WO2010125369A2 - Catalyst preparation method - Google Patents
Catalyst preparation method Download PDFInfo
- Publication number
- WO2010125369A2 WO2010125369A2 PCT/GB2010/050624 GB2010050624W WO2010125369A2 WO 2010125369 A2 WO2010125369 A2 WO 2010125369A2 GB 2010050624 W GB2010050624 W GB 2010050624W WO 2010125369 A2 WO2010125369 A2 WO 2010125369A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- support
- catalyst
- range
- calcium aluminate
- metal
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 19
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 19
- 210000003278 egg shell Anatomy 0.000 claims abstract description 19
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 12
- 239000008188 pellet Substances 0.000 claims description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 30
- 238000005470 impregnation Methods 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000004568 cement Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 238000000629 steam reforming Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000006703 hydration reaction Methods 0.000 description 12
- 238000002407 reforming Methods 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910000480 nickel oxide Inorganic materials 0.000 description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 150000004684 trihydrates Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- -1 Calcium aluminates Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001960 metal nitrate Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 238000000399 optical microscopy Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical group Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000008859 change Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- UFZOPKFMKMAWLU-UHFFFAOYSA-N ethoxy(methyl)phosphinic acid Chemical compound CCOP(C)(O)=O UFZOPKFMKMAWLU-UHFFFAOYSA-N 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 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
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- KOWXKIHEBFTVRU-UHFFFAOYSA-N nga2 glycan Chemical compound CC.CC KOWXKIHEBFTVRU-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
-
- 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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/55—Cylinders or rings
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- 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
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- 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
- C01B2203/1076—Copper or zinc-based catalysts
-
- 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
- C01B2203/1082—Composition of support materials
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1252—Cyclic or aromatic hydrocarbons
-
- 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
Definitions
- This invention relates to a method of preparing catalysts supported on calcium aluminate.
- Calcium aluminate-supported catalysts are used in a number of industrial processes, including methanation and steam reforming processes, such as pre-reforming, primary reforming and secondary reforming.
- the catalytically-active metal is typically nickel, but other transition metals or precious metals, may also be used.
- pellets comprising nickel oxide on alumina or calcium aluminate are typically installed and the reduction of the nickel oxide to the active elemental nickel carried out in-situ.
- US4707351 describes steam-reforming catalysts made of a low-silica calcium aluminate cement composition in a saddle configuration.
- the catalysts were prepared by mixing calcium aluminate with water and polyvinylacetate, stamping shapes from the resulting material, drying and calcining the saddles at up to 1400 0 C before impregnation with nickel nitrate.
- the impregnated saddles were further dried and calcined to generate the catalyst precursor.
- the calcium aluminate support was hydrated during the shaping process and then calcined to increase its strength and define the micromimetric properties prior to impregnation with nickel nitrate.
- the support once impregnated with a metal compound provides an egg-shell catalyst precursor in which the metal oxide formed upon calcination is concentrated as an outer surface layer on the support and is not uniformly distributed.
- the invention provides a method for preparing a catalyst comprising the steps of:
- the invention further provides an eggshell catalyst obtainable by the method.
- the invention further provides a process for the steam reforming of hydrocarbons comprising the step of contacting a mixture of hydrocarbon and steam at elevated temperature and pressure with the eggshell catalyst.
- the catalytically active metal or metals are not uniformly distributed within the catalyst support but are concentrated at the surface and therefore form a thin layer, with the metal or metals being absent beneath this layer.
- the thickness of the eggshell layer is preferably ⁇ 1000 ⁇ m, more preferably ⁇ 800 ⁇ m, most preferably ⁇ 300 ⁇ m.
- the catalyst support is prepared from a calcium aluminate cement.
- calcium aluminate cement we include those hydraulic cements containing one or more calcium aluminate compounds of the formula nCaO. InAI 2 O 3 where n and m are integers.
- Example of such calcium aluminate compounds include calcium monoaluminate (CaO-AI 2 O 3 ), tricalcium aluminate (3CaO-AI 2 O 3 ), penta calcium trialuminate (5CaO.3AI 2 O 3 ), tricalcium penta aluminate (3CaO.5AI 2 O 3 ), and dodeca calcium hepta aluminate (12CaO.7AI 2 O 3 ).
- Some calcium aluminate cements may contain alumina in admixture with, dissolved in, or combined with, such calcium aluminate compounds.
- a well known commercial high alumina cement has a composition corresponding to about 18% calcium oxide, 79% alumina and 3% water and other oxides. This material has a calcium:aluminium atomic ratio of about 1 :5, i.e. 2CaO.5AI 2 O 3 .
- Calcium aluminates are often contaminated with iron compounds, but these are not believed to be detrimental to the present invention.
- Suitable cements include the commercially available Ciment Fondu, and Secar 50, Secar 71 , Secar 80 available from Kerneos and CA-25, CA-14, CA-270 available from Almatis.
- the support composition employed in the present invention preferably has a calcium:aluminium atomic ratio within the range 1 :3 to 1 :12, more preferably 1 :3 to 1 :10, most preferably 1 :4 to 1 :8.
- the calcium aluminate cement is a "high alumina" cement
- no additional alumina may be necessary but, in general, the support is desirably made from a calcium aluminate cement to which an additional amount of alumina, which may be in the form of a transition alumina, monohydrate or trihydrate, has been added.
- an amount of lime (CaO) e.g. up to 15% by weight of the composition, may also be incorporated into the support composition.
- the support will usually be a refractory composition consisting of a calcined mixture of alumina, one or more of said calcium aluminate compounds and optionally lime.
- oxidic materials e.g. titania, zirconia or lanthana
- oxidic materials may be present in the calcium aluminate support composition.
- silica may in some cases be incorporated, for use as a steam reforming support, a low silica content, i.e. less than 1 % by weight, preferably less than 0.5% by weight, based on the weight of the oxidic material in the support composition is desirable, as silica has an appreciable volatility under steam reforming conditions.
- the support composition preferably contains ⁇ 25% by weight, more preferably ⁇ 15 % by weight, most preferably ⁇ 10% by weight of oxidic material other than calcium aluminate and alumina.
- the shaped catalyst support may be made by forming a calcium aluminate cement powder, optionally with additional alumina and/or lime, into the desired shape, curing the cement and subsequently calcining the shaped support.
- Processing aids such as graphite and/or a metal stearate (e.g. Mg or Al stearate), may be incorporated into the composition prior to shaping: typically the proportion of graphite is 1 to 5% by weight of the composition.
- the amounts of metal stearate included may be in the range 0.1 to 2.0% by weight.
- a typical composition suitable for pellet formation comprises 30 to 70% by weight of a calcium aluminate cement (comprising 65 to 85% by weight of alumina and 15 to 35% by weight of CaO) mixed with 24 to 48% by weight of alumina, 0 to 15% by weight of lime, and 2 to 5% by weight of graphite.
- a calcium aluminate cement comprising 65 to 85% by weight of alumina and 15 to 35% by weight of CaO
- 24 to 48% by weight of alumina 0 to 15% by weight of lime, and 2 to 5% by weight of graphite.
- the composition is desirably shaped into pellets using known techniques, but may also be prepared as extrudates or granules.
- the length, width and height of such shaped units may be in the range 3-50 mm.
- the support may be in the form of saddles as described in the aforesaid US 4707351 but preferably the support is pressed into pellets in the form of cylinders, which may have one or more through holes, for example as described in WO 2004/014549. More preferably the shaped support is in the form of a cylindrical pellet having between 1 and 12 holes extending there-through, especially 3-10 holes of circular cross section, and optionally between 2 and 20 flutes or lobes running along the length of the pellet.
- Suitable diameters for such pellets are in the range 4-40 mm and the aspect ratio (length/diameter) is preferably ⁇ 2.
- a particularly preferred shape is a highly domed cylindrical pellet in the form of a cylinder having a length C and diameter D, which has one or more holes extending therethrough, wherein the cylinder has domed ends of lengths A and B, such that (A+B+C)/D is in the range 0.50 to 2.00, and (A+B)/C is in the range 0.40 to 5.00.
- Such shapes are described in co- pending pending WO 2010/029323 A1 and WO 2010/029324 Al C is preferably in the range 1 to 25mm and D is preferably in the range 4 to 40 mm.
- the cement in the shaped catalyst support should be cured and the support dried, typically at under 200°C, and then calcined.
- Curing of the calcium aluminate cement may take place before or during a drying step, e.g. by spraying or immersing the shaped catalyst support with water prior to drying or by heating the shaped catalyst support under conditions of controlled relative humidity prior to volatilising residual water. Calcination is typically carried out by heating the shaped units to between 500 and 1400 0 C in air for between 1 and 16 hours.
- the catalyst support strength increases, while the porosity and surface area decrease, as the calcination temperature increases. Hence the support calcination should be effected at sufficient temperature to obtain the required mechanical strength but should not be so high that the surface area and porosity are unduly reduced.
- the shaped calcined catalyst support preferably has a total surface area, as measured by nitrogen absorption, of 0.5 to 40, particularly 1 to 15, m 2 g "1 , and a pore volume of 0.1 to 0.3 cm 3 .g "1 , as determined by mercury porosimetry.
- the support Prior to the final calcination, the support may be "alkalised” by impregnation with a solution of an alkali such as potassium hydroxide. This serves to minimise lay down of carbon on the catalyst during steam reforming resulting from high temperature cracking of hydrocarbons and from the reaction of carbon oxides with hydrogen.
- Alkali oxide e.g. potash
- levels of up to about 5% wt on the calcined support may be used.
- the calcined shaped calcium aluminate support prior to impregnation with a metal compound, is subjected to a re-hydration step by treating the support with water.
- the water is desirably free of salts and is preferably demineralised water or deionised water. Small amounts of organic base or ammonia may be added to the water.
- the treatment of the shaped calcium aluminate support with water may be by immersion or spraying with water at ambient or elevated temperature.
- the re-hydration step should be performed for a period sufficient to react the surface of the calcined shaped calcium aluminate support with water.
- the treatment with water is by immersing the shaped support in water for a period of between 1 and 120 minutes at a temperature in the range 10-95°C.
- Using water at a temperature of ⁇ 3O 0 C has been found to give thinner metal oxide layers, which is advantageous, particularly for small catalysts or catalysts with through-holes.
- the re-hydration step may be performed at atmospheric or elevated pressure.
- the support is dried to remove the water, preferably to remove the physisorbed water and not the chemisorbed water.
- the support drying is preferably performed at a temperature in the range 25-25O 0 C, more preferably in the range 50-15O 0 C at atmospheric or reduced pressure. Drying times may be in the range 1-24 hours depending upon the water content.
- the re-hydrated and dried catalyst support is then impregnated with a solution comprising one or more soluble metal compounds.
- the impregnation solution preferably comprises one or more transition metals, preferably one or more selected from the group consisting of chromium, manganese, nickel, cobalt, iron, copper and zinc. More preferably the impregnation solution comprises one or more of nickel, cobalt, iron or copper, most preferably nickel.
- Aqueous impregnation solutions are particularly suitable.
- the impregnation solution preferably comprises one or more acidic compounds, i.e. compounds that dissolve in water to give acidic solutions (i.e. the impregnation solution desirably has a pH ⁇ 7.0).
- Suitable acidic metal compounds include metal nitrate, metal acetate metal citrate and metal oxalate.
- the impregnated metal is nickel
- the metal compound used to impregnate the support is preferably nickel nitrate or nickel acetate.
- the concentration of metal in the impregnating solution is desirably in the range 100-30Og metal/litre.
- Impregnation may be performed at ambient or elevated temperature and at atmospheric or elevated pressure using known techniques, including immersion of the re-hydrated and dried catalyst support in a metal-containing solution or by so-called "incipient wetness" impregnation where the volume of solution used equates approximately to the pore volume of the support material. Impregnation of the metal compound at ambient temperature (i.e. 10 to 25 0 C), and at atmospheric pressure (about 1 bar abs) may be used, however it has been found that by impregnating the support at temperatures in the range 50-90°C, improved control over the thickness of the eggshell layer may be obtained.
- the eggshell layer thickness on pelleted materials may be ⁇ 800 ⁇ m at 20-30°C, but impregnation at 50-90°C can produce thicknesses of ⁇ 300 ⁇ m.
- the impregnated support is dried and calcined. Drying conditions are preferably the same as those used following the re-hydration step.
- the calcination step to convert the impregnated metal compound to its corresponding metal oxide is preferably performed in air at a temperature in the range 250-850°C.
- the catalytic metal content of the resulting catalyst may be determined by a number of factors such as the metal content of the solution and the impregnation conditions.
- Steam reforming catalysts formed by impregnation typically have a NiO content in the range 10-35% wt.
- Precipitated pre-reforming catalysts can have NiO contents of 40-80% wt or more.
- Methanation catalysts typically have a NiO content in the region of 30-35% wt.
- the catalytic metal oxide content of the calcined catalyst is preferably in the range 2-25% wt, preferably 4-15% wt.
- the re-hydration, drying and impregnation steps may be repeated until the metal oxide content of the calcined material is above 2.5% wt, preferably above 5% wt, more preferably above 7.5% wt, most preferably above 10% wt.
- the metal oxide containing support should be re- hydrated, dried and calcined prior to each metal impregnation.
- the specific surface area of the catalytic metal is suitably in the range 0.1 to 50 m 2 /g of catalyst. Within this range, larger areas are preferred for reactions under 600 0 C.
- One or more promoter compounds may be impregnated into the dried support and/or the metal oxide coated support. Hence one or more promoter compounds may be included in the metal impregnating solution or the promoter may be added subsequently by a separate impregnation.
- the promoter may be confined to the eggshell layer or may be distributed throughout the catalyst support. Promoters include precious metals such as platinum, palladium, iridium, ruthenium, rhodium and gold. Lanthanide metals such as lanthanum and cerium may also be included as promoters. Water-soluble salts, particularly nitrates, may be used as sources of the metal promoters. More than one promoter may be present and additional alkali may also be added.
- the amount of promoter metal will typically be in the range 0.1 - 5% wt on the calcined catalyst material.
- the catalysts may be provided and used in their oxidic form. E.g. oxidic Co catalysts may be used for oxidation reactions.
- the calcined product may be provided in its oxidic form and reduction of the metal oxide, if required, to form elemental metal carried out in-situ, i.e. in the reactor in which the catalyst is to be used, with a hydrogen-containing gas.
- Known reduction techniques may be used.
- the oxidic catalyst may be reduced ex-situ and then the elemental metal coated with a thin passivating layer of oxide using an oxygen containing gas.
- the catalyst may be transported safely to the user, and the reduction time to generate the active catalyst and quantity of hydrogen used during the subsequent activation, reduced.
- the method for preparing the catalyst further comprises the steps of reducing a reducible metal oxide to elemental form with a hydrogen-containing gas mixture and subsequently passivating the surface of the elemental metal with an oxygen-containing gas.
- Oxygen and carbon dioxide gases may be used for example as described in US 4090980.
- the eggshell catalysts prepared according to the invention may be used in steam reforming processes such as primary steam reforming, secondary reforming of a primary reformed gas mixture and pre-reforming.
- the catalysts may also be used for methanation reactions, hydrogenation reactions and, in oxidic unreduced form, for the decomposition of hypochlorite in aqueous solutions.
- a hydrocarbon typically a methane-containing gas such as natural gas or naphtha is reacted with steam and/or, where appropriate, carbon dioxide, over a catalytically active material, often comprising nickel, to produce a gas containing hydrogen and carbon oxides.
- the hydrogen producing reactions are:
- CH2 represents hydrocarbons higher than methane, for example normally gaseous hydrocarbons and normally liquid hydrocarbons boiling at up to 200°C).
- the analogous reactions with carbon dioxide can be carried out separately or with the steam reaction.
- the steam reforming process is operated preferably in net endothermic conditions and the hydrogen containing gas produced contains at least 30% v/v of hydrogen on a dry basis. Preferably it contains less than 30, especially less than 10, % v/v of methane on a dry basis.
- the outlet temperature is preferably at least 600°C to ensure low methane content. While the temperature is generally in the range 750 -900°C for making synthesis gas for ammonia or methanol production, it may be as high as 1100°C for the production of metallurgical reducing gas, or as low as 700°C for the production of town gas.
- the temperature may be as high as 1300 0 C in the hottest part of the catalyst bed.
- a hydrocarbon / steam mixture is subjected to a step of adiabatic low temperature steam reforming.
- the hydrocarbon/steam mixture is heated, typically to a temperature in the range 400-650 0 C, and then passed adiabatically through a fixed bed of a suitable particulate catalyst, usually a catalyst having a high nickel content, for example above 40% by weight.
- a suitable particulate catalyst usually a catalyst having a high nickel content, for example above 40% by weight.
- the catalysts may be simple cylinders or a multiholed, lobed shape.
- Pre-reforming catalysts are typically provided in a pre-reduced and passivated form, although oxidic catalyst may also be installed.
- any hydrocarbons higher than methane react with steam on the catalyst surface to give a mixture of methane, carbon oxides and hydrogen.
- the use of such an adiabatic reforming step is desirable to ensure that the feed to the steam reformer contains no hydrocarbons higher than methane and also contains a significant amount of hydrogen. This is desirable in order to minimise the risk of carbon formation on the catalyst in the downstream steam reformer.
- the pressure in steam reforming processes is typically in the range 1-50 bar abs. but pressures up to 120 bar abs. are proposed. An excess of steam and/or carbon dioxide is normally used, especially in the range 1.5 to 6, for example 2.5 to 5, mols of steam or carbon dioxide per gram atom of carbon in the starting hydrocarbon.
- the hydrogen-containing gas is typically passed through a particulate fixed bed of a nickel-containing catalyst at a temperature in the range 230-450 0 C and pressures up to about 50 bar abs or higher up to about 250 bar abs.
- the catalyst are preferably simple cylindrical pellets without through holes, although such pellets may be used if desired. Typical pellet diameters are in the range 2.5-6 mm, with lengths in the same range.
- the catalysts may be provided in oxidic form or pre-reduced and passivated form.
- Figure 1 depicts an image of a cylindrical catalyst pellet cut in two to show an eggshell layer of catalyst prepared according to the present invention
- Figure 2 depicts an image of a similar catalyst pellet prepared according to the prior art
- Figure 3 depicts an electron-probe micro-analyser (EMPA) image of a cross section of a lobed 4-hole cylindrical catalyst pellet with an eggshell layer of catalyst prepared according to the present invention.
- EMPA electron-probe micro-analyser
- Example 1 Preparation of a catalyst support a) Calcium aluminate cement was blended with alumina trihydrate and lime to obtain a mixture with a Ca:AI ratio of 10:43. Graphite (4 wt%) was added, and the resulting mixture pelleted using a hydraulic tabletting machine to give cylinders of diameter 3.3mm and length 3.3mm. The pellets were subjected to water-curing and calcination to obtain a calcined shaped support with the following properties.
- Example 1(a) The method of Example 1(a) was repeated to produce pellets of diameter 5.4 mm and length 3.0 mm.
- Example 2 The method of Example 1(a) was repeated except that calcium aluminate cement was blended with alumina trihydrate to obtain a mixture with a Ca:AI ratio of 10:74.
- Example 2. Preparation of a Ni catalyst a) Re-hyd ration.
- the shaped calcined calcium aluminate support from Example 1(b) was treated with water by immersing the pellets in de-mineralised water at 3O 0 C for 40 minutes. The pellets were removed and dried at 11O 0 C for 16 hours.
- Example 1(a) The procedure was repeated on the support of Example 1(a), using the same water treatment conditions but carrying out the Ni impregnation each time for 5 minutes at 7O 0 C instead of 25 0 C.
- the weight increase after each calcination was measured on 20 pellets and an average taken. The results were as follows;
- catalyst 2A This material was termed catalyst 2A.
- Example 1(a) The procedure applied to the support of Example 1(a) was repeated on the support of Example 1(c), using the same water treatment and impregnation conditions. An egg-shell catalyst material was produced.
- the Ni was distributed throughout the catalyst pellet as seen in Figure 2.
- the impregnated pellets were then removed and allowed to drain for 10 minutes and dried at 11O 0 C for 6 hours.
- the dried impregnated pellets were then heated at 100°C/hour to 65O 0 C and then held at 65O 0 C for 6 hours to convert the nickel nitrate to nickel oxide.
- the impregnating, drying and calcining procedure was repeated on the nickel oxide containing pellets a further two times.
- the NiO content of this material after the final calcination was about 16.5 wt%.
- This comparative material was termed catalyst 2B.
- the catalysts 2A and 2B were tested in a laboratory scale steam reformer with a reformer tube internal diameter of 1-inch.
- the catalysts were diluted with fused alumina chips (sieve fraction 3.35mm - 4.74mm) and reduced using 50 vol% H 2 in N 2 at 480 0 C for 2 hours. After catalyst reduction, catalyst performance was assessed over the temperature range 480 0 C to 750 0 C.
- the feed gas was natural gas mixed with steam at a stearrrcarbon ratio of 3.0:1.
- the exit gas composition was analysed by infra-red and gas chromatography.
- Example 4 Preparation of catalysts a) Catalyst Support. Calcium aluminate cement was blended with alumina trihydrate and lime to obtain a mixture with a Ca:AI ratio of 10:43. Graphite (4 wt%) was added, and the resulting mixture pelleted using a hydraulic tabletting machine to give cylinders of diameter 5.4mm and length 5.4mm. The pellets were subjected to water-curing and calcination to obtain a calcined shaped support with the same properties as example 1(a).
- the impregnated pellets were then removed and allowed to drain for 10 minutes and dried at 11O 0 C for 12 hours.
- the pellets were analysed by optical microscopy and in each case it was found that the metal compound was concentrated around the edge of the pellet, i.e. that an eggshell material had been formed.
- the shaped calcined calcium aluminate support without the re-hydration step (b), was immersed in the solution of metal nitrate in de-mineralised water as detailed above for 5 minutes at 25 0 C.
- the impregnated pellets were then removed and allowed to drain for 10 minutes and dried at 11O 0 C for 12 hours.
- the pellets were analysed by optical microscopy and in each case the metal was distributed throughout the catalyst.
- Example 5 Preparation of catalyst with Ni acetate a) Catalyst Support. Calcium aluminate cement was blended with alumina trihydrate and lime to obtain a mixture with a Ca:AI ratio of 10:43. Graphite (4 wt%) was added, and the resulting mixture pelleted using a hydraulic tabletting machine to give cylinders of diameter 5.4mm and length 5.4mm. The pellets were subjected to water-curing and calcination to obtain a calcined shaped support with the same properties as example 1(a). b) Re-hyd ration. The shaped calcined calcium aluminate support from was treated with water by immersing the pellets in de-mineralised water at 3O 0 C for 40 minutes. The pellets were removed and dried at 110 0 C for 16 hours.
- the impregnated pellets were then removed and allowed to drain for 5 minutes and dried at 11O 0 C for 4 hours.
- the pellet was analysed by optical microscopy and it was found that the nickel was concentrated around the edge of the pellet.
- Example 6 Shaped catalyst support with through holes
- a 4-holed, 4-lobed catalyst calcined calcium aluminate catalyst support was prepared according to the method of Example 1. The catalyst support was re-hydrated and impregnated three times at 25 0 C with nickel nitrate according to the method of Example 2. Electron-probe micro-analysis (EPMA) of a cross section of the resulting dried and calcined catalyst pellet showed a thin layer of nickel oxide (lighter area) around the outside of the pellet and around the circumference of each of the through holes.
- EPMA image is depicted in Figure 3.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL18201717T PL3453451T3 (en) | 2009-05-01 | 2010-04-15 | Catalyst |
EP10716013.7A EP2424657B1 (en) | 2009-05-01 | 2010-04-15 | Catalyst preparation method |
EP18201717.8A EP3453451B1 (en) | 2009-05-01 | 2010-04-15 | Catalyst |
US13/318,273 US9480971B2 (en) | 2009-05-01 | 2010-04-15 | Catalyst preparation method |
ES10716013T ES2712937T3 (en) | 2009-05-01 | 2010-04-15 | Catalyst preparation method |
LTEP10716013.7T LT2424657T (en) | 2009-05-01 | 2010-04-15 | Catalyst preparation method |
PL10716013T PL2424657T3 (en) | 2009-05-01 | 2010-04-15 | Catalyst preparation method |
DK10716013.7T DK2424657T3 (en) | 2009-05-01 | 2010-04-15 | PROCEDURE FOR THE PREPARATION OF A CATALYST |
CN201080019209.2A CN102413923B (en) | 2009-05-01 | 2010-04-15 | Catalyst preparation method |
US15/279,964 US9981252B2 (en) | 2009-05-01 | 2016-09-29 | Catalyst preparation method |
US15/953,678 US10076744B1 (en) | 2009-05-01 | 2018-04-16 | Catalyst preparation method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0907539.1 | 2009-05-01 | ||
GBGB0907539.1A GB0907539D0 (en) | 2009-05-01 | 2009-05-01 | Catalyst preparation method |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/318,273 A-371-Of-International US9480971B2 (en) | 2009-05-01 | 2010-04-15 | Catalyst preparation method |
US15/279,964 Division US9981252B2 (en) | 2009-05-01 | 2016-09-29 | Catalyst preparation method |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2010125369A2 true WO2010125369A2 (en) | 2010-11-04 |
WO2010125369A3 WO2010125369A3 (en) | 2011-03-31 |
Family
ID=40792122
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2010/050624 WO2010125369A2 (en) | 2009-05-01 | 2010-04-15 | Catalyst preparation method |
Country Status (11)
Country | Link |
---|---|
US (3) | US9480971B2 (en) |
EP (2) | EP3453451B1 (en) |
CN (1) | CN102413923B (en) |
DK (2) | DK2424657T3 (en) |
ES (2) | ES2847477T3 (en) |
GB (1) | GB0907539D0 (en) |
HU (2) | HUE042451T2 (en) |
LT (2) | LT2424657T (en) |
PL (2) | PL2424657T3 (en) |
TR (1) | TR201900395T4 (en) |
WO (1) | WO2010125369A2 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012056211A1 (en) * | 2010-10-27 | 2012-05-03 | Johnson Matthey Public Limited Company | Catalyst preparation method |
WO2012110781A1 (en) * | 2011-02-14 | 2012-08-23 | Johnson Matthey Public Limited Company | Catalysts for use in steam reforming processes |
EP2602024A1 (en) | 2011-12-08 | 2013-06-12 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Catalytic architecture with high S/V ratio, low DP and high void fraction for industrial applications |
WO2015023740A1 (en) * | 2013-08-13 | 2015-02-19 | Celanese International Corporation | Catalyst for aldol condensation |
EP3275309A4 (en) * | 2015-03-25 | 2018-05-09 | Daiki Co., Ltd. | Water absorption treatment material and a manufacturing method thereof |
US9981252B2 (en) | 2009-05-01 | 2018-05-29 | Johnson Matthey Plc | Catalyst preparation method |
CN111389405A (en) * | 2020-01-21 | 2020-07-10 | 天津大学 | Method for preactivating methane steam hydrogen production catalyst |
EP3129142B1 (en) | 2014-04-07 | 2020-11-18 | Haldor Topsøe A/S | Shell impregnated catalyst and process for producing a shell impregnated catalyst body |
WO2020234561A1 (en) | 2019-05-20 | 2020-11-26 | Johnson Matthey Public Limited Company | Catalyst preparation method |
WO2022034283A1 (en) | 2020-08-13 | 2022-02-17 | Johnson Matthey Public Limited Company | Steam reforming |
WO2022034285A1 (en) | 2020-08-13 | 2022-02-17 | Johnson Matthey Public Limited Company | Steam reforming |
RU2806094C2 (en) * | 2019-05-20 | 2023-10-26 | Джонсон Мэттей Паблик Лимитед Компани | Method for obtaining catalyst |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9579628B2 (en) | 2015-04-15 | 2017-02-28 | Air Products And Chemicals, Inc. | Perforated adsorbent particles |
CN105255531B (en) * | 2015-10-19 | 2018-07-06 | 中国华能集团清洁能源技术研究院有限公司 | A kind of system and method for low temperature distillation coal gas preparing natural gas parallel connection hydrogen producing |
CN107999080A (en) * | 2018-01-08 | 2018-05-08 | 四川天科技股份有限公司 | It is a kind of for the hydrocarbons reforming catalyst of Direct Reducing Iron Process, preparation and application |
CN109433199B (en) * | 2018-10-22 | 2020-10-13 | 武汉大学 | Ruthenium-based catalyst for carbon dioxide reduction and preparation method and application thereof |
BR102020000434A2 (en) * | 2020-01-08 | 2021-07-13 | Petróleo Brasileiro S.A. - Petrobras | METHOD OF PREPARING STEAM REFORM CATALYST, CATALYST AND ITS USE |
CN115722221B (en) * | 2021-08-26 | 2024-04-09 | 中国石油化工股份有限公司 | Catalytic oxidation catalyst and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4329530A (en) | 1979-11-20 | 1982-05-11 | Imperial Chemical Industries Limited | Hydrogenation catalyst and process for the selective hydrogenation of highly unsaturated hydrocarbons |
US4707351A (en) | 1985-01-22 | 1987-11-17 | Imperial Chemical Industries Plc | Catalyst and catalytic process |
US4906603A (en) | 1987-02-18 | 1990-03-06 | Sud-Chemie Aktiengesellschaft | Catalyst for the steam reforming of hydrocarbons |
WO2004014549A1 (en) | 2002-08-12 | 2004-02-19 | Combs Glenn A | Heterogeneous gaseous chemical reactor catalyst |
WO2010029323A1 (en) | 2008-09-12 | 2010-03-18 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
WO2010029324A1 (en) | 2008-09-12 | 2010-03-18 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4090980A (en) | 1975-11-20 | 1978-05-23 | Exxon Research & Engineering Co. | Method for preparing reduced metal catalyst having metal surface area |
US4380589A (en) | 1981-12-24 | 1983-04-19 | The Dow Chemical Company | Novel Fischer-Tropsch catalysts |
US7767619B2 (en) * | 2004-07-09 | 2010-08-03 | Sud-Chemie Inc. | Promoted calcium-aluminate supported catalysts for synthesis gas generation |
GB0907539D0 (en) | 2009-05-01 | 2009-06-10 | Johnson Matthey Plc | Catalyst preparation method |
-
2009
- 2009-05-01 GB GBGB0907539.1A patent/GB0907539D0/en not_active Ceased
-
2010
- 2010-04-15 ES ES18201717T patent/ES2847477T3/en active Active
- 2010-04-15 CN CN201080019209.2A patent/CN102413923B/en active Active
- 2010-04-15 WO PCT/GB2010/050624 patent/WO2010125369A2/en active Application Filing
- 2010-04-15 EP EP18201717.8A patent/EP3453451B1/en active Active
- 2010-04-15 HU HUE10716013A patent/HUE042451T2/en unknown
- 2010-04-15 LT LTEP10716013.7T patent/LT2424657T/en unknown
- 2010-04-15 DK DK10716013.7T patent/DK2424657T3/en active
- 2010-04-15 EP EP10716013.7A patent/EP2424657B1/en active Active
- 2010-04-15 PL PL10716013T patent/PL2424657T3/en unknown
- 2010-04-15 DK DK18201717.8T patent/DK3453451T3/en active
- 2010-04-15 TR TR2019/00395T patent/TR201900395T4/en unknown
- 2010-04-15 PL PL18201717T patent/PL3453451T3/en unknown
- 2010-04-15 US US13/318,273 patent/US9480971B2/en active Active
- 2010-04-15 HU HUE18201717A patent/HUE052735T2/en unknown
- 2010-04-15 ES ES10716013T patent/ES2712937T3/en active Active
- 2010-04-15 LT LTEP18201717.8T patent/LT3453451T/en unknown
-
2016
- 2016-09-29 US US15/279,964 patent/US9981252B2/en active Active
-
2018
- 2018-04-16 US US15/953,678 patent/US10076744B1/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4329530A (en) | 1979-11-20 | 1982-05-11 | Imperial Chemical Industries Limited | Hydrogenation catalyst and process for the selective hydrogenation of highly unsaturated hydrocarbons |
US4707351A (en) | 1985-01-22 | 1987-11-17 | Imperial Chemical Industries Plc | Catalyst and catalytic process |
US4906603A (en) | 1987-02-18 | 1990-03-06 | Sud-Chemie Aktiengesellschaft | Catalyst for the steam reforming of hydrocarbons |
WO2004014549A1 (en) | 2002-08-12 | 2004-02-19 | Combs Glenn A | Heterogeneous gaseous chemical reactor catalyst |
WO2010029323A1 (en) | 2008-09-12 | 2010-03-18 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
WO2010029324A1 (en) | 2008-09-12 | 2010-03-18 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10076744B1 (en) | 2009-05-01 | 2018-09-18 | Johnson Matthey Plc | Catalyst preparation method |
US9981252B2 (en) | 2009-05-01 | 2018-05-29 | Johnson Matthey Plc | Catalyst preparation method |
US9463441B2 (en) | 2010-10-27 | 2016-10-11 | Johnson Matthey Plc | Catalyst preparation method |
EP3549667A1 (en) * | 2010-10-27 | 2019-10-09 | Johnson Matthey Public Limited Company | Eggshell catalyst |
US10071366B2 (en) | 2010-10-27 | 2018-09-11 | Johnson Matthey Plc | Catalyst preparation method |
WO2012056211A1 (en) * | 2010-10-27 | 2012-05-03 | Johnson Matthey Public Limited Company | Catalyst preparation method |
RU2580548C2 (en) * | 2011-02-14 | 2016-04-10 | Джонсон Мэтти Паблик Лимитед Компани | Catalysts intended for use in steam reforming methods |
US9511351B2 (en) | 2011-02-14 | 2016-12-06 | Johnson Matthey Public Limited Company | Catalysts for use in steam reforming processes |
WO2012110781A1 (en) * | 2011-02-14 | 2012-08-23 | Johnson Matthey Public Limited Company | Catalysts for use in steam reforming processes |
WO2013083373A1 (en) | 2011-12-08 | 2013-06-13 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Catalytic architecture with high s/v ratio, low dp and high void fraction for industrial applications |
EP2602024A1 (en) | 2011-12-08 | 2013-06-12 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Catalytic architecture with high S/V ratio, low DP and high void fraction for industrial applications |
WO2015023740A1 (en) * | 2013-08-13 | 2015-02-19 | Celanese International Corporation | Catalyst for aldol condensation |
EP3129142B1 (en) | 2014-04-07 | 2020-11-18 | Haldor Topsøe A/S | Shell impregnated catalyst and process for producing a shell impregnated catalyst body |
US10549262B2 (en) | 2015-03-25 | 2020-02-04 | Daiki Co., Ltd. | Water absorption treatment material and method for manufacturing the same |
EP3275309A4 (en) * | 2015-03-25 | 2018-05-09 | Daiki Co., Ltd. | Water absorption treatment material and a manufacturing method thereof |
WO2020234561A1 (en) | 2019-05-20 | 2020-11-26 | Johnson Matthey Public Limited Company | Catalyst preparation method |
RU2806094C2 (en) * | 2019-05-20 | 2023-10-26 | Джонсон Мэттей Паблик Лимитед Компани | Method for obtaining catalyst |
US11958040B2 (en) | 2019-05-20 | 2024-04-16 | Johnson Matthey Public Limited Company | Catalyst preparation method |
CN111389405A (en) * | 2020-01-21 | 2020-07-10 | 天津大学 | Method for preactivating methane steam hydrogen production catalyst |
CN111389405B (en) * | 2020-01-21 | 2023-09-15 | 天津大学 | Method for preactivating methane vapor hydrogen production catalyst |
WO2022034283A1 (en) | 2020-08-13 | 2022-02-17 | Johnson Matthey Public Limited Company | Steam reforming |
WO2022034285A1 (en) | 2020-08-13 | 2022-02-17 | Johnson Matthey Public Limited Company | Steam reforming |
Also Published As
Publication number | Publication date |
---|---|
US10076744B1 (en) | 2018-09-18 |
US20170014809A1 (en) | 2017-01-19 |
EP3453451B1 (en) | 2020-10-28 |
ES2847477T3 (en) | 2021-08-03 |
HUE042451T2 (en) | 2019-07-29 |
DK2424657T3 (en) | 2019-03-11 |
PL3453451T3 (en) | 2021-05-31 |
WO2010125369A3 (en) | 2011-03-31 |
EP3453451A1 (en) | 2019-03-13 |
ES2712937T3 (en) | 2019-05-16 |
EP2424657A2 (en) | 2012-03-07 |
US9480971B2 (en) | 2016-11-01 |
US20180264442A1 (en) | 2018-09-20 |
PL2424657T3 (en) | 2019-05-31 |
HUE052735T2 (en) | 2021-05-28 |
US20120135860A1 (en) | 2012-05-31 |
LT2424657T (en) | 2019-02-25 |
CN102413923B (en) | 2014-06-04 |
CN102413923A (en) | 2012-04-11 |
TR201900395T4 (en) | 2019-02-21 |
US9981252B2 (en) | 2018-05-29 |
LT3453451T (en) | 2021-01-25 |
EP2424657B1 (en) | 2018-11-28 |
GB0907539D0 (en) | 2009-06-10 |
DK3453451T3 (en) | 2021-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10076744B1 (en) | Catalyst preparation method | |
US10071366B2 (en) | Catalyst preparation method | |
EP1802394B1 (en) | Promoted calcium-aluminate supported catalysts for synthesis gas generation | |
JP4414951B2 (en) | Catalyst for catalytic partial oxidation of hydrocarbons and process for producing synthesis gas | |
WO2015155175A1 (en) | Shell impregnated catalyst and process for producing a shell impregnated catalyst body | |
AU5054999A (en) | Catalyst carrier carrying nickel ruthenium and lanthanum | |
JP7506095B2 (en) | Method for preparing the catalyst | |
RU2575351C2 (en) | Method for obtaining catalyst | |
RU2806094C2 (en) | Method for obtaining catalyst | |
WO2024156978A1 (en) | Steam reforming catalyst and process | |
MXPA01007377A (en) | Catalyst carrier carrying nickel ruthenium and lanthanum |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080019209.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10716013 Country of ref document: EP Kind code of ref document: A2 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010716013 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 9167/DELNP/2011 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13318273 Country of ref document: US |