CN117399014B - Preparation method and application of finite field ammonia decomposition catalyst - Google Patents
Preparation method and application of finite field ammonia decomposition catalyst Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 15
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 14
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 22
- 239000002245 particle Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003446 ligand Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241001573881 Corolla Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
Classifications
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a preparation method and application of a finite field ammonia decomposition catalyst, comprising the following steps: dissolving aluminum potassium sulfate dodecahydrate and urea in deionized water to obtain a reaction solution, and drying and calcining a product after hydrothermal reaction to obtain a corolla-shaped alumina carrier; dissolving nickel acetate in ethanol, adding phenanthroline, stirring for reaction, adding a corolla-shaped alumina carrier, and stirring uniformly to obtain a dispersion; removing ethanol in the dispersion liquid after the impregnation reaction to obtain a precursor; and calcining the precursor to obtain the finite field ammonia decomposition catalyst. The alumina carrier with the corolla-shaped structure is prepared, and is used for loading the metal nickel, so that the dispersibility of the active metal can be effectively improved, and the metal particles can be isolated and limited through the corolla-shaped structure, so that the migration of the active metal particles is effectively prevented; when the catalyst is used as an ammonia decomposition catalyst, the catalyst has high ammonia decomposition activity under medium temperature conditions and excellent stability.
Description
Technical Field
The invention relates to the technical field of ammonia decomposition catalysts, in particular to a preparation method and application of a finite field ammonia decomposition catalyst.
Background
Hydrogen is one of the most potent clean energy sources, however, hydrogen is extremely difficult to transport and store due to its own chemical characteristics, and the development and application and popularization of hydrogen energy are seriously hindered. This requires the search for an effective hydrogen storage medium to efficiently store hydrogen and release it when needed for use. The catalyst can be used as a chemical hydrogen storage carrier, such as natural gas, methanol and ammonia. Ammonia has significant advantages over the former two. The hydrogen content of ammonia gas is 17.6% and is higher than 12.5% of methanol. And secondly, ammonia is not inflammable in the air, the explosion limit is 16% -25%, and the use safety is higher than that of natural gas. More importantly, ammonia gas itself contains no carbon, and no greenhouse gas (CO 2) is discharged during the use process. Ammonia is also the second most productive chemical in the world and its transportation and storage facilities are well established. The cost of ammonia input from production to storage is only 69% of that of hydrogen and 82% of that of methanol. Ammonia gas is considered to be the most desirable hydrogen storage medium.
However, ammonia has high chemical stability, and the hydrogen production by decomposing ammonia generally needs to be carried out under the conditions of a catalyst and high temperature, which has high requirements on the stability of the catalyst at high temperature. Currently, ammonia decomposition catalysts mainly include nickel-based catalysts, ruthenium-based catalysts, iron-based catalysts, and composite catalysts, and their preparation methods include impregnation, coprecipitation, and fusion. Compared with other catalysts, the nickel-based ammonia decomposition catalyst prepared by the impregnation method has the advantages of stable performance, better catalytic efficiency, difficult poisoning failure, longer service life, lower cost and most wide application. For example, "a high activity ammonia decomposition catalyst", publication No. CN1245737A, the active components of which are molybdenum and nickel, and the carrier of which is Al 2O3 or MgO, are disclosed in Chinese patent literature, and the preparation method is to prepare salts of two metals into an aqueous solution or an ammonia solution to impregnate the carrier together.
However, the nickel-based ammonia decomposition catalyst in the prior art generally needs to react at a high temperature of above 600 ℃, nickel metal particles are easy to agglomerate and sinter at a high temperature in the reaction process, and the stability of the catalyst is poor, so that the application of the catalyst is limited.
Disclosure of Invention
The invention provides a preparation method and application of a limited-domain ammonia decomposition catalyst, which are used for solving the problems of high reaction temperature and poor stability of the catalyst in the ammonia decomposition catalyst in the prior art, and the aluminum potassium sulfate dodecahydrate is used as a raw material to prepare an alumina carrier with a corolla-shaped structure under the action of a template agent, and the alumina carrier is used for loading metallic nickel, so that the dispersibility of active metal can be effectively improved, and metal particles can be isolated and limited by the corolla-shaped structure, so that the migration of the active metal particles is effectively prevented; when the catalyst is used as an ammonia decomposition catalyst, the catalyst has high ammonia decomposition activity under the medium temperature condition of 500-600 ℃ and excellent stability.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A preparation method of a finite field ammonia decomposition catalyst comprises the following steps:
(1) Dissolving aluminum potassium sulfate dodecahydrate and urea in a molar ratio of 1:1.8-2.2 in deionized water to obtain a reaction solution with the concentration of 0.1-0.2 mol/L of aluminum potassium sulfate dodecahydrate;
(2) Carrying out hydrothermal reaction on the reaction liquid; the hydrothermal reaction temperature is 150-200 ℃ and the reaction time is 2-4 hours;
(3) Drying and calcining the hydrothermal product in the step (2) to obtain a corolla-shaped alumina carrier; the calcination temperature is 550-650 ℃ and the calcination time is 3-5 h;
(4) Dissolving nickel acetate in ethanol, adding phenanthroline, stirring for reaction, adding a corolla-shaped alumina carrier, and stirring uniformly to obtain a dispersion; removing ethanol in the dispersion liquid after the impregnation reaction to obtain a precursor;
(5) Calcining the precursor obtained in the step (4) to obtain the finite field ammonia decomposition catalyst.
According to the invention, aluminum potassium sulfate dodecahydrate is used as a raw material, hydrothermal reaction conditions are controlled under the action of a template agent urea, an alumina carrier with a corolla-shaped structure is prepared, and nickel particles are loaded on the surface of the corolla-shaped alumina carrier by an impregnation method, so that the finite field ammonia decomposition catalyst is obtained.
The corolla-shaped alumina carrier prepared by the method is spherical, the surface of the corolla-shaped alumina carrier is formed by interweaving a plurality of flaky alumina, the petal thickness is thinner and is about 5nm, the specific surface area of the carrier is greatly improved, and the dispersity of active metals is effectively improved; the corolla-shaped structure divides the surface of the alumina carrier into a plurality of independent small areas, can play a role in limiting the area of active metal particles loaded on the surface of the alumina carrier, effectively prevents migration of the active metal particles, and avoids agglomeration and sintering of the active metal particles at high temperature, thereby remarkably improving the stability of the catalyst. Meanwhile, when nickel is loaded by dipping, the phenanthroline ligand is added, nickel and the ligand form a coordination compound and then are loaded on the surface of the corolla-shaped alumina carrier, so that smaller nickel metal particles with the particle size of about 2-3 nm can be generated, can be uniformly dispersed and limited between petal-shaped structures of the carrier, can reduce the temperature of ammonia decomposition reaction when being used as an ammonia decomposition catalyst, can have high ammonia decomposition activity under the medium temperature condition of 500-600 ℃, and can obviously reduce reaction energy consumption compared with the reaction condition of more than 600 ℃ of the traditional catalyst.
Preferably, the drying temperature in the step (3) is 75-85 ℃ and the drying time is 8-12 hours.
Preferably, in the step (4), the mass ratio of the nickel element in the nickel acetate to the corolla-shaped alumina carrier is 5-10:95-90.
Preferably, in the step (4), the molar ratio of the nickel acetate to the phenanthroline is 1:2.5-3.5, and the stirring reaction time is 20-40 min.
Preferably, in the step (4), the corolla alumina carrier is dispersed in ethanol to obtain a pre-dispersion liquid, and then the pre-dispersion liquid is added into a solution of nickel acetate and phenanthroline.
Preferably, the concentration of nickel acetate in the dispersion liquid obtained in the step (4) is 0.02-0.03 mol/L.
Preferably, in the step (4), during the impregnation reaction, stirring the dispersion liquid in an oil bath at 55-65 ℃ for 5-8 hours; and then raising the temperature of the oil bath to 75-80 ℃, and preserving the heat until the ethanol is completely volatilized.
Preferably, the calcination temperature in the step (5) is 400-500 ℃ and the calcination time is 3-5 h.
The invention also provides an application of the finite field ammonia decomposition catalyst prepared by the preparation method in an ammonia decomposition hydrogen production reaction.
Preferably, the temperature of the ammonia decomposition hydrogen production reaction is 500-600 ℃.
Preferably, the limited-area ammonia decomposition catalyst is reduced in the hydrogen atmosphere before the ammonia decomposition hydrogen production reaction, and nickel on the surface of the limited-area ammonia decomposition catalyst is reduced from an oxidation state to a metal state.
Therefore, the invention has the following beneficial effects:
(1) The aluminum potassium sulfate dodecahydrate is used as a raw material, and the aluminum oxide carrier with a corolla-shaped structure is prepared through hydrothermal reaction under certain conditions under the action of a template agent urea, so that the extremely thin petal structure on the surface of the aluminum oxide carrier can effectively prevent migration of active metal particles, and the stability of the catalyst is improved;
(2) When nickel is loaded in a dipping way, the phenanthroline ligand is added, the nickel and the ligand form a coordination compound and then are loaded on the surface of the corolla-shaped alumina carrier, so that smaller nickel metal particles with the particle size of about 2-3 nm can be generated, can be uniformly dispersed and limited between petal-shaped structures of the carrier, is favorable for reducing the reaction temperature, and can have high ammonia decomposition activity under the medium temperature condition of 500-600 ℃.
Drawings
FIG. 1 is an SEM test chart of a crown-shaped alumina carrier prepared in example 1.
FIG. 2 is a TEM test chart of the crown-shaped alumina carrier obtained in example 1.
FIG. 3 is an EDS test chart of the limiting-area ammonia decomposition catalyst prepared in example 1.
Fig. 4 is a graph showing ammonia conversion test curves of the ammonia decomposition catalysts of example 1, example 2 and comparative example 1 at different reaction temperatures.
Fig. 5 is a stability test curve of the ammonia decomposition catalyst in example 1 and comparative example 1.
Detailed Description
The invention is further described below in connection with the following detailed description.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
General examples:
A preparation method of a finite field ammonia decomposition catalyst comprises the following steps:
(1) Dissolving aluminum potassium sulfate dodecahydrate and urea in a molar ratio of 1:1.8-2.2 in deionized water to obtain a reaction solution with the concentration of 0.1-0.2 mol/L of aluminum potassium sulfate dodecahydrate;
(2) Carrying out hydrothermal reaction on the reaction liquid; the hydrothermal reaction temperature is 150-200 ℃ and the reaction time is 2-4 hours;
(3) Drying and calcining the hydrothermal product in the step (2) to obtain a corolla-shaped alumina carrier; the drying temperature is 75-85 ℃ and the drying time is 8-12 hours; the calcination temperature is 550-650 ℃ and the calcination time is 3-5 h;
(4) Dissolving nickel acetate in ethanol, adding phenanthroline, stirring for reacting for 20-40 min, adding a corolla-shaped alumina carrier, and uniformly stirring to obtain a dispersion liquid with the concentration of nickel acetate of 0.02-0.03 mol/L; the molar ratio of the nickel acetate to the phenanthroline is 1:2.5-3.5; the mass ratio of nickel element in the nickel acetate to the corolla-shaped alumina carrier is 5-10:95-90; stirring the dispersion liquid in an oil bath at 55-65 ℃ for 5-8 hours to carry out an impregnation reaction, then raising the temperature of the oil bath to 75-80 ℃, and preserving heat until ethanol is completely volatilized to obtain a precursor;
(5) And (3) calcining the precursor obtained in the step (4) at 400-500 ℃ for 3-5 hours to obtain the finite field ammonia decomposition catalyst.
Example 1:
A preparation method of a finite field ammonia decomposition catalyst comprises the following steps:
(1) 4.74g of aluminum potassium sulfate dodecahydrate (0.01 mol) was dissolved in 80mL of deionized water, and 1.2g of urea (0.02 mol) was added thereto, followed by stirring at room temperature for 30 minutes to obtain a reaction solution;
(2) Transferring the reaction solution into a 100mL reaction kettle, performing hydrothermal synthesis for 3h at 180 ℃, and centrifugally collecting a product;
(3) Drying the hydrothermal product in the step (2) at 80 ℃ for 10 hours, and calcining in a muffle furnace at 600 ℃ for 4 hours to obtain a corolla-shaped alumina carrier; scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) tests were performed thereon, and the results are shown in fig. 1 and 2;
(4) Dissolving 0.212g of Ni (CH 3COO)2•4H2 O in 20mL of ethanol, adding 0.507g of phenanthroline, stirring at room temperature for 30min, adding a pre-dispersion liquid of 0.95g of corolla-shaped alumina carrier in 10mL of ethanol, continuously stirring at room temperature for 60min to obtain a dispersion liquid, transferring the dispersion liquid into an oil bath, stirring at 60 ℃ for 6h for impregnation reaction, then raising the temperature of the oil bath to 75 ℃, and preserving heat until the ethanol is completely volatilized to obtain a precursor;
(5) Placing the precursor obtained in the step (4) in a muffle furnace, and calcining for 4 hours at 450 ℃ to obtain a finite-area ammonia decomposition catalyst with nickel loading of 5 wt%; it was subjected to an energy dispersive x-ray Energy (EDS) test, the results of which are shown in fig. 3.
As can be seen from figures 1 and 2, the alumina carrier prepared by the invention is spherical as a whole, the surface of the alumina carrier is formed into a corolla-shaped structure by interweaving a plurality of flaky alumina, and the thickness of petals is thinner, which is about 5 nm. As can be seen from fig. 3, in the limited-area ammonia decomposition catalyst prepared by the present invention, nickel particles are uniformly distributed on the alumina carrier.
Example 2:
A preparation method of a finite field ammonia decomposition catalyst comprises the following steps:
(1) 4.74g of aluminum potassium sulfate dodecahydrate (0.01 mol) was dissolved in 80mL of deionized water, and 1.2g of urea (0.02 mol) was added thereto, followed by stirring at room temperature for 30 minutes to obtain a reaction solution;
(2) Transferring the reaction solution into a 100mL reaction kettle, performing hydrothermal synthesis for 4 hours at 150 ℃, and centrifugally collecting a product;
(3) Drying the hydrothermal product in the step (2) at 80 ℃ for 10 hours, and calcining in a muffle furnace at 600 ℃ for 4 hours to obtain a corolla-shaped alumina carrier;
(4) Dissolving 0.042g of Ni (CH 3COO)2•4H2 O in 20mL of ethanol, adding 0.103g of phenanthroline, stirring at room temperature for 30min, adding a pre-dispersion of 0.99g of corolla-shaped alumina carrier in 10mL of ethanol, continuing stirring at room temperature for 60min to obtain a dispersion, transferring the dispersion into an oil bath, stirring at 60 ℃ for 6h for impregnation reaction, then heating the oil bath to 75 ℃, and preserving heat until the ethanol is completely volatilized to obtain a precursor;
(5) And (3) placing the precursor obtained in the step (4) in a muffle furnace, and calcining at 450 ℃ for 4 hours to obtain the finite field ammonia decomposition catalyst with the nickel loading of 1 wt%.
Comparative example 1:
the difference between comparative example 1 and example 1 is that the carrier adopts commercial alumina (Ara Ding Shiji A102005-100g, particle size 5-6 [ mu ] m); the loading method of nickel was the same as in step (4) and step (5) in example 1.
Comparative example 2 (change of hydrothermal conditions in preparation of alumina carrier):
comparative example 2 differs from example 1 in that the hydrothermal reaction time in step (2) was 15h, and the rest was the same as in example 1.
Comparative example 3 (varying the amount of ligand used in the preparation of the alumina support):
comparative example 3 differs from example 1 in that in step (1), 4.74g of aluminum potassium sulfate dodecahydrate (0.01 mol) was dissolved in 80mL of deionized water, and 2.4g of urea (0.04 mol) was added, and stirred at room temperature for 30min to obtain a reaction solution; the remainder was the same as in example 1.
Comparative example 4 (changing the ligand species at the time of alumina support preparation):
Comparative example 4 was different from example 1 in that in step (1), 4.74g of aluminum potassium sulfate dodecahydrate (0.01 mol) was dissolved in 80mL of deionized water, and 3.6g of glucose (0.02 mol) was added thereto, and stirred at room temperature for 30 minutes to obtain a reaction solution; the remainder was the same as in example 1.
Comparative example 5 (no phenanthroline ligand added during immersion):
comparative example 5 differs from example 1 in that no phenanthroline is added in step (4), and the remainder is the same as in example 1.
Application example:
The ammonia decomposition catalysts prepared in the above examples and comparative examples were applied to an ammonia decomposition hydrogen production reaction, and their catalytic ammonia decomposition activities and stabilities were tested, and the results are shown in fig. 4 and 5 and tables 1 and 2.
The reaction is carried out in a fixed bed reactor, and a catalyst is placed in the middle of a reaction tube and is placed in a vertical tube furnace; before the reaction starts, the catalyst is reduced in the hydrogen atmosphere, and the metal is reduced from an oxidized state to a metal state; then, the activity of the catalyst under different conditions is researched by changing different temperatures and ammonia gas flow rates; the resulting tail gas was analyzed by gas chromatography (Gas Chromatography, GC) equipped with a Porapak Q packed column and thermal conductivity detector (Thermal Conductivity Detector, TCD) and unreacted ammonia was quantified by an internal standard method (argon as internal standard), thereby calculating the conversion of ammonia as follows:
。
Table 1: catalytic Activity test results
Table 2: catalyst stability test results
As can be seen from fig. 4 and table 1, the catalysts of examples 1,2 and comparative example 1 were almost inert at low temperatures of 300 ℃ at a space velocity (GHSV) of 30000 mL g -1h-1, with very low ammonia conversion (< 5%); on the other hand, it was also clearly found that the ammonia conversion rates of the catalysts of examples 1,2 and comparative example 1 all exhibited a phenomenon of increasing with increasing temperature, which corresponds to the strong endothermic characteristic of the ammonia decomposition reaction. When the temperature reaches 550 ℃, the ammonia conversion rate of the nickel catalyst with the loading capacity of 5% prepared in the embodiment 1 reaches 100%, the complete ammonia conversion is realized, the ammonia conversion rate of the nickel catalyst with the loading capacity of 1% in the embodiment 2 is also higher and reaches 90.9%, and the ammonia conversion rate of the catalyst loaded by the traditional alumina in the comparative embodiment 1 is only 61.5%; the ammonia conversion rate of the blank test of the corolla-shaped alumina carrier without nickel load is only 7.5%; illustrating that the catalyst of the present invention can achieve complete conversion of ammonia at lower temperatures. Furthermore, as can be seen from Table 1, the catalyst prepared by the method of the present invention in example 1 can maintain complete conversion of ammonia at a space velocity as high as 35000 mL g -1h-1, and the ammonia conversion rate can still reach 82.1% even when the space velocity is raised to 50000 mL g -1h-1. In contrast, the space velocity increased from 30000 mL g -1h-1 to 50000 mL g -1h-1 and the ammonia conversion of the catalyst of comparative example 1 using conventional alumina as the support decreased from 61.5% to 40.6%. It is apparent that the catalyst prepared by using the corolla-shaped alumina as a carrier in the present invention has higher activity than the catalyst using the conventional alumina as a carrier. And as can be seen from fig. 5 and table 2, the catalyst prepared in example 1 of the present invention has ammonia conversion rate substantially stabilized at 100% at a space velocity of 30000 mL g -1h-1 and 100h, and ammonia conversion rate in 100h is almost unchanged at a high space velocity of 40000 mL g -1h-1; the catalyst of comparative example 1 was severely deactivated after 100 hours of operation under the same conditions, and the ammonia conversion was significantly reduced. The invention shows that the nickel particles have high stability even under severe reaction conditions by the limiting action of the corolla-shaped alumina carrier on the nickel active particles.
However, in comparative example 2, the hydrothermal reaction conditions were changed during the preparation of the alumina carrier, and the hydrothermal reaction time was too long, which resulted in excessive growth of alumina crystals, occurrence of alumina hollowness, and excessive crystal grains, reduced the specific surface area of the carrier, and no limitation of nickel particles was performed, thereby resulting in a significant decrease in the catalytic activity and stability of the catalyst compared with that in example 1.
The excessive amount of the template added in the preparation of the alumina carrier in comparative example 3 resulted in overgrowth of crystals, reduced specific surface area of the carrier and lost the corolla-like structure, resulting in a significant decrease in catalytic activity and stability of the catalyst as compared with that in example 1.
In comparative example 4, glucose was used as a template agent instead of urea, and glucose molecules were much larger than urea, and thus, alumina carriers having a corolla structure according to the present invention could not be produced, and effective confinement of nickel particles could not be achieved, and the stability and catalytic activity of the catalyst were reduced as compared with those in example 1.
In comparative example 5, no phenanthroline ligand is added when Ni is loaded, the particle size of nickel particles formed on the surface of a carrier is increased, and the catalytic activity of the catalyst is reduced compared with that in example 1; meanwhile, larger nickel particles are not beneficial to limiting the range through petal-shaped structures, and the stability of the catalyst is also reduced.
Claims (10)
1. The preparation method of the finite field ammonia decomposition catalyst is characterized by comprising the following steps:
(1) Dissolving aluminum potassium sulfate dodecahydrate and urea in a molar ratio of 1:1.8-2.2 in deionized water to obtain a reaction solution with the concentration of 0.1-0.2 mol/L of aluminum potassium sulfate dodecahydrate;
(2) Carrying out hydrothermal reaction on the reaction liquid; the hydrothermal reaction temperature is 150-200 ℃ and the reaction time is 2-4 hours;
(3) Drying and calcining the hydrothermal product in the step (2) to obtain a corolla-shaped alumina carrier; the calcination temperature is 550-650 ℃ and the calcination time is 3-5 h;
(4) Dissolving nickel acetate in ethanol, adding phenanthroline, stirring for reaction, adding a corolla-shaped alumina carrier, and stirring uniformly to obtain a dispersion; removing ethanol in the dispersion liquid after the impregnation reaction to obtain a precursor;
(5) Calcining the precursor obtained in the step (4) to obtain the finite field ammonia decomposition catalyst.
2. The preparation method according to claim 1, wherein the drying temperature in the step (3) is 75-85 ℃ and the drying time is 8-12 hours.
3. The preparation method of claim 1, wherein the mass ratio of nickel element in nickel acetate to the corolla-shaped alumina carrier in the step (4) is 5-10:95-90.
4. The preparation method of claim 1 or 3, wherein in the step (4), the molar ratio of nickel acetate to phenanthroline is 1:2.5-3.5, and the stirring reaction time is 20-40 min.
5. The method according to claim 1 or 3, wherein the concentration of nickel acetate in the dispersion obtained in the step (4) is 0.02 to 0.03mol/L.
6. The preparation method according to claim 1, wherein in the step (4), the dispersion liquid is stirred in an oil bath at 55-65 ℃ for 5-8 hours during the impregnation reaction; and then raising the temperature of the oil bath to 75-80 ℃, and preserving the heat until the ethanol is completely volatilized.
7. The preparation method according to claim 1, wherein the calcination temperature in the step (5) is 400-500 ℃ and the calcination time is 3-5 hours.
8. Use of a finite field ammonia decomposition catalyst prepared by the preparation method of any one of claims 1-7 in an ammonia decomposition hydrogen production reaction.
9. The use according to claim 8, wherein the temperature of the ammonia decomposition hydrogen production reaction is 500-600 ℃.
10. The use according to claim 8, wherein the finite ammonia decomposition catalyst is reduced in a hydrogen atmosphere prior to the ammonia decomposition hydrogen production reaction.
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Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1717279A (en) * | 2002-11-20 | 2006-01-04 | 埃克森美孚研究工程公司 | Hydrogenation catalyst, preparation thereof and hydrogenation processes using this catalyst |
DE102008055914A1 (en) * | 2008-11-05 | 2010-05-06 | Clariant International Limited | A process for the preparation of mono-hydroxy-functionalized dialkylphosphinic acids, esters and salts by means of acroleins and their use |
CN104709932A (en) * | 2015-02-13 | 2015-06-17 | 上海交通大学 | Gamma-aluminium oxide nanometer material and preparation method of nickel/gamma-aluminium oxide catalyst |
CN104707614A (en) * | 2015-02-13 | 2015-06-17 | 上海交通大学 | Nickel/gamma-aluminum oxide nano catalyst and synthesis method thereof |
KR20160073061A (en) * | 2014-12-16 | 2016-06-24 | 서울대학교산학협력단 | A nickel catalyst chemically immobilized on mesoporous alumina support, preparation method thereof and production method of hydrogen gas by steam reforming of liquefied natural gas using said catalyst |
CN106955709A (en) * | 2017-01-13 | 2017-07-18 | 北京化工大学 | A kind of preparation method of three-dimensional flower-shaped load type double-metal cupro-nickel nanocatalyst |
CN107159212A (en) * | 2017-05-08 | 2017-09-15 | 上海大学 | Nano-metal particle is carried on the preparation method of mesoporous gamma-alumina composite |
CN107321352A (en) * | 2017-07-19 | 2017-11-07 | 武汉凯迪工程技术研究总院有限公司 | Ni-based reforming catalyst of recirculating fluidized bed and its preparation method and application |
CN108295837A (en) * | 2017-12-20 | 2018-07-20 | 湖南大学 | The preparation method of the Mo/ titanium pillared montmorillonite catalyst of dibenzothiophenes in a kind of removal oil product |
CN210088870U (en) * | 2019-04-23 | 2020-02-18 | 武汉天和技术股份有限公司 | Plasma non-metal material melting device capable of continuously feeding and discharging materials |
WO2020083854A1 (en) * | 2018-10-26 | 2020-04-30 | Universiteit Antwerpen | Ammonia deposition precipitation process for producing a copper-nickel/gamma-alumina catalyst, said catalyst and its use in the conversion of exhaust gases |
CN113198476A (en) * | 2021-04-09 | 2021-08-03 | 东南大学 | Transition metal doped ammonia decomposition catalyst and preparation method and application thereof |
CN113578326A (en) * | 2021-08-18 | 2021-11-02 | 哈尔滨工业大学(深圳) | SiO2Ni-loaded double-layer core-shell catalyst and preparation method and application thereof |
CN113663707A (en) * | 2021-08-13 | 2021-11-19 | 中山大学 | Method for macro-preparation of multiple formaldehyde decomposition catalysts |
WO2023090776A1 (en) * | 2021-11-18 | 2023-05-25 | 희성촉매 주식회사 | Method for preparing catalyst for steam reforming of sulfur-containing methane gas, and method for preparing hydrogen by using same |
CN116786126A (en) * | 2023-06-19 | 2023-09-22 | 华东理工大学 | Nickel-silicon catalyst applied to ammonia decomposition and preparation method thereof |
CN117025447A (en) * | 2023-07-07 | 2023-11-10 | 中国科学院过程工程研究所 | Municipal sludge functionalized iron-based material coupled iron-dissimilatory reduction bacteria system construction and heavy metal passivation method and application thereof |
-
2023
- 2023-12-15 CN CN202311724206.4A patent/CN117399014B/en active Active
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1717279A (en) * | 2002-11-20 | 2006-01-04 | 埃克森美孚研究工程公司 | Hydrogenation catalyst, preparation thereof and hydrogenation processes using this catalyst |
DE102008055914A1 (en) * | 2008-11-05 | 2010-05-06 | Clariant International Limited | A process for the preparation of mono-hydroxy-functionalized dialkylphosphinic acids, esters and salts by means of acroleins and their use |
KR20160073061A (en) * | 2014-12-16 | 2016-06-24 | 서울대학교산학협력단 | A nickel catalyst chemically immobilized on mesoporous alumina support, preparation method thereof and production method of hydrogen gas by steam reforming of liquefied natural gas using said catalyst |
CN104709932A (en) * | 2015-02-13 | 2015-06-17 | 上海交通大学 | Gamma-aluminium oxide nanometer material and preparation method of nickel/gamma-aluminium oxide catalyst |
CN104707614A (en) * | 2015-02-13 | 2015-06-17 | 上海交通大学 | Nickel/gamma-aluminum oxide nano catalyst and synthesis method thereof |
CN106955709A (en) * | 2017-01-13 | 2017-07-18 | 北京化工大学 | A kind of preparation method of three-dimensional flower-shaped load type double-metal cupro-nickel nanocatalyst |
CN107159212A (en) * | 2017-05-08 | 2017-09-15 | 上海大学 | Nano-metal particle is carried on the preparation method of mesoporous gamma-alumina composite |
CN107321352A (en) * | 2017-07-19 | 2017-11-07 | 武汉凯迪工程技术研究总院有限公司 | Ni-based reforming catalyst of recirculating fluidized bed and its preparation method and application |
CN108295837A (en) * | 2017-12-20 | 2018-07-20 | 湖南大学 | The preparation method of the Mo/ titanium pillared montmorillonite catalyst of dibenzothiophenes in a kind of removal oil product |
WO2020083854A1 (en) * | 2018-10-26 | 2020-04-30 | Universiteit Antwerpen | Ammonia deposition precipitation process for producing a copper-nickel/gamma-alumina catalyst, said catalyst and its use in the conversion of exhaust gases |
CN210088870U (en) * | 2019-04-23 | 2020-02-18 | 武汉天和技术股份有限公司 | Plasma non-metal material melting device capable of continuously feeding and discharging materials |
CN113198476A (en) * | 2021-04-09 | 2021-08-03 | 东南大学 | Transition metal doped ammonia decomposition catalyst and preparation method and application thereof |
CN113663707A (en) * | 2021-08-13 | 2021-11-19 | 中山大学 | Method for macro-preparation of multiple formaldehyde decomposition catalysts |
CN113578326A (en) * | 2021-08-18 | 2021-11-02 | 哈尔滨工业大学(深圳) | SiO2Ni-loaded double-layer core-shell catalyst and preparation method and application thereof |
WO2023090776A1 (en) * | 2021-11-18 | 2023-05-25 | 희성촉매 주식회사 | Method for preparing catalyst for steam reforming of sulfur-containing methane gas, and method for preparing hydrogen by using same |
CN116786126A (en) * | 2023-06-19 | 2023-09-22 | 华东理工大学 | Nickel-silicon catalyst applied to ammonia decomposition and preparation method thereof |
CN117025447A (en) * | 2023-07-07 | 2023-11-10 | 中国科学院过程工程研究所 | Municipal sludge functionalized iron-based material coupled iron-dissimilatory reduction bacteria system construction and heavy metal passivation method and application thereof |
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