CN115501899B - Method for preparing mesoporous carbon-loaded metal nitride and application thereof - Google Patents
Method for preparing mesoporous carbon-loaded metal nitride and application thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000000967 suction filtration Methods 0.000 claims abstract description 52
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000003892 spreading Methods 0.000 claims description 8
- 230000007480 spreading Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical group [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- ZEYKLMDPUOVUCR-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC=C(Cl)C(S(Cl)(=O)=O)=C1 ZEYKLMDPUOVUCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 68
- 239000003054 catalyst Substances 0.000 abstract description 42
- 229910021529 ammonia Inorganic materials 0.000 abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000354 decomposition reaction Methods 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 7
- 229910001337 iron nitride Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- -1 nickel nitride Chemical class 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention is thatRelates to the technical field of ammonia decomposition hydrogen production, in particular to a method for preparing mesoporous carbon-loaded metal nitride by a suction filtration method and application thereof in ammonia decomposition hydrogen production. The method comprises the steps of obtaining mesoporous carbon loaded metal nitride by an in-situ suction filtration method through a precursor containing Ni and/or Fe and mesoporous carbon in the presence of a nitrogen-containing solution, wherein the metal nitride is NiN x 、FeN x Or NiFeN x . The catalyst prepared by the invention can completely decompose ammonia into hydrogen and nitrogen when the reaction temperature is as low as 390-550 ℃, and has higher stability; compared with noble metal catalysts, the catalyst has lower price and wide industrial application prospect.
Description
Technical Field
The invention relates to the technical field of ammonia decomposition hydrogen production, in particular to a method for preparing mesoporous carbon-loaded metal nitride by a suction filtration method and application thereof in ammonia decomposition hydrogen production.
Background
Along with the continuous improvement of energy demand and environmental protection requirements, hydrogen energy is taken as secondary energy, and is favored by the advantages of no pollution, reusability, high combustion value and the like. The hydrogen can be supplied with energy through the power generation of the fuel cell, and no CO exists in the use process x And NO x And the like. However, hydrogen has low volumetric energy density, high storage cost, and low transport efficiency. Ammonia gas is used as a chemical hydrogen storage material, has the characteristics of higher hydrogen content, easiness in liquefaction, high energy density and the like, and is considered as one of ideal hydrogen storage carriers. Therefore, hydrogen production by ammonia decomposition is considered to be a desirable solution. In the catalytic decomposition of ammonia, the search for a suitable catalyst has become an important point of research.
Currently, ammonia decomposition hydrogen production catalysts mainly include nickel-based, ruthenium-based and iron-based catalysts. Ruthenium-based catalysts have higher ammonia decomposition activity, but the increase in cost caused by high loadings is always a bottleneck for industrial applications. The invention discloses a Ru-based catalyst for preparing hydrogen by ammonia decomposition and a preparation method thereof, wherein the Ru-based catalyst is prepared by the method, the active component is noble metal ruthenium, the carrier is carbon layer coated silicon dioxide, the ammonia decomposition rate is only 61.8% when the optimal catalyst is at 500 ℃, the activity at low temperature is poor, the ammonia decomposition rate is obviously reduced after the catalyst is continuously catalyzed for 50 hours, the stability is poor, and the large-scale application of the ammonia decomposition hydrogen preparation technology is limited.
Disclosure of Invention
The invention aims to solve the problems of more catalyst components and complex preparation method, and provides a method for preparing mesoporous carbon-loaded metal nitride by a suction filtration method and application of the mesoporous carbon-loaded metal nitride in hydrogen production by ammonia decomposition.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a method for preparing mesoporous carbon-loaded metal nitride comprises the steps of obtaining mesoporous carbon-loaded metal nitride from a precursor containing Ni and/or Fe and mesoporous carbon by an in-situ suction filtration method in the presence of a nitrogen-containing solution, wherein the metal nitride is NiN x 、FeN x Or NiFeN x 。
The method comprises the following steps:
(1) Dissolving a precursor containing Ni and/or Fe to obtain a precursor solution;
(2) Spreading the soaked filtering membrane on a Buchner funnel or a sand core funnel;
(3) Spreading mesoporous carbon on the filtering membrane soaked in the step (2), and wetting the mesoporous carbon by dilute nitric acid;
(4) Slowly adding the precursor solution in the step (1) into the step (3);
(5) Slowly adding ammonia water and acetone (mass ratio of 1:1) into the step (4), and starting a vacuum pump (pressure is-0.02 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into the funnel, and starting a vacuum pump (the pressure is-0.04 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding acetone (the mass is 1/2 of that of the first acetone), and starting a vacuum pump (the pressure is-0.08 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding ammonia water (the mass is 1/2 of that of the ammonia water added for the first time), and starting a vacuum pump (the pressure is-0.08 Mpa) for suction filtration for 1min;
(6) Deionized water (about 50 mL) is added into the funnel in the step (5), and a vacuum pump (the pressure is-0.1 Mpa) is started for carrying out suction filtration and washing for 2min;
(7) Freeze-drying the sample after suction filtration and washing for 2 hours, vacuum-drying at 80 ℃ for 6 hours, and calcining at 550-700 ℃ for 4-8 hours to obtain a mesoporous carbon-loaded metal nitride precursor;
(8) Mesoporous carbon-loaded metal nitride precursor is filled into a quartz reaction tube, and NH is controlled by a mass flowmeter 3 The flow rate of (2) is 150mL/min, and the temperature is raised to 300 ℃ from room temperature at a speed of 5 ℃/min; and then raising the temperature to 550-700 ℃ at the speed of 1 ℃/min, and keeping the temperature for 2-5 h to obtain the mesoporous carbon loaded metal nitride.
The precursor solution is prepared by dissolving a precursor containing Ni and/or Fe in a mixed solution of deionized water and absolute ethyl alcohol under the condition of stirring; wherein the Ni-containing precursor is nickel acetate or nickel chloride, the Fe-containing precursor is ferrous oxalate or ferric ammonium oxalate, and the Ni-containing precursor and/or the Fe-containing precursor is a mixture of the Ni-containing precursor and the Fe-containing precursor (the molar ratio of Fe to Ni is 1.24).
The mass ratio of the deionized water to the absolute ethyl alcohol is 10-15: 1, the mass ratio of the precursor containing Ni and/or Fe to deionized water is 1: 20-30, wherein the mass ratio of mesoporous carbon to the precursor containing Ni and/or Fe is 2-4: 1.
the filter membrane is selected to have different pore diameters according to the difference of metal in the precursor solution; the filter membrane used by the Ni-containing precursor is a filter membrane with the pore diameter of 0.8 mu m; the filter membrane used for the Fe-containing precursor is a filter membrane with a pore size of 0.22 μm, and the filter membrane used for the Ni-and/or Fe-containing precursor is a filter membrane with a pore size of 0.45. Mu.m.
The mesoporous carbon-loaded metal nitride prepared by the method is prepared according to the method.
The application of the mesoporous carbon-loaded metal nitride as a catalyst in ammonia decomposition hydrogen production.
A method for producing hydrogen by decomposing ammonia, which uses pure ammonia as raw material and uses the mesoporous carbon-supported metal nitride as catalyst according to claim 6, wherein the mass airspeed is 5000-30000 mL NH3 g cat -1 h -1 Ammonia can be completely decomposed into hydrogen and nitrogen when the reaction temperature is as low as 390-550 ℃.
The invention has the following advantages:
(1) The invention prepares the mesoporous carbon-loaded metal nitride catalyst by a suction filtration method, the preparation method is simple, and the mesoporous carbon and the metal nitride (NiN x 、FeN x Or NiFeN x ) The coupling effect solves the problem of lower ammonia decomposition performance of the non-noble metal catalyst.
(2) When the reaction temperature of the catalyst is as low as 390-550 ℃, ammonia can be completely decomposed into hydrogen and nitrogen, and the catalyst has good thermal stability; compared with noble metal catalysts, the catalyst has lower price and higher ammonia decomposition activity, thus having better application prospect.
Drawings
Fig. 1 is an XRD pattern of the catalysts prepared in examples 1, 2 and 3 of the present invention.
FIG. 2 is N of the catalyst prepared in example 1 of the present invention 2 Adsorption and desorption curves and pore size distribution diagrams.
FIG. 3 is an ammonia decomposition effect curve of the catalysts prepared in examples 1, 2 and 3 of the present invention.
FIG. 4 shows the life test results of the catalyst prepared in example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the following examples are given, but are not limited thereto.
Example 1
2.8g of nickel acetate is added into a mixed solution of 56g of deionized water and 5.6g of absolute ethyl alcohol, and the mixture is stirred for 15min; tiling a 0.8 μm filter membrane to a Buchner drainOn the bucket, soaking the filtering membrane with a small amount of water; spreading 5.6g of mesoporous carbon on a filtering membrane, and wetting the mesoporous carbon with a small amount of dilute nitric acid; slowly adding the stirred nickel acetate solution to the surface of the mesoporous carbon. Then respectively adding 10g of ammonia water and 10g of acetone, and starting a vacuum pump (the pressure is-0.02 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into the funnel, and starting a vacuum pump (the pressure is-0.04 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding 5g of acetone, and starting a vacuum pump (the pressure is-0.08 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding 5g of ammonia water, and starting a vacuum pump (the pressure is-0.08 Mpa) for suction filtration for 1min; finally, 50mL of deionized water is added into the funnel, and a vacuum pump (the pressure is-0.1 Mpa) is started for suction filtration and washing for 2min. And freeze-drying the sample after suction filtration and washing for 2 hours, vacuum-drying at 80 ℃ for 6 hours, and calcining at 700 ℃ for 4 hours to obtain the mesoporous carbon-loaded nickel nitride precursor. Loading the obtained mesoporous carbon-loaded nickel nitride precursor into a quartz reaction tube, and controlling NH by a mass flowmeter 3 The flow rate of (2) is 150mL/min, and the temperature is raised to 300 ℃ from room temperature at a speed of 5 ℃/min; then the temperature is increased to 700 ℃ at the speed of 1 ℃/min and kept for 2 hours, thus obtaining the mesoporous carbon supported nickel nitride catalyst which is named NiN x C (FIG. 1). Granulating, grinding, sieving to 40 mesh, and bagging.
As can be seen from the figure, niN is formed x Structure, successfully prepare NiN x catalyst/C. As shown in Table 1, niN x Specific surface area of catalyst/C of 603.5m 2 /g; niN, as shown in FIG. 2 x The catalyst/C had a mesoporous structure with an average pore diameter of 4.8nm.
Table 1 results of specific surface area of each catalyst
Example 2
3.1g of ferrous oxalate is added into a mixed solution of 124g of deionized water and 8.27g of absolute ethyl alcohol, and the mixture is stirred for 15min; spreading a filtering membrane with the diameter of 0.22 mu m on a sand core funnel, and soaking the filtering membrane with a small amount of water; will be12.4g of mesoporous carbon is flatly paved on a filtering membrane, and a small amount of dilute nitric acid is used for wetting the mesoporous carbon; and slowly adding the stirred ferrous oxalate solution to the surface of the mesoporous carbon. Then respectively adding 12g of ammonia water and 12g of acetone, and starting a vacuum pump (the pressure is-0.02 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into the funnel, and starting a vacuum pump (the pressure is-0.04 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding 6g of acetone at the same time, and starting a vacuum pump (the pressure is-0.08 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding 6g of ammonia water, and starting a vacuum pump (the pressure is-0.08 Mpa) for suction filtration for 1min; finally, 50mL of deionized water is added into the funnel, and a vacuum pump (the pressure is-0.1 Mpa) is started for suction filtration and washing for 2min. And freeze-drying the sample subjected to suction filtration and washing for 2 hours, vacuum-drying at 80 ℃ for 6 hours, and calcining at 550 ℃ for 8 hours to obtain the mesoporous carbon-loaded iron nitride precursor. Filling the obtained mesoporous carbon-loaded iron nitride precursor into a quartz reaction tube, and controlling NH by a mass flowmeter 3 The flow rate of (2) is 150mL/min, and the temperature is raised to 300 ℃ from room temperature at a speed of 5 ℃/min; then the temperature is increased to 550 ℃ at the speed of 1 ℃/min and kept for 5 hours, thus obtaining the mesoporous carbon-supported iron nitride catalyst which is marked as FeN x C (FIG. 1). Granulating, grinding, sieving to 40 mesh, and bagging.
As can be seen from the figure, feN is formed x Structurally, feN is successfully prepared x catalyst/C. As shown in Table 1, feN x Specific surface area of catalyst/C of 611.2m 2 /g。
Example 3
Will be 8.2gNH 4 Fe(SO 4 ) 2 ·12H 2 O and 4gNiCl 2 ·6H 2 O is added into a mixed solution of 366g of deionized water and 30.5g of absolute ethyl alcohol, and the mixture is stirred for 15min; spreading a filtering membrane with the diameter of 0.45 mu m on a sand core funnel, and soaking the filtering membrane with a small amount of water; spreading 36.6g of mesoporous carbon on a filtering membrane, and wetting the mesoporous carbon with a small amount of dilute nitric acid; stirring the NH 4 Fe(SO 4 ) 2 ·12H 2 O and 4gNiCl 2 ·6H 2 The O mixed solution is slowly added to the surface of the mesoporous carbon. Then respectively adding 16g of ammonia water and 16g of acetone, and starting a vacuum pumpCarrying out suction filtration for 1min at the pressure of-0.02 Mpa; slowly adding the liquid in the suction filtration bottle into the funnel, and starting a vacuum pump (the pressure is-0.04 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding 8g of acetone, and starting a vacuum pump (the pressure is-0.08 Mpa) for suction filtration for 1min; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding 8g of ammonia water, and starting a vacuum pump (the pressure is-0.08 Mpa) for suction filtration for 1min; finally, 50mL of deionized water is added into the funnel, and a vacuum pump (the pressure is-0.1 Mpa) is started for suction filtration and washing for 2min. And freeze-drying the sample subjected to suction filtration and washing for 2 hours, vacuum-drying at 80 ℃ for 6 hours, and calcining at 600 ℃ for 6 hours to obtain the mesoporous carbon-loaded ferronickel nitride precursor. The obtained mesoporous carbon-loaded nickel-iron nitride precursor is filled into a quartz reaction tube, and NH is controlled by a mass flowmeter 3 The flow rate of (2) is 150mL/min, and the temperature is raised to 300 ℃ from room temperature at a speed of 5 ℃/min; then the temperature is increased to 600 ℃ at the speed of 1 ℃/min and kept for 4 hours, thus obtaining the mesoporous carbon-supported iron nitride catalyst which is named as NiFeN x C (FIG. 1). Granulating, grinding, sieving to 40 mesh, and bagging.
As can be seen from the figure, niFeN is formed x The structure is successfully used for preparing NiFeN x catalyst/C. As shown in Table 1, niFeN x Specific surface area of catalyst/C of 628.6m 2 /g。
Example 4
0.2g of NiN from example 1 was weighed out x The catalyst/C is placed in a fixed bed reactor, the ammonia gas is pure ammonia, and the mass space velocity is
The reaction temperature is 320-550 ℃. NiN x The ammonia decomposition effect of the catalyst/C is shown in FIG. 3.
The reaction results show that: NH at 450 DEG C 3 The conversion rate reaches more than 80 percent; at 500 ℃, the ammonia gas is completely decomposed.
Example 5
0.1g of FeN in example 2 was weighed out x The catalyst/C is placed in a fixed bed reactor, the ammonia gas is pure ammonia, and the mass space velocity is
The reaction temperature is 320-600 ℃. FeN (FeN) x The ammonia decomposition effect of the catalyst/C is shown in FIG. 3.
The reaction results show that: at 400 ℃, NH 3 The conversion rate reaches about 60%; at 550 ℃, the ammonia gas realizes complete decomposition.
Example 6
0.1g of NiFeN in example 3 was weighed out x The catalyst/C is placed in a fixed bed reactor, the ammonia gas is pure ammonia, and the mass space velocity is
The reaction temperature is 300-450 ℃. NiFeN x The ammonia decomposition effect of the catalyst/C is shown in FIG. 3.
The reaction results show that: at 360 ℃, NH 3 The conversion rate reaches about 70%; at 420 ℃, the ammonia gas is completely decomposed.
Example 7
0.1g of NiFeN in example 3 was weighed out x The catalyst/C is placed in a fixed bed reactor, the ammonia gas is pure ammonia, and the mass space velocity is
The reaction temperature was 400℃and the reaction time was 140 hours, and the test results are shown in FIG. 4.
The reaction results show that: at 400 ℃, NH 3 The conversion rate is kept above 90%, and the stability is high.
Claims (4)
1. A method of preparing a mesoporous carbon-supported metal nitride, characterized by: the method comprises the steps of obtaining mesoporous carbon loaded metal nitride by an in-situ suction filtration method through a precursor containing Ni and/or Fe and mesoporous carbon in the presence of a nitrogen-containing solution, wherein the metal nitride is NiN x 、FeN x Or NiFeN x ；
The method comprises the following steps: (1) Dissolving a precursor containing Ni and/or Fe to obtain a precursor solution;
(2) Spreading the soaked filtering membrane on a Buchner funnel or a sand core funnel;
(3) Spreading mesoporous carbon on the filtering membrane soaked in the step (2), and wetting the mesoporous carbon by dilute nitric acid;
(4) Slowly adding the precursor solution in the step (1) into the step (3);
(5) Slowly adding ammonia water and acetone into the step (4), wherein the mass ratio of the ammonia water to the acetone is 1:1, starting a vacuum pump, and performing suction filtration for 1min under the pressure of-0.02 MPa; slowly adding the liquid in the suction filtration bottle into a funnel, starting a vacuum pump, and performing suction filtration for 1min under the pressure of-0.04 MPa; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding acetone, starting a vacuum pump, and performing suction filtration for 1min under the pressure of-0.08 MPa; slowly adding the liquid in the suction filtration bottle into a funnel, slowly adding ammonia water, starting a vacuum pump, and performing suction filtration for 1min under the pressure of-0.08 MPa;
(6) Adding deionized water into the funnel in the step (5), starting a vacuum pump, and performing suction filtration washing for 2min under the pressure of-0.1 MPa;
(7) Freeze-drying the sample after suction filtration and washing for 2 hours, vacuum-drying at 80 ℃ for 6 hours, and calcining at 550-700 ℃ for 4-8 hours to obtain a mesoporous carbon-loaded metal nitride precursor;
(8) Mesoporous carbon-loaded metal nitride precursor is filled into a quartz reaction tube, and NH is controlled by a mass flowmeter 3 The flow rate of (2) is 150mL/min, and the temperature is raised to 300 ℃ from room temperature at a speed of 5 ℃/min; and then raising the temperature to 550-700 ℃ at the speed of 1 ℃/min, and keeping the temperature for 2-5 h to obtain the mesoporous carbon loaded metal nitride.
2. A method of preparing a mesoporous carbon supported metal nitride according to claim 1, wherein: the precursor solution is prepared by dissolving a precursor containing Ni and/or Fe in a mixed solution of deionized water and absolute ethyl alcohol under the condition of stirring; wherein the Ni-containing precursor is nickel acetate or nickel chloride, the Fe-containing precursor is ferrous oxalate or ferric ammonium oxalate, and the Ni-containing precursor and the Fe-containing precursor are a mixture of the Ni-containing precursor and the Fe-containing precursor.
3. A method of preparing a mesoporous carbon supported metal nitride according to claim 1, wherein: the mass ratio of the deionized water to the absolute ethyl alcohol is 10-15: 1, the mass ratio of the precursor containing Ni and/or Fe to deionized water is 1: 20-30, wherein the mass ratio of mesoporous carbon to the precursor containing Ni and/or Fe is 2-4: 1.
4. a method of preparing a mesoporous carbon supported metal nitride according to claim 2, wherein: the filter membrane is selected to have different pore diameters according to the difference of metal in the precursor solution; the filter membrane used by the precursor containing Ni is a filter membrane with the aperture of 0.8 mu m; the filter membrane used by the precursor containing Fe is a filter membrane with the aperture of 0.22 mu m, and the filter membrane used by the precursor containing Ni and Fe is a filter membrane with the aperture of 0.45 mu m.
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