CN113332987A - Finned ammonia decomposition catalyst and preparation method and application thereof - Google Patents
Finned ammonia decomposition catalyst and preparation method and application thereof Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 72
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910026161 MgAl2O4 Inorganic materials 0.000 claims abstract description 23
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910020068 MgAl Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052759 nickel Inorganic materials 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a finned ammonia decomposition catalyst and a preparation method and application thereof, wherein the catalyst comprises an active component and a carrier; the active component is nickel, and the carrier is a finned metal oxide MgAl2O4The mass fraction of the active component is 5% -10%, and the mass fraction of the carrier is 90% -95%. The invention adopts a hydrothermal method to prepare a finned metal oxide MgAl2O4Then loading nickel by adopting an immersion method to prepare the finned Ni/MgAl2O4A catalyst. The catalyst prepared by the invention has a finned structure, has a large specific surface area and can be NH3Providing more active sites. The catalyst prepared by the preparation method has the advantages of high activity, uniform particle distribution, better sintering resistance and obvious ammonia decomposition effectHigh.
Description
Technical Field
The invention relates to an ammonia decomposition catalysis technology, in particular to a finned ammonia decomposition catalyst and a preparation method and application thereof.
Background
In recent years, with the shortage of fossil energy and the gradual increase of environmental pollution, the search for a clean novel energy carrier becomes a focus of attention in the present society. Hydrogen energy is considered to be the most likely energy carrier to replace fossil energy as an environmentally friendly renewable energy source. However, there are still many technical problems that are not effectively solved in the process of utilizing hydrogen, and hydrogen has great difficulty in storage and transportation due to its flammability and explosiveness and difficult compressibility. Among them, ammonia is receiving increasing attention as a highly efficient hydrogen storage medium. Compared with hydrogen, ammonia has the unique advantages of high volume energy density, small explosion range, easy liquefaction and storage and the like, and the current synthetic ammonia industry is mature and the production cost of ammonia is relatively low. Currently, Proton Exchange Membrane Fuel Cells (PEMFCs) are gradually applied to the field of hydrogen energy vehicles by virtue of low operating temperature, and ammonia is used as a hydrogen carrier to prevent carbon oxides from being generated, thereby preventing damage to the proton exchange membrane. At the same time, only hydrogen and nitrogen are present in the ammonia decomposition products, which also provides a good reducing and inert atmosphere for some industrial processes.
In the process of preparing hydrogen by decomposing ammonia, the ammonia decomposition catalyst plays an important role. Ruthenium is currently the most effective ammonia decomposition catalyst known, but the expensive cost limits its potential for large-scale applications. Nickel is becoming the first choice for industrial applications due to its superior catalytic performance and low cost compared to other alkali metal catalysts. However, studies on the cost, catalytic activity, lifetime, and the like of ammonia decomposition catalysts have yet to be perfected, with catalyst supports being an important research direction.
The existing catalyst carrier is mainly prepared by a sol-gel method, a mechanical mixing method, an impregnation method and other methods, but the materials prepared by the methods have small specific surface area and low catalytic performance, so the method has important significance for the research of the catalyst carrier.
Disclosure of Invention
The invention provides a finned ammonia decomposition catalyst, and a preparation method and application thereof, and aims to overcome the defect of low catalytic activity caused by small specific surface area of the ammonia decomposition catalyst in the prior art.
The technical scheme adopted by the invention is as follows:
a finned ammonia decomposition catalyst comprises a carrier and an active component loaded on the carrier, and is characterized in that the carrier is a finned metal oxide MgAl2O4The active component is Ni; the mass fraction of the active component Ni is 5-10%, and the finned metal oxide MgAl is2O4The mass fraction of (A) is 90-95%.
The further technical scheme is as follows:
the finned metal oxide MgAl2O4In the method, the raw material of Mg is magnesium chloride, and the raw material of Al is aluminum chloride.
The active component is prepared from Ni (NO)3)2。
A preparation method of a finned ammonia decomposition catalyst comprises the following steps:
(1) dissolving magnesium chloride and aluminum chloride in water to prepare a solution a;
(2) adding a proper amount of complexing agent into the solution a to form a solution b, heating the solution b at 180 ℃ for 12h, drying at 105 ℃ to obtain a solid sample, crushing the solid sample, and calcining at 750 ℃ for 2h to obtain the finned metal oxide MgAl2O4；
(3) The finned metal oxide MgAl obtained in the step (2)2O4Adding to Ni (NO)3)2Stirring the solution at 90 deg.C for 8 hr, evaporating the solvent at 60 deg.C, and heating at 100 deg.CDrying for 8-12h to obtain finned Ni/MgAl2O4A catalyst.
The further technical scheme is as follows:
the complexing agent is urea.
In the step (2), a container for heating the solution b at 180 ℃ for 12 hours adopts a high-pressure reaction kettle.
The finned ammonia decomposition catalyst or the application of the finned ammonia decomposition catalyst prepared by the preparation method in ammonia decomposition is characterized in that the catalyst needs to be reduced for 3 hours in a hydrogen atmosphere at 600 ℃ before ammonia decomposition hydrogen production reaction.
The invention has the following beneficial effects:
the invention adopts a hydrothermal method to prepare a finned metal oxide MgAl2O4Then loading nickel by adopting an immersion method to prepare the finned Ni/MgAl2O4A catalyst. The catalyst prepared by the invention has a finned structure, has a large specific surface area and can be NH3More active sites are provided, the catalyst activity is effectively improved, the particles are uniformly distributed, the anti-sintering performance is better, and the ammonia decomposition effect is obviously improved. The invention also has the following advantages:
1. the fin prepared by the method has the advantages of thickness of only about 25nm, obvious interval and high structural uniformity.
2. The pre-stage product of the carrier part of the catalyst prepared by the invention has an obvious LDHs structure, no obvious agglomeration structure is formed after the catalyst particles are calcined, the particles are uniformly distributed, and the sintering resistance is obviously improved.
3. The catalyst prepared by the invention can be applied to the field of hydrogen production by ammonia decomposition, has high ammonia conversion rate, time stability, temperature stability and reproducibility, and is very suitable for industrial popularization.
Drawings
FIG. 1 is an evaluation of ammonia decomposition reaction performance of the ammonia decomposition catalysts prepared in example 1 of the present application and comparative examples 1 to 3.
FIG. 2 is an Arrhenius curve of the ammonia decomposition catalysts prepared in example 1 of the present application and comparative examples 1 to 3.
FIG. 3 is a graph showing the ammonia conversion at 550 ℃ as a function of the mass space velocity of ammonia gas for the ammonia decomposition catalysts prepared in example 1 of the present application and comparative examples 1 to 3.
FIG. 4 is a graph showing the ammonia conversion rate at 550 ℃ with time of the ammonia decomposition catalysts prepared in example 1 of the present application and comparative examples 1 to 3.
FIG. 5 is a graph showing the stability of the ammonia decomposition catalyst prepared in example 1 of the present application at a gas space velocity of 30000 ml/(g.h) in the temperature range of 550 ℃ and 650 ℃.
FIG. 6 is an SEM spectrum of ammonia decomposition catalysts prepared in example 1 of the present application and comparative examples 1 to 3.
Fig. 7 is a catalytic mechanism of the finned ammonia decomposition catalyst of the present application.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
Example 1 preparation of 5 wt% Fin-like Ni/MgAl by the hydrothermal-impregnation method of the present application2O4Catalyst, i.e. preparation of finned metal oxide MgAl by hydrothermal method2O4Then loading nickel by adopting an immersion method to finally prepare the finned Ni/MgAl2O4A catalyst comprising the steps of:
(1) 6.09g of MgCl were weighed2·6H2O and 14.49g AlCl3·6H2Dissolving O in 0.1L of deionized water, adding 12.61g of urea, and fully stirring to obtain a mixed solution;
(2) transferring the mixed solution prepared in the step (1) into a high-pressure reaction kettle, heating at 180 ℃ for 12 hours, and then drying at 105 ℃ to obtain a solid sample;
(3) transferring the solid sample prepared in the step (2) into a mortar for full grinding and crushing, and then calcining at 750 ℃ for 2h to obtain the finned metal oxide MgAl2O4；
(4) Weigh 0.99gNi (NO)3)2·6H2O and 3.8g of MgAl prepared in step (3)2O4Adding into 0.1L deionized water, magnetically stirring at 90 deg.C for 8 hr to dissolve completely, evaporating to dry at 60 deg.C,drying at 100 deg.C for 8-12h to obtain 5 wt% finned Ni/MgAl2O4Catalyst, denoted as Ni @ MgAl2O4-LDH。
In example 1, the precursor product of the finned metal oxide carrier prepared by the hydrothermal method forms an obvious hydrotalcite-like compound (LDHs) structure, the hydrotalcite-like compound is a novel inorganic functional material with a layered structure, and the chemical composition of the host layer of the LDHs is closely related to the cation characteristics, the charge density or anion exchange capacity of the layer, the supramolecular intercalation structure and other factors of the layer.
The catalyst prepared in example 1 has a finned structure and a large specific surface area, and can be NH3More active sites are provided, the catalyst activity is effectively improved, and the catalyst has the advantages of uniform particle distribution, better sintering resistance and the like.
Comparative example 1 preparation of 5 wt% Ni/MgAl by Sol-gel method2O4A catalyst comprising the steps of:
(1) weighing 7.68g Mg (NO)3)2·6H2O、22.5gAl(NO3)3·9H2O and 1.11gNi (NO)3)2·6H2Dissolving O in 0.1L deionized water, adding 19.81g of citric acid and 10.32g of polyethylene glycol-400, and fully stirring to obtain a mixed solution;
(2) drying the mixed solution prepared in the step (1) to dryness at 95 ℃, and then drying at 110 ℃ for 6h to obtain a solid sample;
(3) transferring the solid sample prepared in the step (2) into a mortar for full grinding and crushing, and then calcining at 750 ℃ for 2 hours to prepare 5 wt% Ni/MgAl2O4Catalyst, denoted as Ni @ MgAl2O4-SG-1。
Comparative example 2 preparation of 5 wt% Ni/MgAl by Sol-gel impregnation2O4A catalyst comprising the steps of:
(1) weighing 7.68g Mg (NO)3)26H2O and 22.5gAl (NO)3)3·9H2Dissolving O in 0.1L deionized water, adding 19.01g citric acid and 9.9g polyethylene glycol-400, and stirring to obtain a mixed solutionLiquid;
(2) drying the mixed solution prepared in the step (1) to dryness at 95 ℃, and then drying at 110 ℃ for 6h to obtain a solid sample;
(3) transferring the solid sample prepared in the step (2) into a mortar for full grinding and crushing, and then calcining at 750 ℃ for 2h to obtain a metal oxide MgAl2O4；
(4) Weigh 0.99gNi (NO)3)2·6H2O and 3.8g of MgAl prepared in step (3)2O4Adding into 0.1L deionized water, magnetically stirring at 90 deg.C for 8 hr to dissolve completely, evaporating to dry at 60 deg.C, and drying at 100 deg.C for 8-12 hr to obtain 5 wt% Ni/MgAl2O4Catalyst, denoted as Ni @ MgAl2O4-SG-2。
Comparative example 3 preparation of 5 wt% Ni/MgAl by mechanical mixing2O4A catalyst comprising the steps of:
(1) weighing 7.68g Mg (NO)3)2·6H2O and 22.5g Al (NO)3)3·9H2Dissolving O in 0.1L of deionized water, adding 19.01g of citric acid and 9.9g of polyethylene glycol-400, and fully stirring to obtain a mixed solution;
(2) drying the mixed solution prepared in the step (1) to dryness at 95 ℃, and then drying at 110 ℃ for 6h to obtain a solid sample;
(3) transferring the solid sample prepared in the step (2) into a mortar for full grinding and crushing, and then calcining at 750 ℃ for 2h to obtain a metal oxide MgAl2O4；
(4) 0.25g of NiO and 3.8g of MgAl prepared in step (3) were weighed2O4Adding the mixture into a mortar, and fully stirring and mixing the mixture to obtain the Ni @ MgAl2O4-MM。
Application example: the ammonia decomposition catalysts prepared in example 1 and comparative examples 1, 2 and 3 were evaluated for ammonia decomposition reaction performance on a fixed bed reactor, and the specific test procedures were as follows:
loading 0.5g of 20-60 mesh catalyst to be tested in a fixed bed reactor, and introducing 10% H at 600 deg.C2Reduction of the catalyst/Ar for 3h,then introducing pure argon to purge for 1h, finally introducing pure ammonia with the mass space velocity of 30000 ml/(g.h) into the fixed bed reactor, and testing the catalytic performance of the ammonia decomposition reaction within the range of 250-800 ℃.
Fig. 7 is a schematic diagram showing the catalytic mechanism of the finned ammonia decomposition catalyst prepared in example 1, wherein the upper part shows the catalytic mechanism of the overall structure of the catalyst during the catalytic process, and the lower part is a partial schematic diagram.
Fig. 6 is an SEM image of the ammonia decomposition catalyst prepared in the above example 1 and comparative examples 1, 2, and 3. As can be seen, example 1 forms a significant fin-like structure with a thickness of only about 25nm, significant fin spacing, and high structural uniformity. Comparison of example 1 with comparative examples 1, 2 and 3 shows that the finned Ni/MgAl alloy2O4The particles of the ammonia decomposition catalyst do not form an obvious agglomeration structure after being calcined, the particles are uniformly distributed, and the anti-sintering performance is obviously improved.
FIG. 1 is an evaluation of the ammonia decomposition reaction performance of the ammonia decomposition catalysts obtained in example 1 and comparative examples 1, 2 and 3. As can be seen from the figure, the comparison of the example 1 with the comparative examples 1, 2 and 3 shows that the finned structure carrier obtained in the example 1 can remarkably improve the catalytic performance of the ammonia decomposition catalyst, the ammonia conversion rate reaches more than 99% at 600 ℃, and the ammonia conversion rate is always higher than that of the ammonia decomposition catalyst prepared by the sol-gel method and the mechanical mixing method within the range of 250-800 ℃.
Fig. 2 is an arrhenius curve of the ammonia decomposition catalyst prepared in the above example 1 and comparative examples 1, 2 and 3. As can be seen, Ni @ MgAl2O4-LDH、Ni@MgAl2O4-SG-1、Ni@MgAl2O4-SG-2 and Ni @ MgAl2O4Activation energies of the MM catalysts were 39.84kJ/mol, 43.67kJ/mol, 42.79kJ/mol and 67.73kJ/mol, respectively, Fin-shaped Ni/MgAl2O4The activation energy of the ammonia decomposition catalyst is the lowest, which shows that the fin-shaped structure obtained in example 1 can effectively reduce the reaction energy barrier of the ammonia decomposition reaction, thereby improving the catalytic performance of the ammonia decomposition reaction.
FIG. 3 is a graph showing the ammonia conversion at 550 ℃ as a function of the mass space velocity of ammonia gas for the ammonia decomposition catalysts obtained in example 1 and comparative examples 1, 2 and 3. As can be seen from the figure, the ammonia conversion rate of the catalyst obtained in example 1 is almost unchanged along with the increase of the mass space velocity of ammonia gas, which shows that the catalyst can effectively adapt to ammonia decomposition catalytic reaction under different mass space velocities alternately and still has good catalytic performance at higher mass space velocity.
FIG. 4 is a graph showing the change of the ammonia conversion rate at 550 ℃ with time of the ammonia decomposition catalysts obtained in the above example 1 and comparative examples 1, 2 and 3. As can be seen, the catalyst obtained in example 1 was in NH3The catalytic performance of the catalyst is almost unchanged after 30 hours of exposure, which shows that the catalytic performance of the catalyst has high time stability.
FIG. 5 is a graph showing the stability of the ammonia decomposition catalyst prepared in the above example 1 in the temperature range of 30000 ml/(g.h) at 550 ℃ and 650 ℃ at a gas space velocity. Under the temperature cycle of 550 ℃, 600 ℃ and 650 ℃, the catalyst is in NH3The catalyst performance is almost unchanged at corresponding temperature after the exposure for 24 hours, and the reproducibility is high. This indicates finned Ni/MgAl2O4The ammonia decomposition catalyst can effectively adapt to different reaction temperatures and has high temperature stability.
Claims (7)
1. A finned ammonia decomposition catalyst comprises a carrier and an active component loaded on the carrier, and is characterized in that the carrier is a finned metal oxide MgAl2O4The active component is Ni; the mass fraction of the active component Ni is 5-10%, and the finned metal oxide MgAl is2O4The mass fraction of (A) is 90-95%.
2. The finned ammonia decomposition catalyst of claim 1, wherein the finned metal oxide MgAl2O4In the method, the raw material of Mg is magnesium chloride, and the raw material of Al is aluminum chloride.
3. The finned ammonia decomposition catalyst of claim 1 wherein the active component is fed from Ni (NO)3)2。
4. A method of preparing a finned ammonia decomposition catalyst according to claim 1, comprising the steps of:
(1) dissolving magnesium chloride and aluminum chloride in water to prepare a solution a;
(2) adding a proper amount of complexing agent into the solution a to form a solution b, heating the solution b at 180 ℃ for 12h, drying at 105 ℃ to obtain a solid sample, crushing the solid sample, and calcining at 750 ℃ for 2h to obtain the finned metal oxide MgAl2O4；
(3) The finned metal oxide MgAl obtained in the step (2)2O4Adding to Ni (NO)3)2Stirring the solution at 90 deg.C for 8 hr, evaporating the solvent at 60 deg.C, and drying at 100 deg.C for 8-12 hr to obtain finned Ni/MgAl2O4A catalyst.
5. The method for preparing a finned ammonia decomposition catalyst according to claim 4, wherein the complexing agent is urea.
6. The method for preparing a finned ammonia decomposition catalyst according to claim 4, wherein in the step (2), the solution b is heated at 180 ℃ for 12 hours in a high-pressure reaction vessel.
7. The fin-shaped ammonia decomposition catalyst according to claim 1 or the ammonia decomposition catalyst prepared by the preparation method according to claim 4 is used for ammonia decomposition, and the catalyst is reduced for 3 hours in a hydrogen atmosphere at 600 ℃ before ammonia decomposition hydrogen production reaction.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114160150A (en) * | 2021-12-31 | 2022-03-11 | 西南化工研究设计院有限公司 | Large-scale high-pressure ammonia decomposition catalyst and preparation method thereof |
| CN115555015A (en) * | 2022-09-16 | 2023-01-03 | 福州大学 | Supported Ru and/or Ni catalyst and preparation method thereof |
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| US11912574B1 (en) | 2022-10-06 | 2024-02-27 | Amogy Inc. | Methods for reforming ammonia |
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| CN116159568B (en) * | 2023-02-28 | 2023-09-26 | 福大紫金氢能科技股份有限公司 | Self-contained nano-sheet nickel-based ammonia decomposition catalyst and preparation method and application thereof |
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