CN111974401A - Catalyst for hydrogen production by methane steam reforming, preparation method and application thereof - Google Patents
Catalyst for hydrogen production by methane steam reforming, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for hydrogen production by methane steam reforming, wherein a carrier of the catalyst is cerium oxide existing in a nanorod form, an active component comprises nickel oxide nanoparticles positioned on the carrier, and the loading amount of Ni is 0.1-40% based on the total mass of the catalyst. Furthermore, praseodymium (Pr) is doped in the catalyst, and the doping amount of the Pr in the catalyst is 0-50%. The method adopts the means of regulating the shape and doping of the carrier to promote the oxygen vacancy on the surface of the catalyst. The surface oxygen vacancy of the catalyst is increased by preparing the shape of a regulation carrier of the cerium oxide nanorod; the surface oxygen vacancy of the catalyst is further increased by doping the element Pr in the cerium oxide nanorod carrier. The abundant oxygen vacancies on the carrier are beneficial to the activation and dissociation of raw material water, thereby increasing the activity and stability of methane steam reforming. The method is simple, has extremely low cost, reduces the process danger, shortens the process flow, and reduces the energy consumption and the capital of the methane steam reforming conversion, thereby increasing the efficiency of the methane steam reforming hydrogen production.
Description
Technical Field
The invention belongs to the field of hydrogen production by methane steam reforming, and particularly relates to a catalyst for hydrogen production by methane steam reforming, and a preparation method and application thereof.
Background
Fossil energy, including coal, oil, and natural gas, provides a solid foundation for the development of human society, but the inherent disadvantages of fossil energy include limited resources, non-renewable resources, and the generation of a large amount of toxic and harmful waste after use. Therefore, the development of clean and pollution-free new energy is a major problem to be solved urgently at present. Hydrogen energy is a clean, efficient and pollution-free green energy, and is concerned by people because of large combustion heat value, high fuel efficiency, pollution-free combustion products of water and recyclable products. Further, hydrogen gas may be used in various manners, and may be directly combusted in an internal combustion engine or chemically converted by a fuel cell. Hydrogen is a secondary energy source. Currently, commercial production is accomplished by steam reforming of methane. But the process requires a large amount of energy consumption and is inefficient in producing hydrogen. Therefore, it is very important to develop a high performance catalyst to reduce the energy consumption of the reaction and to improve the conversion efficiency of methane and the yield of hydrogen.
The current hydrogen production process, which is capable of large scale and industrial application, is hydrogen production by steam reforming of methane. Over 50% of the hydrogen worldwide is produced by this process, with the specific reaction:
CH4+H2O＝CO+3H2ΔH＝+207kJ/mol
CO+H2O＝CO2+H2ΔH＝-43.5kJ/mol
the catalysts used in steam methane reforming processes are typically nickel-based catalysts that are inexpensive and highly active. The carrier used in the methane steam reforming process is generally alumina, silica, zirconia, lanthana or a mixture thereof, etc. which has high temperature resistance and sintering resistance. The support plays an extremely important role in the preparation of high performance reforming catalysts: the existence of the carrier can improve the dispersion of the active components of the catalyst to a greater extent; some carriers can activate reactant molecules, thereby improving the reaction rate. At present, the biggest defects of the nickel-based catalyst are that carbon deposition is too serious, the sintering resistance is not strong, and the integral reaction stability and efficiency are reduced.
Commercial-grade nickel-based catalysts are generally supported on suitable supports in the form of passivated oxides (NiO) before use, which facilitates storage and transport. However, the active site for steam reforming of methane is Ni in the metallic state. Therefore, the catalyst needs to be pre-activated with a reducing atmosphere before use to convert the oxidized NiO to metallic Ni. The conventional method for preactivation treatment is generally by H2The mixed gas of/Ar is pretreated at a certain temperature to convert the passivated NiO into active Ni. The effect of the pre-activation treatment directly affects the activity and stability of the catalytic reaction for converting methane into steam reforming. The use of this method has the following disadvantages: 1. large consumption of hydrogen gas increases the cost of industrial production; 2. the activity and stability of the catalyst of nickel oxide loaded on a pure cerium oxide carrier are not high.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation and pre-activation treatment method of a methane steam reforming hydrogen production catalyst. The method adopts the means of regulating and controlling the shape and doping of the carrier to promote the oxygen vacancy on the surface of the catalyst, and prepares the cerium oxide in the form of a nano rod by regulating and controlling the shape so as to increase the oxygen vacancy on the surface of the catalyst; the surface oxygen vacancy of the catalyst is further increased by doping the element Pr in the cerium oxide nanorod carrier. The abundant oxygen vacancy of carrier is favorable to the activation and the dissociation of raw materials water, and then increases the activity and the stability of methane steam reforming to increase the efficiency of reforming. The invention directly adopts raw material water vapor to pretreat the activated catalyst without using H2the/Ar pretreatment process increases the efficiency of hydrogen production by methane steam reforming. The effect of the pre-activation treatment directly influences the activity of the methane steam reformingSex and stability.
The invention provides a catalyst for hydrogen production by methane steam reforming, wherein a carrier of the catalyst is cerium oxide in a nanorod form, an active component comprises nickel oxide nanoparticles positioned on the carrier, and the loading amount of Ni in the catalyst is 0.1-40% based on the total mass of the catalyst.
Preferably, praseodymium Pr is further doped in the catalyst, and the doping amount of the praseodymium Pr in the catalyst is 0-50% based on the total mass of the catalyst.
Preferably, the length of the carrier nanorod is 20-200 nm; the size of the active component nickel oxide nano-particles is 5-20 nm.
The second aspect of the invention provides a preparation method of the catalyst for hydrogen production by methane steam reforming, which comprises the following steps:
(1) preparing cerium oxide nanorods by a hydrothermal crystallization method;
(2) loading nickel oxide on the cerium oxide nanorod obtained in the step (1) by an impregnation method;
preferably, the specific steps of step (1) are:
(1A) mixing a cerous nitrate hexahydrate aqueous solution and a sodium hydroxide solution, stirring, transferring the mixed solution to a hydrothermal crystallization kettle, and carrying out hydrothermal crystallization;
(1B) and after the hydrothermal crystallization is finished, filtering and collecting solid, washing and drying the solid, placing the solid in a muffle furnace for roasting, and collecting solid powder after roasting to obtain the cerium oxide nano rod.
Preferably, the molar ratio of the cerium nitrate hexahydrate to the sodium hydroxide in the step (1A) is 1: 120; the crystallization temperature is 80-120 ℃; the crystallization time is 12-48 h; washing the mixture in the step (1B) by deionized water to be neutral, wherein the drying temperature is 60-120 ℃, the drying time is 6-24h, the roasting temperature is 400-.
Preferably, praseodymium is also doped in the cerium oxide nanorods in the step (1), and a cerium nitrate hexahydrate aqueous solution, a praseodymium nitrate hexahydrate aqueous solution and a sodium hydroxide solution are directly mixed in the preparation process; the molar ratio of the cerium nitrate hexahydrate to the praseodymium nitrate hexahydrate is 1: 0-1.
Preferably, the specific steps of step (2) are: preparing nickel nitrate hexahydrate aqueous solution, then dropwise adding the nickel nitrate hexahydrate aqueous solution to a cerium oxide carrier, drying and roasting to prepare the catalyst for hydrogen production by methane steam reforming.
Preferably, the concentration of the nickel nitrate hexahydrate aqueous solution in the step (2) is 1-6 mol/L; and (2) drying after standing at normal temperature for 6-24h, wherein the drying temperature is 60-120 ℃, the drying time is 6-24h, the roasting temperature is 400-.
The third aspect of the invention provides an application of the catalyst for preparing hydrogen by reforming methane steam. The catalyst activation method comprises the following steps: directly treating with raw material steam for 1-60min for activation; praseodymium is doped in the catalyst to improve the in-situ activation efficiency of water vapor and improve the activity and stability of the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts nickel oxide loaded by a cerium oxide carrier as a catalyst for preparing hydrogen by reforming methane and steam. The carrier cerium oxide has certain oxygen vacancy, so that the sintering of the nickel-based catalyst and the formation of carbon deposit can be well inhibited due to the existence of the oxygen vacancy. Cerium oxide in the form of nanorods with different morphologies mainly exposes a (110) crystal plane, and cerium oxide nanoparticles expose a (111) crystal plane, which is the dominant crystal plane. The (110) crystal plane is relatively capable of generating more abundant oxygen vacancies. Therefore, the carrier of the invention is cerium oxide existing in the form of nano-rods.
2. In a preferred embodiment of the invention, praseodymium is further doped in the catalyst, and the doping amount of the praseodymium in the catalyst is 0-50% based on the total mass of the catalyst. The praseodymium-doped cerium oxide nanorod is prepared by a hydrothermal crystallization method. By doping the element praseodymium, oxygen vacancies are more easily formed due to the difference in ionic radii and valence states of praseodymium and cerium.
3. The invention directly adopts raw material water vapor to pretreat the activated catalyst without using H2the/Ar pretreatment process simplifies the treatment flow and increasesThe efficiency of hydrogen production by methane steam reforming. The method adopts the means of regulating and controlling the shape and doping of the carrier to promote the oxygen vacancy on the surface of the catalyst: the morphology of the carrier is regulated and controlled by preparing cerium oxide in a nano rod form so as to increase the surface oxygen vacancy of the catalyst; the surface oxygen vacancy of the catalyst is further increased by doping the element praseodymium in the cerium oxide nanorod carrier. The rich oxygen vacancies of the carrier are beneficial to the activation and dissociation of raw material water, so that the activity and stability of methane steam reforming are increased, and the efficiency of hydrogen production by methane steam reforming is improved.
4. The catalyst is directly pre-activated by using raw material steam without H2Pretreating with mixed gas of/Ar. The method is very simple, has extremely low cost, reduces the risk of the process, shortens the process flow and reduces the energy consumption and the fund of the reforming conversion of the methane and the steam. Therefore, the catalyst prepared by the method increases the efficiency of hydrogen production by methane steam reforming.
Drawings
FIG. 1 shows comparative example-example 3 preparation of NiO/CeO separately2、NiO/CePrO、NiO/CeO2-XRD pattern of Rod, NiO/CePrO-Rod catalyst;
FIG. 2 is a NiO/CeO solution prepared in example 22-Rod, scanning electron micrograph of NiO/CePrO-Rod catalyst prepared in example 3;
FIG. 3 is NiO/CeO prepared in example 22-Rod, transmission electron micrograph of NiO/CePrO-Rod catalyst prepared in example 3;
FIG. 4 shows the preparation of NiO/CeO separately in comparative example-example 32、NiO/CePrO、NiO/CeO2-raman spectra of Rod, NiO/CePrO-Rod catalysts;
FIG. 5 shows the preparation of NiO/CeO separately in comparative example-example 32、NiO/CePrO、NiO/CeO2-electron paramagnetic resonance spectra of Rod, NiO/CePrO-Rod catalysts;
FIG. 6 NiO/CeO prepared by comparative example2The reforming conversion rate of the catalyst methane steam and the selectivity of the product change along with time;
FIG. 7 NiO/CePrO methane steam reforming conversion and product selectivity over time as prepared in example 1;
FIG. 8 NiO/CeO prepared in example 22-Rod methane steam reforming conversion and product selectivity over time;
FIG. 9 steam reforming conversion of NiO/CePrO-Rod methane and product selectivity over time as prepared in example 3;
FIG. 10 NiO/CeO prepared by comparative example2The reforming conversion rate of methane steam and the selectivity of the product change with time at low temperature of the catalyst;
FIG. 11 the steam methane reforming conversion and product selectivity over time at low temperature for the NiO/CePrO-Rod catalyst prepared in example 3.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Preparation of catalyst
This embodiment prepares a catalyst in which nickel oxide is supported on a cerium oxide support. Wherein the cerium oxide carrier is in the form of nanoparticles and nanorods, respectively, and praseodymium is doped or undoped in the cerium oxide carrier. The loading of Ni in the final catalyst was 10% based on the total mass of the catalyst. The prepared catalyst is dried, roasted, pressed into tablets, screened and filled into a fixed bed. The purity of the chemical reagent is analytical purity.
Comparative example: NiO/CeO2Preparation of the catalyst
(1) Weighing 6.7 g of cerous nitrate hexahydrate and 8 g of citric acid, mixing and dissolving in 17ml of water, stirring at 60 ℃ until the mixture is clear, transferring the mixture to a water bath at 90 ℃ to evaporate the water to form gel, transferring the gel to an oven at 120 ℃ to dry for 24 hours until solid foam is formed, grinding the solid foam, placing the solid foam in a muffle furnace at 600 ℃ to bake for 4 hours, and cooling to obtain a yellow cerium oxide carrier.
(2) Weighing 1.483g of nickel nitrate hexahydrate to prepare 1.5ml of solution, weighing 2.7g of cerium oxide carrier, and dropwise adding the prepared nickel nitrate hexahydrate solution to the cerium oxide carrier by using a suction tubeThe mixture is evenly mixed, placed for 6 hours at normal temperature, transferred to a 120 ℃ oven for drying for 24 hours, and then roasted for 4 hours in a 600 ℃ muffle furnace to prepare cerium oxide supported NiO (NiO/CeO)2) Wherein the final loading of Ni is 10% based on the total mass of the catalyst.
Example 1: preparation of NiO/CePrO catalyst
The preparation method of the catalyst in example 1 is similar to that of the catalyst in the comparative example, except that 1.67 g of praseodymium nitrate hexahydrate is simultaneously added in the step (1), and the doping amount of praseodymium in the prepared NiO/CePrO catalyst is 20%. The preparation of other praseodymium doping amount NiO/CePrO catalyst samples is basically the same as that of the embodiment, only the mass of the added praseodymium nitrate hexahydrate is slightly adjusted, and the mass of the added praseodymium nitrate hexahydrate is adjusted between 1.67 and 6.7 grams to obtain the NiO/CePrO catalysts with different doping amounts.
Example 2: NiO/CeO2Preparation of-Rod catalyst
(1) Weighing 1.74g of cerous nitrate hexahydrate and dissolving in 5ml of water, weighing 19.2g of sodium hydroxide and dissolving in 20ml of water, mixing the two solutions, then adding 15ml of water, mixing and stirring for 30min, transferring the uniformly stirred solution to a 100ml hydrothermal crystallization kettle, and keeping the temperature of 100 ℃ for crystallization for 24 h. After crystallization is finished, filtering, washing with deionized water to be neutral, collecting solid, drying the solid at 80 ℃ for 12h, then placing the solid in a muffle furnace for roasting for 4h, and recording the final solid powder as cerium oxide nanorods as CeO2And Rod, which represents that the catalyst is in a Rod-shaped structure.
(2) 1.483g of nickel nitrate hexahydrate was weighed to prepare 1.5ml of solution, and 2.7g of CeO was weighed2A Rod carrier, prepared nickel nitrate hexahydrate solution is dripped to CeO by a suction pipe2the-Rod carrier is evenly mixed, placed for 6 hours at normal temperature, transferred to an oven at 120 ℃ for drying for 24 hours, and then roasted for 4 hours in a muffle furnace at 600 ℃ to prepare NiO (NiO/CeO) loaded by cerium oxide2-Rod), wherein the final loading of Ni is 10% based on the total mass of the catalyst.
Example 3: preparation of NiO/CePrO-Rod catalyst
The preparation method of the catalyst in example 3 is similar to that of the catalyst in example 2, except that 1.67 g of praseodymium nitrate hexahydrate is simultaneously added in the step (1), and the doping amount of praseodymium in the prepared NiO/CePrO-Rod catalyst is 20%. The preparation of other praseodymium doping amount NiO/CePrO-Rod catalyst samples is basically the same as that of the embodiment, only the mass of the added praseodymium nitrate hexahydrate is slightly adjusted, and the mass of the added praseodymium nitrate hexahydrate is adjusted between 1.67 and 6.7 grams, so that the NiO/CePrO-Rod catalysts with different doping amounts are obtained.
(II) catalyst characterization
FIG. 1 shows NiO/CeO2、NiO/CePrO、NiO/CeO2XRD patterns of-Rod, NiO/CePrO-Rod catalysts, from which it can be seen that the prepared catalysts have ceria fluorite structure, and maintain fluorite structure after doping with Pr without additional characteristic peak of praseodymium oxide, indicating that Pr is uniformly doped into the crystal lattice of cerium oxide. After loading NiO, a characteristic peak of NiO was found.
FIG. 2 and FIG. 3 are NiO/CeO, respectively2SEM and TEM images of-Rod, NiO/CePrO-Rod catalysts, from which the cerium oxide in the form of a strip or Rod and the Pr-doped cerium oxide can be seen.
FIG. 4 shows NiO/CeO2、NiO/CePrO、NiO/CeO2Raman spectra of-Rod, NiO/CePrO-Rod catalysts, from which it can be seen that the oxygen vacancies on the catalyst surface increase after Pr doping. The number of oxygen vacancies on the surface of the catalyst with the nano-rod-shaped structure is better than that of the catalyst in the form of nano-particles.
FIG. 5 shows NiO/CeO2、NiO/CePrO、NiO/CeO2Electron paramagnetic resonance spectra of-Rod, NiO/CePrO-Rod catalysts, further illustrating NiO/CeO2The oxygen vacancy of the Rod surface is more than NiO/CeO2. The oxygen vacancy on the surface of the catalyst after doping with Pr is increased.
(III) evaluation of catalyst
The prepared catalyst is pressed into tablets and molded, and is screened to prepare 20-40 mesh catalyst particles, and the particles are filled in a fixed bed tubular reactor, wherein the inner diameter of the reactor is phi 6mm, and the length of the reactor is 40 cm.
Firstly, preactivating the prepared catalyst for 15min by adopting raw material water vapor, then introducing methane gas, reacting at the temperature of 700 ℃, under the pressure of normal pressure, with the mass of the catalyst of 0.15g, and mixing methane and nitrogen gas (volume ratio N)2:CH41:1) was 100 mL/min.
The reaction data are shown below:
FIG. 6 shows NiO/CeO2The methane steam reforming conversion and product selectivity varied with time. The initial methane conversion reached 87%, with the conversion of methane decreasing gradually as the reaction time increased. After 3000 minutes of reaction the methane conversion was only 68%. The hydrogen selectivity evolution law is similar, with initial hydrogen selectivity approaching 70%. The selectivity gradually decreased with increasing time, and after 3000 minutes, the hydrogen selectivity was only 65%. Compared with the comparative example, the conversion rate and the hydrogen selectivity of the NiO/CePrO methane steam reforming hydrogen production in the example 1 are increased. The NiO/CePrO methane steam reforming conversion and product selectivity shown in fig. 7 changed with time, the methane conversion reached over 90%, and the hydrogen selectivity reached 70%. After 3000 minutes of reaction, the conversion of methane was still 78% and the hydrogen selectivity was greater than 65%. This result demonstrates the increased activity of the Pr-doped catalyst and the increased selectivity to hydrogen.
FIG. 8 shows NiO/CeO2-Rod methane steam reforming conversion and product selectivity as a function of time. NiO/CeO2The initial methane conversion of the Rod catalyst is close to 89% and the hydrogen selectivity reaches 64%. And the conversion of methane and the selectivity of hydrogen remained unchanged over 3000 minutes. This indicates that the catalyst stability of the nanorod structures is superior to that of the nanoparticulate catalyst. FIG. 9 shows the NiO/CePrO-Rod methane steam reforming conversion and product selectivity over time. The catalyst is Pr-doped cerium oxide-supported nickel oxide with a nano rod-shaped structure. The catalyst has initial methane conversion rate over 90% and hydrogen selectivity over 70%. The catalyst can maintain methane conversion rate of more than 90% and hydrogen concentration of more than 70% in the whole reaction process of 3000 minAnd (4) selectivity. This shows that the activity and stability of the Pr-doped nanorod catalyst are improved.
Further, at 600 ℃ under normal pressure, the mass of the catalyst was 0.15g, and the methane-nitrogen mixed gas (N) was used2:CH41:1) NiO/CeO was tested at 100mL/min2And the performance of the NiO/CePrO-Rod catalyst for catalyzing the steam reforming of the methane. The data under reduced temperature reaction conditions are shown in fig. 10 and 11. As shown in FIG. 10, NiO/CeO2The highest conversion of methane at the initial stage of the reaction on the catalyst was 72.7%, and the selectivity of hydrogen was 62.5%; after 1800min, the conversion of methane was reduced to 66.7% and the selectivity of hydrogen was reduced to 59.3%. As shown in FIG. 11, the conversion of methane at the initial reaction stage on the NiO/CePrO-Rod catalyst was 80.2%, and the selectivity to hydrogen was 64.2%; and after 1800min reaction, the conversion rate of methane and the selectivity of hydrogen are kept stable. The reaction data of fig. 10 and 11 further illustrate that the activity and stability of the Pr-doped nanorod catalyst are improved.
Claims (10)
1. The catalyst for hydrogen production by methane steam reforming is characterized in that a carrier of the catalyst is cerium oxide in the form of nanorods, an active component comprises nickel oxide nanoparticles positioned on the carrier, and the loading amount of Ni is 0.1-40% based on the total mass of the catalyst.
2. The catalyst for hydrogen production through methane steam reforming as claimed in claim 1, wherein praseodymium (Pr) is further doped in the catalyst, and the doping amount of Pr is 0-50% based on the total mass of the catalyst.
3. The catalyst for hydrogen production by methane steam reforming as claimed in claim 1, wherein the length of the support nanorods is 20-200 nm; the size of the active component nickel oxide nano-particles is 5-20 nm.
4. A method for preparing a catalyst for hydrogen production by steam reforming of methane according to claim 1, characterized by comprising the steps of:
(1) preparing cerium oxide nanorods by a hydrothermal crystallization method;
(2) and (2) loading nickel oxide on the cerium oxide nanorods obtained in the step (1) by an impregnation method.
5. The preparation method according to claim 4, wherein the specific steps of step (1) are as follows:
(1A) mixing a cerous nitrate hexahydrate aqueous solution and a sodium hydroxide solution, stirring, transferring the mixed solution to a hydrothermal crystallization kettle, and carrying out hydrothermal crystallization;
(1B) and after the hydrothermal crystallization is finished, filtering and collecting solid, washing and drying the solid, placing the solid in a muffle furnace for roasting, and collecting solid powder after roasting to obtain the cerium oxide nano rod.
6. The method according to claim 5, wherein the molar ratio of cerium nitrate hexahydrate to sodium hydroxide in step (1A) is 1: 120; the crystallization temperature is 80-120 ℃; the crystallization time is 12-48 h; washing the mixture in the step (1B) by deionized water to be neutral, wherein the drying temperature is 60-120 ℃, the drying time is 6-24h, the roasting temperature is 400-.
7. The preparation method according to claim 5, wherein praseodymium is further doped in the cerium oxide nanorods in the step (1), and the preparation is carried out by directly mixing an aqueous solution of cerium nitrate hexahydrate, an aqueous solution of praseodymium nitrate hexahydrate and a sodium hydroxide solution; the molar ratio of the cerium nitrate hexahydrate to the praseodymium nitrate hexahydrate is 1 (0-1).
8. The preparation method according to claim 3, wherein the specific steps of the step (2) are as follows: preparing nickel nitrate hexahydrate aqueous solution, then dropwise adding the nickel nitrate hexahydrate aqueous solution to a cerium oxide carrier, drying and roasting to prepare the catalyst for hydrogen production by methane steam reforming.
9. The production method according to claim 7, wherein the concentration of the nickel nitrate hexahydrate aqueous solution in step (2) is 1 to 6 mol/L; and (2) drying after standing at normal temperature for 6-24h, wherein the drying temperature is 60-120 ℃, the drying time is 6-24h, the roasting temperature is 400-.
10. The application of the catalyst for preparing hydrogen by reforming methane steam as set forth in claim 1, wherein the catalyst activation method comprises the following steps: directly treating with raw material steam for 1-60min for activation; praseodymium is doped in the catalyst to improve the in-situ activation efficiency of water vapor and improve the activity and stability of the catalyst.
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Cited By (4)
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| CN112467154A (en) * | 2020-12-03 | 2021-03-09 | 福州大学 | Preparation method of cerium oxide loaded nickel-iron catalyst |
| CN114192152A (en) * | 2022-01-03 | 2022-03-18 | 西南石油大学 | Anti-carbon deposition photo-thermal catalytic methane dry reforming catalyst and preparation method and application thereof |
| CN115090293A (en) * | 2022-06-29 | 2022-09-23 | 贵州大学 | Core-shell cerium dioxide nanorod supported nickel catalyst and preparation method thereof |
| CN115228475A (en) * | 2022-08-05 | 2022-10-25 | 天津大学 | Mixed valence state nickel-based methane steam reforming catalyst and preparation method thereof |
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| CN115090293A (en) * | 2022-06-29 | 2022-09-23 | 贵州大学 | Core-shell cerium dioxide nanorod supported nickel catalyst and preparation method thereof |
| CN115228475A (en) * | 2022-08-05 | 2022-10-25 | 天津大学 | Mixed valence state nickel-based methane steam reforming catalyst and preparation method thereof |
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