WO2010060736A1 - Catalyseurs à base de métaux non nobles pour la décomposition de l'ammoniac et leur préparation - Google Patents
Catalyseurs à base de métaux non nobles pour la décomposition de l'ammoniac et leur préparation Download PDFInfo
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- WO2010060736A1 WO2010060736A1 PCT/EP2009/064425 EP2009064425W WO2010060736A1 WO 2010060736 A1 WO2010060736 A1 WO 2010060736A1 EP 2009064425 W EP2009064425 W EP 2009064425W WO 2010060736 A1 WO2010060736 A1 WO 2010060736A1
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- Prior art keywords
- ammonia
- hydrogen
- catalysts
- noble metals
- catalyst
- Prior art date
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 title claims description 19
- 238000000354 decomposition reaction Methods 0.000 title abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 15
- 230000008021 deposition Effects 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000011368 organic material Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910003320 CeOx Inorganic materials 0.000 claims description 3
- -1 MgAI2O4 Chemical compound 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 5
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 5
- 239000011147 inorganic material Substances 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 238000007669 thermal treatment Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J23/74—Iron group 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
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
Definitions
- the present invention refers to the non-noble metals based catalysts, in particular to their preparation and use for decomposition of ammonia.
- ammonia is its availability both from degradation processes of organic waste and from direct synthesis, and its density that allows, for the same volume of gas, to contain more hydrogen than pure H 2 gas, providing an effective intermediate for hydrogen storage that does not require the drastic conditions of pressure and temperature demanded by pure hydrogen storage. Furthermore, while the large scale employment of hydrogen powered vehicles would require a drastic change in the local distribution network to adequate it to the security parameters required for the storage of such material, ammonia can be transported more easily, and in some countries such as USA it is already widely distributed to be used as fertilizer. Moreover, when new technologies for providing hydrogen from renewable sources will become available, since the efficiency of conversion process from hydrogen to ammonia is about 90 %, this technique would make an advantageous solution in terms of hydrogen storage.
- these catalysts contains together with non-noble metals such as copper also small amounts of platinum, thus not showing its ability to perform the reforming of ammonia using only metals easily available. Furthermore, the amount of ammonia treated is very small (1 wt.% in air) and is not guaranteed the possibility to treat larger amounts as required by an internal combustion engine. Moreover in this case the reaction of ammonia decomposition has not place, but rather its oxidation in air. It is therefore evident the need of catalysts based on non-noble metals that are capable of promoting the decomposition of ammonia.
- Figure 1 - shows conversion values as a function of temperature for decomposition of ammonia, using some of the catalysts of this invention compared to the commercial catalyst G90-B (S ⁇ d Chemie)
- Figure. 2 - shows for some catalysts of the invention the influence of polymer loading on the support surface area and activity for ammonia decomposition at
- the present invention relates to nanoparticled catalysts based on non-noble metals or their corresponding oxides or mixture thereof supported on a porous inorganic material obtained by a process comprising the following steps: i. preparation of the support by coating the porous inorganic material with an organic material and subsequent pyrolysis; ii. deposition onto the support of ions of the above mentioned non-noble metals by impregnation and subsequent reducing or oxidizing thermal treatment, depending on the required active metal phase metal form with the zero oxidation grade, or metal oxides or mixture thereof.
- non-noble metals or metal oxides are selected from the first series of transition metals, preferable Fe, Co and Ni and/or their mixtures and/or alloys.
- Said porous inorganic material is selected from metal oxides or their mixtures such as AI 2 O 3 , ZrO 2 , CeO x , MgO, MgAI 2 O 4 , La 2 O 3 , SiO 2 , Y 2 O 3 ; preferably AI 2 O 3 , ZrO 2 , CeOx, MgO or MgAI 2 O 4 (which have been proved to be some of the most active for these catalysts) eventually enriched with doping amounts of promoters such as
- Preparation of the support able to activate and promote the catalytic activity for catalytic decomposition of ammonia consists in covering fine particles of metal oxides (the porous inorganic material) by impregnation (or combination in various forms of some metal oxides) with a nano-structured organic material comprising carbon, nitrogen and oxygen, at least two aromatic or heteroaromatic groups and at least one conjugated double bond, in order to arrange the organic coating, through intra- and intermolecular binding bond in a structure very rigid and stable.
- R1 is chosen from the group consisting of: H and a hydrocarbon radical having from 1 to 10 carbon atoms, possible halogenated
- R2 and R3 independently represent preferentially a electron-attractor group consisting of hydrogen, halogen, acyl, ester, carboxylic acid, formyl, nitrile, sulfonic acid, aryl groups, linear or branched alkyl groups having 1 to 15 carbon atoms possible functionalized with halogens or linked together to form one or more condensed cycles with phenyl ring and nitro groups or a polymer selected from those described in WO2004/036674A2 represented by the formula (C)
- the coating of an inorganic support with an organic material can be done using classic impregnation methods (e.g. wet or incipient wetness) at a temperature comprised between 20 and 90 °C, according to the solvent and to the pressure used to dissolve the organic material.
- solvent depending on the concentration and the solubility of the organic matrix, can be used for example water, alcohols, aldehydes and/or ketones or other solvents that are efficient for such purpose.
- the solvents used in this phase of the process are water, at a pH comprised between 9 and 12, or ethanol, acetone, DMF, DMSO.
- the ratio between the organic material and inorganic support play a fundamental role, inducing very important and substantial structural modifications in the obtained composite materials, especially related to surface area and porosity of the support (see Table 2).
- the investigations regarding catalyst composition pointed out that the amount of organic material used to coat the inorganic support and thus the ratio between organic material and inorganic support could advantageously be varied between 0.5:1 and 2:1 in weight, but more preferably between 0.75:1 and 1.5:1 in weight.
- wet or incipient wetness at a temperature comprised between 20 and 90 °C, according to the solvent and to the pressure.
- a thermal treatment that requires, depending which chemical nature of the metallic particle is needed (metal with zero valence or metal oxide, or a mixture of them), a reduction with hydrogen (pure or diluted with another inert gas) or a calcination with oxygen (pure or diluted with another inert gas).
- Such thermal treatment can be carried on at a temperature comprised between 300 and 1000 °C, obtaining a total metal loading in the final product comprised between 5 and 50 wt% of total catalyst weight.
- the surface area of the so obtained catalyst can be comprised between 30 and 350 m 2 g "1 . Moreover, it has to be pointed out that during the thermal treatment the catalyst undergoes to structural and chemical modifications, which trigger processes devoted to increase stability of the resultant material when exposed to reaction conditions (see example 10 and Table 3).
- the deposition process can be carried out either in one (by means of co-impregnation) or multiple steps (by means of consecutive impregnations). In the latter case, each impregnation is alternated with a thermal treatment.
- the composite support can be firstly impregnated with an iron salt solution and then thermally treated at a temperature T 1 .
- the resultant solid can be then impregnated with a cobalt salt solution and again thermally treated at a temperature T 2 in order to obtain the final material formulation.
- Such thermal treatments can be either oxidative or reductive, depending on desired product.
- Temperatures values T 1 and T 2 might be equal or different depending from the case and comprised between 300 and 1000 °C. In fact, it has been found that in some cases consecutive impregnations might drive to different nanoparticles composition and morphology (e.g. core-shell type or alloy nanoparticles), with different activities for the ammonia decomposition reaction. Catalyst stability under ammonia stream at high temperature was also found to be influenced from this aspect.
- the precursor of said non-noble active metals can be salts such as acetates, halides, nitrates, carbonates, bicarbonates, sulfates, oxides, malonates, and analogous organic salts and their mixtures.
- the catalyst composition can be doped with other elements which could be considered as promoters, able to increase both structural stability and catalytic activity.
- the addition of such elements, typically belonging to the alkaline, earth- alkaline and lanthanides gruops of the periodic table, and in particular but not limited to Cs, K, Ba, Mg, Y, Ce and La, can be performed by classic impregnation methods (e.g.
- wet or incipient wetness at a temperature comprised between 20 and 90 °C, according to the solvent and to the pressure employed.
- the addition of such elements can be performed at any step of the catalyst preparation process, but preferably it is performed after the nanostructured support has been prepared.
- the promoter to non noble metal(s) ratio can be varied in the range 2-0.01 taking into account the complete amount of non noble metal(s) composing the end product. After the addition of the promoter precursor the material can undergoes either to a thermal treatment (which could be either performed under oxidative or reducing atmosphere) or to an another impregnation step.
- the precursor of said promoters can be salts such as nitrates, sulfates, bromides, carbonates, chlorides, fluorides, iodides, oxalates, hydroxides, perchlorates, and phosphates.
- the catalysts of this inventions are useful for ammonia decomposition; thus object of the invention is a method for producing hydrogen from ammonia, said method wherein a catalyst as described above is used.
- Catalysts of the invention as described above can be used in devices for ammonia reforming.
- ammonia reformers comprising at least a catalyst as above described.
- the dried material was thus pyrolyzed in argon flow at 900 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
- 0.9 g of the composite material obtained as reported above are impregnated via incipient wetness with a aqueous solution containing 0.31 g of Iron (II) acetate in order to obtain a 10 wt %. final metal load.
- the material is dried in oven at 70 °C and finally reduced in hydrogen flow at 500 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
- EXAMPLE 3 Preparation of a "Catalyst C" In a 250 ml_ flask 5 g of ⁇ -AI 2 O 3 (Sasol) or alumina (Disperal 40, Sasol), 7 g of polymer (as described in WO2004/036674A2, Example 1 ), 7 g of ammonium nitrate and 150 ml_ of distilled water were added. A 30 wt% ammonia solution was added dropwise till the pH of the solution was 9. The suspension was then heated up to 50 °C and left stirring for 8 h. At this point, the solvent was removed via vacuum evaporation, and the obtained solid was dried in oven at 70 °C overnight. The dried material was thus pyrolyzed in argon flow at 900 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
- EXAMPLE 4 Preparation of a "Catalyst D" In a 250 mL flask 5 g of alumina (Disperal 40, Sasol), 7 g of polymer (as described in WO2004/036674A2, Example 1 ), 7 g of ammonium nitrate and 150 mL of distilled water were added. A 30 wt% ammonia solution was added drop wise till the pH of the solution was 9. The suspension was then heated up to 50 °C and left stirring for 8 h. Then the solvent was removed via vacuum evaporation, and the obtained solid was dried in oven at 70 °C overnight.
- the dried material was thus pyrolyzed in argon flow at 900 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
- 0.8 g of the composite material obtained as reported above are impregnated via incipient wetness with a aqueous solution containing 1.44 g of Iron (III) nitrate in order to obtain a 20 wt %. final metal load.
- the material is dried in oven at 70 °C and finally reduced in hydrogen flow at 800 °C for 2 h (heating rate from room temperature: 10 °C min "1 ).
- EXAMPLE 7 Activity evaluation on ammonia decomposition 75 mg of Catalysts A, D and F prepared respectively as reported in Examples 1 , 4 and 6 have been placed in a quartz reactor (4 mm inner diameter) and then placed inside a tubular furnace. The furnace temperature was heated up to 600 °C (heating rate 10 °C min "1 ) under argon flow and then in hydrogen for 30 minutes. At the end of this pretreatment, pure ammonia (18.8 ml_/min) was fluxed and the catalytic activity was measured keeping the catalyst at the temperature of 600 °C, 550 °C, 500 °C, 450 °C and 400 °C for 30 minutes each.
- EXAMPLE 9 Influence of polymer/alumina ratio on the activity of resultant catalysts It has been found that the amount of polymer used for the composite support preparation, and thus the polymer/alumina ratio, has a great influence on the composite surface area and porosity.
- 75 mg of the catalyst was first tested following the protocol described in example 7. Successively, the temperature was raised (10 °C min "1 ) to 700 °C and the catalyst was kept at this temperature for 100 h. Then, temperature was further raised (10 °C min "1 ) to 800°C and the catalyst was kept at this temperature for 3 h.
- EXAMPLE 1 1 Metal particle size determination.
- Non-noble metals size and particles dispersion were determinated by
- TEM Transmission Electron Microscopy
- Catalyst A shows a bimodal size distribution, most of nanoparticles being characterized by a average diameter of 3 nm, but also few bigger iron clusters were observed (Table 4).
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Abstract
La présente invention concerne des catalyseurs basés sur des nanoparticules de métaux non précieux, d’oxydes ou de mélanges de ceux-ci reposant par des matériaux inorganiques, obtenus par un procédé comprenant plusieurs étapes qui peuvent être divisées en (a) la préparation du support et (b) le dépôt de la phase active. Les catalyseurs ci-décrits sont actifs dans la réaction de décomposition de l'ammoniac pour produire de l'hydrogène.
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IT000210A ITFI20080210A1 (it) | 2008-11-03 | 2008-11-03 | Catalizzatori a base di metalli non nobili per la decomposizione dell'ammoniaca e loro preparazione |
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CN102161526A (zh) * | 2011-03-04 | 2011-08-24 | 北京化工大学 | 氧化镁负载钴铁金属磁性纳米材料在降解废水中橙黄ⅱ的应用 |
EP2530125A1 (fr) * | 2011-05-30 | 2012-12-05 | Total SA | Particules coeur/enveloppe dotées d'une activité catalytique |
EP2796198A1 (fr) * | 2013-04-23 | 2014-10-29 | Danmarks Tekniske Universitet | Catalyseurs pour l'oxydation sélective de l'ammoniac dans un gaz contenant de l'hydrogène |
CN105289656A (zh) * | 2015-11-25 | 2016-02-03 | 吉林大学 | 一种光催化分解水产氢固溶体催化剂及其制备方法 |
CN108212166A (zh) * | 2018-01-16 | 2018-06-29 | 江西慧骅科技有限公司 | 便于拆卸实施再生的氨分解催化剂及其制备方法 |
WO2018229770A1 (fr) * | 2017-06-15 | 2018-12-20 | Technology Innovation Momentum Fund (Israel) Limited Partnership | Catalyseurs à base de métaux de transition supportés par des lanthanides et leurs utilisations |
US11478784B2 (en) | 2020-02-04 | 2022-10-25 | Saudi Arabian Oil Company | Catalyst compositions for ammonia decomposition |
CN115814799A (zh) * | 2022-11-16 | 2023-03-21 | 武汉理工大学 | 非贵金属氨热解制氢催化剂及其制备方法和应用 |
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CN102161526B (zh) * | 2011-03-04 | 2012-12-12 | 北京化工大学 | 氧化镁负载钴铁金属磁性纳米材料在降解废水中橙黄ⅱ的应用 |
CN102161526A (zh) * | 2011-03-04 | 2011-08-24 | 北京化工大学 | 氧化镁负载钴铁金属磁性纳米材料在降解废水中橙黄ⅱ的应用 |
EA024839B1 (ru) * | 2011-05-30 | 2016-10-31 | Тотал Раффинаге Кимие | Частицы ядро-оболочка с каталитической активностью |
US9539563B2 (en) | 2011-05-30 | 2017-01-10 | Total Raffinage Chimie | Core-shell particles with catalytic activity |
CN103649234A (zh) * | 2011-05-30 | 2014-03-19 | 道达尔炼油化学公司 | 具有催化活性的芯-壳颗粒 |
WO2012163969A1 (fr) * | 2011-05-30 | 2012-12-06 | Total Sa | Particules cœur-écorce à activité catalytique |
AU2012264715B2 (en) * | 2011-05-30 | 2015-07-16 | Total Raffinage Chimie | Core-shell particles with catalytic activity |
EP2530125A1 (fr) * | 2011-05-30 | 2012-12-05 | Total SA | Particules coeur/enveloppe dotées d'une activité catalytique |
EP2796198A1 (fr) * | 2013-04-23 | 2014-10-29 | Danmarks Tekniske Universitet | Catalyseurs pour l'oxydation sélective de l'ammoniac dans un gaz contenant de l'hydrogène |
CN105289656A (zh) * | 2015-11-25 | 2016-02-03 | 吉林大学 | 一种光催化分解水产氢固溶体催化剂及其制备方法 |
WO2018229770A1 (fr) * | 2017-06-15 | 2018-12-20 | Technology Innovation Momentum Fund (Israel) Limited Partnership | Catalyseurs à base de métaux de transition supportés par des lanthanides et leurs utilisations |
CN108212166A (zh) * | 2018-01-16 | 2018-06-29 | 江西慧骅科技有限公司 | 便于拆卸实施再生的氨分解催化剂及其制备方法 |
US11478784B2 (en) | 2020-02-04 | 2022-10-25 | Saudi Arabian Oil Company | Catalyst compositions for ammonia decomposition |
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