CN113351204A - Graphene composite material ammonia-hydrogen conversion catalyst and preparation method thereof - Google Patents
Graphene composite material ammonia-hydrogen conversion catalyst and preparation method thereof Download PDFInfo
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- CN113351204A CN113351204A CN202110779371.4A CN202110779371A CN113351204A CN 113351204 A CN113351204 A CN 113351204A CN 202110779371 A CN202110779371 A CN 202110779371A CN 113351204 A CN113351204 A CN 113351204A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 105
- 239000001257 hydrogen Substances 0.000 title claims abstract description 99
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 15
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
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- 150000004681 metal hydrides Chemical class 0.000 claims description 19
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- -1 oxygen ions Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 229910001422 barium ion Inorganic materials 0.000 claims description 4
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 4
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 14
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 229910052742 iron Inorganic materials 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
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- 230000008859 change Effects 0.000 description 3
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- 239000012495 reaction gas Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910019841 Ru—Al2O3 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
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- 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
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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Abstract
The invention belongs to the technical field of ammonia-hydrogen conversion, and particularly relates to a graphene composite material ammonia-hydrogen conversion catalyst and a preparation method thereof. The graphene composite material ammonia-hydrogen conversion catalyst comprises graphene composite oxyhydroxide, and a metal-based graphene composite oxyhydroxide with catalytic activity is obtained by introducing a metal compound solution with ammonia synthesis activity. The graphene composite material ammonia-hydrogen conversion catalyst prepared by the invention has higher decomposition activity than metal oxides, reduces the use amount of Ru, Fe, Co and Ni catalysts and other metal loads, thereby reducing the cost of the synthetic ammonia catalyst, designs and realizes the ammonia-hydrogen conversion catalyst with low metal load, reduces economic benefit and improves the catalytic activity of ammonia-hydrogen conversion.
Description
Technical Field
The invention belongs to the technical field of ammonia-hydrogen conversion, and particularly relates to a graphene composite material ammonia-hydrogen conversion catalyst and a preparation method thereof.
Background
Hydrogen, as a fuel with high reaction characteristics, is considered to be one of the most important green clean energy sources in the future. The hydrogen combustion rate is high, the heat release rate is high, the combustion product is only water, and no carbon dioxide is discharged. The development of new combustion technologies and equipment using hydrogen as fuel has become a breakthrough to alleviate global warming and energy shortage.
Catalytic ammonia decomposition is a very promising zero-carbon hydrogen production scheme. Currently, the ammonia-hydrogen conversion catalyst mainly includes noble metal catalysts, transition metal oxide and nitride catalysts, and the like. The noble metal ruthenium (Ru) is most active for the catalytic conversion of ammonia hydrogen, but its high cost and limited reserves limit its large-scale application. Transition metal (such as Fe, Co, Ni and the like) catalysts are low in price and have good activity, but the catalysts have the problems of unstable structure, easy inactivation caused by easy sintering of active components at high temperature and the like. Therefore, the development of a catalytic material having high activity and high temperature resistance is of great significance.
In view of the above, the invention provides a graphene composite material ammonia-hydrogen conversion catalyst, a preparation method and a hydrogen preparation method, aiming at the traditional Ru (2% -5%, Ru-TiO)2，Ru-ZrO2And Ru-Al2O3,Decomposition rate of ammonia was 10gNH3g-1h-1) Fe (2-3% of Fe remained in commercial carbon nanotube, 2.8g NH could be obtained at 700 deg.C3g-1h-1) Co (2% -5%), Ni (the particle size of which has a direct relation with the ammonia-hydrogen conversion activity, and when Ni particles are loaded on the carbon nano tube, the ammonia-hydrogen conversion catalytic activity superior to that of an activated carbon carrier is also shown, but the catalyst is easy to inactivate in the ammonia-hydrogen conversion state due to the lack of an effective structural stabilizer), the dosage of the catalyst is too large, the dosages of Ru, Fe, Co and Ni catalysts and other metal loads are reduced, the stability of the catalyst is improved, the content of noble metal is reduced, and the graphene composite material ammonia-hydrogen conversion catalyst with low metal load is designed and realized.
Disclosure of Invention
The invention aims to provide a graphene composite material ammonia-hydrogen conversion catalyst and a preparation method thereof aiming at overcoming the defects of the prior art, so that the cost of the ammonia synthesis catalyst is reduced by reducing the use amounts of Ru, Fe and Co and other metal loads, the ammonia-hydrogen conversion catalyst with low metal load is designed and realized, the economic benefit is reduced, and the catalytic activity of ammonia-hydrogen conversion is improved.
In order to solve the technical problems, the following technical scheme is adopted:
the graphene composite material ammonia-hydrogen conversion catalyst comprises graphene composite oxyhydroxide, and a metal-based graphene composite oxyhydroxide with catalytic activity is obtained by introducing a metal compound solution with ammonia synthesis activity.
Further, the graphene composite oxide includes a composite metal oxide containing graphene and a composite metal hydride containing graphene.
Further, the graphene composite metal oxide is prepared from graphene and a metal oxide by a hydrothermal method.
Further, the graphene composite metal hydride is prepared from graphene and a metal hydride by a hydrothermal method.
Further, the preparation method of the graphene comprises the following steps: graphene is obtained by carrying out pyrolysis on graphene oxide and benzene serving as an additional carbon source at the high temperature of 400-600 ℃ in a vacuum reaction furnace under the protection of nitrogen atmosphere.
Further, the metal oxide is Li-bearing+,、Na+,、K+、Mg2+、Ca2+、Sr2+、Ba2+、Ti6+、V6+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Al3+Or Ga3+One or more oxides composed of the above metal ions.
Further, the metal hydride is NaH, KH, MgH2Or CaH2One or more of (a).
Further, the metal compound solution is Ru3(CO)12Solution, Fe (acac)3Solutions or Co (acac)3One or more of the solutions.
The other technical scheme of the invention is as follows: the preparation method of the graphene composite material ammonia-hydrogen conversion catalyst comprises the following steps:
(1) heating graphene, metal oxide and metal hydride in a temperature range of 100-500 ℃ for 72-120 hours in a gas atmosphere filled with nitrogen or argon, and replacing part of oxygen ions in the oxide with hydride ions, wherein the molar ratio of the graphene, the metal oxide and the metal hydride is (0.1-1): (1-1.2): (3-3.5) removing redundant metal oxides to obtain vacuum-dried graphene composite oxyhydroxide powder;
(2) dispersing the prepared graphene composite oxide powder in a metal compound solution with ammonia-hydrogen conversion activity by adopting an impregnation method, and impregnating metal ions in the metal compound solution on the graphene composite oxide and permeating the metal ions into the inner surface of the graphene composite oxide; and after the impregnation balance, removing the solvent in vacuum, collecting the metal-based powder containing the graphene composite oxyhydroxide, and heating the metal-based powder containing the graphene composite oxyhydroxide in a reducing atmosphere to decompose carbonyl compounds under the condition of vacuum sealing to obtain the graphene composite material ammonia-hydrogen conversion catalyst.
The other technical scheme of the invention is as follows: the method for preparing hydrogen by using the graphene composite material ammonia-hydrogen conversion catalyst comprises the following steps:
(1) suspending a graphene composite material ammonia-hydrogen conversion catalyst on a fixed bed in a glass tube of the fixed bed under a normal pressure environment;
(2) the graphene composite material ammonia-hydrogen conversion catalyst is used for carrying out pure ammonia-hydrogen conversion under the conditions of ammonia gas with the flow rate of 50-80 ml/min and the temperature of 100-500 ℃ to obtain decomposed nitrogen and hydrogen.
Due to the adoption of the technical scheme, the method has the following beneficial effects:
the graphene composite material ammonia-hydrogen conversion catalyst prepared by the invention has higher decomposition activity than metal oxide, and aims at the traditional Ru (2% -5%, Ru-TiO)2，Ru-ZrO2And Ru-Al2O3,Decomposition rate of ammonia was 10gNH3g-1h-1) Fe (2-3% of Fe remained in commercial carbon nanotube, 2.8g NH could be obtained at 700 deg.C3g-1h-1) Co (2% -5%), Ni (the particle size has direct relation with the ammonia decomposition activity, when Ni particles are loaded on the carbon nano-tubeThe ammonia decomposition catalytic activity is superior to that of an active carbon carrier, but the catalyst is easy to inactivate in an ammonia decomposition state due to the lack of an effective structural stabilizer), the dosage of the catalyst is too large, the dosages of Ru, Fe, Co and Ni catalysts and other metal loads are reduced, the stability of the catalyst is improved, the dosage of the Ru, Fe, Co and Ni catalysts and other metal loads are reduced aiming at the condition that the dosages of the traditional Ru, Fe, Co and Ni catalysts are too large, so that the cost of the synthetic ammonia catalyst is reduced, the graphene composite material ammonia-hydrogen conversion catalyst with low metal load capacity is designed and realized, the economic benefit is reduced, and the catalytic activity of ammonia-hydrogen conversion is improved.
Drawings
The invention will be further described with reference to the accompanying drawings in which:
FIG. 1 is a flow diagram of a graphene composite ammonia-hydrogen conversion catalyst of the present invention for producing hydrogen;
fig. 2 is an XRD data pattern of the composite graphene oxyhydroxide containing Ba ions, Ca ions and Sc ions according to the present invention.
Fig. 3 is a graph comparing the ammonia-hydrogen conversion of the graphene composite ammonia-hydrogen conversion catalyst containing different metal bases with the temperature change.
Fig. 4 is a TEM image of a precursor of graphene in the present invention.
FIG. 5 is a TEM image of the morphology of the graphene composite ammonia-hydrogen conversion catalyst containing 1% Ru in the invention.
FIG. 6 is a TEM image of the morphology of the graphene composite ammonia-hydrogen conversion catalyst containing 0.5% Ru in the invention.
Fig. 7 is a graph comparing the ammonia conversion rates of the Ru-containing graphene composite ammonia-hydrogen conversion catalyst and the Ru-free graphene composite ammonia-hydrogen conversion catalyst according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
The graphene composite material ammonia-hydrogen conversion catalyst comprises graphene composite oxyhydroxide, and a metal-based graphene composite oxyhydroxide with catalytic activity is obtained by introducing a metal compound solution with ammonia synthesis activity.
The carrier of the ammonia-hydrogen conversion catalyst needs large specific surface area, strong basicity, interaction with metal and the like. The carbon carrier has the characteristics of large specific surface area, good electronic conductivity, abundant surface functional groups and the like. The graphene composite material ammonia-hydrogen conversion catalyst prepared by the application adopts a graphene composite material subjected to high-temperature pretreatment as a carrier, and the graphene composite material is used for constructing surface unsaturated sites by introducing defects, so that the graphene composite material is a very effective strategy for constructing active sites. Localized electrons such as oxygen, nitrogen or sulfur vacancies in the catalyst can enhance the adsorption and activation of ammonia molecules by the catalyst surface. The oxyhydroxide-supported graphene-based metal-based catalyst catalyzes the conversion of ammonia into hydrogen having a higher decomposition activity than the conventional oxide support. Greatly reduces the dosage of Ru, Fe, Co and Ni catalysts and other metal loads, thereby reducing the cost of the ammonia synthesis catalyst, designing and realizing the ammonia-hydrogen conversion catalyst with low metal load, reducing economic benefit and improving the catalytic activity of ammonia-hydrogen conversion.
In addition to the present embodiment, the graphene composite oxyhydroxide includes a compound containing a graphene composite metal oxide and a graphene composite metal hydride.
In addition to this embodiment, the graphene composite metal oxide is prepared from graphene and a metal oxide by a hydrothermal method.
The required graphene is shown in fig. 4, which is a precursor of graphene in the present invention.
In addition to this embodiment, the graphene composite metal hydride is prepared from graphene and a metal hydride by a hydrothermal method.
In addition to this embodiment, the preparation method of the graphene is as follows: graphene is obtained by carrying out pyrolysis on graphene oxide and benzene serving as an additional carbon source at the high temperature of 400-600 ℃ in a vacuum reaction furnace under the protection of nitrogen atmosphere.
In addition to this embodiment, the metal oxide is Li-bearing+,、Na+,、K+、Mg2+、Ca2+、Sr2+、Ba2 +、Ti6+、V6+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Al3+Or Ga3+One or more oxides composed of the above metal ions.
In addition to this embodiment, the metal hydride is NaH, KH, MgH2Or CaH2One or more of (a).
In addition to this example, the metal compound solution was Ru3(CO)12Solution, Fe (acac)3Solutions or Co (acac)3One or more of the solutions.
Referring to fig. 1, a preparation method of a graphene composite material ammonia-hydrogen conversion catalyst includes the following steps:
(1) heating graphene, metal oxide and metal hydride in a temperature range of 100-500 ℃ for 72-120 hours in a gas atmosphere filled with nitrogen or argon, and replacing part of oxygen ions in the oxide with hydride ions, wherein the molar ratio of the graphene, the metal oxide and the metal hydride is (0.1-1): (1-1.2): (3-3.5) removing redundant metal oxides to obtain vacuum-dried graphene composite oxyhydroxide powder;
wherein the excess metal oxide is removed by NH4Cl/methanol (0.1mol/300 ml) was washed to remove excess metal oxide. Due to NH4Cl is a weak acid that helps remove various impurities during the washing process.
The graphene is powder with the particle diameter distribution ranging from 100 nanometers to 200 nanometers.
The gold isThe metal oxide being with Li+,、Na+,、K+、Mg2+、Ca2+、Sr2+、Ba2+、Ti6+、V6+、Cr3+、Mn2+、Fe3 +、Co2+、Ni2+、Cu2+、Zn2+、Al3+Or Ga3+One or more oxides composed of the above metal ions.
The metal hydride is NaH, KH or MgH2Or CaH2One or more of (a).
(2) Dispersing the prepared graphene composite oxide powder in a metal compound solution with ammonia-hydrogen conversion activity by adopting an impregnation method, and impregnating metal ions in the metal compound solution on the graphene composite oxide and permeating the metal ions into the inner surface of the graphene composite oxide; and after the impregnation balance, removing the solvent in vacuum, collecting the metal-based powder containing the graphene composite oxyhydroxide, and heating the metal-based powder containing the graphene composite oxyhydroxide in a reducing atmosphere to decompose carbonyl compounds under the condition of vacuum sealing to obtain the graphene composite material ammonia-hydrogen conversion catalyst. The decomposed carbonyl compound is a metal compound (Ru) remaining in the metal-based powder of graphene complex oxyhydroxide3(CO)12、Fe(acac)3Or Co (acac)3)。
The metal compound solution is Ru3(CO)12Solution, Fe (acac)3Solutions or Co (acac)3One or more of the solutions. Because the Ru group, the Co group and the Fe group are only loaded, the dosage is very small and is 0.1-1% of the original single Ru, Co and Fe used as the catalyst. Thereby achieving the same or even better catalytic activity with a very small amount of Ru3(CO)12Solution, Fe (acac)3Solutions or Co (acac)3The decomposition of ammonia can be achieved by the solution.
Referring to fig. 1, a method for preparing hydrogen by using a graphene composite material ammonia-hydrogen conversion catalyst comprises the following steps:
(1) suspending a graphene composite material ammonia-hydrogen conversion catalyst on a fixed bed in a glass tube of the fixed bed under a normal pressure environment;
(2) the graphene composite material ammonia-hydrogen conversion catalyst is used for carrying out pure ammonia-hydrogen conversion under the conditions of ammonia gas with the flow rate of 50-80 ml/min and the temperature of 100-500 ℃ to obtain decomposed nitrogen and hydrogen. Decomposing nitrogen and hydrogen in a flow H2SO4The solution (25% to remove NH3) was then measured with a flow meter.
The graphene composite material ammonia-hydrogen conversion catalyst prepared by the invention can realize ammonia synthesis under certain conditions, and specifically comprises the following steps:
(1) suspending a graphene composite material synthetic ammonia catalyst in a stainless steel tube and placing the stainless steel tube on a quartz cotton bed;
(2) the graphene composite material ammonia-hydrogen conversion catalyst is under flowing reaction gas, and the reaction gas is N2、H2And Ar with a reaction gas composition of N2:H2Ar 22.5 (67.5-70) (10-12), the temperature is controlled at 300 ℃ and 500 ℃, the catalytic reaction is carried out under the pressure of 0.1 to 5 MPa, the flow rate is 80 to 110 ml/min, the heating reaction is carried out for 2 to 3 hours, stable ammonia gas is formed by the reaction, the efficiency is about 20mmol g-1h-1. The ammonia gas is qualitatively monitored by a mass spectrometer, and NH is monitored by the mass spectrometer3+Or NH2+Can pass through 1.87 multiplied by 10-5M NH4Cl (333mL) and NH3The electrode performs quantization.
The following description will be made by specific examples with respect to the preparation method of the graphene composite material ammonia-hydrogen conversion catalyst, and the yield and efficiency of hydrogen generation. Specific results are shown in table 1:
TABLE 1
As can be seen from examples 1 to 3 and fig. 3, in fig. 3, curves 1,2 and 3 are a Ru-based graphene composite ammonia-hydrogen conversion catalyst, a Co-based graphene composite ammonia-hydrogen conversion catalyst and a Fe-based graphene composite ammonia-hydrogen conversion catalyst, respectively. Using Ru3(CO)12Solution, Fe (acac)3Solutions or Co (acac)3The graphene composite material ammonia-hydrogen conversion catalyst prepared from the solution has almost no difference on the conversion rate of catalyzing ammonia-hydrogen conversion, and is basically stable at 60% conversion rate at 450 ℃.
In fig. 3, the Ru-based graphene composite ammonia-hydrogen conversion catalyst, the Co-based graphene composite ammonia-hydrogen conversion catalyst, and the Fe-based graphene composite ammonia-hydrogen conversion catalyst used are changed according to the temperature change, substantially the same as the conventional noble metal ruthenium (Ru) to ammonia-hydrogen conversion.
From examples 4 to 8, it can be seen that, with the graphene composite material ammonia-hydrogen conversion catalyst of the present application, the conversion rate for catalyzing ammonia-hydrogen conversion changes with the temperature change as the conventional noble metal ruthenium (Ru) to ammonia-hydrogen conversion. Shows that the original single Ru, Co and Fe are used as 0.1-1% of catalyst to prepare Ru3(CO)12Solution, Fe (acac)3Solutions or Co (acac)3Loading Ru groups, Co groups and Fe groups on graphene composite oxyhydroxide powder by using an impregnation method to obtain metal-based powder containing the graphene composite oxyhydroxide, heating and drying to obtain the graphene composite material ammonia-hydrogen conversion catalyst, and adopting a small amount of Ru on the basis of achieving the same or even better catalytic activity3(CO)12Solution, Fe (acac)3Solutions or Co (acac)3The decomposition of ammonia can be achieved by the solution.
Referring to fig. 5, 6 and 7, the ammonia conversion rate of the graphene composite ammonia-hydrogen conversion catalyst containing Ru is improved significantly compared with that of the graphene composite ammonia-hydrogen conversion catalyst containing no Ru when 0.1g of the graphene composite ammonia-hydrogen conversion catalyst is at normal pressure of 200-650 ℃.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the same technical problems and achieve the same technical effects are all covered in the protection scope of the present invention.
Claims (10)
1. The graphene composite material ammonia-hydrogen conversion catalyst is characterized in that: the method comprises the steps of introducing a metal compound solution with ammonia synthesis activity to obtain a metal-based graphene composite oxyhydroxide with catalytic activity.
2. The graphene composite ammonia-hydrogen conversion catalyst according to claim 1, characterized in that: the graphene composite oxide includes a graphene composite metal oxide and a graphene composite metal hydride.
3. The graphene composite ammonia-hydrogen conversion catalyst according to claim 2, characterized in that: the graphene composite metal oxide is prepared from graphene and metal oxide by a hydrothermal method.
4. The graphene composite ammonia-hydrogen conversion catalyst according to claim 2, characterized in that: the graphene composite metal hydride is prepared from graphene and metal hydride by a hydrothermal method.
5. The graphene composite ammonia-hydrogen conversion catalyst according to claim 3 or 4, characterized in that: the preparation method of the graphene comprises the following steps: graphene is obtained by carrying out pyrolysis on graphene oxide and benzene serving as an additional carbon source at the high temperature of 400-600 ℃ in a vacuum reaction furnace under the protection of nitrogen atmosphere.
6. The graphene composite ammonia-hydrogen conversion catalyst according to claim 3, characterized in that: the metal oxide is Li-bearing+、Na+,、K+、Mg2+、Ca2+、Sr2+、Ba2+、Ti6+、V6+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Al3 +Or Ga3+One or more oxides composed of the above metal ions.
7. The graphene composite ammonia-hydrogen conversion catalyst according to claim 4, characterized in that: the metal hydride is NaH, KH or MgH2Or CaH2One or more of (a).
8. The graphene composite ammonia-hydrogen conversion catalyst according to claim 1, characterized in that: the metal compound solution is Ru3(CO)12Solution, Fe (acac)3Solutions or Co (acac)3One or more of the solutions.
9. The preparation method of the graphene composite material ammonia-hydrogen conversion catalyst is characterized by comprising the following steps:
(1) heating graphene, metal oxide and metal hydride in a temperature range of 100-500 ℃ for 72-120 hours in a gas atmosphere filled with nitrogen or argon, and replacing part of oxygen ions in the oxide with hydride ions, wherein the molar ratio of the graphene, the metal oxide and the metal hydride is (0.1-1): (1-1.2): (3-3.5) removing redundant metal oxides to obtain vacuum-dried graphene composite oxyhydroxide powder;
(2) dispersing the prepared graphene composite oxide powder in a metal compound solution with ammonia-hydrogen conversion activity by adopting an impregnation method, and impregnating metal ions in the metal compound solution on the graphene composite oxide and permeating the metal ions into the inner surface of the graphene composite oxide; and after the impregnation balance, removing the solvent in vacuum, collecting the metal-based powder containing the graphene composite oxyhydroxide, and heating the metal-based powder containing the graphene composite oxyhydroxide in a reducing atmosphere to decompose carbonyl compounds under the condition of vacuum sealing to obtain the graphene composite material ammonia-hydrogen conversion catalyst.
10. The method for preparing hydrogen by using the graphene composite material ammonia-hydrogen conversion catalyst is characterized by comprising the following steps of:
(1) suspending a graphene composite material ammonia-hydrogen conversion catalyst on a fixed bed in a glass tube of the fixed bed under a normal pressure environment;
(2) the graphene composite material ammonia-hydrogen conversion catalyst is used for carrying out pure ammonia-hydrogen conversion under the conditions of ammonia gas with the flow rate of 50-80 ml/min and the temperature of 100-500 ℃ to obtain decomposed nitrogen and hydrogen.
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