WO2021137643A1 - 루테늄 전구체, 이를 이용한 암모니아 반응 촉매 및 그 제조방법 - Google Patents
루테늄 전구체, 이를 이용한 암모니아 반응 촉매 및 그 제조방법 Download PDFInfo
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- WO2021137643A1 WO2021137643A1 PCT/KR2020/019461 KR2020019461W WO2021137643A1 WO 2021137643 A1 WO2021137643 A1 WO 2021137643A1 KR 2020019461 W KR2020019461 W KR 2020019461W WO 2021137643 A1 WO2021137643 A1 WO 2021137643A1
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- WIPO (PCT)
- Prior art keywords
- ruthenium
- catalyst
- integer
- ammonia decomposition
- ruthenium precursor
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 171
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 151
- 239000002243 precursor Substances 0.000 title claims abstract description 93
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 84
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 103
- 229910052746 lanthanum Inorganic materials 0.000 claims description 20
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- 239000001257 hydrogen Substances 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 description 29
- 239000002184 metal Substances 0.000 description 29
- 238000005245 sintering Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- -1 bis (ethylcyclopentadienyl) ruthenium (II) (Bis (ethylcyclopentadienyl) ruthenium (II)) Chemical compound 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- WOSOOWIGVAKGOC-UHFFFAOYSA-N azanylidyneoxidanium;ruthenium(2+);trinitrate Chemical compound [Ru+2].[O+]#N.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WOSOOWIGVAKGOC-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical group [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VNBCLZZFHLADIG-UHFFFAOYSA-K butanoate ruthenium(3+) Chemical compound [Ru+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O VNBCLZZFHLADIG-UHFFFAOYSA-K 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052747 lanthanoid Inorganic materials 0.000 description 4
- 150000002602 lanthanoids Chemical class 0.000 description 4
- LEIZJJNFNQIIKH-UHFFFAOYSA-K propanoate;ruthenium(3+) Chemical compound [Ru+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O LEIZJJNFNQIIKH-UHFFFAOYSA-K 0.000 description 4
- BNBKCTCLPAQLAH-UHFFFAOYSA-K ruthenium(3+) triformate Chemical compound [Ru+3].[O-]C=O.[O-]C=O.[O-]C=O BNBKCTCLPAQLAH-UHFFFAOYSA-K 0.000 description 4
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- ADUHWSSSJSJHRI-UHFFFAOYSA-N ruthenium(2+) 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound [Ru++].Cc1[cH-]c(C)c(C)c1C.Cc1[cH-]c(C)c(C)c1C ADUHWSSSJSJHRI-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- WYILUGVDWAFRSG-UHFFFAOYSA-N 2,4-dimethylpenta-1,3-diene;ruthenium(2+) Chemical compound [Ru+2].CC(C)=CC(C)=[CH-].CC(C)=CC(C)=[CH-] WYILUGVDWAFRSG-UHFFFAOYSA-N 0.000 description 2
- OXJUCLBTTSNHOF-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene;ruthenium(2+) Chemical compound [Ru+2].CC[C-]1C=CC=C1.CC[C-]1C=CC=C1 OXJUCLBTTSNHOF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JFLCCNYEBDYEIR-UHFFFAOYSA-N CC(C)=CC(C)=C[Ru]C=C(C)C=C(C)C Chemical compound CC(C)=CC(C)=C[Ru]C=C(C)C=C(C)C JFLCCNYEBDYEIR-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- VLTZUJBHIUUHIK-UHFFFAOYSA-N ethylcyclopentane;ruthenium Chemical compound [Ru].CC[C]1[CH][CH][CH][CH]1.CC[C]1[CH][CH][CH][CH]1 VLTZUJBHIUUHIK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910020203 CeO Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- HVMFKXBHFRRAAD-UHFFFAOYSA-N lanthanum(3+);trinitrate;hydrate Chemical compound O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVMFKXBHFRRAAD-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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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
- C01B2203/1064—Platinum group metal catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a ruthenium precursor compound, and more particularly, to a ruthenium precursor compound for providing ruthenium to an ammonia decomposition reaction catalyst, and a method for preparing a ruthenium-based ammonia reaction catalyst using the same.
- Fossil fuels are currently the most widely used resource, but the problem of global warming due to their indiscriminate use is emerging. Accordingly, research and development of clean energy sources is considered important, and in particular, various studies on the production and utilization of hydrogen are in progress.
- the representative hydrogen produced by current hydrogen production technology is fossil fuel-based byproduct hydrogen, extracted hydrogen, and renewable energy-based electrolyzed hydrogen.
- a representative production method of extracted hydrogen obtained from fossil fuels is a method of producing a mixed gas of hydrogen and carbon monoxide using steam reforming reaction and separating and refining it to produce hydrogen, but it does not meet the decarbonization policy from a long-term perspective. .
- ammonia can be decomposed only with nitrogen and hydrogen as shown in the following reaction formula, and unlike hydrogen production through the decomposition of fossil fuels, it does not cause environmental problems, so active research is required.
- Japanese Patent No. 5778309 discloses a method of using a catalyst containing cobalt or nickel, and a metal compound to produce hydrogen by decomposing ammonia
- Korean Patent No. 1938333 discloses a catalyst for ammonia oxidation. Square platinum nanoparticles are disclosed.
- Korea Patent No. 1924952 discloses a catalyst for generating hydrogen from ammonia containing a metal such as ruthenium, but research on a ruthenium precursor essential for preparing such a ruthenium-containing catalyst is insufficient. .
- the ruthenium precursor compound of the present invention has been devised to solve the above problems, and an object of the present invention is to present a ruthenium precursor compound for providing ruthenium to an ammonia decomposition reaction catalyst.
- Another object of the present invention is to provide a method for preparing an ammonia decomposition catalyst using the ruthenium precursor compound.
- the present invention may also have as its object to achieve these objects and other objects that can be easily derived by a person skilled in the art from the general description of the present specification in addition to the above clear objects.
- the ruthenium precursor compound of the present invention has been devised to solve the above problems, and is a ruthenium precursor compound for providing ruthenium to an ammonia decomposition catalyst, wherein the ruthenium precursor is represented by the following Chemical Formula 1.
- x is an integer from 3 to 20
- y is an integer from 0 to 32
- z is an integer from 0 to 20
- m is an integer from 0 to 10
- n is an integer from 1 to 3.
- the ruthenium precursor may include a carbonyl group, an ester group, a carboxyl group, a nitrile, a nitro group, an amine group, or a carboxylate.
- the ruthenium precursor may not include a halogen element.
- At least one carbonyl may be directly bonded to ruthenium.
- the ruthenium precursor may be selected from the group consisting of ruthenium pentacarbonyl, triruthenium dodecacarbonyl, ruthenium (III) nitrosyl nitrate, ruthenium (III) acetylacetonate, and mixtures thereof.
- ruthenium may form a coordination bond with at least one compound of an unsaturated compound, an aromatic compound, and a nitrogen oxide.
- the ruthenium precursor is ruthenocene, ruthenium (III) nitrosyl nitrate solution (Ruthenium (III) nitrosyl nitrate solution), bis (ethylcyclopentadienyl) ruthenium (II) (Bis (ethylcyclopentadienyl) ruthenium (II)) , Bis(cyclopentadienyl)ruthenium(II)(Bis(cyclopentadienyl)ruthenium(II)), Bis(2,4-dimethylpentadienyl)ruthenium(II)(Bis(2,4-dimethylpentadienyl)ruthenium(II) )), bis(cyclopentadienylruthenium dicarbonyl) dimer (Bis(cyclopentadienylruthenium dicarbonyl) dimer), octamethylruthenocene, ruthenium formate,
- ammonia decomposition reaction catalyst may include a support doped with a lanthanum element.
- the lanthanide element may be selected from the group consisting of lanthanum, cerium, and mixtures thereof.
- the support is SiO 2 , CeO 2 , ZrO 2 , TiO 2 , MgO, Al 2 O 3 , V 2 O 5 , Fe 2 O 3 , Co 3 O 4 , Ce-ZrO x , MgO-Al 2 O 3 , and may be selected from the group consisting of mixtures thereof.
- ammonia decomposition reaction catalyst may be lanthanum aluminate.
- x is an integer from 3 to 20
- y is an integer from 0 to 32
- z is an integer from 0 to 20
- m is an integer from 0 to 10
- n is an integer from 1 to 3.
- the ruthenium precursor may include a carbonyl group, an ester group, a carboxyl group, a nitrile, a nitro group, an amine group, or a carboxylate.
- At least one carbonyl may be directly bonded to ruthenium.
- the ruthenium precursor is, ruthenium pentacarbonyl, triruthenium dodecacarbonyl, ruthenocene, ruthenium (III) nitrosyl nitrate solution (Ruthenium (III) nitrosyl nitrate solution), bis (ethylcyclopentadienyl) ruthenium (II)(Bis(ethylcyclopentadienyl)ruthenium(II)), bis(cyclopentadienyl)ruthenium(II)(Bis(cyclopentadienyl)ruthenium(II)), bis(2,4-dimethylpentadienyl)ruthenium(II) ) (Bis (2,4-dimethylpentadienyl) ruthenium (II)), bis (cyclopentadienylruthenium dicarbonyl) dimer (Bis (cyclopentadienylruthenium dicarbonyl) dimer
- ruthenium may form a coordination bond with at least one of unsaturated compounds, aromatic compounds, and nitrogen oxides.
- the ruthenium precursor may be selected from the group consisting of ruthenium formate, ruthenium acetate, ruthenium propionate, ruthenium butyrate, tris(acetylacetonate)ruthenium, and mixtures thereof.
- the solvent may be selected from the group consisting of water, hexane, toluene, and mixtures thereof.
- the catalyst support may include a lanthanide element.
- the lanthanide element may be selected from the group consisting of lanthanum, cerium, and mixtures thereof.
- the catalyst support is SiO 2 , CeO 2 , ZrO 2 , TiO 2 , MgO, Al 2 O 3 , V 2 O 5 , Fe 2 O 3 , Co 3 O 4 , Ce-ZrO x , MgO-Al 2 O 3 , and mixtures thereof.
- the catalyst support may be lanthanum aluminate.
- the catalyst support may be a powder type, a pellet type, or a monolith type.
- (C) removing the liquid component by boiling may further include.
- step (C) may be carried out under the conditions of 10 to 100 °C, preferably 30 to 90 °C, more preferably 40 to 80 °C.
- (D) drying may further include.
- step (D) may be carried out at 50 to 200 °C, preferably 80 to 150 °C, more preferably 100 to 120 °C conditions.
- It may contain; 0.1 to 100 mole parts of lanthanum, preferably 2 to 60 mole parts, more preferably 5 to 30 mole parts.
- ammonia decomposition catalyst of the present invention is characterized in that it was prepared according to the method for preparing the ruthenium-based ammonia decomposition catalyst.
- It may contain; 0.01 to 5 parts by weight of ruthenium, preferably 0.02 to 3 parts by weight, more preferably 0.1 to 2 parts by weight.
- the ruthenium-based ammonia decomposition reaction catalyst may exhibit an ammonia conversion rate of 65 to 100%, preferably 72 to 100%, more preferably 76.5 to 100% under the following reaction conditions.
- GHSV ml/h g cat : 1,000 to 100,000.
- hydrogen chloride is not generated during the reduction treatment of the ruthenium precursor, thereby preventing corrosion inside the reactor and deterioration of durability of the device.
- ammonia decomposition reaction catalyst according to the present invention has excellent thermal stability, thereby suppressing sintering at high temperatures and inhibiting the growth of ruthenium metal to maintain a large surface area, so that the performance as a catalyst is very excellent.
- the method for preparing the ammonia decomposition catalyst according to the present invention is a method of introducing ruthenium into the ammonia decomposition reaction catalyst using the ruthenium precursor. has significantly improved performance.
- FIG. 2 is a view showing that the gasket and the inside of the reactor are contaminated by the reduction treatment of the conventional ruthenium precursor.
- the ruthenium precursor compound of the present invention is a ruthenium precursor compound for providing ruthenium to the ammonia decomposition reaction catalyst, wherein the ruthenium precursor is represented by the following formula (1).
- x is an integer from 3 to 20
- y is an integer from 0 to 32
- z is an integer from 0 to 20
- m is an integer from 0 to 10
- n is an integer from 1 to 3.
- Table 1 shows the results of performing IC (Ion chromatography) analysis to confirm the presence of the Cl ⁇ component in the catalyst phase and whether the Cl ⁇ component is decreased according to the H 2 reduction treatment.
- IC IC
- Table 1 shows the results of performing IC (Ion chromatography) analysis to confirm the presence of the Cl ⁇ component in the catalyst phase and whether the Cl ⁇ component is decreased according to the H 2 reduction treatment.
- the ruthenium precursor compound of the present invention is a compound represented by the above formula (1), characterized in that it does not contain a halogen element, and in particular does not contain chlorine, so unlike a ruthenium precursor such as ruthenium chloride, hydrogen chloride is generated even during reduction treatment I never do that. Therefore, the ruthenium precursor compound according to the present invention can prevent the generation of by-products affecting the reactor, thereby solving the conventional device durability degradation problem and achieving high economic efficiency.
- the ruthenium precursor of the present invention may include a carbonyl group, an ester group, a nitrile, a nitro group, an amine group, or a carboxyl group, and the ruthenium precursor is ruthenium (III) nitrosyl nitrate.
- ruthenium (III) formate ruthenium (III) acetate, ruthenium (III) propionate, ruthenium (III) butyrate, ruthenium (III) nitrosyl nitrate solution (Ruthenium (III) nitrosyl nitrate solution), bis (ethyl Cyclopentadienyl)ruthenium(II)(Bis(ethylcyclopentadienyl)ruthenium(II)), Bis(cyclopentadienyl)ruthenium(II)(Bis(cyclopentadienyl)ruthenium(II)), Bis(2,4-dimethylpenta Dienyl) ruthenium (II) (Bis (2,4-dimethylpentadienyl) ruthenium (II)), bis (cyclopentadienylruthenium dicarbonyl) dimer (Bis (cyclopentadienylruthenium di
- one or more carbonyls may be directly bonded to ruthenium, and preferably 2 to 4 carbonyls may be bonded to ruthenium.
- the ruthenium precursor compound is preferably selected from ruthenium pentacarbonyl, triruthenium dodecacarbonyl, and mixtures thereof, but is not limited thereto.
- ruthenium may form a coordination bond with at least one of unsaturated compounds, aromatic compounds, and nitrogen oxides.
- a ruthenium precursor composed of the above bonds without including a halogen such as chlorine the performance of the catalyst can be improved without by-products.
- the unsaturated compound may be a carbonyl compound, an enol compound, an ester compound, or a carboxylic acid compound, and the aromatic compound may be an aromatic cyclic hydrocarbon or an aromatic cyclic hydrocarbon having a substituent.
- a ruthenium precursor it is preferable to be selected from ruthenocene, octamethylruthenocene, ruthenium formate, ruthenium acetate, ruthenium propionate, ruthenium butyrate, tris(acetylacetonate)ruthenium, and mixtures thereof.
- the present invention is not limited thereto.
- ammonia decomposition reaction catalyst receiving ruthenium through the ruthenium precursor of the present invention may be a catalyst in which a support is doped with a lanthanum group.
- the lanthanum group may be selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and mixtures thereof, but lanthanum (La ) is preferred.
- the support is alumina, SiO 2 , CeO 2 , ZrO 2 , TiO 2 , MgO, Al 2 O 3 , V 2 O 5 , Fe 2 O 3 , Co 3 O 4 , Ce-ZrO x , MgO-Al 2 O 3 , and mixtures thereof.
- ruthenium is introduced into lanthanum aluminate (LaAlO 3 ) in which lanthanum is doped into alumina using the lanthanum precursor according to the present invention, an excellent ammonia conversion rate may be exhibited.
- the ammonia reaction catalyst formed using the ruthenium precursor according to the present invention is ruthenium under reducing conditions of 650 to 1000 °C, 700 to 900 °C, or 800 to 900 °C, 60 to 100 hours, 70 to 90 hours, 75 to 85 hours.
- the particle size may be 10 nm or less, 8 nm or less, 5 nm or less, 4 nm or less, 3 nm or less, 2 nm or less, or 1 nm or less.
- the lower limit of the particle size is not particularly limited, but may be 0.01 nm or more, 0.1 nm or more, or 0.5 nm or more.
- the ammonia reaction catalyst according to the present invention is characterized in that growth by sintering of ruthenium metal at 650 to 1000 °C, 700 to 900 °C, or 800 to 900 °C is very suppressed. This maximizes the surface area of the metal so that the function of the catalyst can be efficiently exhibited.
- this feature is a feature of the ruthenium-based catalyst formed by the ruthenium precursor according to the present invention, and the ammonia reaction catalyst formed by the ruthenium precursor containing chlorine, such as ruthenium chloride, is used for the growth of ruthenium metal by sintering under the reducing conditions. This is in contrast to the disadvantage of high-temperature operation.
- x is an integer from 3 to 20
- y is an integer from 0 to 32
- z is an integer from 0 to 20
- m is an integer from 0 to 10
- n may be an integer from 1 to 3 .
- the method for preparing an ammonia decomposition catalyst according to the present invention has a technical feature in using the ruthenium precursor according to the present invention represented by Chemical Formula 1 described above.
- the performance of the catalyst could be significantly increased or decreased depending on the ruthenium precursor used when ruthenium was introduced.
- each step will be described in detail.
- a ruthenium precursor solution is prepared by dissolving the ruthenium precursor represented by Chemical Formula 1 in a solvent.
- the solvent may be selected from the group consisting of water, hexane, toluene, and mixtures thereof, and the water is preferably pure (D.I.water).
- the catalyst support and the ruthenium precursor solution are mixed to provide ruthenium to the catalyst support.
- the ruthenium precursor does not contain a halogen such as chlorine, and may include a carbonyl group, an ester group, a carboxyl group, a nitrile, a nitro group, an amine group, or a carboxylic acid salt, of which two or more functional groups may include
- at least one carbonyl may be directly bonded to each ruthenium element, preferably 2 to 5 carbonyls, more preferably 4 or 5 carbonyl atoms may be bonded to each other.
- the catalyst support may include a lanthanide element, preferably lanthanum (La).
- the catalyst support doped with the lanthanum group is preferably a powder type, a pellet type, or a monolith type from the viewpoint of catalyst performance.
- ammonia decomposition catalyst preparation method of the present invention is after the step (B),
- (C) removing the liquid component by hot water may further include, which is 10 to 100 °C, preferably 30 to 90 °C, more preferably 40 to 80 °C 1 hour to 6 hours, Preferably it may be carried out for 1 hour to 4 hours, more preferably 1 hour to 3 hours, and an evaporator may be used.
- the reaction temperature exceeds the above range, the solvent volatilizes too quickly and the components included in the precursor may be supported non-uniformly. It may cause uneven loading.
- ammonia decomposition catalyst preparation method of the present invention is after the step (C),
- (D) drying step may further include; 50 to 200 °C, preferably 80 to 150 °C, more preferably from 100 to 120 °C 8 hours to 16 hours, preferably 9 hours to 15 hours, more preferably 10 hours to 12 hours.
- the drying temperature exceeds the above range, partially supported Ru may be lost due to non-uniform drying of the catalyst surface due to excessively rapid drying.
- lanthanum preferably 2 to 60 mol parts, more preferably 5 to 30 mol parts;
- the specific surface area is significantly reduced, which may result in lowering the dispersion degree of Ru, which is an active metal.
- the ammonia decomposition catalyst according to the present invention is prepared using the ruthenium precursor of the present invention, characterized in that it contains ruthenium, and can be prepared according to the method for preparing the ammonia decomposition catalyst according to the present invention.
- It may contain 0.01 to 5 parts by weight of ruthenium, preferably 0.02 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight.
- weight part of ruthenium is less than the above range, the effect of improving catalyst performance is insignificant, and when it exceeds the above range, efficiency is reduced and a problem of high cost occurs.
- the ammonia decomposition reaction catalyst prepared as described above may exhibit an ammonia conversion rate of 65 to 100%, preferably 72 to 100%, and more preferably 76.5 to 100% under the following reaction conditions.
- GHSV ml/h ⁇ gcat: 1,000 to 100,000, preferably 1,000 to 50,000, more preferably 1,000 to 10,000.
- the ammonia conversion rate refers to the amount of ammonia gas decomposed relative to the amount of ammonia gas input.
- FIG. 3 is an external (first row) and internal (second row) image as an image before reaction of a catalyst prepared by changing a ruthenium precursor
- FIG. 4 is an external (first row) and internal image as an image after reaction of the catalyst (Second row) This is a view from the left, respectively, when RuCl 3 , Ru 3 (CO) 12 , C 16 H 22 O 2 Ru, and C 18 H 26 Ru are used as ruthenium precursors.
- ruthenium precursor in the case of a catalyst prepared by using triruthenium dodecacarbonyl as a ruthenium precursor, a large amount of ruthenium may be present on the surface of the catalyst because the ruthenium precursor is supported outside the pellet, and they are actively involved in the reaction of ammonia to produce ammonia. It can be seen that the conversion rate is greatly improved.
- Ru 3 (CO) 12 triruthenium dodecacarbonyl, DCR
- An ammonia decomposition reaction catalyst was prepared in the same manner as in Example 1, except that RuCl 3 was used as the ruthenium precursor.
- An ammonia decomposition catalyst was prepared in the same manner as in Example 1, except that Ru(C 5 H 7 O 2 ) 3 was used as a ruthenium precursor.
- An ammonia decomposition catalyst was prepared in the same manner as in Example 1, except that C 7 H 9 RuC 7 H 9 was used as the ruthenium precursor.
- Ammonia gas was supplied here at a flow rate of 100 to 500 sccm, and the ammonia conversion rate was measured in the range of 450 to 550 °C under the conditions of GHSV 1,000 to 5000 ml/h g cat (FIG. 1).
- the ammonia conversion rate measurement results of Example 1 and Comparative Example 1 together with the control example in the equilibrium state are shown in Table 2 below.
- the ammonia decomposition catalyst according to Example 1 that is, the catalyst prepared using the Ru 3 (CO) 12 compound exhibited an excellent conversion rate throughout the temperature range, and in particular, the ammonia conversion rate at 450° C. was 76.5% ruthenium chloride (RuCl 3 ) As a precursor, it was confirmed that the conversion rate was significantly better than that of the ammonia decomposition catalyst of Comparative Example 1 of 65.1%.
- the catalyst prepared with Ru 3 (CO) 12 according to the present invention suppressed the growth of Ru metal under the conditions in which high-temperature sintering is induced, and it is expected that the catalyst can be operated stably under high-temperature conditions.
- the growth of the Ru metal was achieved by the sintering phenomenon as the reduction temperature increased compared to before the reduction (FIG. 7), but in the case of Example 1, the growth of the Ru metal was suppressed even under the condition in which high-temperature sintering was induced was able to confirm that Through this, it can be seen that the Ru catalyst according to the present invention has excellent thermal stability, prevents performance decrease due to sintering under high-temperature operating conditions, and maintains a large surface area, thereby exhibiting excellent performance as a catalyst.
- FIGS. 9 and 10 The reduction of the Ru/LaAlO 3 catalyst prepared using RuCl 3 as a precursor according to Comparative Example 1 and the sintering of Ru metal according to operating temperatures (700° C. and 1000° C.) were observed ( FIGS. 9 and 10 ).
- 9 is a reduction treatment at 700° C. for 2 hours
- FIG. 10 is an observation result after reduction treatment at 1000° C. for 2 hours.
- the scale bar units at the bottom are 100 nm, 50 nm, and 20 nm, respectively. While magnifying, sintering of Ru metal was observed.
- a portion indicated by a large dotted line box in the left image of FIG. 9 corresponds to the central image of FIG. 9
- FIG. 9 corresponds to the right image of FIG. 9 .
- a portion indicated by a large dotted line box in the left image of FIG. 10 corresponds to the center image of FIG. 10
- a small dotted line box in the left image of FIG. 10 corresponds to the right image of FIG. 10 .
- Ru metal grew in the range of 5 ⁇ 21 nm, and in the case of the sample operated at 1000 °C or higher, the Ru metal grew in the range of 9 ⁇ 58 nm.
- Such an increase in metal diameter causes a decrease in the metal surface area and can be a direct cause of the decrease in catalyst performance.
- the Ru metal showed distinct growth in the sample operated at 1000°C or higher compared to the 700°C reduction operation sample.
- Ru and Cl were distributed in similar positions, and it was determined that the presence of Cl had a direct or indirect effect on the growth of Ru.
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Abstract
Description
Concentration of chloride (%) | |
w/o H2 reduction | 5.35 |
w/ H2 reduction | 1.05 |
암모니아 전환율(%) | |||||
450℃ | 475℃ | 500℃ | 525℃ | 550℃ | |
Equilibrium | 99.5 | 99.6 | 99.7 | 99.99 | 99.99 |
실시예1 | 76.5 | 91.5 | 98.5 | 99.9 | 99.99 |
비교예1 | 65.1 | 89.1 | 98.3 | 99.9 | 99.99 |
Claims (9)
- 암모니아 분해 반응 촉매에 루테늄을 제공하기 위한 루테늄 전구체 화합물로서, 상기 루테늄 전구체는 하기 화학식 1로 표시되는 것을 특징으로 하는, 루테늄 전구체 화합물:[화학식 1]CxHyOzNmRun상기 화학식 1에서, x는 3 내지 20의 정수이고, y는 0 내지 32의 정수이고, z는 0 내지 20의 정수이고, m은 0 내지 10의 정수이고, n은 1 내지 3의 정수임.
- 청구항 1에 있어서,상기 루테늄 전구체는 카르보닐기, 에스테르기, 카르복실기, 나이트릴, 니트로기, 아민기, 또는 카르복실산염을 포함하는 것을 특징으로 하는, 루테늄 전구체 화합물.
- 청구항 1에 있어서,상기 루테늄 전구체는 루테늄이 불포화 화합물, 방향족 화합물, 및 질소산화물 중 적어도 1 이상의 화합물과 배위결합을 형성하고 있는 것을 특징으로 하는, 루테늄 전구체 화합물.
- 청구항 1에 있어서,상기 암모니아 분해 반응 촉매는 란타넘족 원소가 도핑된 지지체를 포함하는 것을 특징으로 하는, 루테늄 전구체 화합물.
- (A) 하기 화학식 1로 표시되는 루테늄 전구체를 용매에 녹여 루테늄 전구체 용액을 제조하는 단계; 및(B) 촉매 지지체와 상기 루테늄 전구체 용액을 혼합하여 촉매 지지체에 루테늄을 제공하는 단계;를 포함하는, 루테늄계 암모니아 분해 반응 촉매의 제조방법:[화학식 1]CxHyOzNmRunx는 3 내지 20의 정수이고, y는 0 내지 32의 정수이고, z는 0 내지 20의 정수이고, m은 0 내지 10의 정수이고, n은 1 내지 3의 정수임.
- 청구항 5에 있어서,상기 단계 (B) 이후,(C) 중탕하여 액상성분을 제거하는 단계;를 더 포함하는, 루테늄계 암모니아 분해 반응 촉매의 제조방법.
- 청구항 5에 있어서,상기 루테늄계 암모니아 분해 반응 촉매는,루테늄계 암모니아 분해 반응 촉매 100 몰부; 및란타늄 0.1 내지 100 몰부;를 포함하는 것을 특징으로 하는, 루테늄계 암모니아 분해 반응 촉매의 제조방법.
- 청구항 5 내지 7 중 어느 한 항의 제조방법에 따라 제조된 루테늄계 암모니아 분해 반응 촉매.
- 청구항 8에 있어서,상기 루테늄계 암모니아 분해 반응 촉매는,루테늄계 암모니아 분해 반응 촉매 100 중량부; 및루테늄 0.01 내지 5 중량부;를 포함하는 것을 특징으로 하는, 루테늄계 암모니아 분해 반응 촉매.
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JP2022540806A JP7400111B2 (ja) | 2019-12-30 | 2020-12-30 | ルテニウム前駆体、それを用いたアンモニア反応触媒及びその製造方法 |
EP20908711.3A EP4085997A4 (en) | 2019-12-30 | 2020-12-30 | RUTHENIUM PRECURSOR, AMMONIA REACTION CATALYST USING SAME, AND ASSOCIATED MANUFACTURING METHOD |
CN202080091145.0A CN114929381A (zh) | 2019-12-30 | 2020-12-30 | 利用钌前体的氨化反应催化剂及相关制作方法 |
US17/789,640 US20230041936A1 (en) | 2019-12-30 | 2020-12-30 | Ruthenium precursor, ammonia reaction catalyst using same, and preparation method thereof |
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US20230041936A1 (en) | 2023-02-09 |
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