CN115814799A - Non-noble metal catalyst for preparing hydrogen by ammonolysis and preparation method and application thereof - Google Patents
Non-noble metal catalyst for preparing hydrogen by ammonolysis and preparation method and application thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000005915 ammonolysis reaction Methods 0.000 title claims abstract description 32
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 106
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 51
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 238000000197 pyrolysis Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 11
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
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- 238000003756 stirring Methods 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 239000011543 agarose gel Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
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- 238000006555 catalytic reaction Methods 0.000 description 6
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 239000012614 Q-Sepharose Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention discloses a non-noble metal catalyst for hydrogen production by ammonia pyrolysis and a preparation method and application thereof. The catalyst comprises a foam nickel framework, and carbonized agarose and nano metal cobalt loaded on the foam nickel framework. The preparation method comprises the following steps: mixing agarose and cobalt acetate in a solvent, heating and stirring to obtain a cobalt ion dispersed agarose solution; immersing foamed nickel in a cobalt ion dispersed agarose solution, then placing the solution in a negative pressure environment for standing, taking the solution out for solidification at normal temperature, and calcining the solution in an inert atmosphere after freeze drying to obtain the non-noble metal catalyst for hydrogen production by ammonolysis. The catalyst has the advantages that the metal cobalt is uniformly dispersed on the foam nickel, the catalytic activity of the catalyst for ammonia pyrolysis hydrogen production is improved under the synergistic effect of the cobalt and the nickel, the use of noble metal is avoided while the catalytic effect is ensured, the cost of the catalyst is greatly reduced, the structural strength of the catalyst is endowed by the foam nickel, the catalyst is more convenient to use, and the catalyst has wide application prospect.
Description
Technical Field
The invention relates to the technical field of ammonia decomposition, in particular to a catalyst for hydrogen production by ammonia pyrolysis and a preparation method and application thereof.
Background
With the continuous development of economy and science and technology, the social demand for energy is continuously increased, and an ideal alternative energy source is urgently needed. The hydrogen has the characteristics of extremely high mass energy density, zero carbon emission and the like, and is considered as the most ideal renewable energy source. However, the industrialization of hydrogen energy is hindered due to the safety problems of flammability and explosiveness, high storage and transportation cost and the like. Therefore, there is a critical need for a low cost, safe and reliable source of hydrogen. Ammonia (NH) 3 ) The hydrogen-containing catalyst contains 17wt.% of hydrogen, can be liquefied under mild conditions, and is a good hydrogen energy storage and transportation carrier. And the ammonia is used as an important industrial and agricultural raw material and has complete supporting facilities for production, storage, transportation and the like. The hydrogen production technology by ammonia pyrolysis and the high hydrogen content of ammonia gas are an effective way for solving the problems of hydrogen storage, transportation and the like. Because the reaction of the ammonolysis hydrogen production has low conversion rate under the condition of simple heating, a catalyst is generally adopted for reaction catalysis. However, the conventional catalyst for producing hydrogen by pyrolyzing ammonia has several disadvantages that limit its large-scale application: (1) high-efficiency catalysts represented by ruthenium are expensive; (2) The single non-noble metal catalyst has low activity, resulting in high complete conversion temperature and low conversion efficiency.
Therefore, the development of a high-performance low-cost non-noble metal catalytic system and an efficient and low-energy-consumption ammonia synthesis and pyrolysis technology has important scientific significance and practical application value for promoting low-cost hydrogen storage and transportation.
Disclosure of Invention
The invention aims to provide a non-noble metal catalyst for hydrogen production by ammonia pyrolysis as well as a preparation method and application thereof.
Provides a non-noble metal catalyst for hydrogen production by ammonia pyrolysis, which comprises a foam nickel framework, and carbonized agarose and nano metal cobalt loaded on the foam nickel framework.
According to the scheme, the catalyst is prepared by soaking foamed nickel in a cobalt ion dispersed agarose solution, solidifying into gel, freeze-drying and calcining.
The preparation method of the non-noble metal catalyst for hydrogen production by ammonolysis comprises the following steps:
1) Mixing agarose and cobalt acetate in a solvent, heating and stirring to obtain a cobalt ion dispersed agarose solution;
2) Immersing the pretreated foamed nickel in the cobalt ion dispersed agarose solution obtained in the step 1), and then putting the solution into a negative pressure environment for standing so that the solution is fully immersed in the foamed nickel and bubbles in the solution are removed; taking out and solidifying at normal temperature to obtain gel with foamed nickel as skeleton;
3) Freezing and drying the gel with the foamed nickel as the skeleton obtained in the step 2), and calcining the gel in an inert atmosphere to obtain the non-noble metal catalyst (Co-C @ NF) for hydrogen production by ammonia pyrolysis; wherein the calcination temperature is 550-650 ℃.
According to the scheme, in the step 1), the agarose is agarose powder or agarose gel.
Preferably, the agarose powder is at least one of standard agarose, low-melting agarose, low-electroosmosis agarose and the like; the sepharose is at least one of DEAE-sepharose and Q-sepharose.
According to the scheme, in the step 1), the mass ratio of the agarose to the cobalt acetate is 70:1 to 4. Preferably 70:2 to 4; more preferably 70:3 to 4.
According to the scheme, in the step 1), the mass ratio of the cobalt acetate to the solvent is 1-4: 1000.
according to the scheme, in the step 1), the solvent is deionized water.
According to the scheme, in the step 1), the heating temperature is 50-200 ℃, and the time is 0.5-2 h; preferably, the heating temperature is 80-110 ℃, and the time is 0.8-1.5 h; more preferably, the heating temperature is 90-100 ℃ and the reaction time is 0.9-1.1 h.
According to the scheme, in the step 2), the pretreatment process of the foamed nickel comprises the following steps: immersing the foamed nickel in 2-3mol/L HCl for ultrasonic treatment for 20-30min, immersing in ethanol for ultrasonic treatment for 8-10min after the ultrasonic treatment is finished, and immersing in deionized water for ultrasonic treatment for 8-10min after the ultrasonic treatment is finished.
According to the scheme, in the step 2), the negative pressure environment is as follows: the temperature is 50-100 ℃; vacuumizing to make the pressure between 0.02MPa and 0.09MPa, and keeping the pressure for 1 to 30min. Preferably, the temperature is 65-75 ℃, the pressure is 0.05-0.06 MPa, and the holding time is 10-15 min.
According to the scheme, in the step 3), the freeze drying time is 20-40 h.
According to the scheme, in the step 3), the inert gas is nitrogen, helium, neon or argon.
According to the scheme, in the step 3), the calcining temperature is 580-620 ℃.
According to the scheme, in the step 3), the calcination time is 1-2.5h; preferably 1.5-2.5h.
The application of the non-noble metal catalyst for hydrogen production by ammonia pyrolysis is provided, and specifically comprises the following steps: the catalyst is used for ammonia conversion catalysis and catalytic ammonia pyrolysis hydrogen production.
According to the scheme, the catalytic temperature is 520-580 ℃, and the space velocity is 5500-6500h -1 The conversion catalytic efficiency of ammonia gas is 90% or more in the state of (1). Wherein space velocity refers to the amount of feedstock processed per unit of catalyst per unit of time.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a non-noble metal catalyst for hydrogen production by ammonia pyrolysis, wherein agarose is used for loading non-noble metal cobalt on foam Nickel (NF), the cobalt is uniformly dispersed on the foam nickel, the catalytic activity of the catalyst for hydrogen production by ammonia pyrolysis is improved by the synergistic action of the cobalt and the nickel, and the catalytic efficiency can reach more than 90% when the catalyst is used for ammonia conversion catalysis; meanwhile, the structure of the foamed nickel has certain strength, so that the structural strength of the catalyst can be improved, and the use is more convenient; the catalyst provided by the invention avoids the use of noble metals while ensuring the catalytic effect, greatly reduces the cost of the catalyst, and has a wide application prospect.
2. The invention provides a preparation method of a non-noble metal catalyst for hydrogen production by ammonia pyrolysis, which is prepared by soaking foamed nickel in a cobalt ion dispersed agarose solution, solidifying the solution into gel, freeze-drying and calcining, wherein the agarose is used as a medium to realize uniform dispersion of metal cobalt on the foamed nickel, and the preparation method has the advantages of simple preparation process, convenient operation, no toxic hazard in the whole reaction process, environmental friendliness and easy large-scale and large-area production.
Drawings
FIG. 1 is an SEM photograph of Co-C @ NF prepared in example 1 of the present invention.
FIG. 2 is an XPS plot of Co-C @ NF prepared in example 1 of the present invention.
FIG. 3 is a graph of the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in examples 1-3 of the present invention at different temperatures.
FIG. 4 is a graph of the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in examples 1 and 4 to 5 of the present invention at different temperatures.
FIG. 5 is a graph showing the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in example 1 of the present invention and comparative examples 1-2 at different temperatures.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The ammonia conversion catalysis efficiency testing method of the ammonia pyrolysis hydrogen production catalyst comprises the following steps: the performance test of the catalyst for preparing hydrogen by pyrolyzing ammonia is carried out in a fixed bed reactor. The mass flow meter is adopted to control the gas flow, the gas chromatograph is used to detect and analyze the gas concentration, and argon is used as carrier gas. The reaction temperature is controlled by an automatic temperature controller, the reaction temperature is set to be 550 ℃, the heating rate is 10K/min, and the airspeed is 6000h -1 . Foaming nickelThe catalyst is loaded into the quartz tube and the quartz tube is mounted at the corresponding position of the detector. Reducing for 2h at 773K in Ar gas of 10mL/min at constant temperature, then cooling to 573K, purging the catalyst with ammonia gas to reduce the temperature to room temperature, and increasing the temperature to the set temperature at the rate of 25K/min. Ammonia conversion catalytic efficiency = (initial ammonia content-treated ammonia content)/initial ammonia content 100%.
Example 1
A preparation method of a catalyst for preparing hydrogen by ammonolysis of a supported cobalt foam nickel material comprises the following steps:
(1) Dispersing 7g of standard agarose powder and 0.3g of cobalt acetate in 100mL of deionized water, placing the mixture in a water bath kettle, heating and stirring the mixture at 90 ℃ for 1 hour, and preparing a cobalt ion dispersed agarose solution (colloidal pink solution) after the reaction is finished;
(2) Pretreating foamed nickel, specifically: immersing the foamed nickel in 3M HCl for ultrasonic treatment for 30min, immersing in ethanol for ultrasonic treatment for 10min after the ultrasonic treatment is finished, and immersing in deionized water for ultrasonic treatment for 10min after the ultrasonic treatment is finished. Immersing the pretreated foamed nickel in the cobalt ion dispersed agarose solution in the step (1), placing the solution in a vacuum drying oven with the internal temperature of 70 ℃, vacuumizing the vacuum drying oven until the pressure is 0.05MPa, keeping the pressure for 10min, then quickly boosting the pressure to the atmospheric pressure, opening the vacuum drying oven, taking out the sample, placing the sample at normal temperature, and cooling the sample to obtain gel taking the foamed nickel as a framework;
(3) And (3) sealing and punching a preservative film for a container containing the gel, putting the container into a prepared freeze dryer, vacuumizing to below 50Pa, and operating for 24 hours.
(4) And calcining the gel in a tubular furnace in the atmosphere of argon, heating to 600 ℃ at the heating rate of 3 ℃ per minute, preserving the heat at the temperature for two hours, and naturally cooling after the heat preservation is finished to obtain the catalyst (Co-C @ NF) for the hydrogen production by ammonia pyrolysis of the supported cobalt foam nickel material.
Through ammonia conversion catalysis efficiency test of the catalyst for preparing hydrogen by ammonia pyrolysis, the ammonia conversion catalysis efficiency of the catalyst for preparing hydrogen by ammonia pyrolysis prepared in example 1 is 95% at 550 ℃.
FIG. 1 is an SEM photograph of Co-C @ NF obtained in example 1 of the present invention; it can be seen from the figure that the carbonized agarose is wrapped on the nickel foam.
FIG. 2 is an XPS plot of Co-C @ NF prepared in example 1 of the present invention; it can be seen from the figure that cobalt was successfully doped on the nickel foam.
Example 2
Example 2 differs from example 1 in that: the amount of cobalt acetate added in step (1) was 0.4g.
The ammonia conversion catalytic efficiency test of the catalyst for preparing hydrogen by ammonolysis shows that the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in example 2 at 550 ℃ is 93%.
Example 3
Example 3 differs from example 1 in that: the amount of cobalt acetate added in step (1) was 0.2g.
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in example 3 at 550 ℃ is 90%.
Example 4
Example 4 differs from example 1 in that: the calcination temperature used in step (4) was 550 ℃.
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in example 4 at 550 ℃ is 92%.
Example 5
Example 5 differs from example 1 in that: the calcination temperature used in step (4) was 650 ℃.
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in example 5 at 550 ℃ is 90%.
FIG. 3 is a graph of the ammonia pyrolysis conversion efficiency of the catalyst for hydrogen production by ammonia pyrolysis prepared in examples 1-3 of the present invention at different temperatures, wherein the abscissa is the Reaction temperature (deg.C) and the ordinate is the ammonia gas conversion catalytic efficiency (NH) 3 conversion,%); the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis of examples 1-3 at 550 ℃ is above 90%, wherein the mass of the cobalt acetate added in the step (1) of example 2 is 0.4g, the amount of Co is large, and part of the cobalt acetate existsAgglomeration phenomenon, and the catalytic efficiency of the obtained catalyst is reduced compared with that of the catalyst in the example 1; in example 3, the mass of the cobalt acetate added in the step (1) is 0.2g, the Co loading amount in example 2 is small, and the overall activity of the catalyst is reduced.
FIG. 4 is a graph of the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in examples 1 and 4 to 5 of the present invention at different temperatures, with the abscissa representing the Reaction temperature (Reaction temperature)%, and the ordinate representing the catalytic efficiency for ammonia conversion (NH) 3 conversion, deg.C); example 4 calcining at 550 ℃, the temperature is slightly low, the agarose is not carbonized completely, the cobalt sites are not exposed completely, and the catalytic activity is reduced to some extent; example 5 calcination at 650 c, a slightly higher temperature, resulted in excessive carbonization causing partial cobalt agglomeration, reduction of active sites and a decrease in catalytic activity.
Comparative example 1
Comparative example 1 differs from example 1 in that: in the step (1), the non-noble metal salt adopts ferric acetate.
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in the comparative example 1 at 550 ℃ is 85 percent.
Comparative example 2
Comparative example 2 differs from example 1 in that: in the step (1), copper acetate is used as the non-noble metal salt.
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in the comparative example 2 at 550 ℃ is 81 percent.
FIG. 5 is a graph of the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in example 1 and comparative examples 1-2 of the present invention at different temperatures, with the abscissa representing the Reaction temperature (percent) and the ordinate representing the catalytic efficiency for ammonia conversion (NH) 3 conversion, deg.C); comparative examples 1 and 2, which used iron acetate and copper acetate as non-noble metal salts, had poor catalytic efficiency compared to example 1 due to poor dissociation of ammonia at the surface atoms of iron and copper.
Claims (10)
1. The catalyst for preparing hydrogen by ammonolysis of non-noble metal is characterized by comprising a foamed nickel framework, and carbonized agarose and nano-metal cobalt loaded on the foamed nickel framework.
2. The catalyst according to claim 1, wherein the catalyst is prepared by soaking foamed nickel in a cobalt ion dispersed agarose solution, solidifying the foamed nickel into gel, freeze-drying and calcining.
3. A method for preparing a non-noble metal catalyst for hydrogen production by ammonolysis according to any of claims 1 to 2, comprising the steps of:
1) Mixing agarose and cobalt acetate in a solvent, heating and stirring to obtain a cobalt ion dispersed agarose solution;
2) Immersing the pretreated foamed nickel in the cobalt ion dispersed agarose solution obtained in the step 1), and then placing the solution in a negative pressure environment for standing to enable the solution to be fully immersed in the foamed nickel and remove bubbles in the solution; taking out and solidifying at normal temperature to obtain gel with foamed nickel as skeleton;
3) Freezing and drying the gel with the foamed nickel as the skeleton obtained in the step 2), and calcining the gel in an inert atmosphere to obtain the non-noble metal catalyst for hydrogen production by ammonia pyrolysis; wherein the calcination temperature is 550-650 ℃.
4. The method according to claim 3, wherein in the step 1), the agarose is agarose powder or agarose gel; the solvent is deionized water.
5. The preparation method according to claim 3, wherein the mass ratio of agarose to cobalt acetate in step 1) is 70:1 to 4; the mass ratio of the cobalt acetate to the solvent is 1-4: 1000.
6. the preparation method according to claim 3, wherein the heating temperature in step 1) is 50 to 200 ℃ and the time is 0.5 to 2 hours.
7. The preparation method according to claim 3, wherein in the step 2), the negative pressure environment is: the temperature is 50-100 ℃; vacuumizing to make the pressure between 0.02MPa and 0.09MPa, and keeping the pressure for 1 to 30min.
8. The preparation method according to claim 3, wherein in the step 3), the freeze-drying time is 20 to 40 hours; the calcination time is 1-2.5h.
9. The application of the non-noble metal catalyst for hydrogen production by ammonia pyrolysis as recited in any one of claims 1-2, is characterized in that: is used for catalyzing the ammonolysis to prepare hydrogen.
10. The use of claim 9, wherein the catalytic temperature is 520-580 ℃ and the space velocity is 5500-6500h -1 。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211436324.0A CN115814799B (en) | 2022-11-16 | 2022-11-16 | Non-noble metal catalyst for preparing hydrogen by ammonia pyrolysis and preparation method and application thereof |
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| CN202211436324.0A CN115814799B (en) | 2022-11-16 | 2022-11-16 | Non-noble metal catalyst for preparing hydrogen by ammonia pyrolysis and preparation method and application thereof |
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| CN115814799A true CN115814799A (en) | 2023-03-21 |
| CN115814799B CN115814799B (en) | 2024-08-20 |
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