw materials in deionized water to ensure that they are completely dissolved to obtain a mixed solution; heat the mixed solution to 120°C with a magnetic stirring electric heating mantle, and continue heating and stirring until it becomes a gel; transfer the gel to a crucible, place it in a muffle furnace and dry it at 400°C for 2h; then increase the temperature to 800°C, keep it warm for 6h and calcine it. After the calcination is completed, grind and press the calcined product into tablets, and finally anneal it at 1200°C for 6h to obtain Y 1.98 Ni 0.02 O3 powder.
[0049] Y 1.98 Ni 0.02 O3 powder and CaH2 were mixed in a molar ratio of 1:4 and ground under an argon atmosphere for 30 min. After grinding, the pellets were pressed, sealed in a vacuum tube, and calcined at 900 ° C for 48 h. The calcined pellets were ground, washed with 400 mL of 0.1 mol / L ammonium chloride methanol solution, and finally dried to obtain Y 0.99 Ni 0.01 HO catalyst.
[0050] Example 2
[0051] The difference from Example 1 is that the mass of Ni(CH3COO)2·4H2O is 65.0 mg, and other conditions are the same. 1.96 Ni 0.04 O3 powder.
[0052] Y 1.96 Ni 0.04 O3 powder and CaH2 were mixed in a molar ratio of 1:4 and ground under an argon atmosphere for 30 min. After grinding, the pellets were pressed, sealed in a vacuum tube, and calcined at 900 ° C for 48 h. The calcined pellets were ground, washed with 400 mL of 0.1 mol / L ammonium chloride methanol solution, and finally dried to obtain Y 0.98 Ni 0.02HO catalyst.
[0053] Example 3
[0054] The difference from Example 1 is that the mass of Ni(CH3COO)2·4H2O is 162.4 mg. Other conditions are the same. 1.9 Ni 0.1 O3 powder.
[0055] Y 1.9 Ni 0.1 O3 powder and CaH2 were mixed in a molar ratio of 1:4 and ground under an argon atmosphere for 30 min. After grinding, the pellets were pressed, sealed in a vacuum tube, and calcined at 900 ° C for 48 h. The calcined pellets were ground, washed with 400 mL of 0.1 mol / L ammonium chloride methanol solution, and finally dried to obtain Y 0.95 Ni 0.05 HO catalyst.
[0056] Example 4
[0057] Weigh 5g of Y(NO3)3·6H2O and 97.5mg of Ni(CH3COO)2·4H2O, dissolve the above raw materials in deionized water to ensure that they are completely dissolved to obtain a mixed solution; heat the mixed solution to 120°C using a magnetic stirring electric heating mantle, and continue heating and stirring until it becomes a gel; transfer the gel to a crucible, place it in a muffle furnace and dry it at 400°C for 2h; then increase the temperature to 800°C, keep it warm for 6h for calcination, grind and tablet the calcined product after calcination, and finally anneal it at 1200°C for 6h to obtain Y 1.94 Ni 0.06 O3 powder.
[0058] Y 1.94 Ni 0.06 O3 powder and CaH2 were mixed in a molar ratio of 1:4 and ground under an argon atmosphere for 30 min. After grinding, the pellets were pressed, sealed in a vacuum tube, and calcined at 900 ° C for 48 h. The calcined pellets were ground, washed with 400 mL of 0.1 mol / L ammonium chloride methanol solution, and finally dried to obtain Y 0.97 Ni 0.03 HO catalyst.
[0059] Comparative Example 1
[0060] Weigh 5 g of Y(NO3)3·6H2O and dissolve it in deionized water to ensure complete dissolution to obtain a solution; heat the solution to 120°C using a magnetic stirring electric heating mantle and continue heating and stirring until it becomes a gel; transfer the gel to a crucible and place it in a muffle furnace at 400°C for 2 hours; then increase the temperature to 800°C and keep it warm for 6 hours for calcination. After the calcination is completed, the calcined product is ground and pressed into tablets, and finally annealed at 1200°C for 6 hours to obtain Y2O3 powder.
[0061] Y2O3 powder and CaH2 were mixed in a molar ratio of 1:4 and ground under an argon atmosphere for 30 minutes. After grinding, the pellets were pressed, vacuum-sealed, and calcined at 900°C for 48 hours. The calcined pellets were ground, washed with 400 mL of 0.1 mol / L ammonium chloride methanol solution, and finally dried to obtain a YHO catalyst.
[0062] The strong alkalinity of Y2O3 may lead to excessive adsorption of carbonates, which will interfere with the catalyst surface, hinder the adsorption and reaction of other reactants, and affect the progress of the methanation reaction.
[0063] Figure 1 Y 1.98 Ni 0.02 O3, Y 1.96 Ni 0.04 O3, Y 1.9 Ni 0.1 XRD patterns of O3 and Y2O3 powders, from Figure 1 It can be seen that Y 1.98 Ni 0.02 O3, Y 1.96 Ni 0.04 O3, Y 1.9 Ni 0.1 The diffraction peak of O3 corresponds to the characteristic diffraction peak of Y2O3 powder. Figures 2-4 Y 1.98 Ni 0.02 O3, Y 1.96 Ni 0.04 O3, Y 1.9 Ni 0.1 SEM image of O3. It can be seen from the SEM image that the powders have porous, irregular and rough surface morphology.
[0064] Figure 5 Y 1.94 Ni 0.06 EDS pattern of O3 powder, Figure 6 Y 1.9 Ni 0.1 EDS diagram of O3 powder, from Figure 5 and Figure 6It can be seen that the powder contains Y, Ni, and O elements.
[0065] Figure 7 Y 1.94 Ni 0.06 O3 powder, Y 0.97 Ni 0.03 XRD patterns of HO catalyst, Y2O3 powder and YHO catalyst, from Figure 7 It can be seen that Y 1.94 Ni 0.06 O3 powder, Y 0.97 Ni 0.03 The diffraction peaks of HO catalyst correspond to the characteristic diffraction peaks of Y2O3 powder and YHO catalyst, respectively.
[0066] Y prepared in Example 4 0.97 Ni 0.03 TG-MS test of HO catalyst: 10 mg of catalyst was weighed and heated to 800 °C at 10 °C / min in 50 mL / min argon flow, and TG-MS test was performed. The test results are shown in the figure. Figure 8 As shown, from Figure 8 It can be seen that: Y 0.97 Ni 0.03 A large amount of H overflowed from the HO catalyst during the heating process, and H signals were observed at several different temperatures, indicating that Ni doping increased the lattice H content in the catalyst.
[0067] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.
Claims
1. A method for preparing a nickel-doped yttrium oxyhydride catalyst, characterized in that: The steps include: (1) Yttrium salt and nickel salt are mixed in water and heated to evaporate to form a gel; (2) drying, calcining and annealing the gel of step (1) to obtain Y 2-x Ni x O3; (3) Y 2-x Ni x O3 and metal hydride are mixed, and then ground, pressed and calcined in sequence to prepare nickel-doped yttrium oxyhydride catalyst.
2. The method for preparing the nickel-doped yttrium oxyhydride catalyst according to claim 1, wherein: In step (2), the drying temperature is 300-400° C. and the drying time is 1-3 hours.
3. The method for preparing the nickel-doped yttrium oxyhydride catalyst according to claim 1 or 2, characterized in that: In step (2), the calcination temperature is 700-900° C. and the calcination time is 4-8 hours.
4. The method for preparing the nickel-doped yttrium oxyhydride catalyst according to claim 3, wherein: In step (2), the annealing temperature is 1000-1200° C., and the time is 4-8 hours.
5. The method for preparing the nickel-doped yttrium oxyhydride catalyst according to claim 1, 2 or 4, wherein: In step (2), the Y 2-x Ni x In O3, 0<x≤0.
1.
6. The method for preparing the nickel-doped yttrium oxyhydride catalyst according to claim 5, characterized in that: In step (3), the Y 2-x Ni x The molar ratio of O3 to metal hydride is 1:3-4; the metal hydride comprises calcium hydride, magnesium hydride or barium hydride.
7. The method for preparing the nickel-doped yttrium oxyhydride catalyst according to claim 4 or 6, characterized in that: In step (3), the grinding is carried out in an inert atmosphere for 30 to 40 minutes; the calcination temperature is 800 to 900° C. for 40 to 48 hours.
8. The method for preparing the nickel-doped yttrium oxyhydride catalyst according to claim 7, wherein: In step (3), washing is performed with an ammonium chloride methanol solution after calcination; the concentration of the ammonium chloride methanol solution is 0.05 to 0.2 mol / L.
9. The nickel-doped yttrium oxyhydride catalyst prepared by the method for preparing the nickel-doped yttrium oxyhydride catalyst according to any one of claims 1 to 8.
10. Use of the nickel-doped yttrium oxyhydride catalyst according to claim 9 in carbon dioxide methanation.