EP2608882A1 - Highly active water gas shift catalyst, preparation process and use thereof - Google Patents
Highly active water gas shift catalyst, preparation process and use thereofInfo
- Publication number
- EP2608882A1 EP2608882A1 EP11819508.0A EP11819508A EP2608882A1 EP 2608882 A1 EP2608882 A1 EP 2608882A1 EP 11819508 A EP11819508 A EP 11819508A EP 2608882 A1 EP2608882 A1 EP 2608882A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- alkaline earth
- alkali
- catalyst according
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 42
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 32
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 30
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 25
- 239000002019 doping agent Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 239000012876 carrier material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 11
- 150000001340 alkali metals Chemical class 0.000 abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 239000000446 fuel Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000009434 installation 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSQMSOYAHMZLJC-UHFFFAOYSA-N [Cr].[Ti].[V] Chemical compound [Cr].[Ti].[V] XSQMSOYAHMZLJC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011157 data evaluation Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 229910000311 lanthanide oxide 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
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- -1 manganese, iron compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical class [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J37/0213—Preparation of the impregnating solution
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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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- 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
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- 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
-
- 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
- the present invention relates to a highly active water gas conversion catalyst and a process for its preparation, and to a process for converting a gas mixture containing at least carbon monoxide and water into hydrogen and carbon dioxide over a wide temperature range using this catalyst.
- the fuel is reformed and split into CO and H 2 .
- This is followed by a water-gas conversion stage in which the CO formed is converted with water in a temperature-dependent equilibrium to C0 2 and H 2 :
- the water gas conversion stage usually occurs in two temperature stages. At temperatures between 150 ° C and 280 ° C is referred to a low temperature conversion (TTK).
- TTK low temperature conversion
- the TTK is mostly catalytically using Cu / Zn oxide catalysts. Between 280 ° C and 550 ° C is referred to a high-temperature conversion (HTK).
- HTK high-temperature conversion
- EP 1 571 125 A2 discloses a catalyst for separating carbon monoxide from hydrogen gas.
- This consists of an oxidic support material comprising zirconia, titania, alumina, silica, silica-alumina, zeolites and ceria.
- the catalytically active metal is platinum.
- there may be alkali metals such as lithium, sodium, potassium, rubidium or cesium, thus improving the activity of the catalyst for separating carbon monoxide by converting into carbon dioxide in the water-gas shift reaction.
- the catalytically active metal is present in the catalyst according to EP 1 571 125 A2 in an amount of 2% by weight.
- WO 2005/072871 A1 discloses a catalyst for the water gas shift reaction which contains metallic particles and particles of metal oxide. Suitable metal oxides are, for example, cerium oxide, titanium dioxide, iron oxide, manganese oxide or zinc oxide. Suitable metal particles are, for example, gold or platinum and are present in an amount of from 0.5 to 25% by weight with respect to the oxidic material.
- US 2006/0002848 A1 discloses a catalyst comprising a support material of, for example, alumina, titania, silica, zirconia or a combination thereof.
- alkali metals or alkaline earth metals can be present, as well as metals selected from lead, bismuth, polonium, magnesium, titanium vanadium chromium, manganese iron, nickel or cobalt, etc.
- catalytically active metals are platinum, palladium, copper, rhodium, etc.
- EP 1 908 517 A1 discloses a catalyst for converting H 2 O / carbon monoxide into hydrogen and the use of this catalyst for hydrogen enrichment of a stream used to supply a fuel cell.
- This catalyst is a solid comprising an active phase containing elements of the eighth group on a support material consisting of alumina, silica, zirconia or mixtures thereof and a promoter from the group of rare earths, for example lanthanum or cerium.
- US 2005/0207958 A1 discloses a process for reducing the amount of carbon monoxide in a water gas shift reactor without formation of methane.
- a catalyst is used which has a carrier material based on cerium oxide and zirconium oxide or cerium oxide and lanthanum oxide. Promoters which avoid methanation use copper, manganese, iron compounds or combinations thereof. Other promoters may be alkali or alkaline earth metals.
- the amount of platinum present on the catalyst is at least 1% by weight.
- US 2005/0191224 A1 discloses a catalyst for separating carbon monoxide from hydrogen gas.
- the catalyst used for this purpose has a support of metal oxide, a platinum component and an alkali metal, applied to this support.
- zirconia, titania, alumina, silica, silica-alumina, zeolites or ceria are suitable as the carrier material. It was therefore the task of finding an active catalyst which can be used over a wide temperature window and in this case forms little methane.
- the catalyst should have the lowest possible noble metal entry.
- Noble metal-containing catalysts are prepared either by impregnation of a shaped carrier material with metal salt solutions of the noble metal component or by impregnation of the carrier powder and subsequent shaping.
- the object of the invention was therefore further to provide a method in which the least possible precious metal component is deposited at inaccessible to the reaction points.
- a catalyst comprising at least one noble metal in an amount of 0.001 to 1, 10 wt .-%, based on the total weight of the catalyst, at least one alkali and / or alkaline earth metal and at least one dopant selected from the group consisting of Fe, Cr, Cu, Zn and mixtures thereof, on a support material.
- Further objects of the present invention are a process for the preparation of such a catalyst and a process for the conversion of a gas mixture containing at least carbon monoxide and water, to hydrogen and carbon dioxide, using such a catalyst.
- the catalyst of the invention comprises at least one noble metal and at least one alkali and / or alkaline earth metal, each in specific amounts, as well as a doping with at least one element selected from the group consisting of Fe, Cr, Cu, Zn and mixtures thereof, on a support material.
- the at least one noble metal is preferably selected from the group consisting of Au, Pt, Pd, Rh and Ru. Particular preference is given to using Pt. Also advantageous are combinations of Pt with one or more of said noble metals or combinations of one or more of said precious metals without Pt.
- the present invention particularly preferably relates to the catalyst according to the invention, wherein the noble metal is selected from the group consisting of Au, Pt, Pd, Rh, Ru and mixtures thereof. Very particular preference is given to using Pt as the noble metal, and it is particularly preferable for Pt to be the only noble metal on the catalyst according to the invention.
- the concentration of the at least one noble metal according to the invention is advantageously from 0.001 to 1, 10 wt .-%, preferably 0.01 to 1, 00 wt .-%, particularly preferably 0.1 to 0.99 wt .-%, for example 0.1 to 0.96 wt .-%, each based on the total weight of the catalyst. Due to the specific combination of features of the catalyst according to the invention, it is possible to be able to use very small amounts of expensive noble metal, and yet to achieve a high catalytic activity. According to the invention, Li, Na, K, Rb, Cs, Mg, Ca and / or Sr are preferably used as at least one alkali metal and / or alkaline earth metal. Particular preference is given to Li, Na, K and Rb, in particular Na or K.
- the present invention therefore particularly preferably relates to the catalyst according to the invention, wherein the alkali and / or alkaline earth metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof.
- the concentration of the at least one alkali metal and / or alkaline earth metal in a preferred embodiment is 1.0 to 4.0% by weight, more preferably 1.2 to 4.0% by weight, most preferably 1.8 to 3 , 5 wt .-%, particularly preferably 2.0 to 3.2 wt .-%, each based on the total weight of the catalyst. In a further preferred embodiment, from 1.2 to 3.5% by weight, based on the total weight of the catalyst, of K or Na is used. Therefore, in a preferred embodiment, the present invention relates to the catalyst according to the invention, wherein the at least one alkali and / or alkaline earth metal in an amount of 1, 0 to 4.0 wt .-%, based on the total catalyst, is present.
- the catalyst according to the invention contains at least one doping agent selected from the group consisting of Fe, Cr, Cu, Zn and mixtures thereof. Very particular preference is given to using iron as doping agent according to the invention. Particularly preferred is exclusively Fe used as a dopant.
- the at least one doping agent, in particular iron is present in a concentration of generally 0.01 to 5% by weight, preferably 0.05 to 2.5% by weight, particularly preferably 0.1 to 1, 5 wt .-%, each based on the total weight of the catalyst, before.
- the catalyst according to the invention may contain further dopants, for example rare earth metals and / or main group elements of groups 13 to 15. Such further dopants may have concentrations of altogether at most 15% by weight. exhibit.
- Suitable carrier materials according to the invention are all materials which can usually be used for this purpose in catalyst chemistry and which have a sufficiently high BET surface area.
- the BET surface area should be at least 50 m 2 / g.
- the carrier materials containing combinations of lanthanide oxides and transition metals particularly preferably Ce / Zr oxide.
- the ratio of Ce oxide to Zr oxide should advantageously be from 15 to 25 to 85 to 75 wt .-%, each based on the total weight of the carrier material.
- the Ce / Zr oxide support material contains dopants of further oxides, for example Al 2 O 3 and / or La oxide.
- a preferred ratio of Al 2 O 3 to Ce / Zr oxide according to the invention is 5 to 20 to 95 to 80, more preferably 8 to 12 to 92 to 88, for example 10 to 90.
- the amount of La oxide (La 2 O 3 ) may for example be 1 to 10 wt .-%, preferably 3 to 8 wt .-%, particularly preferably 4 to 6 wt .-%, each based on the total weight of the carrier material ,
- the present invention therefore particularly preferably relates to the catalyst according to the invention, wherein the support material contains at least Ce and / or Zr.
- the present invention relates to the catalyst according to the invention, wherein the support material additionally contains La and / or Al.
- the present invention relates to the catalyst according to the invention, wherein Pt is present as a noble metal, the alkali and / or alkaline earth metal is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof, the Dopant is Fe, and a carrier material containing Ce and / or Zr is present.
- Pt is present as a noble metal
- the alkali and / or alkaline earth metal is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof
- the Dopant is Fe
- a carrier material containing Ce and / or Zr is present.
- the present invention particularly preferably relates to this catalyst according to the invention, wherein the support material additionally contains La.
- the present or optionally present in the catalyst according to the invention components d. H. the said noble metals, alkali metals and / or alkaline earth metals, dopants and support materials are present in elemental and / or oxidic form.
- the present invention relates to the catalyst according to the invention, wherein the at least one noble metal, in particular Pt, in an amount of 0.001 to 1, 10 wt .-%, preferably 0.01 to 1, 00 wt .-%, especially preferably 0.1 to 0.99 wt .-%, for example 0.1 to 0.96 wt .-%, the at least one alkali and / or alkaline earth metal, in particular Na or K, in an amount of 1, 2 to 4 , 0 wt .-%, preferably 1, 8 to 3.5 wt .-%, particularly preferably 2.0 to 3.2 wt .-%, and the at least one dopant, in particular Fe, in an amount of 0.05 to 2.5 wt .-%, particularly preferably 0.1 to 1, 5 wt .-%, each based on the total weight of the catalyst, is present, and the carrier material contains at least Ce and / or Zr. Very particularly preferred embodiments of the present invention
- a catalyst which, used in a shift reaction, has a very high reactivity, combined with a very high efficiency, shows.
- the high reactivity of the catalysts according to the invention can be demonstrated, for example, by the fact that said shift reaction takes place even at a relatively low temperature with almost complete thermodynamically possible conversion.
- the particularly high efficiency of the catalyst according to the invention can be demonstrated by the fact that the catalyst in the shift reaction has little tendency to methanation, ie. h., That only a small proportion of the hydrogen formed is converted by the formation of methane.
- the catalyst according to the invention can be prepared by impregnating the individual components onto the support material.
- the active components are applied to powdered carrier material, which is then at least partially kneaded and extruded. It is also possible that one combines the production variants with each other and, for example, only a part of the active components applied to the powdered carrier material and thus kneaded and extruded and the remaining active components or their remaining subsets are then impregnated.
- the active components are preferably used in the form of their salts or their oxides.
- Suitable salts according to the invention are, for example, oxides, nitrates, hydroxides, acetates, acetylacetonates, carbonates, nitrosyl nitrates or halides, such as fluorides, chlorides, bromides and iodides.
- the components are in an advantageous embodiment soaked in the carrier material. Since due to conditions to be observed, such as pH, concentrations, etc., usually different metal salts can not be impregnated in parallel, the preparation of a catalyst with different promoters is often but not exclusively in a variety of impregnation steps, for example, two steps of impregnation, carried out sequentially become.
- the application of the active components by impregnation on the carrier material can be carried out in the usual manner, such. B. as a washcoat on a monolith.
- the active material is first applied at least in part to the carrier material, preferably powdered carrier material, and then kneaded and then extruded, the kneading and extrusion of the carrier material with the active materials can be carried out in the usual manner with known apparatuses.
- the carrier material preferably powdered carrier material
- the present invention therefore relates in particular to a process for the preparation of the catalyst according to the invention, wherein the at least one noble metal, at least one alkali and / or alkaline earth metal, and the at least one dopant are applied to the support material as a solution or dispersion or a part or all of the at least one noble metal, the at least one alkali and / or alkaline earth metal and / or the at least one doping agent are applied to a carrier material as a solution or dispersion and this carrier material is mixed with the remaining part of the components.
- moldings from pulverulent raw materials can be carried out by customary methods known to the person skilled in the art, such as, for example, tableting, aggregation or extrusion, as described i.a. in the Handbook of Heterogenous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp. 414-417.
- auxiliaries known to the person skilled in the art such as binders, lubricants and / or solvents, may be added.
- the described production methods are simple and inexpensive.
- the inventive catalyst is highly active with respect to the shift reaction, but suppresses the methanation reaction, for example by the catalyst according to the invention a methane content of less than 100 ppm, preferably less than 50 ppm (each at 350 ° C) and less than 500 ppm, preferably less than 300 ppm, (each at 450 ° C) reached.
- the catalyst described can be used in the process according to the invention for the conversion of a gas mixture containing at least carbon monoxide and water to hydrogen and carbon dioxide.
- the process can be carried out under the usual conditions of a conversion reaction, both in the TTK range at temperatures of usually 150-280 ° C., and in the HTK range at temperatures of usually 280-550 ° C. Due to the low tendency of methanation of the catalyst according to the invention even at high temperatures, this is particularly recommended for the HTK, are unsuitable in the previous catalysts of the prior art.
- the conversion reaction according to the invention in a temperature range of 180 to 550 ° C. It is thus possible and advantageous, both in the stage the HTK and in the stage of TTK use the catalyst of the invention.
- the process according to the invention for reducing carbon monoxide (CO) by the process of a conversion reaction on the highly active conversion catalyst according to the invention is carried out in customary apparatuses and under customary conditions for carrying out a conversion reaction, as described, for example, in the Handbook of heterogeneous catalysis, 2nd edition, Vol. 1, VCH Verlagsgesellschaft Weinheim, 2008, pages 354-355, and with overflow of the catalyst with a CO and water-containing process gas.
- the process gas used is a gas mixture, in addition to carbon monoxide and water, which are reacted in the conversion reaction described, usually also other gases such. As hydrogen, carbon dioxide and nitrogen.
- the present invention therefore also relates to the use of the catalyst according to the invention, the conversion of carbon monoxide and water to carbon dioxide and hydrogen.
- the present invention relates to a process for the conversion of a gas mixture containing at least carbon monoxide and water, to carbon dioxide and hydrogen, wherein a catalyst according to the invention is used.
- FIG. 1 shows an exemplary measuring scheme.
- the abbreviations have the following meanings:
- Catalysts and catalysts according to the invention which serve as a comparison are prepared by the following processes:
- the preparation of the catalysts according to the invention and the comparative catalysts can be carried out by impregnation, as shown by the following example for the preparation of a catalyst:
- the required amount of iron nitrate is dissolved in the stated amount of platinum nitrate solution and distilled with H 2 0. diluted to a volume corresponding to 90% of the water absorption of the Ce / Zr support material.
- the strands are presented and spray-impregnated while circulating with the platinum / iron nitrate solution. After soaking, the strands are circulated for a further 5 minutes, then dried and then calcined.
- potassium hydroxide is distilled with H 2 0. diluted to a volume equivalent to 90% of the water uptake of the resulting Pt / Fe doped strands. These strands are then spray-impregnated with the resulting dilute potassium hydroxide solution with constant circulation. After soaking, the strands are recirculated for another 5 minutes, then dried and then calcined. Drying: 4h at 200 ° C in a convection oven
- the preparation of the catalysts according to the invention and of the comparative catalysts can be carried out by kneading, as shown by the following example for the preparation of a catalyst:
- Kneader submitted The least with H 2 0. Nitric acid diluted to 20 ml total volume is added slowly and kneaded for 10 minutes. Then the iron nitrate is dissolved in the platinum nitrate solution, destilled with H 2 0. diluted to 30 ml total volume, added and kneaded for 5 minutes. Subsequently, the potassium hydroxide solution is added undiluted and kneaded again for 10 minutes. H 2 0 dist. Is added in small portions until a plastic mass is obtained. stands. The plastic mass is deformed by means of an extruder to 1, 5 mm strands.
- Catalyst installation 15 mL catalyst (bed) or 8 to 12 mL (volume of a monolith) are installed in the reactor,
- composition of the reaction gas used for the testing is:
- test method M 26% by weight of H 2 O
- the catalyst loading GHSV during testing is 12,279 / h.
- This test variant is referred to below as test method M.
- the temperature program can be changed, for example, by reducing the final temperature to 380 ° C. with the starting temperature unchanged for method M and the heating rate (° C./min).
- Heating convection oven with temperature range up to max. 600 ° C,
- Linseis-36 channel recorder as interface for data storage
- Table 1 shows the results of the catalysts according to the invention and the catalysts prepared for comparison: Table 1: Results of the various catalysts according to the invention and the catalysts for comparison
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11819508.0A EP2608882A4 (en) | 2010-08-26 | 2011-08-25 | Highly active water gas shift catalyst, preparation process and use thereof |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10174163 | 2010-08-26 | ||
PCT/IB2011/053729 WO2012025897A1 (en) | 2010-08-26 | 2011-08-25 | Highly active water gas shift catalyst, preparation process and use thereof |
EP11819508.0A EP2608882A4 (en) | 2010-08-26 | 2011-08-25 | Highly active water gas shift catalyst, preparation process and use thereof |
Publications (2)
Publication Number | Publication Date |
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EP2608882A1 true EP2608882A1 (en) | 2013-07-03 |
EP2608882A4 EP2608882A4 (en) | 2014-11-12 |
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EP11819508.0A Withdrawn EP2608882A4 (en) | 2010-08-26 | 2011-08-25 | Highly active water gas shift catalyst, preparation process and use thereof |
Country Status (5)
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EP (1) | EP2608882A4 (en) |
JP (1) | JP5961166B2 (en) |
KR (1) | KR101854941B1 (en) |
CA (1) | CA2805259A1 (en) |
WO (1) | WO2012025897A1 (en) |
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JP5968465B2 (en) * | 2012-12-28 | 2016-08-10 | 三菱重工業株式会社 | CO shift catalyst, CO shift reaction apparatus, and purification method of gasification gas |
EP2939739B1 (en) * | 2012-12-28 | 2023-12-20 | Mitsubishi Heavy Industries, Ltd. | Co shift catalyst |
BR102016022962B1 (en) * | 2016-10-03 | 2021-10-26 | Petróleo Brasileiro S.A. - Petrobras | PREPARATION PROCESS OF AN IRON-CHROME CATALYST PROMOTED WITH PLATINUM, AND, COMPOSITE IRON-CHROME CATALYST PROMOTED WITH PLATINUM |
Citations (2)
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US4956330A (en) * | 1989-06-19 | 1990-09-11 | Phillips Petroleum Company | Catalyst composition for the oxidation of carbon monoxide |
US5830425A (en) * | 1993-02-09 | 1998-11-03 | Sud-Chemie Ag | Chromium-free catalyst based on iron oxide for conversion of carbon monoxide |
Family Cites Families (16)
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DE4303715A1 (en) * | 1993-02-09 | 1994-08-11 | Sued Chemie Ag | Chromium-free catalyst based on iron oxide for the conversion of carbon monoxide |
DE69534557T2 (en) * | 1994-02-22 | 2006-06-01 | The Standard Oil Co., Cleveland | Process for the preparation of a catalyst for the production of vinyl acetate in a fluidized bed |
JPH08243355A (en) * | 1995-03-10 | 1996-09-24 | Agency Of Ind Science & Technol | Removing method of nitrogen oxide by catalytic reduction |
DE19929281A1 (en) * | 1999-06-25 | 2000-12-28 | Basf Ag | Process and catalyst for the production of C¶2¶ oxygenates from synthesis gas |
US6969505B2 (en) | 2002-08-15 | 2005-11-29 | Velocys, Inc. | Process for conducting an equilibrium limited chemical reaction in a single stage process channel |
US7160533B2 (en) * | 2002-12-20 | 2007-01-09 | Honda Giken Kogyo Kabushiki Kaisha | Platinum-ruthenium containing catalyst formulations for hydrogen generation |
EP1578688A2 (en) * | 2002-12-20 | 2005-09-28 | Honda Giken Kogyo Kabushiki Kaisha | Catalyst formulations for hydrogen generation |
EP1578529A2 (en) * | 2002-12-20 | 2005-09-28 | Honda Giken Kogyo Kabushiki Kaisha | Platinum and rhodium and/or iron containing catalyst formulations for hydrogen generation |
JP2006511425A (en) * | 2002-12-20 | 2006-04-06 | 本田技研工業株式会社 | Platinum-free ruthenium-cobalt catalyst formulation for hydrogen generation |
US7744849B2 (en) * | 2002-12-20 | 2010-06-29 | Honda Giken Kogyo Kabushiki Kaisha | Platinum-alkali/alkaline-earth catalyst formulations for hydrogen generation |
GB0402104D0 (en) | 2004-02-02 | 2004-03-03 | Johnson Matthey Plc | Water gas shift catalyst |
JP4537091B2 (en) | 2004-03-01 | 2010-09-01 | エヌ・イーケムキャット株式会社 | Catalyst for removing carbon monoxide from hydrogen gas |
US7238333B2 (en) | 2004-03-18 | 2007-07-03 | General Motors Corporation | High activity water gas shift catalysts with no methane formation |
JP4296430B2 (en) * | 2004-12-27 | 2009-07-15 | 戸田工業株式会社 | Catalyst for water gas shift reaction and process for producing the same |
ES2279691B1 (en) | 2005-07-08 | 2008-08-01 | Consejo Sup. De Invest. Cientificas | CATALYSTS FOR CONVERSION OF CARBON MONOXIDE IN HYDROGEN AND ITS USE IN THE CATALYTIC PROCESS OF ENRICHMENT IN HYDROGEN OF A GAS CURRENT THAT CAN FEED A BATTERY OF FUEL. |
KR100761512B1 (en) * | 2006-08-22 | 2007-10-04 | 주식회사 효성 | Dehydrogenation process of dimethylnaphthalene by metal catalyst |
-
2011
- 2011-08-25 CA CA2805259A patent/CA2805259A1/en not_active Abandoned
- 2011-08-25 WO PCT/IB2011/053729 patent/WO2012025897A1/en active Application Filing
- 2011-08-25 EP EP11819508.0A patent/EP2608882A4/en not_active Withdrawn
- 2011-08-25 JP JP2013525407A patent/JP5961166B2/en not_active Expired - Fee Related
- 2011-08-25 KR KR1020137007248A patent/KR101854941B1/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4956330A (en) * | 1989-06-19 | 1990-09-11 | Phillips Petroleum Company | Catalyst composition for the oxidation of carbon monoxide |
US5830425A (en) * | 1993-02-09 | 1998-11-03 | Sud-Chemie Ag | Chromium-free catalyst based on iron oxide for conversion of carbon monoxide |
Non-Patent Citations (1)
Title |
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See also references of WO2012025897A1 * |
Also Published As
Publication number | Publication date |
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JP2013536076A (en) | 2013-09-19 |
KR101854941B1 (en) | 2018-05-04 |
CA2805259A1 (en) | 2012-03-01 |
KR20140002618A (en) | 2014-01-08 |
JP5961166B2 (en) | 2016-08-02 |
WO2012025897A1 (en) | 2012-03-01 |
EP2608882A4 (en) | 2014-11-12 |
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