CN116273031A - Preparation method of catalyst for producing hydrogen by ammonia decomposition - Google Patents
Preparation method of catalyst for producing hydrogen by ammonia decomposition Download PDFInfo
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- CN116273031A CN116273031A CN202310157543.3A CN202310157543A CN116273031A CN 116273031 A CN116273031 A CN 116273031A CN 202310157543 A CN202310157543 A CN 202310157543A CN 116273031 A CN116273031 A CN 116273031A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 42
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 238000007639 printing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000816 inconels 718 Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000006378 damage Effects 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 238000010146 3D printing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011960 computer-aided design Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- 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
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- B01J35/30—
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- B01J35/40—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/38—Process control to achieve specific product aspects, e.g. surface smoothness, density, porosity or hollow structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/80—Data acquisition or data processing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y50/00—Data acquisition or data processing for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
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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
Abstract
The invention discloses a preparation method of a catalyst for producing hydrogen by ammonia decomposition, which takes nickel-based alloy powder as a raw material and prepares a tubular nickel-based catalyst by using a metal 3D printer, wherein the tubular nickel-based catalyst is formed by connecting regular hexagons as units, and each regular hexagon is formed by connecting rod-shaped alloy and spherical alloy. The tubular nickel-based catalyst has good mechanical property, good catalytic action on hydrogen production by ammonia decomposition and great application potential.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a preparation method of a catalyst for producing hydrogen by ammonia decomposition.
Background
Hydrogen is an ideal energy carrier and can efficiently generate electricity in a fuel cell. However, since the bulk density of hydrogen is low (81. g.m -3 ) And a low boiling point (-252.8 ℃), the storage and transportation of hydrogen becomes a major obstacle to commercialization of hydrogen fuel cells.
In hydrogen fuel cell applications, the source of hydrogen has been of great concern. The advantage of utilizing ammonia to decompose and produce hydrogen is that: first, ammonia has a high hydrogen content (17.6 wt%), a high volumetric energy density (13.6 MJ L) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the Second, the CO and CO in the hydrogen product are eliminated by ammonia decomposition hydrogen production 2 The impurities are removed, so that the poisoning probability of the fuel cell electrode is reduced; furthermore, ammonia is a mature base chemical, and the storage and transportation modes of the ammonia are fully guaranteed. Therefore, the use of ammonia to produce hydrogen is a preferred way for hydrogen fuel cells to obtain a hydrogen source.
However, advancing the optimization reform of catalysts for ammonia destruction hydrogen production in the process of ammonia destruction hydrogen production remains a significant challenge. Currently, catalysts used for industrial ammonia decomposition are mainly oxide supported catalysts (e.g., ni/Al 2 O 3 Etc.). The preparation method of the catalyst mainly comprises a traditional impregnation method, a hydrothermal method, a coprecipitation method, a template method and the like. These method stepsComplicated preparation process, high energy and reagent consumption, and insufficient mechanical property and chemical stability of the catalyst. Therefore, development and design of a novel efficient and stable catalyst for producing hydrogen by decomposing ammonia are imperative.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a novel preparation method of the catalyst for producing hydrogen by decomposing ammonia, so as to simplify the preparation process of the catalyst for producing hydrogen by decomposing ammonia, enhance the preparation efficiency and mechanical property of the catalyst and improve the catalytic efficiency of producing hydrogen by decomposing ammonia.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of catalyst for producing hydrogen by ammonia decomposition uses nickel-based alloy powder as raw material, and prepares tubular nickel-based catalyst by metal 3D printer for producing hydrogen by ammonia decomposition.
Further, the nickel-based alloy powder is derived from Inconel 718 alloy.
Further, the tubular nickel-based catalyst is formed by connecting regular hexagons as units, and each regular hexagon is formed by connecting rod-shaped alloy and spherical alloy.
Further, the diameter of the tubular nickel-based catalyst is 2-4 mm, and the length of the tubular nickel-based catalyst is 3-4 mm.
Further, the diameter of the spherical alloy is 0.2-0.4 mm; the length of the rod-shaped alloy is 0.3-0.8 mm, and the width of the rod-shaped alloy is 0.1-0.3 mm.
The preparation of the tubular nickel-based catalyst comprises the following steps:
1) Designing and forming a required catalyst structure by using computer aided design software, and performing three-dimensional modeling according to the obtained catalyst structure model;
2) Taking nickel-based alloy powder as a raw material, and printing out a designed catalyst by a metal 3D printer;
3) Cutting and post-processing the printed catalyst to obtain the final tubular nickel-based catalyst.
Further, the post-treatment in the step 3) is to bake at a high temperature of 500-1000 ℃ for 8-20 hours, preferably at a baking temperature of 700-900 ℃ for 8-12 hours.
The invention also provides a method for producing hydrogen by ammonia decomposition by using the tubular nickel-based catalyst, which comprises filling the tubular nickel-based catalyst into an ammonia decomposition quartz reactor according to 5-20 groups, and introducing H 2 And (3) carrying out pretreatment and activation on the Ar mixed gas, then introducing argon for purging, and finally introducing high-purity ammonia and carrying out ammonia decomposition reaction at 500-700 ℃ to prepare the hydrogen.
Further, the pretreatment and activation are carried out at a temperature of 400-700 ℃ for 2-8 hours.
Further, the H 2 In Ar gas mixture, H 2 And Ar in a volume ratio of 1:1.
Further, the flow rate of the high-purity ammonia is 20-60 ml/min.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the invention uses 3D printing technology for the first time to prepare ammonia decomposition catalyst. Compared with the traditional catalyst preparation, the method simplifies the catalyst preparation process, reduces the catalyst molding and production procedures, and is beneficial to repeated preparation.
2. The invention can control the geometry of the printed catalyst during the catalyst preparation process. Compared with the traditional catalyst, the 3D printing can print out a unique catalyst suitable for hydrogen production by ammonia decomposition, the surface area of a catalyst bed and air flow disturbance are controlled, and the adaptability is high. The printed catalyst has higher mechanical property, improved heat and mass transfer efficiency, reduced pressure drop of the catalyst bed layer, good chemical stability and long service life.
3. The production process of the invention is environment-friendly and cost-effective. Compared with the traditional catalyst, the invention uses the alloy powder mainly containing nickel as the raw material, is an easily available industrialized raw material, can prevent the waste of the raw material to a great extent, has low preparation cost, can be recycled, has low energy consumption, meets the actual production requirements, and has great application potential and prospect.
Drawings
FIG. 1 is a schematic diagram of a tubular nickel-based catalyst of example 1; wherein a) is a whole structure schematic diagram, b) is a detail schematic diagram, c) is a top view schematic diagram;
FIG. 2 is an SEM image of the catalyst prepared in examples 1-3 and comparative example 1;
FIG. 3 is a graph showing the activity of the catalysts prepared in examples 1-3 and comparative example 1 for producing hydrogen by ammonia decomposition;
FIG. 4 is a schematic diagram of the catalyst prepared in comparative example 2;
FIG. 5 is a schematic diagram of the catalyst prepared in comparative example 3;
FIG. 6 is a graph showing the comparison of the activities of the catalysts prepared in example 3 and comparative examples 1 to 3 for producing hydrogen by ammonia decomposition.
Detailed Description
A preparation method of catalyst for producing hydrogen by ammonia decomposition uses nickel-based alloy powder as raw material, and prepares tubular nickel-based catalyst by metal 3D printer for producing hydrogen by ammonia decomposition.
Wherein the nickel-based alloy powder is derived from Inconel 718 alloy.
The tubular nickel-based catalyst is formed by connecting regular hexagons as units, and each regular hexagon is formed by connecting rod-shaped alloy and spherical alloy. The diameter of the tubular nickel-based catalyst is 2-4 mm, and the length of the tubular nickel-based catalyst is 3-4 mm. The diameter of the spherical alloy is 0.2-0.4 mm; the length of the rod-shaped alloy is 0.3-0.8 mm, and the width of the rod-shaped alloy is 0.1-0.3 mm.
The preparation of the tubular nickel-based catalyst comprises the following steps:
1) Designing and forming a required catalyst structure by using computer aided design software, and performing three-dimensional modeling according to the obtained catalyst structure model;
2) Taking nickel-based alloy powder as a raw material, and printing out a designed catalyst by a metal 3D printer;
3) Cutting and post-processing the printed catalyst to obtain the final tubular nickel-based catalyst.
And step 3) the post-treatment is carried out at a high temperature of 500-1000 ℃ for 8-20 h, preferably at a temperature of 700-900 ℃ for 8-12 h.
By means ofThe method for producing hydrogen by ammonia decomposition of the tubular nickel-based catalyst comprises filling the tubular nickel-based catalyst into an ammonia decomposition quartz reactor according to a group of 5-20, and introducing H 2 And (3) carrying out pretreatment and activation on the Ar mixed gas, then introducing argon for purging, and finally introducing high-purity ammonia and carrying out ammonia decomposition reaction at 500-700 ℃ to prepare the hydrogen.
The pretreatment activation temperature is 400-700 ℃ and the pretreatment activation time is 2-8 h.
The H is 2 In Ar gas mixture, H 2 And Ar in a volume ratio of 1:1.
The flow rate of the high-purity ammonia is 20-60 ml/min.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Performance testing
The ammonolysis reaction performance of the catalyst was evaluated in an atmospheric fixed bed reactor. The specific operation is that a group of catalysts (15 tubular nickel-based catalysts with the height of 3.6 and mm) are firstly placed in a quartz reactor, and firstly, the catalyst is added in the presence of 50% H 2 Heating to 600 ℃ at a heating rate of 5 ℃/min in Ar atmosphere, and carrying out reduction treatment on the mixture to 3 h; subsequently, ar gas was switched to purge 1H (for the purpose of purging H remaining on the catalyst surface for chemical or physical adsorption) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Finally, at 50 mL min -1 NH of (C) 3 The catalyst activity was evaluated in the atmosphere. In the reaction process, the reaction temperature interval is 500-700 ℃.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified; the experimental methods in the following examples are conventional methods unless otherwise specified.
Example 1
The preparation method of the tubular nickel-based catalyst for 3D printing comprises the steps of taking Inconel 718 alloy powder (the components of which are shown in table 1) mainly containing metallic nickel as a raw material, carrying out catalyst structure design by using computer-aided software, and preparing the tubular nickel-based catalyst by adopting a selective laser melting 3D printing technology;
TABLE 1 composition Table of Inconel 718 alloy
The method specifically comprises the following steps:
(1) Designing a required catalyst structure by using Computer Aided Design (CAD) software, and performing three-dimensional modeling according to the obtained catalyst structure model;
(2) Printing out a designed catalyst by using Inconel 718 alloy powder as a raw material through a metal 3D printer;
(3) Cutting into small sections with the length of 3.6mm after printing;
(4) And (3) placing the cut catalyst into a muffle furnace for high-temperature roasting treatment, wherein the roasting temperature is 700 ℃, the roasting time is 10 h, and the heating rate is 5 ℃/min, so that the tubular nickel-based catalyst is obtained.
As shown in FIG. 1, the tubular nickel-based catalyst model had a total height of 70mm, a diameter of 3.2mm, and a spherical diameter of 0.3 mm in the regular hexagon formed by the spherical rod model, a rod length of 0.5 mm, and a width of 0.2 mm.
Example 2
The procedure of example 1 was repeated except that the baking temperature in step (4) was adjusted to 800 ℃.
Example 3
The procedure of example 1 was repeated except that the baking temperature in step (4) was adjusted to 900 ℃.
Comparative example 1
The procedure of example 1 was followed except that the cut catalyst was not calcined at high temperature.
FIG. 2 is an SEM image of the catalysts prepared in examples 1-3 and comparative example 1, where a is comparative example 1, b is example 1, c is example 2, and d is example 3. As can be seen from the graph, after roasting, the surface of the catalyst changes to different degrees, the higher the roasting temperature is, the larger the surface changes are, and after the catalyst obtained in the example 3 is roasted at 900 ℃, the irregular lamellar concave-convex structure appears on the surface of the catalyst, so that the exposure of active sites is increased, and the activity is improved.
FIG. 3 is an implementationComparative graphs of the activity of catalysts prepared in examples 1 to 3 and comparative example 1 for producing hydrogen by ammonia decomposition. As can be seen from FIG. 3, the highest ammonia decomposition activity is example 3, up to 58 mmol/(m) 2 S) whereas the unfired comparative example 1 catalyst had significantly lower ammonia decomposition activity.
Comparative example 2
A solid cylindrical catalyst is designed. As shown in FIG. 4, the catalyst was 3.2mm in diameter and 70mm in height, and cut into 3.6mm long after printing was completed.
Comparative example 3
A solid wall hollow cylinder type catalyst is designed. As shown in fig. 5, the catalyst was 3.2. 3.2mm in diameter, 70. 70mm in height, 0.2mm in wall, and cut to 3.6. 3.6mm in length after printing.
The activity comparison graph of the catalysts prepared in example 3 and comparative examples 1-3 for hydrogen production by ammonia decomposition is shown in FIG. 6. As can be seen from fig. 6, the tubular catalyst has a higher catalytic activity, since the club structure increases its vortex perturbation effect on the gas flow, thus increasing the contact time between the phases.
Comparative example 4
Method for preparing load type 5% Ni/Al by using traditional impregnation method 2 O 3 A catalyst. Specifically, 1.24 g of Ni (NO 3 ) 2 ·6H 2 O and 5 g gamma-Al 2 O 3 Mixing the mixture with deionized water at room temperature, stirring and standing, drying and roasting at 900 ℃ to obtain the traditional supported catalyst.
The obtained traditional supported catalyst is used for the reaction of producing hydrogen by ammonia decomposition (space velocity is 30000 h) -1 ) And calculate TOF at 600 ℃. Similar results, the TOF in example 3 was 3.58, and the TOF in comparative example 4 was 2.56, which is significantly lower than example 3.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A preparation method of a catalyst for producing hydrogen by ammonia decomposition is characterized in that nickel-based alloy powder is used as a raw material, and a tubular nickel-based catalyst is prepared by using a metal 3D printer and is used for producing hydrogen by ammonia decomposition.
2. The method of preparing an ammonia destruction hydrogen production catalyst according to claim 1, wherein the nickel-based alloy powder is derived from Inconel 718 alloy.
3. The method for preparing a catalyst for producing hydrogen by decomposing ammonia according to claim 1, wherein the tubular nickel-based catalyst is formed by connecting regular hexagons as units, each regular hexagon being formed by connecting a rod-shaped alloy with a spherical alloy.
4. The method for preparing a catalyst for producing hydrogen by decomposing ammonia according to claim 3, wherein the tubular nickel-based catalyst has a diameter of 2-4 mm and a length of 3-4 mm.
5. The method for producing an ammonia decomposition hydrogen production catalyst according to claim 3, wherein the diameter of the spherical alloy is 0.2 to 0.4mm; the length of the rod-shaped alloy is 0.3-0.8 mm, and the width of the rod-shaped alloy is 0.1-0.3 mm.
6. A method of preparing a catalyst for producing hydrogen from ammonia decomposition according to claim 3, comprising the steps of:
1) Designing and forming a required catalyst structure by using computer aided design software, and performing three-dimensional modeling according to the obtained catalyst structure model;
2) Taking nickel-based alloy powder as a raw material, and printing out a designed catalyst by a metal 3D printer;
3) Cutting and post-processing the printed catalyst to obtain the final tubular nickel-based catalyst.
7. The method of producing hydrogen by ammonia decomposition according to claim 6, wherein the post-treatment in step 3) is a high-temperature calcination at 500 to 1000 ℃ for 8 to 20 hours.
8. A process for producing hydrogen by ammonia decomposition using the catalyst as claimed in claim 1, wherein the tubular nickel-based catalyst is packed into an ammonia decomposition quartz reactor in groups of 5 to 20, and H is introduced first 2 And (3) carrying out pretreatment and activation on the Ar mixed gas, then introducing argon for purging, and finally introducing high-purity ammonia and carrying out ammonia decomposition reaction at 500-700 ℃ to prepare the hydrogen.
9. The method for producing hydrogen by decomposing ammonia according to claim 8, wherein the pretreatment and activation are carried out at a temperature of 400 to 700 ℃ for a time of 2 to 8 hours.
10. The method for producing hydrogen by ammonia decomposition according to claim 8, wherein said H 2 In Ar gas mixture, H 2 And Ar is 1:1 by volume; the flow rate of the high-purity ammonia is 20-60 ml/min.
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