CN117619390A - Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof - Google Patents
Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof Download PDFInfo
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- CN117619390A CN117619390A CN202311578477.3A CN202311578477A CN117619390A CN 117619390 A CN117619390 A CN 117619390A CN 202311578477 A CN202311578477 A CN 202311578477A CN 117619390 A CN117619390 A CN 117619390A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000001257 hydrogen Substances 0.000 title claims abstract description 68
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 68
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 35
- 238000011068 loading method Methods 0.000 claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 28
- 150000003624 transition metals Chemical group 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229910052788 barium Inorganic materials 0.000 claims abstract description 14
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 112
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 claims description 3
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000006378 damage Effects 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 46
- 239000012498 ultrapure water Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 239000002064 nanoplatelet Substances 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002073 nanorod Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020514 Co—Y Inorganic materials 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000625836 Ochrolechia Species 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 belongs to the technical field of environment-friendly hydrogen production, and particularly relates to an ammonia decomposition hydrogen production catalyst and a preparation method and application thereof. The catalyst comprises an active component, a cocatalyst and a carrier; the active component is transition metal; the promoter is alkaline earth barium; the carrier is rare earth metal oxide; the loading of the active component is 25-35 parts and the loading of the cocatalyst is 8-20 parts based on 100 parts of the mass of the rare earth metal oxide of the carrier. By adding the promoter alkaline earth metal barium, the electronic structure of the transition metal catalyst can be changed, the electron donating capability of the transition metal catalyst is promoted, the dispersity of the metal active component is improved, the overall catalytic activity is further improved, and ammonia can be decomposed at a lower temperature. The rare earth metal oxide is used as a carrier, so that the interaction between the metal and the carrier can be enhanced, the adsorption of ammonia molecules is promoted, the activity is improved, the reaction temperature is reduced, and the catalyst stability is promoted.
Description
Technical Field
The invention belongs to the technical field of environment-friendly hydrogen production, and particularly relates to an ammonia decomposition hydrogen production catalyst and a preparation method and application thereof.
Background
With the continuous development of modern society, the demand of human beings for energy is increasing; however, since the industrial revolution, humans have caused serious over-exploitation and use of traditional fossil resourcesEnvironmental pollution problem and emission of a large amount of CO 2 The representative greenhouse gases cause global climate warming, and seriously threaten the stabilization of the ecological system and the survival and development of human society. Therefore, development and utilization of novel energy sources that are environmentally friendly and pollution-free have become an important point of attention. Among these, hydrogen energy is considered as one of the most practical new energy sources in the future because of its advantages such as zero pollution, high energy, abundant resources, and wide application. However, the hydrogen has the characteristics of low density and inflammability and explosiveness, so that the transportation and storage of the hydrogen are very difficult, and the large-scale commercial application of the hydrogen is seriously hindered. The most dominant hydrogen storage and transportation technology is high-pressure gas storage and transportation technology at present, and although the technology is primarily commercialized, the technology is only suitable for short-distance and small-reserve transportation and storage at present, and cannot meet the requirement of large-scale hydrogen utilization.
The hydrogen-containing compounds such as ammonia, methanol, calcium hydride and the like are used as hydrogen carriers, and the hydrogen can be produced on line through chemical reaction, so that the transportation and storage efficiency of the hydrogen can be greatly improved. Among these, ammonia has the advantages of high hydrogen mass density (17.8 wt%), easiness in liquefying, no secondary pollution caused by decomposed byproducts, low energy loss in the synthesis process, low cost, easiness in obtaining and the like, and becomes one of the most valuable hydrogen storage compounds at present. However, ammonia decomposition hydrogen production is an endothermic reaction, and the high-purity hydrogen can be produced only at high temperature, so that the energy consumption is huge; as such, it is important to develop a highly efficient ammonolysis reaction catalyst having low temperature activity.
At present, the catalyst for producing hydrogen by ammonia decomposition mainly uses noble metal (Ru, ir and the like) catalysts, but the noble metal catalysts are expensive and have small reserves, so that commercial application is difficult to realize, and the catalytic activity of the cheap and easily-obtained transition metal catalysts at low temperature is obviously different from that of the noble metal catalysts, so that the problem of how to improve the catalytic activity of the transition metal catalysts for producing hydrogen by ammonia decomposition at low temperature is needed to be solved.
Disclosure of Invention
In order to overcome the problems, the invention provides a catalyst for producing hydrogen by decomposing ammonia, a preparation method and application thereof. The invention prepares the supported transition metal-rare earth oxide-alkaline earth metal barium catalyst by a deposition precipitation method, takes transition metal as active metal, takes alkaline earth metal barium as cocatalyst and takes rare earth oxide as carrier, and applies the catalyst to the reaction of preparing hydrogen by ammonia decomposition, thereby realizing the high-efficiency preparing hydrogen by ammonia decomposition of the transition metal-based catalyst at low temperature.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided a catalyst for producing hydrogen by ammonia decomposition, the catalyst comprising an active component, a promoter and a support;
the active component is transition metal; the promoter is alkaline earth barium; the carrier is rare earth metal oxide;
the loading amount of the active component is 25-35 parts and the loading amount of the cocatalyst is 8-20 parts based on 100 parts of the mass of the carrier rare earth metal oxide.
In a second aspect of the present invention, there is provided a method for preparing the catalyst for producing hydrogen by decomposing ammonia, comprising the steps of:
(1) Dissolving rare earth metal nitrate in deionized water, dropwise adding NaOH solution, and placing the mixed solution in an autoclave for hydrothermal reaction to synthesize rare earth metal oxide;
(2) Dispersing the metal oxide synthesized in the step (1) in deionized water, dropwise adding a mixed solution of transition metal nitrate and barium nitrate, and simultaneously dropwise adding Na 2 CO 3 The pH value of the solution is controlled to be stabilized at 8-10, the solution is stirred at room temperature and then aged, the solid is filtered, then dried and calcined in a muffle furnace to obtain the catalyst for preparing hydrogen by decomposing ammonia.
In a third aspect of the invention, there is provided the use of the ammonia decomposition hydrogen production catalyst described above in an ammonia decomposition hydrogen production reaction.
The invention has the beneficial effects that:
(1) The activity of the cobalt-based transition metal catalytic ammonia decomposition hydrogen production is higher than that of other transition metal catalysts, but the catalytic activity of the cobalt-based transition metal catalytic ammonia decomposition hydrogen production is obviously different from that of the noble metal catalysts, and the electron structure of the catalyst can be changed by adding the promoter alkaline earth metal barium, so that the electron donating capacity of the catalyst is promoted, the dispersity of metal active components is promoted, the overall catalytic activity is further promoted, and ammonia can be decomposed at a lower temperature. The rare earth metal oxide is used as a carrier, so that the interaction between the metal and the carrier can be enhanced, the adsorption of ammonia molecules is promoted, the activity is improved, the reaction temperature is reduced, and the catalyst stability is promoted.
(2) The addition of the promoter Ba not only improves the Co-based catalyst, but also improves the transition metal-based catalyst commonly used for ammonia decomposition, thereby indicating the universality of improving the catalytic ammonia decomposition reaction activity of the transition metal-based catalyst after the Ba is combined with the rare earth oxide as an auxiliary agent.
(3) The decomposition of ammonia is a gradual dehydrogenation process, the hydrogen production is carried out by catalyzing ammonia with a metal catalyst, the block speeds of different metal catalysts are different, it is generally considered that the block speeds of noble metal (Ru, ir and the like) catalysts are used, N-H bond breakage in ammonia is the block speeds, but the analysis of nitrogen is the block speeds for transition metals (Co, fe, ni and the like), and the activity of the noble metal (Ru, ir and the like) catalysts can be improved by taking alkaline earth metal barium as a cocatalyst, but the mechanism of improving the activity of the different catalysts by taking alkaline earth metal barium as the cocatalyst is different due to the different block speeds of the different catalysts.
(4) The test result shows that the catalyst for preparing hydrogen by ammonia decomposition can achieve high conversion rate of 87.5 percent and hydrogen production rate of 29.3mmol g per gram of catalyst when the catalyst for preparing hydrogen by ammonia decomposition is used for decomposing catalyst ammonia at 500 DEG C cat -1 min -1 The catalyst exceeds the catalyst for preparing hydrogen by decomposing transition metal-based ammonia in the prior art, and is even higher than part of noble metal Ru-based catalyst.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 shows the application of the catalysts prepared in comparative example 1, comparative example 4, comparative example 5 and comparative example 6 to ammoniaNH in decomposition reaction 3 A conversion profile;
FIG. 2 shows the application of the catalysts prepared in example 1, example 4, example 5, comparative example 1, comparative example 5 and comparative example 6 to NH in an ammonia decomposition reaction 3 A conversion profile;
FIG. 3 is an NH value of the catalysts prepared in example 1, comparative example 4 and comparative example 7 applied to ammonia decomposition reaction 3 A conversion profile;
FIG. 4 is a schematic representation of the NH of the catalysts prepared in example 1, example 2, example 3, comparative example 1, comparative example 2 and comparative example 3 applied in an ammonia decomposition reaction 3 A conversion profile;
FIG. 5 shows the temperature stability of the catalysts prepared in example 1 and comparative example 1, where a is comparative example 1 and b is example 1;
FIG. 6 is XRD patterns of the catalysts prepared in example 1 and comparative example 1;
fig. 7 is a TEM image of the catalyst prepared in example 1 and comparative example 1, wherein a is a TEM image of the catalyst prepared in comparative example 1, and b is a TEM image of the catalyst prepared in example 1;
FIG. 8 shows the application of the catalyst of example 6 with different cocatalyst levels to H in an ammonia decomposition reaction 2 A yield graph;
FIG. 9 is a graph showing NH values obtained by applying the catalyst of example 7 with different cobalt contents to an ammonia decomposition reaction 3 Conversion graph.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In a first exemplary embodiment of the present invention, there is provided a catalyst for producing hydrogen by decomposing ammonia, the catalyst comprising an active component, a cocatalyst and a carrier;
the active component is transition metal; the promoter is alkaline earth barium; the carrier is rare earth metal oxide;
the loading amount of the active component is 25-35 parts and the loading amount of the cocatalyst is 8-20 parts based on 100 parts of the mass of the carrier rare earth metal oxide.
In one or more embodiments, the transition metal includes Co, fe and Ni, preferably Co.
In one or more embodiments, the rare earth metal oxide includes Y 2 O 3 、Sm 2 O 3 And CeO 2 Preferably Y 2 O 3 。
In one or more embodiments, the active component is loaded at 30 parts and the promoter is loaded at 10 parts.
In a second exemplary embodiment of the present invention, a method for preparing the catalyst for producing hydrogen by decomposing ammonia as described above is provided, comprising the steps of:
(1) Dissolving rare earth metal nitrate in deionized water, dropwise adding NaOH solution, and placing the mixed solution in an autoclave for hydrothermal reaction to synthesize rare earth metal oxide;
(2) Dispersing the metal oxide synthesized in the step (1) in deionized water, dropwise adding a mixed solution of transition metal nitrate and barium nitrate, and simultaneously dropwise adding Na 2 CO 3 The pH value of the solution is controlled to be stabilized at 8-10, the solution is stirred at room temperature and then aged, the solid is filtered, then dried and calcined in a muffle furnace to obtain the catalyst for preparing hydrogen by decomposing ammonia.
In one or more embodiments, the temperature of the hydrothermal reaction in step (1) is 95 to 105 ℃, preferably 100 ℃; the reaction time is 10-30 h.
In one or more embodiments, in step (2), the pH is controlled to stabilize at 9.
In one or more embodiments, in step (2), the stirring time at room temperature is 20 to 40 minutes, preferably 30 minutes.
In one or more embodiments, in step (2), the aging time is from 0.5 to 1.5 hours, preferably 1 hour.
In one or more embodiments, in step (2), the temperature of calcination is 550 to 650 ℃, preferably 600 ℃; the calcination time is 3 to 5 hours, preferably 4 hours.
In a third exemplary embodiment of the present invention, there is provided the use of the above catalyst for producing hydrogen by ammonia decomposition in a reaction for producing hydrogen by ammonia decomposition.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Solution preparation:
cobalt nitrate solution: 2.91g of cobalt nitrate hexahydrate was weighed and dissolved in 100mL of high purity water;
ferric nitrate solution: 4.04g of ferric nitrate nonahydrate is weighed and dissolved in 100mL of high-purity water;
nickel nitrate solution: 2.91g of nickel nitrate hexahydrate was weighed out and dissolved in 100mL of high purity water.
Preparation of the carrier:
Y 2 O 3 preparation of nanosheet carrier: 6.9g of yttrium nitrate hexahydrate is weighed and dissolved in 360mL of deionized water, 10wt% NaOH solution (5 g of NaOH is dissolved in 50mL of deionized water) is dropwise added, and the pH value of the solution is controlled to be stable at 12. And transferring the obtained mixed solution into a polytetrafluoroethylene lining, placing the lining into a stainless steel reaction kettle, setting the temperature in an oven to be 100 ℃, and reacting for 12 hours. Centrifugally washing the obtained product after the hydrothermal treatment, respectively washing with deionized water for 4 times and absolute ethanol for 1 time, drying the precipitate in an oven at 80 ℃ for 4 hours after washing, and grinding with an agate mortar after dryingFine powder to obtain Y 2 O 3 A nanoplatelet carrier.
Sm 2 O 3 Nanorods and CeO 2 Preparation of nanorods: 14.4g NaOH was dissolved in 40mL deionized water, and then 3mmol of nitrate (Sm (NO) 3 ) 3 ·6H 2 O or Ce (NO) 3 ) 3 ·6H 2 The aqueous solution of O) is added into NaOH solution and stirred for 30min to disperse the solution uniformly. And carrying out hydrothermal reaction for 24 hours at 100 ℃, transferring the obtained mixed solution into a polytetrafluoroethylene lining, placing the lining into a stainless steel reaction kettle, setting the temperature in an oven to be 100 ℃, and reacting for 24 hours. Centrifugal washing the obtained product after hydrothermal treatment, respectively washing with deionized water for 4 times and absolute ethanol for 1 time, drying the precipitate in an oven at 60deg.C for 24 hr to obtain Sm 2 O 3 Nanorods and CeO 2 A nanorod.
Example 1
Will be 0.5g Y 2 O 3 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until complete dispersion, designated as solution A, and 25.5mL of 0.1M Co (NO) was removed 3 ) 2 6H 2 O solution and 0.0953g of Ba (NO) 3 ) 2 Stirring, and ultrasonic treating to obtain solution B, adding 0.5M Na dropwise 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Co-Y for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 O 3 10Ba (the loading of the active component Co is 30 parts based on 100 parts of the mass of the rare earth metal oxide of the carrier, and the loading of the promoter Ba is 10 parts).
Example 2
Will be 0.5g Y 2 O 3 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until complete dispersion, designated as solution C, 26.8mL of 0.1M Fe (NO) was removed 3 ) 3 9H 2 O solution and 0.0953g of Ba (NO) 3 ) 2 Stirring, and ultrasonic treating to obtain solution D, adding 0.5M Na dropwise into solution C 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Fe-Y for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 O 3 10Ba (the loading of the active component Fe is 30 parts and the loading of the promoter Ba is 10 parts based on 100 parts of the mass of the rare earth metal oxide of the carrier).
Example 3
Will be 0.5g Y 2 O 3 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until complete dispersion, designated as solution E, and 25.5mL of 0.1M Ni (NO) was removed 3 ) 2 6H 2 O solution and 0.0953g of Ba (NO) 3 ) 2 Stirring, and ultrasonic treating to obtain solution F, adding 0.5M Na dropwise 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Ni-Y for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 O 3 10Ba (the loading of the active component Ni is 30 parts based on 100 parts of the mass of the rare earth metal oxide of the carrier, and the loading of the promoter Ba is 10 parts).
Example 4
0.5g Sm 2 O 3 The nanosheet carrier was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, designated as solution H, and 25.5mL of 0.1M Co (NO) was removed 3 ) 2 6H 2 O solution and 0.0953g of Ba (NO) 3 ) 2 Stirring thoroughly, ultrasound to mix the two uniformly, recording as solution I, dripping solution I into solution H, and dripping 0.5M Na simultaneously 2 CO 3 The solution is stabilized at 9 pH, stirred for 0.5h and aged for 1h at room temperature, the solid is filtered by suction, dried for 10h at 70 ℃, and placed in a muffle furnace at a heating rate of 2 ℃/minRaising the temperature to 600 ℃ from room temperature, calcining for 4 hours to obtain the catalyst 30Co-Sm for preparing hydrogen by ammonia decomposition 2 O 3 10Ba (the loading of the active component Co is 30 parts based on 100 parts of the mass of the rare earth metal oxide of the carrier, and the loading of the promoter Ba is 10 parts).
Example 5
0.5g CeO 2 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until complete dispersion, designated as solution G, and 25.5mL of 0.1M Co (NO) was removed 3 ) 2 6H 2 O solution and 0.0953g of Ba (NO) 3 ) 2 Stirring thoroughly, ultrasound to mix the two uniformly, recording as solution K, adding dropwise solution K into solution G, and simultaneously adding dropwise 0.5M Na 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Co-CeO for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 10Ba (the loading of the active component Co is 30 parts based on 100 parts of the mass of the rare earth metal oxide of the carrier, and the loading of the promoter Ba is 10 parts).
Example 6
Will be 0.5g Y 2 O 3 The nanosheet carrier was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, designated as solution L, and 25.5mL of 0.1M Co (NO) was removed 3 ) 2 6H 2 O solution and adding Ba (NO) of different masses 3 ) 2 Stirring, and ultrasonic treating to obtain solution M, adding 0.5M Na dropwise 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Co-Y for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 O 3 XBa (30 parts of active component Co and X parts of promoter Ba, based on 100 parts of rare earth oxide of the support).
Example 7
Will be 0.5g Y 2 O 3 The nanoplatelet support was dispersed in 25mL high purity water and stirred at room temperature until completely dispersed, designated as solution P, and varying volumes of 0.1M Co (NO) were removed 3 ) 2 6H 2 O solution and 0.0953g of Ba (NO) 3 ) 2 Stirring thoroughly, ultrasound to mix the two uniformly, recording as solution Q, dripping solution Q into solution P, and dripping 0.5M Na 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the ammonia decomposition hydrogen production catalyst YCo-Y is obtained after calcination for 4h 2 O 3 10Ba (the loading of the active component Co is Y parts based on 100 parts of the mass of the rare earth metal oxide of the carrier, and the loading of the promoter Ba is 10 parts).
Comparative example 1
Will be 0.5g Y 2 O 3 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, and 25.5mL of 0.1M Co (NO) was added dropwise to the solution 3 ) 2 6H 2 O solution, simultaneously dropwise adding 0.5M Na 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Co-Y for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 O 3 (the loading of the active component Co is 30 parts based on 100 parts of the mass of the carrier rare earth metal oxide).
Comparative example 2
Will be 0.5g Y 2 O 3 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, 26.8mL of 0.1M Fe (NO) was added dropwise to the solution 3 ) 3 9H 2 O solution, 0.5MNA was added dropwise at the same time 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Fe-Y for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 O 3 (as a carrier dilute)The mass of the active component Fe is 30 parts based on 100 parts of the mass of the earth metal oxide).
Comparative example 3
Will be 0.5g Y 2 O 3 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, and 25.5mL of 0.1M Ni (NO) was added dropwise to the solution 3 ) 2 6H 2 O solution, 0.5MNA was added dropwise at the same time 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Ni-Y for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 O 3 (the loading of the active component Ni is 30 parts based on 100 parts of the mass of the carrier rare earth metal oxide).
Comparative example 4
0.5g of SiO 2 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, and 25.5mL of 0.1M Co (NO) was added dropwise to the solution 3 ) 2 6H 2 O solution, simultaneously dropwise adding 0.5M Na 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Co-SiO for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 (according to SiO) 2 The loading of the active component Co was 30 parts by mass per 100 parts by mass.
Comparative example 5
0.5g Sm 2 O 3 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, and 25.5mL of 0.1M Co (NO) was added dropwise to the solution 3 ) 2 6H 2 O solution, simultaneously dropwise adding 0.5M Na 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Co-Sm for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 O 3 (based on 100 parts by mass of the rare earth metal oxide as the carrier)The loading of the active component Co was 30 parts).
Comparative example 6
0.5g CeO 2 The nanoplatelet support was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, and 25.5mL of 0.1M Co (NO) was added dropwise to the solution 3 ) 2 6H 2 O solution, simultaneously dropwise adding 0.5M Na 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Co-CeO for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 (the loading of the active component Co is 30 parts based on 100 parts of the mass of the carrier rare earth metal oxide).
Comparative example 7
0.5g of SiO 2 The nanosheet carrier was dispersed in 25mL of high purity water and stirred at room temperature until completely dispersed, designated as dissolved N, and 25.5mL of 0.1M Co (NO) was removed 3 ) 2 6H 2 O solution and 0.0953g of Ba (NO) 3 ) 2 Stirring, and ultrasonic treating to obtain solution O, adding 0.5M Na dropwise 2 CO 3 The pH value of the solution is controlled to be stabilized at 9, then the solution is stirred for 0.5h at room temperature and aged for 1h, the solid is filtered by suction, then the solution is dried for 10h at 70 ℃, the solution is placed in a muffle furnace to be heated to 600 ℃ from room temperature at a heating rate of 2 ℃/min, and the catalyst 30Co-SiO for preparing hydrogen by ammonia decomposition is obtained after calcination for 4h 2 -10Ba (per SiO) 2 The loading of the active component Co is 30 parts and the loading of the promoter Ba is 10 parts based on 100 parts by mass.
Experimental example 1
Performance tests were performed on the catalysts prepared in examples 1 to 5 and comparative examples 1 to 7: 50mg of the catalyst (20-40 mesh) was mixed with 500mg of quartz sand (20-40 mesh) and charged into a reaction tube having an inner diameter of 8 mm. The catalyst was first pure NH at 600 ℃ prior to catalytic testing 3 Activation in an atmosphere for 1h, followed by conversion testing at between 450 and 600 ℃ with a reactor temperature interval of 50 ℃ at one point (ghsv=30,000 cm 3 ·g cat -1 ·h -1 ). The outlet gas is analyzed by an on-line gas chromatograph, and then N is obtained in real time 2 And NH 3 The content is as follows. NH (NH) 3 The conversion of (2) is calculated by the following formula.
1.1 selection of catalyst support
Performance test of ammonia catalytic decomposition by using the catalysts prepared in comparative example 1, comparative example 4, comparative example 5 and comparative example 6, respectively, without supporting alkaline earth metal barium, the results are shown in FIG. 1, rare earth oxide (Y 2 O 3 、Sm 2 O 3 、CeO 2 ) When the catalyst is used as a carrier, the ammonia decomposition conversion rate of the catalyst is obviously better than that of the catalyst prepared by SiO 2 30Co-SiO as a support 2 Catalyst and catalytic Activity at 30Co-Y 2 O 3 The catalyst is optimal and can reach 51% conversion at 500 ℃. This is illustrated by Y 2 O 3 The activity can be improved when the represented rare earth oxide is used as a carrier for the catalyst for the ammonolysis reaction to carry a transition metal.
Performance test of catalytic decomposition of Ammonia by the catalysts prepared in example 1, example 4, example 5, comparative example 1, comparative example 5 and comparative example 6, respectively, the addition of alkaline earth barium as a catalyst promoter, as shown in FIG. 2, significantly improves the activity of the catalyst, especially 30Co-Y prepared in comparative example 1 2 O 3 Catalyst, catalyst after Ba addition (30 Co-Y in example 1) 2 O 3 -10 Ba) the ammonia decomposition conversion was increased by nearly 40% (from 51% to 88%) at 500℃to give 30Co-Y 2 O 3 The hydrogen production rate of the-10 Ba catalyst can reach 29.3mmol g per gram of catalyst at 500 DEG C cat -1 min -1 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst for preparing hydrogen by decomposing transition metal-based ammonia is superior to the catalyst for preparing hydrogen by decomposing transition metal-based ammonia in the prior art, and is even superior to partial noble metal Ru-based catalyst.
To further verify whether rare earth oxide has unique advantages as a carrier in an ammonolysis reaction, example 1, comparative example were used, respectively1. Performance test of the catalysts prepared in comparative example 4 and comparative example 7 for catalytic decomposition of ammonia, the results are shown in FIG. 3, 30Co-SiO after addition of Ba 2 The activity of the catalyst is not improved, even the catalyst is slightly reduced, so that the transition metal-rare earth oxide-based catalyst has higher activity, and the catalyst activity is improved after the catalyst is further combined with a promoter Ba, which also shows that the rare earth oxide has unique advantages when combined with the transition metal and alkaline earth metal Ba promoter.
1.2 Co-catalyst Ba has the universality for improving the catalytic activity of transition metal
In Y form 2 O 3 As a result of the ammonia decomposition activity test performed after selecting other transition metals (Fe, ni) as carriers, i.e., the catalysts prepared in example 1, example 2, example 3, comparative example 1, comparative example 2 and comparative example 3, as shown in fig. 4, the addition of the Co-catalyst Ba improves not only the Co-based catalyst but also all the transition metal-based catalysts commonly used for ammonia decomposition, which illustrates the versatility of improving the catalytic ammonia decomposition reaction activity of the transition metal-based catalyst after the Ba is combined with the rare earth oxide as an auxiliary agent.
1.3 evaluation of catalyst stability
The catalysts prepared in example 1 and comparative example 1 were evaluated by: heat stability test at 550 ℃ and 500 ℃ (ghsv=60,000 cm 3 ·g cat -1 ·h -1 ) The following was performed for 200 hours in total. As shown in FIG. 5, in the 200h temperature change test, the catalyst NH after Ba addition 3 Conversion was reduced by only 3% (ghsv=60,000 cm 3 ·g cat -1 ·h -1 ) The catalyst exhibits excellent stability; this also represents an advantage of rare earth oxide supported transition metal catalysts in ammonia decomposition reactions.
1.4
The catalysts prepared in example 1, example 4, example 5, comparative example 1, comparative example 2, comparative example 5, comparative example 6 and comparative example 7 were subjected to the ammonia decomposition activity test and the results are shown in table 1.
TABLE 1 summary of catalytic Activity
1.5 promoter alkaline-earth barium improves the dispersity of the metal active component
The catalysts prepared in example 1 and comparative example 1 were characterized, with XRD patterns shown in fig. 6 and TEM patterns shown in fig. 7. As can be seen from FIG. 6, co is used as Co on the catalyst before and after doping Ba 3 O 4 The addition of Ba promotes the dispersion of Co species prior to the reaction. At the same time, 30Co-Y 2 O 3 The presence of the corresponding BaCO on the-10 Ba catalyst 3 Illustrating the diffraction peak of Ba as BaCO before the reaction 3 Is present in the form of (c). In addition, it is clear from TEM image of the catalyst before reaction that the Co species size after Ba addition is significantly smaller than 30Co-Y without Ba addition 2 O 3 The catalyst, which is also consistent with the results of XRD.
Experimental example 2 determination of the amount of active metallic cobalt and barium Co-catalyst
The performance of the catalyst prepared in example 6 was tested, and as a result, as shown in fig. 8, it was found that the Ba content and the catalytic activity exhibited a volcanic type trend change. At 500 ℃, the content of the Ba auxiliary agent of 10% is optimal, the activity of the catalyst is gradually reduced by further increasing the content of the Ba, and after 50% of the Ba is added, the promotion effect of the Ba on the activity is completely disappeared.
Experimental example 3 determination of cobalt addition amount
The catalyst prepared in example 7 was tested for performance, and as shown in fig. 9, it was found that the cobalt content of 30% Co was optimal, and that excessive Co content (50%) resulted in a decrease in activity.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A catalyst for producing hydrogen by decomposing ammonia, which is characterized by comprising an active component, a cocatalyst and a carrier;
the active component is transition metal; the promoter is alkaline earth barium; the carrier is rare earth metal oxide;
the loading amount of the active component is 25-35 parts and the loading amount of the cocatalyst is 8-20 parts based on 100 parts of the mass of the carrier rare earth metal oxide.
2. The ammonia destruction hydrogen production catalyst of claim 1, wherein the transition metal comprises Co, fe, and Ni, preferably Co.
3. The ammonia destruction hydrogen production catalyst of claim 1, wherein the rare earth metal oxide comprises Y 2 O 3 、Sm 2 O 3 And CeO 2 Preferably Y 2 O 3 。
4. The ammonia destruction hydrogen production catalyst of claim 1 wherein the loading of the active component is 30 and the loading of the promoter is 10.
5. The method for producing an ammonia decomposition hydrogen production catalyst according to any one of claims 1 to 4, comprising the steps of:
(1) Dissolving rare earth metal nitrate in deionized water, dropwise adding NaOH solution, and placing the mixed solution in an autoclave for hydrothermal reaction to synthesize rare earth metal oxide;
(2) Dispersing the metal oxide synthesized in the step (1) in deionized water, dropwise adding a mixed solution of transition metal nitrate and barium nitrate, and simultaneously dropwise adding Na 2 CO 3 The pH value of the solution is controlled to be stabilized between 8 and 10, the solution is stirred at room temperature and then aged, the solid is filtered by suction, then dried and calcined in a muffle furnace to obtain the catalystTo obtain the catalyst for producing hydrogen by decomposing ammonia.
6. The process according to claim 5, wherein the hydrothermal reaction in step (1) is carried out at a temperature of 95 to 105 ℃, preferably 100 ℃; the reaction time is 10-30 h.
7. The method according to claim 5, wherein in the step (2), the pH is controlled to be stabilized at 9.
8. The process according to claim 5, wherein in step (2), the stirring time at room temperature is 20 to 40min, preferably 30min;
or, in the step (2), the aging time is 0.5-1.5 h, preferably 1h.
9. The process according to claim 5, wherein in step (2), the calcination temperature is 550 to 650 ℃, preferably 600 ℃; the calcination time is 3 to 5 hours, preferably 4 hours.
10. Use of the catalyst for producing hydrogen by ammonia decomposition according to any one of claims 1 to 4 or the catalyst for producing hydrogen by ammonia decomposition prepared by the preparation method according to any one of claims 5 to 9 in a reaction for producing hydrogen by ammonia decomposition.
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