CN115532256B - Ruthenium-based ammonia synthesis catalyst and preparation method and application thereof - Google Patents
Ruthenium-based ammonia synthesis catalyst and preparation method and application thereof Download PDFInfo
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- CN115532256B CN115532256B CN202211112285.9A CN202211112285A CN115532256B CN 115532256 B CN115532256 B CN 115532256B CN 202211112285 A CN202211112285 A CN 202211112285A CN 115532256 B CN115532256 B CN 115532256B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 57
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 47
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 43
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 39
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 44
- 238000000498 ball milling Methods 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000003575 carbonaceous material Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- -1 salt modified carbon Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 13
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 101100112111 Caenorhabditis elegans cand-1 gene Proteins 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
- B01J35/615—100-500 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a ruthenium-based ammonia synthesis catalyst and a preparation method and application thereof. The catalyst of the invention has the ammonia synthesis rate of 18.7mmol NH3gcat ‑1h‑1 at 400 ℃ and 1MPa, and has extremely high thermal stability, and the catalyst has the advantages of simple preparation method, short preparation period, high efficiency, no solvent in the whole process, environmental protection, and good industrial application prospect in ammonia synthesis reaction.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a ruthenium-based ammonia synthesis catalyst, a preparation method and application thereof.
Background
Ammonia is a guarantee of grain safety, and NH 3 is also considered as an important carbon-free energy carrier due to the characteristics of high energy density, no carbon, convenient storage and transportation and the like. At present, industrial synthetic ammonia takes fossil resources as fuel, H 2 is generated through a water gas shift reaction, the generated H 2 is separated from N 2 in air, and the ammonia is synthesized under the catalysis of an iron-based catalyst at high temperature (450-510 ℃) and high pressure (15.0-32.0 MPa). The important reaction for industrial synthesis of ammonia is highly energy intensive, with a high energy consumption of 1% of the world's energy consumption, and with a CO 2 emission of 1.5 ten thousand tons per generation of 1 ten thousand tons of NH 3. With the recent development of renewable energy sources, researchers have come up with the idea of electrolytically driven ammonia synthesis processes. The method utilizes electrolyzed water to prepare hydrogen as a hydrogen source, combines the hydrogen source with nitrogen ("nitrogen source") separated from air, and utilizes renewable energy sources to realize the synthesis of green ammonia. The output pressure of the large-scale hydrogen production system by the renewable energy power electrolysis of water is less than or equal to 5.0MPa; therefore, to achieve the coupling of renewable energy power and ammonia synthesis technology, there is a need to develop technology for synthesizing ammonia under mild conditions that matches the renewable energy power electrolytic hydrogen production system.
At present, the active carbon material has larger specific surface area, good heat conduction performance and electron conduction performance and rich pore structure. Therefore, it is often used as a carrier for supported catalysts and is widely used in heterogeneous catalytic reactions. However, in the ammonia synthesis catalytic reaction, the activated carbon material may generate methanation, especially for the conventional Ru-based carbon catalyst, ru is a catalyst for methanation of activated carbon, and thus loss of catalyst carrier and sintering of active components may be caused. Therefore, how to develop a synthetic ammonia catalyst carrier with higher stability and capable of greatly reducing methanation problems thereof is a technical problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a ruthenium-based ammonia synthesis catalyst, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of the ruthenium-based catalyst comprises the step of roasting a Ru precursor and a metal salt modified carbon material at a high temperature to obtain the ruthenium-based catalyst.
According to an embodiment of the invention, the reaction mass ratio of the Ru precursor to the metal salt modified carbon material is 1 (1-20), preferably 1 (2-15), and is exemplified by 1:1, 1:2, 1:5, 1:10, 1:12.3, 1:15, 1:20.
According to an embodiment of the present invention, the Ru precursor is selected from at least one of ruthenium acetylacetonate, ruthenium nitrosylnitrate, ruthenium trichloride, ruthenium acetate, and ruthenium dodecacarbonyl.
According to an embodiment of the present invention, the high temperature firing temperature is 300 to 1000 ℃, and is exemplified by 300 ℃, 400 ℃, 500 ℃, 700 ℃, 1000 ℃; the high-temperature roasting time is 0.5-6 h, and is exemplified by 0.5h, 1h, 2h, 4h and 6h.
According to an embodiment of the present invention, the high temperature firing is performed under a mixed atmosphere. Preferably, the mixed gas is one of hydrogen and nitrogen, hydrogen and helium, and hydrogen and argon.
Preferably, the volume ratio of the two gas components in the mixed gas is 0.1-0.6, and exemplary is 0.1, 0.2, 0.4 and 0.6.
Preferably, the gas flow rate of the mixed gas is 40-100 mL/min, and the gas flow rate is exemplified by 40mL/min, 60mL/min, 80mL/min and 100mL/min.
According to an embodiment of the invention, the Ru precursor and the metal salt modified carbon material further comprise ball milling the same before high-temperature calcination. For example, the rotational speed of the ball milling is 200-600r/min, and the ball milling time is 2-10h.
According to the embodiment of the invention, the metal salt modified carbon material is prepared from raw materials comprising a carbon material and a metal salt auxiliary agent through high-temperature roasting.
Preferably, the mass fraction of the metal element in the metal salt relative to the carbon material is 1% -10%, and exemplary is 1%, 2%, 4%, 5%, 6%, 8%, 10%.
Preferably, the metal salt is at least one of nitrate, carbonate or acetate containing at least one of barium, potassium and cesium.
Preferably, the high-temperature roasting temperature in the preparation method of the metal salt modified carbon material is 300-1000 ℃, and the temperature is 300 ℃, 400 ℃, 500 ℃, 700 ℃ and 1000 ℃ in an exemplary way; the high-temperature roasting time is 0.5-6 h, and is exemplified by 0.5h, 1h, 2h, 4h and 6h.
Preferably, the high-temperature roasting is performed in a mixed atmosphere in the preparation method of the metal salt modified carbon material. Preferably, the mixed gas is one of hydrogen and nitrogen, hydrogen and helium, and hydrogen and argon.
Preferably, the volume ratio of the gas components in the mixture is 0.1 to 0.6, and exemplary is 0.1, 0.2, 0.4, 0.6.
Preferably, the gas flow rate of the mixed gas is 40-100 mL/min, and the gas flow rate is exemplified by 40mL/min, 60mL/min, 80mL/min and 100mL/min.
Preferably, the carbon material and metal salt further comprise ball milling them prior to high temperature calcination. For example, the rotational speed of the ball milling is 200-600r/min, and the ball milling time is 2-10h.
Preferably, the preparation method of the metal salt modified carbon material further comprises tabletting the product after high-temperature roasting. For example, the compression forces of the tablets are 30 to 300kN, and exemplary are 30kN, 50kN, 80kN, 100kN, 200kN, 300kN.
Preferably, the preparation method of the metal salt modified carbon material further comprises crushing and sieving the tabletted product.
According to an embodiment of the present invention, the method for preparing a ruthenium-based catalyst comprises the steps of:
(1) Ball milling: ball milling is carried out on the carbon material and the metal salt auxiliary agent;
(2) And (3) reduction: heating the ball-milled carbon material to 300-1000 ℃ in the mixed gas atmosphere, and roasting for 0.5-6 hours to obtain a metal salt modified carbon material;
(3) Ball milling: ball milling is carried out on the Ru precursor and the metal salt modified carbon material obtained in the step (2);
(4) And (3) reduction: heating the ball-milled material to 300-1000 ℃ in the mixed gas atmosphere, and roasting for 0.5-6 h;
(5) And (3) forming: tabletting the material obtained in the step (4);
(6) Granulating: crushing the material obtained in the step (5), and sieving to obtain the ruthenium-based catalyst.
The invention also provides the ruthenium-based catalyst prepared by the preparation method.
According to an embodiment of the present invention, the catalyst includes a carbon support and ruthenium and a metal oxide supported on the support.
Preferably, the mass fraction of ruthenium in the catalyst is 1wt.% to 10wt.%, exemplary 1wt.%, 2wt.%, 4wt.%, 6wt.%, 10wt.% relative to the catalyst.
Preferably, the ruthenium is supported on a carbon support in the form of ruthenium nanoparticles. More preferably, the ruthenium nanoparticles have an average particle diameter of 1 to 10nm (exemplary 2.5 nm); further, the ruthenium is uniformly distributed on the carbon support in the form of ruthenium nanoparticles.
Preferably, the metal oxide is an oxide containing at least one of barium, potassium, cesium.
Preferably, in the catalyst, the mass fraction of the metal element in the metal oxide relative to the catalyst is 1wt.% to 10wt.%, illustratively 1wt.%, 2wt.%, 4wt.%, 6wt.%, 10wt.%.
Preferably, the carbon carrier is graphite carbon with high specific surface area (the specific surface area of common graphite carbon is concentrated in the range of 1-20 m 2 g-1).
Preferably, the specific surface area of the carbon support is 300 to 500m 2 g-1, and exemplary 300m 2 g-1、400m2 g-1、500m2 g-1.
Preferably, the pore volume of the carbon support is 0.10-0.60 cm 3 g-1, exemplary 0.10cm3 g-1、0.20cm3g-1、0.40cm3 g-1、0.60cm3 g-1.
Preferably, the pore size of the carbon support is 1 to 10nm, and exemplary is 1nm, 2nm, 5nm, 8nm, 10nm.
The invention also provides application of the catalyst in the field of ammonia synthesis. Preferably in the synthesis of ammonia by electrolysis of water to produce hydrogen as a "hydrogen source".
The invention has the beneficial effects that:
the research shows that the graphitized carbon has higher stability compared with the traditional carbon material, and the methanation problem of the graphitized carbon can be greatly reduced. Therefore, the graphite carbon with high specific surface area can become a novel efficient potential carrier for mild ammonia synthesis catalysts. Specifically:
(1) The ruthenium-based catalyst is synthesized by a high-speed ball milling method, has higher ammonia synthesis activity and heat-resistant stability under mild conditions when being used in an ammonia synthesis process, is simple to prepare, and has better application prospect in the ammonia synthesis industry.
(2) The Ba-Ru/HGC BM (ball milling) catalyst prepared by the invention has excellent synthetic ammonia reaction rate and good thermal stability compared with the traditional Ru and Fe-based catalyst.
(3) The preparation method of the catalyst provided by the invention is simple and efficient, the catalyst is easy to form, industrial application is facilitated, and the cost is greatly reduced.
(4) The invention does not use solvent in the whole course, has little pollution, and is a green chemical process.
Drawings
FIG. 1 is a TEM image of (a) the ammonia synthesis catalyst prepared in example 1 and a corresponding statistical chart of (b) Ru particle diameters.
FIG. 2 shows the ammonia synthesis reaction rates of the catalysts obtained in example 1 and comparative examples 1 and 2 at different pressures of 400 ℃.
FIG. 3 is an ammonia synthesis stability of the catalyst of example 1 at 400℃and 1 MPa.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1:
A method for preparing a ruthenium-based catalyst, comprising the steps of:
(1) 2g of HIGH specific SURFACE area graphite carbon (HGC, specific SURFACE area 300m 2/g, TIMREX HIGH SURFACE-GRAPHITE available from TIMCAL) and 0.1903g of barium nitrate were weighed and placed in a mortar for grinding for 10min, the barium nitrate and HGC were initially mixed, and the mixture was transferred to a ball milling tank at a ball milling speed of 300r/min for 3h. The obtained product is placed in a tube furnace, mixed gas of hydrogen and argon with the volume ratio of 0.1 is introduced, the flow is 80mL/min, and the roasting is carried out for 2 hours at 400 ℃. Ba/HGC BM is obtained.
(2) 0.1625G of ruthenium acetylacetonate and 2g of Ba/HGC BM obtained in the step (1) were weighed, put into a mortar and ground for 10min, and the mixture was transferred into a ball mill pot at a ball mill rotation speed of 300r/min for 3h. Placing the obtained product in a tube furnace, introducing a mixed gas of hydrogen and argon with the volume ratio of 0.1, wherein the flow is 80mL/min, roasting for 2 hours at 400 ℃, tabletting at 90kN, and granulating to obtain 20-40 mesh Ba-Ru/HGC BM (the mass fraction (load amount) of Ru element relative to the catalyst is 2 wt.%).
Under the conditions that the hydrogen-nitrogen ratio of the mixed gas is 3:1, the airspeed is 60000mL g -1h-1, the reaction pressure is 1MPa, and the reaction temperature is 400 ℃, the ammonia synthesis activity of the Ba-Ru/HGC BM prepared by the embodiment is 18.7mmol NH3 gcat -1h-1.
Example 2:
The difference from example 1 is that: the ruthenium acetylacetonate is replaced by ruthenium nitrosyl nitrate, so that the serial ammonia synthesis catalysts of different ruthenium precursors can be prepared.
The catalyst prepared in this example had an ammonia synthesis activity of 17.1mmol NH3gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa and a reaction temperature of 400 ℃.
Example 3:
the difference from example 1 is that: the ruthenium acetylacetonate is replaced by ruthenium trichloride, so that the serial ammonia synthesis catalysts of different ruthenium precursors can be prepared.
The catalyst prepared in this example had an ammonia synthesis activity of 15.7mmol NH3gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa and a reaction temperature of 400 ℃.
Example 4:
the difference from example 1 is that: the ruthenium acetylacetonate is replaced by ruthenium acetate, and the serial ammonia synthesis catalysts of different ruthenium precursors can be prepared.
The catalyst prepared in this example had an ammonia synthesis activity of 17.3mmol NH3gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa, and a reaction temperature of 400 ℃.
Example 5:
The difference from example 1 is that: the barium nitrate is replaced by barium carbonate, so that the serial ammonia synthesis catalysts of different metal salt assistants can be prepared.
The catalyst prepared in this example had an ammonia synthesis activity of 16.2mmol NH3gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa and a reaction temperature of 400 ℃.
Example 6:
the difference from example 1 is that: the barium nitrate is replaced by the barium acetate, and then the serial ammonia synthesis catalysts of different metal salt assistants can be prepared.
The ammonia synthesis activity of the catalyst prepared in this example was 18.1mmol NH3gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa and a reaction temperature of 400 ℃.
Example 7:
The difference from example 1 is that: the barium nitrate is replaced by potassium nitrate, so that the serial ammonia synthesis catalysts with different metal salt assistants can be prepared.
The catalyst prepared in this example had an ammonia synthesis activity of 16.6mmol NH3gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa and a reaction temperature of 400 ℃.
Example 8:
The difference from example 1 is that: and replacing the barium nitrate with cesium nitrate to obtain the serial ammonia synthesis catalysts with different metal salt assistants.
The catalyst prepared in this example had an ammonia synthesis activity of 16.1mmol NH3gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa and a reaction temperature of 400 ℃.
Comparative example 1:
A method for preparing a ruthenium-based catalyst, comprising the steps of:
(1) 2g of graphite carbon with high specific surface area (HGC, specific surface area is 300m 2/g) and 0.1625g of ruthenium acetylacetonate are weighed, put into a mortar and ground for 10min, ruthenium acetylacetonate and HGC are primarily mixed, and then the mixture is transferred into a ball milling tank, wherein the ball milling speed is 300r/min, and the time is 3h. The obtained product is placed in a tube furnace, mixed gas of hydrogen and argon with the volume ratio of 0.1 is introduced, the flow is 80mL/min, and the roasting is carried out for 2 hours at 400 ℃. Ru/HGC BM (ball milling) was prepared.
(2) Weighing 0.1903g of barium nitrate and 2g of Ru/HGC BM obtained in the step (1), grinding for 10min in a mortar, and transferring the mixture into a ball milling tank, wherein the ball milling speed is 300r/min, and the time is 3h. Placing the obtained product in a tube furnace, introducing a mixed gas of hydrogen and argon with the volume ratio of 0.1, the flow rate being 80mL/min, roasting for 2 hours at 400 ℃, tabletting at 90kN, and granulating again to obtain 20-40 meshes of Ru-Ba/HGC BM.
The ammonia synthesis activity of the catalyst prepared in this comparative example was 7.4mmol NH3 gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa and a reaction temperature of 400 ℃.
Comparative example 2:
A method for preparing a ruthenium-based catalyst, comprising the steps of:
2g of high specific surface area graphite carbon (HGC, specific surface area is 300m 2/g), 0.1903g of barium nitrate and 0.1625g of ruthenium acetylacetonate are weighed and put into a mortar to be ground for 10min, the barium nitrate, the ruthenium acetylacetonate and the HGC are initially mixed, and then the mixture is transferred into a ball milling tank, wherein the ball milling speed is 300r/min, and the time is 3h. Placing the obtained product in a tube furnace, introducing a mixed gas of hydrogen and argon with the volume ratio of 0.1, the flow rate being 80mL/min, roasting for 2 hours at 400 ℃, tabletting and granulating to obtain Ru-Ba/HGC CO-BM (synchronous ball milling).
The ammonia synthesis activity of the catalyst prepared in this comparative example was 14.9mmol NH3 gcat -1h-1 at a mixed gas hydrogen to nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa and a reaction temperature of 400 ℃.
Evaluation of Ammonia Synthesis catalyst Performance
The catalysts of examples 1 to 8 and comparative examples 1 and 2 were taken at 0.20g each, a mass space velocity of 60,000mL g -1h-1, and an ammonia synthesis rate was measured on an ammonia synthesis catalyst performance evaluation device, and the NH 3 concentration change in the outlet tail gas was measured by ion chromatography (Thermo Scientific, DIONEX, ICS-600), and the reaction gas composition was: 25vol% N 2+75vol％H2. The ammonia synthesis rate of the catalyst was measured at 400℃and 1 MPa.
TABLE 1 Ammonia synthesis reaction Rate for ruthenium catalysts
As can be seen from Table 1, the synthetic ammonia performance of Ba-Ru/HGC BM of example 1 is best at 400 ℃ and 1MPa, 18.7mmol NH3 gcat -1h-1, which is 2.5 times that of Ru-Ba/HGC BM of comparative example 1, indicating that the catalyst can be significantly improved by first supporting the metal salt additive on the catalyst.
FIG. 1 is a TEM image of (a) the ammonia synthesis catalyst prepared in example 1 and a corresponding statistical chart of (b) Ru particle diameters. As can be seen from the figures: the catalyst is in a layered structure, and Ru nano particles are uniformly distributed on the surface and between layers of the catalyst. The average particle diameter of Ru nano particles obtained by particle diameter statistics is about 2.5nm, so that the B5 site is formed, and the B5 site is taken as a catalytic active center for ammonia synthesis and plays an important role in catalytic synthesis of ammonia reaction.
FIG. 2 shows the ammonia synthesis reaction rates of the catalysts obtained in example 1 and comparative examples 1 and 2 at different pressures of 400 ℃; as can be seen from fig. 2: the Ba-Ru/HGC BM catalyst prepared by firstly loading the metal salt auxiliary agent on the carrier has higher activity under mild conditions, thereby obviously improving the synthetic ammonia performance of the catalyst.
FIG. 3 is a graph showing the results of thermal stability test at 400℃and 1MPa for the catalyst obtained in example 1. (at a mixed gas hydrogen-nitrogen ratio of 3:1, a space velocity of 60000mL g -1h-1, a reaction pressure of 1MPa, a reaction temperature of 400 ℃, a test time of 120 hours, collecting outlet tail gas at different time periods and measuring the change of ammonia concentration therein). From the graph, the Ba-Ru/HGC BM catalyst prepared in example 1 is still stable after 120 hours of reaction at 400 ℃ and 1MPa, and has no obvious deactivation, thus showing that the Ba-Ru/HGC BM catalyst has good thermal stability.
The above description of exemplary embodiments of the invention has been provided. The scope of protection of the present invention is not limited to the embodiments described above. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, should be made by those skilled in the art, and are intended to be included within the scope of the present invention.
Claims (9)
1. The preparation method of the ruthenium-based catalyst is characterized by comprising the steps of roasting a Ru precursor and a metal salt modified carbon material at a high temperature of 300-400 ℃ for 0.5-4 hours to obtain the ruthenium-based catalyst;
The reaction mass ratio of the Ru precursor to the metal salt modified carbon material is 1 (2-15);
the Ru precursor is selected from at least one of ruthenium acetylacetonate, ruthenium nitrosylnitrate, ruthenium trichloride, ruthenium acetate and ruthenium lauroyl tricarbonyl;
The metal salt modified carbon material is prepared by roasting raw materials comprising a carbon material and a metal salt auxiliary agent at a high temperature of 300-400 ℃ for 0.5-4 hours;
the mass fraction of metal elements in the metal salt relative to the carbon material is 1% -10%;
the metal salt is at least one of nitrate, carbonate or acetate containing at least one of barium, potassium and cesium.
2. The production method according to claim 1, wherein the high-temperature calcination is performed under a mixed atmosphere;
the mixed gas is one of hydrogen and nitrogen, hydrogen and helium, and hydrogen and argon;
The volume ratio of the two gas components in the mixed gas is 0.1-0.6;
The gas flow of the mixed gas is 40-100 mL/min.
3. The method according to claim 1, wherein the Ru precursor and the metal salt modified carbon material are ball-milled at a rotational speed of 200-600r/min for 2-10h before high temperature calcination.
4. The preparation method of the metal salt modified carbon material according to claim 1, wherein the high-temperature roasting is performed in a mixed atmosphere;
the mixed gas is one of hydrogen and nitrogen, hydrogen and helium, and hydrogen and argon;
the volume ratio of the gas components in the mixed gas is 0.1-0.6;
the gas flow of the mixed gas is 40-100 mL/min;
the carbon material and the metal salt are subjected to ball milling before high-temperature roasting, the ball milling rotating speed is 200-600r/min, and the ball milling time is 2-10h.
5. The method of claim 1, further comprising tabletting the high temperature calcined product, wherein the tabletting pressure is between 30 kN and 300kN.
6. The method of any one of claims 1-5, comprising the steps of:
(1) Ball milling: ball milling is carried out on the carbon material and the metal salt auxiliary agent;
(2) And (3) reduction: heating the ball-milled carbon material to 300-400 ℃ in the mixed gas atmosphere, and roasting for 0.5-4 hours to obtain a metal salt modified carbon material;
(3) Ball milling: ball milling is carried out on the Ru precursor and the metal salt modified carbon material obtained in the step (2);
(4) And (3) reduction: heating the ball-milled material to 300-400 ℃ in the mixed gas atmosphere, and roasting for 0.5-4 h;
(5) And (3) forming: tabletting the material obtained in the step (4);
(6) Granulating: crushing the material obtained in the step (5), and sieving to obtain the ruthenium-based catalyst.
7. The ruthenium-based catalyst prepared by the preparation method of any one of claims 1 to 6.
8. The ruthenium-based catalyst according to claim 7, wherein the catalyst comprises a carbon support and ruthenium and a metal oxide supported on the support;
in the catalyst, the mass fraction of ruthenium relative to the catalyst is 1wt.% to 10wt.%;
The metal oxide is an oxide containing at least one of barium, potassium and cesium; in the catalyst, the mass fraction of the metal element in the metal oxide relative to the catalyst is 1wt.% to 10wt.%.
9. Use of the ruthenium-based catalyst prepared by the preparation method according to any one of claims 1 to 6 and/or the ruthenium-based catalyst according to any one of claims 7 to 8 in the field of ammonia synthesis.
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| CN103736487A (en) * | 2013-12-29 | 2014-04-23 | 浙江工业大学 | Method for preparing supported metal catalyst through solvent-free mechanical mixing |
| CN105413683A (en) * | 2015-12-18 | 2016-03-23 | 福州大学 | Preparation method of carbon material-supported ruthenium metal catalyst containing barium auxiliary agent |
| CN110302778A (en) * | 2019-07-05 | 2019-10-08 | 浙江工业大学 | A kind of charcoal loading ruthenium ammonia synthesis catalyst and preparation method thereof |
| CN111185164A (en) * | 2020-03-06 | 2020-05-22 | 福州大学 | Ammonia synthesis catalyst with ruthenium acetate as precursor and preparation method thereof |
| CN114789053A (en) * | 2022-05-06 | 2022-07-26 | 福州大学 | Ruthenium-based mild synthetic ammonia catalyst and preparation method and application thereof |
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| CN103736487A (en) * | 2013-12-29 | 2014-04-23 | 浙江工业大学 | Method for preparing supported metal catalyst through solvent-free mechanical mixing |
| CN105413683A (en) * | 2015-12-18 | 2016-03-23 | 福州大学 | Preparation method of carbon material-supported ruthenium metal catalyst containing barium auxiliary agent |
| CN110302778A (en) * | 2019-07-05 | 2019-10-08 | 浙江工业大学 | A kind of charcoal loading ruthenium ammonia synthesis catalyst and preparation method thereof |
| CN111185164A (en) * | 2020-03-06 | 2020-05-22 | 福州大学 | Ammonia synthesis catalyst with ruthenium acetate as precursor and preparation method thereof |
| CN114789053A (en) * | 2022-05-06 | 2022-07-26 | 福州大学 | Ruthenium-based mild synthetic ammonia catalyst and preparation method and application thereof |
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