WO2018219986A1 - Process for carbon dioxide hydrogenation in the presence of an iridium- and/or rhodium-containing catalyst - Google Patents
Process for carbon dioxide hydrogenation in the presence of an iridium- and/or rhodium-containing catalyst Download PDFInfo
- Publication number
- WO2018219986A1 WO2018219986A1 PCT/EP2018/064142 EP2018064142W WO2018219986A1 WO 2018219986 A1 WO2018219986 A1 WO 2018219986A1 EP 2018064142 W EP2018064142 W EP 2018064142W WO 2018219986 A1 WO2018219986 A1 WO 2018219986A1
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- WIPO (PCT)
- Prior art keywords
- range
- catalyst
- iridium
- rhodium
- carbon dioxide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 69
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 44
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 40
- 239000010948 rhodium Substances 0.000 title claims abstract description 37
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 34
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 39
- 229910052741 iridium Inorganic materials 0.000 claims description 36
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 19
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 150000004645 aluminates Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052566 spinel group Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910015999 BaAl Inorganic materials 0.000 description 1
- 229910003320 CeOx Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; 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
- B01J23/002—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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
- B01J23/38—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
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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
- B01J23/76—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
- B01J23/83—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 rare earths or actinides
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- B01J35/613—
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
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- 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
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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
- C01B2203/1082—Composition of support materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention relates to a process for the hydrogenation of carbon dioxide, which is characterized in that carbon dioxide is reacted with hydrogen in the presence of a catalyst comprising an iridium- and / or rhodium-containing active material.
- a catalyst comprising an iridium- and / or rhodium-containing active material.
- RWGS reverse water gas shift
- JP 3328847 B2 describes the use of rhodium-containing catalysts for the methanation, i. Hydrogenation of carbon dioxide with hydrogen to methane, described at temperatures of 200 to 550 ° C.
- WO 2015/091310 A1 discloses the use of iridium-containing catalysts for the dry reforming of mixtures of hydrocarbons and carbon dioxide to synthesis gas.
- Synthesis gas is to be understood as meaning a gas mixture containing hydrogen and carbon monoxide, which can be used as a basic chemical in a large number of industrial processes. Depending on their use, synthesis gases have different ratios of hydrogen to carbon monoxide.
- C02 emissions in Germany in 2010 amounted to approx. 960 million t C02 equivalent, with the chemical industry contributing around 5%.
- Suitable basic chemicals are, for example, hydrogen and synthesis gas. The latter forms the ideal interface to existing petrochemical processes for production of eg methanol, dimethyl ether or Fischer-Tropsch products.
- the global demand for hydrogen and syngas is currently 50 million t / a, or 220 million t / a.
- WO2015 / 135968 discloses catalysts based on Ni, Co, Zn, Fe mixed oxides.
- noble metal-containing catalysts for the hydrogenation of carbon dioxide to carbon monoxide are described in US Pat. No. 8,961,829 B2.
- a catalyst is disclosed in which platinum has been deposited on cerium, manganese and / or magnesium oxide. In the examples, a Pt loading of 0.3 wt .-% is given.
- US 201 1/0105630 discloses platinum or palladium based catalysts for the hydrogenation of carbon dioxide to carbon monoxide.
- Potential support materials include alumina, magnesia, silica, titania, optionally sulfated zirconia, tungsten zirconia, aluminum trifluoride, fluorinated alumina, bentonites, zeolites, carbon-based supports, molecular sieves, and combinations thereof.
- the stated preferred loading is 10 to 20 wt .-%.
- WO 2013/135710 discloses a carbon dioxide hydrogenation to carbon monoxide in a shell and tube reactor.
- the catalyst disclosed are hexaaluminates having the following formula:
- L Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, Sn, Pb, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu
- M Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cu, Ag and / or Au.
- the method of preparation of these solid hexaaluminate catalysts involves a multi-step process involving the steps of precipitation, filtration, washing, drying, molding and calcining. Examples of carbon dioxide hydrogenation are not disclosed.
- WO 2015/135968 discloses a process for preparing a catalyst for high temperature carbon dioxide hydrogenation to carbon monoxide.
- the disclosed catalyst contains at least one crystalline material comprising yttrium and aluminum, wherein it is characteristic of the crystalline material that it has at least one of the following structures: cubic garnet structure, orthhombic perovskite structure, hexagonal perovskite structure and / or monoclinic perovskite structure (ie Y4AI209), wherein the catalyst contains Cu, Fe, Co, Zn and / or Ni.
- the loading of the yttrium-containing material is 0.1 to 10 mol .-% indicate.
- the examples show good performance in carbon dioxide hydrogenation, as well as low carbon deposition on the catalyst.
- the experiments were carried out at a GHSV of 30,000 and 40,000 r 1 .
- the method of preparation of these catalysts comprises a multistage process comprising the stages, precipitation, filtration, drying, pre-calcination, molding, post-
- One of the objects underlying the invention is to provide a catalyst for carbon dioxide hydrogenation with high activity and stability, i. good resistance to coke buildup. Furthermore, the tendency to methanation should be low.
- this catalyst is inexpensive to produce, i. a manufacturing method can be selected that includes as few process steps.
- a supported catalyst can be prepared with the aid of the process steps impregnation, drying, calcination, whereby a period of typically V2 hours is estimated for impregnation on a laboratory scale.
- a full-body catalyst requires the process steps of precipitation, filtration, washing, drying / calcination, molding and (post) calcination, with half a working day being estimated for a laboratory scale precipitation.
- the active metal loading should be as low as possible to be energy efficient and resource efficient.
- a further object is also that the process according to the invention is suitable for the carbon dioxide hydrogenation to carbon monoxide in the presence of hydrocarbons, in particular methane, i. that methane present in the educt gas mixture is reformed.
- Another object within the scope of the invention is to identify particularly active catalysts which, even at high loads, in particular greater than 10,000 h-1, are still able to convert a reactant gas mixture into a composition close to the thermodynamically predicted equilibrium lies.
- Particularly active catalysts make it possible to make the reactor smaller and thus keep the investment for this part of the plant small.
- high temperature process is meant processes at temperatures of> 600 ° C, in particular> 600 ° C and ⁇ 1400 ° C.
- the invention relates to a process for carbon dioxide hydrogenation, which is characterized in that carbon dioxide is reacted with hydrogen in the presence of a catalyst, wherein the catalyst comprises a support material and an active composition, wherein as support materials Ce, La, Zr, Al, Ti, Ca, Si, Mg oxides, SiC, MgAI spinels, Sr aluminates, La , Ba, Sr-hexa-aluminates and / or mixtures thereof, and the active composition contains at least iridium and / or rhodium as active component, wherein the content of iridium (calculated as metal) with respect to the total weight of the catalyst is in a range of 0.005 to 2 wt .-% and the content of rhodium (calculated as metal) relative to the total weight of the catalyst in a range of 0.005 to ⁇ 1 wt .-% and the temperature of the educt gases, carbon dioxide with Hydrogen, when contacted with the active composition in the range of 600 to 1
- Carbon dioxide is preferably reacted with hydrogen in the presence of a catalyst to give carbon monoxide and water.
- the content of rhodium in relation to the total weight of the catalyst is in a range of preferably 0.005 to 0.75 wt.%, More preferably 0.01 to 0.75 wt.%, In particular 0.025 to 0, 75% by weight.
- the content of iridium is in a range of preferably 0.005 to 1.5% by weight, more preferably 0.01 to 1% by weight, more preferably 0.01 to ⁇ 1% by weight, based on the total weight of the catalyst .-%, more preferably 0.01 to 0.75 wt .-%, in particular 0.025 to 0.75 wt .-%. All mixtures of iridium and rhodium known to the person skilled in the art are conceivable. Particularly preferred is iridium.
- the total content of a mixture of iridium and rhodium in relation to the total weight of the catalyst is in a range of preferably 0.005 to 2% by weight, preferably 0.005 to 1.5% by weight, more preferably 0.01 to 1% by weight %, more preferably 0.01 to ⁇ 1 wt .-%, more preferably 0.01 to 0.75 wt .-%, in particular 0.025 to 0.75 wt .-%.
- oxides As support materials, oxides, aluminates and carbides are preferred. Examples of oxides which may be mentioned as oxides are Ce, La, Zr, Al, Ti, Ca, Si, Mg oxides and mixtures thereof, carbides SiC and aluminates spinels, in particular MgAl spinels, Sr aluminates and La, Ba, Sr 2. Hexa-aluminates.
- the following support materials are preferred: Ce, La, Zr, Al-oxides, Zr-hydroxides doped with La & Ce, Al 2 O 3 (delta-theta), SiC, Y on ZrO 2, Ce on ZrO 2, Ca-Si-ZrO 2, 35% MgO 65% Al 2 O 3, 80% MgO 20% Al 2 O 3, 37% CaO, 63% Al 2 O 3, ZrO 2 (monoclinic), ZrO 2 (tetragonal), 44.6% CaO 54.9% ZnO, TiO 2, MgO, SrAl 2 O 4, BaAl 2 O 4, La 2 Zr 2 O 7.
- the content of doping elements is advantageously in the range from 0 to 5 wt .-%, in particular 1 to 3 wt .-%, with respect to the carrier material.
- the zirconium dioxide-containing active composition has a specific surface area of> 5 m 2 / g, preferably> 20 m 2 / g, more preferably> 50 m 2 / g and in particular> 80 m 2 / g.
- the determination of specific surface area of the catalyst was achieved by gas adsorption by the BET method (ISO 9277: 1995).
- the iridium and / or rhodium it is particularly advantageous for the iridium and / or rhodium to be present in finely divided form on the carrier, in particular zirconium dioxide carrier, since this achieves high catalytic activity with a low content of Ir and / or Rh.
- the iridium-containing and / or rhodium-containing particles have a size ⁇ 50 nm, preferably ⁇ 30 nm, preferably ⁇ 20 nm and more preferably ⁇ 10 nm.
- the iridium-containing and / or rhodium-containing particles have a size in the range from 1 to 100 nm, preferably in the range from 5 to 50 nm.
- the iridium and / or rhodium is homogeneously on the carrier or in the active mass.
- the iridium and / or rhodium is particularly preferably present in homogeneous and finely divided form on the carrier or in the active composition.
- the catalyst used according to the invention is characterized in that the Ir and / or Rh on a carrier, advantageously a zirkoni umdioxid Anlagenn carrier, is present and this doped with further elements.
- a carrier advantageously a zirkoni umdioxid ambiencen carrier
- elements from the group of rare earths ie from the group Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
- the catalyst also contains one or more doping elements in addition to the iridium and / or rhodium and optionally zirconium dioxide, then the proportion by weight of doping elements, in particular rare earth doping elements, based on the total weight of the catalyst is in the range from 0.01 to 80 Wt .-%, preferably in the range of 0.1 to 50 wt .-% and particularly preferably in the range of 1, 0 to 30 wt .-%.
- the catalyst used according to the invention is characterized in that it contains iridium and / or rhodium and a support material, advantageously zirconium dioxide, yttrium as a further doping element, wherein the yttrium is present in oxidic form.
- a support material advantageously zirconium dioxide, yttrium as a further doping element, wherein the yttrium is present in oxidic form.
- the yttria content based on the total weight of the catalyst, in the range of 0.01 to 80 wt .-%, preferably from 0.1 to 50 wt .-% and more preferably from 1, 0 to 30 wt .-% ,
- the catalyst used according to the invention is characterized in that, in addition to iridium and / or rhodium and a support material, preferably zirconium dioxide, additionally contains one or more, preferably two, elements from the group of rare earths as doping elements.
- the content is preferably to doping elements with respect to the total weight of the catalyst, in the range of 0.01-80 wt.%, preferably 0.1-50 wt.%, and more preferably 1-30 wt.%. Particular preference is given to using lanthanum (La) and cerium (Ce) as doping elements.
- catalysts used according to the invention which comprise Ir / ZrO 2 and / or Rh / ZrC 2 active compositions in which the zirconium dioxide has a doping with yttrium and / or a doping with lanthanum and / or cerium.
- the active compounds used according to the invention which are used for the process according to the invention also contain promoters and / or further metal cations, which further increase the efficiency of the catalysts.
- doping elements may include, but are not limited to: noble metal promoters, non-noble metal promoters, and other metal cations:
- the catalyst used according to the invention or the active composition contains at least one noble metal-containing promoter from the group Pt, Pd, Ru, Au, where the proportion of noble metal-containing promoters in relation to the total weight of the catalyst is 0.01. 5 wt .-% and more preferably in the range of 0.1 to 3 wt .-% have.
- the catalyst used according to the invention comprises at least one non-noble metal-containing promoter from the group Ni, Co, Fe, Mn, Mo, W, the fraction of non-noble metal-containing promoters being in the range from 0.1 to 50 based on the total weight of the catalyst Wt .-%, preferably in the range of 0.5 to 30 wt .-% and more preferably in the range 1-20 wt .-% is.
- the catalyst used according to the invention also comprises a proportion of further metal cations, which are preferably selected from the group Mg, Ca, Sr, Ba, Ga, Be, Cr, Mn, with Ca and / or Mg being particularly preferred.
- the components present in the catalyst used in the present invention i. the said noble metals, alkaline earth metals, doping elements, promoters and support materials can be present in elemental and / or oxidic form.
- examples being impregnation with impregnating solution, impregnation with pore volume, spraying of the impregnating solution, washcoating and precipitation powdery raw materials can be carried out by methods known to those skilled in the art, such as tableting, aggregation or extrusion, as described, inter alia, in the Handbook of Heterogenous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp. 414-417.
- the iridium-containing and / or rhodium-containing active composition may also be applied to a carrier, monolith or honeycomb body.
- the monolith or honeycomb body may be made of metal or ceramic.
- the molding of the active composition or the application of the active composition on a carrier or carrier bodies is of great industrial significance for the fields of application of the catalyst used according to the invention.
- the shape of the particles affect the pressure drop caused by the fixed catalyst bed. Impression may be carried out by any method known to those skilled in the art of catalyst preparation (see, eg, Deutschmann, O., Knözinger, H., Kochloefl, K. and Turek, T. 201. 1. Heterogeneous Catalysis and Solid Catalysts, 2. Development and Types of Solid Catalysts, Ullmann's Encyclopedia of Industrial Chemistry).
- the present invention further relates to a catalytic process for the carbon dioxide hydrogenation to carbon monoxide, i. for the production of synthesis gas, characterized in that:
- the pressure of the reactant gas in contacting with the catalyst is in the range of 1 to 100 bar a bs and the temperature of the educt gas in contacting with the catalyst is in the range of 20 to 1400 ° C,
- the GHSV of the process has a value in the range of 1,000 to 1,000,000 r 1 ,
- the synthesis gas produced has a H 2 / CO ratio in the range of 0.1 to 10, more preferably in the range of 1 to 4, and most preferably in the range of 1, 5 to 3.
- the molar ratio of educt gas H2 / CO 2 in the range from 0.1 to 20, preferably from 0.3 to 10, more preferably from 1 to 7, in particular from 2 to 5, is advantageous.
- the educt gas has the following composition:
- the molar fraction of CO 2 is advantageously in the range from 1 to 90%, preferably from 3 to 75%, more preferably from 10 to 60%, in particular from 20 to 50%.
- the molar fraction of H 2 is advantageously in the range from 1 to 99%, preferably from 10 to 90%, more preferably from 20 to 85%, in particular from 40 to 80%.
- the molar fraction of CH4 is advantageously in the range from 0 to 30%, preferably from 0 to 20%, more preferably 0 to 15%, more preferably 0 to 10%, in particular from 0 to 5%.
- the molar fraction of N 2 is advantageously in the range from 0 to 80%, preferably from 0 to 20%, in particular from 0 to 5%.
- the molar fraction of O 2 is advantageously in the range from 0 to 5%, preferably from 0 to 2%, more preferably from 0 to 1%, in particular from 0 to 0.5%.
- the molar fraction of H 2 O is advantageously in the range from 0 to 99%, preferably from 0 to 90%, more preferably from 0 to 40%, more preferably 0 to 20%, further preferably 0 to 15%, further preferably 0 to 10%, in particular 0 to 5%.
- the pressure of the educt gas when contacting with the catalyst is advantageously in the range from 3 to 60 bar a bs, in particular from 10 to 30 bar a bs.
- the temperature of the educt gas when it comes into contact with the catalyst is in the range from 600 to 1300 ° C., preferably from 750 to 1200 ° C., in particular from 850 to 1200 ° C.
- the GHSV of the process is in the range from 2000 to 700,000 hr.sup.- 1 , preferably from 5000 to 500,000 hr.sup.- 1 , in particular from 10,000 to 300,000 hr.sup.- 1 .
- the process according to the invention can be advantageously used as an ATR process (autothermal reforming), such as, for example, in Reimert, et al. , 201 1. Gas Production, 2. Processes. Ullmann's Encyclopedia of Industrial Chemistry. described be performed.
- ATR process oxygen is thus introduced in addition to the educt gas.
- a characteristic of the process according to the invention for the hydrogenation of carbon dioxide, if appropriate in the presence of hydrocarbons, advantageously methane, and / or water, is that ZrO 2 -containing active compositions can be used which have a relatively low content of iridium and / or rhodium and nevertheless one have high catalytic efficiency.
- active compositions which, for example, have only 1% by weight or less than 1% by weight of iridium and / or rhodium.
- the process according to the invention can be carried out with a reactant fluid which has small amounts of water vapor.
- the water vapor / carbon dioxide content in the educt gas is less than 0.2, more preferably less than 0.1, and even more preferably less than 0.05.
- the iridium-containing and / or rhodium-containing active component is exposed to a strong physical and chemical load, since the process is carried out at a temperature in the range of 600 to 1300 "C, the process pressure in the range of 5 to 500 bar , preferably in the range of 10 to 250 bar, and more preferably in the range of 20 to 100.
- the coke deposit is ⁇ 2 wt .-% carbon content with respect to the catalyst used, more preferably ⁇ 1 wt .-%, more preferably ⁇ 0.5 wt .-%, in particular ⁇ 0.2 wt .-%. Due to the very high thermal stability and the operational stability under pressure at pressures of 5 to 40 bar of the catalyst this can be used over long process times, several thousand hours away.
- the corresponding amount of Sr (N 0.3) 2 (4.344 g with a purity of 99.7% by weight) was dissolved in 250 ml DI water with stirring in a 500 ml beaker.
- a dispersion of the AI source (15.462 g Disperal with 42.51 wt% AI) was added to this solution, whereupon a suspension has formed. This suspension was stirred for 30 minutes for homogenization.
- the suspension was flash frozen dropwise in liquid nitrogen. The frozen droplets were freeze-dried at -10 C and 2.56 mbar.
- the freeze-dried powder was calcined in air to decompose the nitrates and chlorides.
- the heating rate was 1 K / min.
- the sample was heated to 150 C, 250 C and 350 C with a residence time of 1 hour at the temperature reached.
- the final calcination temperature was 450 C and the residence time was again 1 hour, then cooled to ambient temperature.
- the precalcined sample was subjected to a molding process. 3% by weight of graphite was added to the sample and mixed thoroughly. The mixture was pelletized with a Korsch XP1 pelletizer in automatic mode. The direction finding tool had a diameter of 13 mm and the applied force for picking up pellets with a height of 2 mm was 40 kN. The pellets were crushed and sieved to 315-500 pm.
- the crushed and sieved sample (315-500 pm) was subjected to final calcination in air to remove the graphite and to form the desired hexaaluminate phase.
- the final calcination temperature was 1400 C with a heating rate of 5 K / min and a residence time of 2 hours.
- W015135968 Catalyst S2 was prepared as described in WO 15/135968 A1.
- the catalysts S3 and S4 were prepared analogously to the prior art, US 201 1/0105630, via impregnation process:
- the dried sample was calcined in air (6 l / min) in an oven (Nabertherm TH120 / 12) as follows: heating rate of 1 K / min up to a temperature of 250 ° C, residence time of 1 h, heating rate of 5 K / min up to a temperature of 400 C, residence time of 4 h, then cool to ambient temperature.
- the drying took place in a drying oven at 80 C for 16 hours.
- the dried sample was calcined as follows under air (6 I / min) in a furnace (Nabertherm TH120 / 12): heating rate of 1 K / min up to a temperature of 250 0 C, residence time of 1 hour, heating rate of 5K / min up to a temperature of 400 0 C, residence time of 4h, then cool to ambient temperature.
- Table III List of carrier materials used
- Table IV List of impregnating solutions used Table V summarizes the catalysts used according to the invention.
- Table V List of Ir and Rh catalysts used in the invention
- the determination of the loss on ignition (LOI) is a crucial point in the production of impregnated catalysts with a well-defined metal loading.
- the carrier used had an LOI of 2.43%.
- the impregnation was carried out as 100% incipient wetness impregnation (100% ICW) (moistening impregnation) using a solution of DI water with a 0.199 molar IrC solution.
- Table 2 Summary of hydrogen conversion, carbon dioxide conversion, and methane yield (without methane in the educt gas) or methane conversion (methane in educt gas) of the catalysts S1-S4 (prior art), E1-E6 (according to the invention) of the phase I - VI of the table 1
- the catalysts used in the invention show a comparable performance as the full catalysts S1 and S2 from the prior art. Furthermore, the performance is stable over all phases.
- the activity of prior art catalysts S3 and S4 decreases from phase V and phase VI, respectively; Furthermore, the conversion of H2 in phases I and II, in which no methane is added, worse than S1 and S2 and E1 -E6.
- Table 3 Carbon deposition from the catalysts after the screening according to Table 5 (indicator of stability)
- Table 7 Summary of hydrogen conversion, carbon dioxide conversion, and methane yield (without methane in the educt gas) or methane conversion (methane in educt gas) of the catalysts E4 (0.5% by weight Ir), E5 (0.05% by weight Ir) and E7 ( 0.1% by weight Ir) of phase I-XI II of Table 6
Abstract
The invention relates to a process for carbon dioxide hydrogenation, characterized in that carbon dioxide is reacted with hydrogen in the presence of a catalyst comprising an iridium- and/or rhodium-containing active composition.
Description
Verfahren zur Kohlenstoffdioxid-Hydrierung in Gegenwart eines iridium- und/oder rhodiumhalti- gen Katalysators Process for the carbon dioxide hydrogenation in the presence of an iridium- and / or rhodium-containing catalyst
Beschreibung description
Die Erfindung betrifft ein Verfahren zur Kohlenstoffdioxid-Hydrierung, das dadurch gekennzeichnet ist, dass Kohlenstoffdioxid mit Wasserstoff in Gegenwart eines Katalysators, der eine iridium- und/oder rhodiumhaltige Aktivmasse beinhaltet, umgesetzt wird. Die Reformierung von Wasserstoff und Kohlenstoffdioxid zu Kohlenstoffmonoxid, auch Kohlenstoffdioxid-Hydrierung oder Reverse-Water-Gas-Shift-Reaktion (RWGS) genannt, ist von großem wirtschaftlichem Interesse, da diese Verfahren die Möglichkeit bietet, Synthesegas als wichtige Basischemikalie unter Verwertung von Kohlenstoffdioxid als Ausgangsstoff herzustellen. Demnach könnte Kohlenstoffdioxid, das in zahlreichen Prozessen als Abfallprodukt anfällt, auf chemischem Weg gebunden werden. Hierdurch besteht die Möglichkeit, Kohlenstoffdioxid- Emission in die Atmosphäre zu vermindern. The invention relates to a process for the hydrogenation of carbon dioxide, which is characterized in that carbon dioxide is reacted with hydrogen in the presence of a catalyst comprising an iridium- and / or rhodium-containing active material. The reforming of hydrogen and carbon dioxide to carbon monoxide, also called carbon dioxide hydrogenation or reverse water gas shift (RWGS) reaction, is of great economic interest as it offers the possibility of using synthesis gas as an important basic chemical utilizing carbon dioxide Produce starting material. Thus, carbon dioxide, which is a by-product of many processes, could be chemically bound. This makes it possible to reduce carbon dioxide emission into the atmosphere.
Neben der Reverse-Water-Gas-Shift-Reaktion sind weitere Verfahren zur klimafreundlichen Verwendung von Kohlenstoffdioxid bekannt, z.B. die Methanisierung und die trockene Refor- mierung. JP 3328847 B2 beschreibt die Verwendung von rhodiumhaltigen Katalysatoren für die Methanisierung, d.h. Hydrierung von Kohlenstoffdioxid mit Wasserstoff zu Methan, bei Temperaturen von 200 bis 550°C beschrieben. WO 2015/091310 A1 offenbart die Verwendung von iridiumhaltigen Katalysatoren für die trockene Reformierung von Gemischen aus Kohlenwasserstoffen und Kohlenstoffdioxid zu Synthesegas. In addition to the reverse water gas shift reaction, other processes for the climate friendly use of carbon dioxide are known, e.g. methanation and dry reforming. JP 3328847 B2 describes the use of rhodium-containing catalysts for the methanation, i. Hydrogenation of carbon dioxide with hydrogen to methane, described at temperatures of 200 to 550 ° C. WO 2015/091310 A1 discloses the use of iridium-containing catalysts for the dry reforming of mixtures of hydrocarbons and carbon dioxide to synthesis gas.
Unter Synthesegas ist ein Wasserstoff und Kohlenmonoxid enthaltendes Gasgemisch zu verstehen, das in einer Vielzahl von industriellen Prozessen als Basischemikalie eingesetzt werden kann. Abhängig von ihrer Verwendung weisen Synthesegase unterschiedlichen Verhältnisse von Wasserstoff zu Kohlenmonoxid auf. Synthesis gas is to be understood as meaning a gas mixture containing hydrogen and carbon monoxide, which can be used as a basic chemical in a large number of industrial processes. Depending on their use, synthesis gases have different ratios of hydrogen to carbon monoxide.
Kommerziell wird Wasserstoff nach wie vor via Dampfreformierungsverfahren hergestellt. Diese Verfahren haben zwar einen inhärenten Preisvorteil, der sich im Wasserstoffpreis niederschlägt, allerdings ist die Wasserstofferzeugung gekoppelt mit einer hohen Emission an Kohlenstoffdioxid. Commercially, hydrogen is still produced by steam reforming. Although these processes have an inherent price advantage, which is reflected in the price of hydrogen, hydrogen production is coupled with high carbon dioxide emissions.
Die C02-Emissionen in Deutschland betrugen im Jahre 2010 rd. 960 Mio. t C02-Äquivalent, wobei die Chemieindustrie mit ca. 5 % beiträgt. Unter ökologischen und ökonomischen Gesichtspunkten bestehen in der Chemie-Branche hohe Anreize, die C02-Emissionen durch Veränderung der Rohstoffbasis, C02-arme Erzeugungstechnologien, Optimierung des Energiebe- darfs und Verwertung von prozessbedingtem C02 zu großvolumigen Basischemikalien zu senken. Geeignete Basischemikalien sind beispielsweise Wasserstoff und Synthesegas. Letzteres bildet die ideale Schnittstelle zu vorhandenen petrochemischen Verfahren für die Produktion
von z.B. Methanol, Dimethylether oder Fischer-Tropsch Produkten. Die weltweiten Bedarfe für Wasserstoff und Synthesegas liegen derzeit bei 50 Mio t/a, bzw. 220 Mio t/a. C02 emissions in Germany in 2010 amounted to approx. 960 million t C02 equivalent, with the chemical industry contributing around 5%. From an ecological and economic point of view, there are strong incentives in the chemical industry to reduce CO 2 emissions by changing the raw material base, low C02 production technologies, optimizing the energy requirement and recycling process-related CO 2 into large-volume basic chemicals. Suitable basic chemicals are, for example, hydrogen and synthesis gas. The latter forms the ideal interface to existing petrochemical processes for production of eg methanol, dimethyl ether or Fischer-Tropsch products. The global demand for hydrogen and syngas is currently 50 million t / a, or 220 million t / a.
Für die Methanolherstellung mittels Kohlenstoffdioxid-Hydrierung zu Kohlenstoffmonoxid wur- den von Graciani et al. Cu/CeOx Katalysatoren (J. Graciani, K. Mudiyanselage, F. Xu, A.E. Baber, J. Evans, S.D. Senanayake, DJ. Stacchiola, P. Liu, J. Hrbek, J. Fernändez Sanz, J.A. Rodriguez, Science 345 (2014) 546-550.) und von Bansode et al. Cu/ZnO/AI203 Katalysatoren (A. Bansode, A. Urakawa, J. Catal. 309 (2014) 66-70) vorgeschlagen. For the production of methanol by means of carbon dioxide hydrogenation to carbon monoxide, Graciani et al. Cu / CeOx catalysts (J. Graciani, K. Mudiyanselage, F. Xu, AE Baber, J. Evans, SD Senanayake, DJ, Stacchiola, P. Liu, J. Hrbek, J. Fernandez Sanz, JA Rodriguez, Science 345 ( 2014) 546-550.) And by Bansode et al. Cu / ZnO / Al 2 O 3 catalysts (A. Bansode, A. Urakawa, J. Catal. 309 (2014) 66-70).
Neben Cu-basierten Katalysatoren werden in WO2015/135968 Katalysatoren auf Basis von Ni, Co, Zn, Fe Mischoxiden offenbart. In addition to Cu-based catalysts, WO2015 / 135968 discloses catalysts based on Ni, Co, Zn, Fe mixed oxides.
Ferner werden Edelmetall enthaltende Katalysatoren für die Hydrierung von Kohlenstoffdioxid zu Kohlenstoffmonoxid in US 8,961 ,829 B2 beschrieben. Es wird ein Katalysator offenbart, bei dem Platin auf Cer-, Mangan- und/oder Magnesiumoxid abgeschieden wurde. In den Beispielen ist eine Pt-Beladung von 0,3 Gew.-% angegeben. Further, noble metal-containing catalysts for the hydrogenation of carbon dioxide to carbon monoxide are described in US Pat. No. 8,961,829 B2. A catalyst is disclosed in which platinum has been deposited on cerium, manganese and / or magnesium oxide. In the examples, a Pt loading of 0.3 wt .-% is given.
US 201 1/0105630 offenbart Platin oder Palladium basierte Katalysatoren für die Hydrierung von Kohlenstoffdioxid zu Kohlenstoffmonoxid. Als potentielle Trägermaterialien werden Aluminiumoxid, Magnesiumoxid, Siliciumdioxid, Titandioxid, ggf. sulfatiertes Zirkoniumdioxid, Wolfram- Zirkoniumoxid, Aluminiumtrifluorid, fluoriertes Aluminiumoxid, Bentonite, Zeolithe, auf Kohlenstoff basierenden Träger, Molekularsieben und Kombinationen davon beschrieben. Die angegebene bevorzugte Beladung liegt bei 10 bis 20 Gew.-%. US 201 1/0105630 discloses platinum or palladium based catalysts for the hydrogenation of carbon dioxide to carbon monoxide. Potential support materials include alumina, magnesia, silica, titania, optionally sulfated zirconia, tungsten zirconia, aluminum trifluoride, fluorinated alumina, bentonites, zeolites, carbon-based supports, molecular sieves, and combinations thereof. The stated preferred loading is 10 to 20 wt .-%.
Neben den genannten geträgerten Katalysatoren werden im Stand der Technik auch Vollkör- perkatalysatoren beschrieben: In addition to the above-mentioned supported catalysts, full-body catalysts are also described in the prior art.
WO 2013/135710 offenbart eine Kohlenstoffdioxid-Hydrierung zu Kohlenstoffmonoxid in einem Rohrbündelreaktor. Als Katalysator sind Hexaaluminate mit folgender Formel offenbart: WO 2013/135710 discloses a carbon dioxide hydrogenation to carbon monoxide in a shell and tube reactor. The catalyst disclosed are hexaaluminates having the following formula:
LOx(M(y/z)AI(2-y/z)03)z wobei L = Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, Sn, Pb, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb und/oder Lu und M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cu, Ag und/oder Au. Die Herstellweise dieser Vollkörper-Hexaaluminate-Katalysatoren umfasst einen mehrstufigen Prozess beinhaltend die Stufen Fällung, Filtration, Waschung, Trocknung, Abformung und Kalzinierung. Beispiele einer Kohlenstoffdioxidhydrierung werden nicht offenbart. LOx (M (y / z) Al (2-y / z) 03) z where L = Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, Sn, Pb, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu and M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cu, Ag and / or Au. The method of preparation of these solid hexaaluminate catalysts involves a multi-step process involving the steps of precipitation, filtration, washing, drying, molding and calcining. Examples of carbon dioxide hydrogenation are not disclosed.
WO 2015/135968 offenbart ein Verfahren zur Herstellung eines Katalysators für eine Hochtemperatur- Kohlenstoffdioxidhydrierung zu Kohlenstoffmonoxid. Der offenbarte Katalysator enthält zumindest ein kristallines Material umfassend Yttrium und Aluminium, wobei kennzeichnend für das kristalline Material ist, dass es zumindest eine der nachfolgenden Strukturen aus der Gruppe kubische Garnetstruktur, or- thorhombische Perovskitstruktur, hexagonale Pero- vskitstruktur und/oder monokline Perovskitstruktur (d.h. Y4AI209) aufweist, wobei der Katalysator Cu, Fe, Co, Zn und/oder Ni enthält. Die Beladung des yttriumhaltigen Materials wird mit 0,1
bis 10 mol.-% angeben. Die Beispiele zeigen gute Performance bei der Kohlenstoffdioxidhydrierung, ferner eine geringe Kohlenstoffabscheidung auf dem Katalysator. Die Versuche wurden bei einer GHSV von 30.000 und 40.000 r1 durchgeführt. Die Herstellweise dieser Katalysatoren umfasst einen mehrstufigen Prozess beinhaltend die Stufen, Fällung, Filtration, Trocknung, Vor- kalzinierung, Abformung, Nachkalzinierung. WO 2015/135968 discloses a process for preparing a catalyst for high temperature carbon dioxide hydrogenation to carbon monoxide. The disclosed catalyst contains at least one crystalline material comprising yttrium and aluminum, wherein it is characteristic of the crystalline material that it has at least one of the following structures: cubic garnet structure, orthhombic perovskite structure, hexagonal perovskite structure and / or monoclinic perovskite structure (ie Y4AI209), wherein the catalyst contains Cu, Fe, Co, Zn and / or Ni. The loading of the yttrium-containing material is 0.1 to 10 mol .-% indicate. The examples show good performance in carbon dioxide hydrogenation, as well as low carbon deposition on the catalyst. The experiments were carried out at a GHSV of 30,000 and 40,000 r 1 . The method of preparation of these catalysts comprises a multistage process comprising the stages, precipitation, filtration, drying, pre-calcination, molding, post-calcination.
Eine der Aufgaben, die der Erfindung zugrunde liegt, besteht in der Bereitstellung eines Katalysators zur Kohlenstoffdioxidhydierung mit hoher Aktivität und Stabilität, d.h. guter Resistenz gegen Koksaufbau. Desweiteren sollte die Neigung zur Methanisierung gering sein. One of the objects underlying the invention is to provide a catalyst for carbon dioxide hydrogenation with high activity and stability, i. good resistance to coke buildup. Furthermore, the tendency to methanation should be low.
Eine weitere Aufgabe liegt darin, dass dieser Katalysator kostengünstig herstellbar ist, d.h. eine Herstellweise gewählt werden kann, die möglichst wenige Prozessschritte umfasst. Ein geträ- gerter Katalysator lässt sich mit Hilfe der Prozessschritte Tränkung, Trocknung, Kalzinierung herstellen, wobei für die Tränkung im Labormaßstab eine Zeitdauer von typischerweise V2 Stunde veranschlagt wird. Ein Vollkörperkatalysator benötigt die Prozessschritte Fällung, Filtration, Waschung, Trocknung/Kalzinierung, Abformung und (Nach-)Kalzinierung, wobei für eine Fällung im Labormaßstab ein halber Arbeitstag veranschlagt wird. Somit liegt eine Aufgabe darin, einen geträgerten Katalysator zur Kohlenstoffdioxidhydierung bereitzustellen, dessen Performance vergleichbar mit denen der Vollkatalysatoren aus dem Stand der Technik ist. Another object is that this catalyst is inexpensive to produce, i. a manufacturing method can be selected that includes as few process steps. A supported catalyst can be prepared with the aid of the process steps impregnation, drying, calcination, whereby a period of typically V2 hours is estimated for impregnation on a laboratory scale. A full-body catalyst requires the process steps of precipitation, filtration, washing, drying / calcination, molding and (post) calcination, with half a working day being estimated for a laboratory scale precipitation. Thus, it is an object to provide a supported catalyst for carbon dioxide hydrogenation, the performance of which is comparable to that of the full catalysts of the prior art.
Ferner sollte die Aktivmetallbeladung so gering wie möglich sein, um energieeffizient und ressourcenschonend zu sein. Furthermore, the active metal loading should be as low as possible to be energy efficient and resource efficient.
Eine weitere Aufgabe ist es auch, dass das erfindungsgemäße Verfahren zur Kohlenstoffdioxid- hydrierung zu Kohlenstoffmonoxid in der Gegenwart von Kohlenwasserstoffen, insbesondere Methan, eignet ist, d.h. dass in der Eduktgasmischung anwesendes Methan reformiert wird. A further object is also that the process according to the invention is suitable for the carbon dioxide hydrogenation to carbon monoxide in the presence of hydrocarbons, in particular methane, i. that methane present in the educt gas mixture is reformed.
Eine weitere Aufgabe im Rahmen der Erfindung besteht darin, besonders aktive Katalysatoren zu identifizieren, die auch bei hohen Lasten, insbesondere bei größer als 10.000 h-1 , noch in der Lage sind, eine Eduktgasmischung in eine Zusammensetzung umzusetzen, die nahe am thermodynamisch vorhergesagten Gleichgewicht liegt. Besonders aktive Katalysatoren erlauben es, den Reaktor kleiner zu dimensionieren und damit den Invest für diesen Anlagenteil klein zu halten. Unter„Hochtemperaturverfahren" werden Verfahren bei Temperaturen von > 600°C verstanden, insbesondere > 600°C und < 1400°C. Another object within the scope of the invention is to identify particularly active catalysts which, even at high loads, in particular greater than 10,000 h-1, are still able to convert a reactant gas mixture into a composition close to the thermodynamically predicted equilibrium lies. Particularly active catalysts make it possible to make the reactor smaller and thus keep the investment for this part of the plant small. By "high temperature process" is meant processes at temperatures of> 600 ° C, in particular> 600 ° C and <1400 ° C.
Alle im Folgenden genannten Gew.-% beziehen sich auf das Gesamtgewicht des Katalysators inklusive Trägermaterialien. All weight percentages below are based on the total weight of the catalyst including support materials.
Die Erfindung betrifft ein Verfahren zur Kohlenstoffdioxid-Hydrierung, das dadurch gekennzeichnet ist, dass Kohlenstoffdioxid mit Wasserstoff in Gegenwart eines Katalysators umgesetzt wird,
wobei der Katalysator ein Trägermaterial und eine Aktivmasse aufweist, wobei als Trägermaterialien Ce-, La-, Zr-, AI-, Ti-, Ca-, Si-, Mg-Oxide, SiC, MgAI-Spinelle, Sr-Aluminate, La-, Ba-, Sr- Hexa-Aluminate und/oder Mischungen hieraus eingesetzt werden, und die Aktivmasse mindestens Iridium und/oder Rhodium als Aktivkomponente enthält, wobei der Gehalt an Iridium- (ge- rechnet als Metall) in Bezug auf das Gesamtgewicht des Katalysators in einem Bereich von 0,005 bis 2 Gew.-% liegt und der Gehalt an Rhodium (gerechnet als Metall) in Bezug auf das Gesamtgewicht des Katalysators in einem Bereich von 0,005 bis < 1 Gew.-% liegt und die Temperatur der Eduktgase, Kohlenstoffdioxid mit Wasserstoff, beim Inkontaktbringen mit der Aktivmasse im Bereich von 600 bis 1300°C liegt. The invention relates to a process for carbon dioxide hydrogenation, which is characterized in that carbon dioxide is reacted with hydrogen in the presence of a catalyst, wherein the catalyst comprises a support material and an active composition, wherein as support materials Ce, La, Zr, Al, Ti, Ca, Si, Mg oxides, SiC, MgAI spinels, Sr aluminates, La , Ba, Sr-hexa-aluminates and / or mixtures thereof, and the active composition contains at least iridium and / or rhodium as active component, wherein the content of iridium (calculated as metal) with respect to the total weight of the catalyst is in a range of 0.005 to 2 wt .-% and the content of rhodium (calculated as metal) relative to the total weight of the catalyst in a range of 0.005 to <1 wt .-% and the temperature of the educt gases, carbon dioxide with Hydrogen, when contacted with the active composition in the range of 600 to 1300 ° C.
Bevorzugt wird Kohlenstoffdioxid mit Wasserstoff in Gegenwart eines Katalysators zu Kohlen- stoffmonoxid und Wasser umgesetzt. Carbon dioxide is preferably reacted with hydrogen in the presence of a catalyst to give carbon monoxide and water.
Der Gehalt an Rhodium liegt in Bezug auf das Gesamtgewicht des Katalysators in einem Be- reich von vorzugsweise 0,005 bis 0,75 Gew.-%, weiter vorzugsweise von 0,01 bis 0,75 Gew.-% liegt, insbesondere 0,025 bis 0,75 Gew.-%. Der Gehalt an Iridium liegt in Bezug auf das Gesamtgewicht des Katalysators in einem Bereich von vorzugsweise 0,005 bis 1 ,5 Gew.-%, weiter vorzugsweise von 0,01 bis 1 Gew.-% liegt, weiter bevorzugt 0,01 bis < 1 Gew.-%, weiter bevorzugt 0,01 bis 0,75 Gew.-%, insbesondere 0,025 bis 0,75 Gew.-%. Es sind alle dem Fachmann bekannten Mischungen von Iridium und Rhodium denkbar. Besonders bevorzugt ist Iridium. The content of rhodium in relation to the total weight of the catalyst is in a range of preferably 0.005 to 0.75 wt.%, More preferably 0.01 to 0.75 wt.%, In particular 0.025 to 0, 75% by weight. The content of iridium is in a range of preferably 0.005 to 1.5% by weight, more preferably 0.01 to 1% by weight, more preferably 0.01 to <1% by weight, based on the total weight of the catalyst .-%, more preferably 0.01 to 0.75 wt .-%, in particular 0.025 to 0.75 wt .-%. All mixtures of iridium and rhodium known to the person skilled in the art are conceivable. Particularly preferred is iridium.
Der Gesamtgehalt an einer Mischung aus Iridium und Rhodium liegt in Bezug auf das Gesamtgewicht des Katalysators in einem Bereich von vorzugsweise 0,005 bis 2 Gew.-%, bevorzugt 0,005 bis 1 ,5 Gew.-%, weiter vorzugsweise von 0,01 bis 1 Gew.-% liegt, weiter bevorzugt 0,01 bis < 1 Gew.-%, weiter bevorzugt 0,01 bis 0,75 Gew.-%, insbesondere 0,025 bis 0,75 Gew.-%. The total content of a mixture of iridium and rhodium in relation to the total weight of the catalyst is in a range of preferably 0.005 to 2% by weight, preferably 0.005 to 1.5% by weight, more preferably 0.01 to 1% by weight %, more preferably 0.01 to <1 wt .-%, more preferably 0.01 to 0.75 wt .-%, in particular 0.025 to 0.75 wt .-%.
Als Trägermaterialien sind Oxide, Aluminate und Carbide bevorzugt. Beispielsweise sind als Oxide Ce, La, Zr, AI, Ti, Ca, Si, Mg-Oxide und Mischungen hieraus zu nennen, als Carbide SiC und als Aluminate Spinelle, insbesondere MgAI-Spinelle, Sr-Aluminate und La, Ba, Sr-Hexa- Aluminate. Folgende Trägermaterialien sind bevorzugt: Ce,La,Zr,AI-oxide, Zr-hydroxide dotiert mit La & Ce, AI203 (delta-theta), SiC, Y auf Zr02, Ce auf Zr02, Ca-Si-Zr02, 35% MgO 65% AI203, 80% MgO 20% AI203, 37% CaO, 63% AI203, Zr02 (monoclinic), Zr02(tetragonal), 44.6%CaO 54.9% ZnO, Ti02, MgO, SrAI204, BaAI204, La2Zr207. Der Gehalt an Dotierungselementen liegt vorteilhaft im Bereich von 0 bis 5 Gew.-%, insbesondere 1 bis 3 Gew.-%, im Be- zug auf das Trägermaterial. As support materials, oxides, aluminates and carbides are preferred. Examples of oxides which may be mentioned as oxides are Ce, La, Zr, Al, Ti, Ca, Si, Mg oxides and mixtures thereof, carbides SiC and aluminates spinels, in particular MgAl spinels, Sr aluminates and La, Ba, Sr 2. Hexa-aluminates. The following support materials are preferred: Ce, La, Zr, Al-oxides, Zr-hydroxides doped with La & Ce, Al 2 O 3 (delta-theta), SiC, Y on ZrO 2, Ce on ZrO 2, Ca-Si-ZrO 2, 35% MgO 65% Al 2 O 3, 80% MgO 20% Al 2 O 3, 37% CaO, 63% Al 2 O 3, ZrO 2 (monoclinic), ZrO 2 (tetragonal), 44.6% CaO 54.9% ZnO, TiO 2, MgO, SrAl 2 O 4, BaAl 2 O 4, La 2 Zr 2 O 7. The content of doping elements is advantageously in the range from 0 to 5 wt .-%, in particular 1 to 3 wt .-%, with respect to the carrier material.
Als Trägermaterial sind Zirkoniumdioxid, Titandioxid und Aluminate besonders bevorzugt, insbesondere Zirkoniumdioxid. In einer bevorzugten Ausführungsform des erfindungsgemäß-verwendeten Katalysators weist die zirkoniumdioxidhaltige Aktivmasse eine spezifische Oberfläche von > 5 m2/g, vorzugsweise > 20 m2/g, weiter vorzugsweise > 50 m2/g und insbesondere > 80 m2/g auf. Die Bestimmung der
spezifischen Oberfläche des Katalysators erfolgte durch Gasadsorption nach dem BET-Verfah- ren (ISO 9277:1995). Zirconium dioxide, titanium dioxide and aluminates are particularly preferred as carrier material, in particular zirconium dioxide. In a preferred embodiment of the catalyst used according to the invention, the zirconium dioxide-containing active composition has a specific surface area of> 5 m 2 / g, preferably> 20 m 2 / g, more preferably> 50 m 2 / g and in particular> 80 m 2 / g. The determination of specific surface area of the catalyst was achieved by gas adsorption by the BET method (ISO 9277: 1995).
Besonders vorteilhaft ist es, dass das Iridium und/oder Rhodium in fein verteilter Form auf dem Träger, insbesondere Zirkoniumdioxid-Träger, vorliegt, da hierdurch eine hohe katalytische Aktivität bei einem geringen Gehalt an Ir und/oder Rh erreicht wird. Vorteilhaft weisen die iridium- haltigen und/oder rhodiumhaltige Partikel eine Größe < 50 nm, bevorzugt < 30 nm, vorzugsweise < 20 nm und weiter vorzugsweise < 10 nm auf. Beispielsweise weisen die iridiumhaltigen und/oder rhodiumhaltigen Partikel eine Größe im Bereich von 1 bis 100 nm, bevorzugt im Be- reich von 5 bis 50 nm auf. It is particularly advantageous for the iridium and / or rhodium to be present in finely divided form on the carrier, in particular zirconium dioxide carrier, since this achieves high catalytic activity with a low content of Ir and / or Rh. Advantageously, the iridium-containing and / or rhodium-containing particles have a size <50 nm, preferably <30 nm, preferably <20 nm and more preferably <10 nm. For example, the iridium-containing and / or rhodium-containing particles have a size in the range from 1 to 100 nm, preferably in the range from 5 to 50 nm.
Weiter bevorzugt liegt das Iridium und/oder Rhodium homogen auf dem Träger bzw. in der Aktivmasse vor. Besonders bevorzugt liegt das Iridium und/oder Rhodium homogen und in fein verteilter Form auf dem Träger bzw. in der Aktivmasse vor. More preferably, the iridium and / or rhodium is homogeneously on the carrier or in the active mass. The iridium and / or rhodium is particularly preferably present in homogeneous and finely divided form on the carrier or in the active composition.
In einer bevorzugten Ausführungsform ist der erfindungsgemäß-verwendete Katalysator dadurch gekennzeichnet, dass das Ir und/oder Rh auf einem Träger, vorteilhaft einem zirkoni- umdioxidhaltigen Träger, vorliegt und dieser mit weiteren Elementen dotiert ist. Zur Dotierung des Trägers werden bevorzugt Elemente aus der Gruppe der Seltenen Erden (d.h. aus der Gruppe Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), Gruppe IIa (d.h. aus der Gruppe Mg, Ca, Sr, Ba,), Gruppe IVa (d.h. aus der Gruppe Si), Gruppe IVb (d.h. aus der Gruppe Ti, Hf) , Gruppe Vb (d.h. aus der Gruppe V, Nb, Ta) des Periodensystems beziehungsweise deren Oxide ausgewählt. Sofern der Katalysator zusätzlich zum Iridium und/oder Rhodium und gegebenenfalls Zirkoniumdioxid auch ein oder mehrere Dotierungselemente enthält, so ist der Gewichtsanteil an Dotierungselementen, insbesondere Dotierungselementen aus der Gruppe der Seltenen Erden, bezogen auf das Gesamtgewicht des Katalysators im Bereich von 0,01 bis 80 Gew.-%, bevorzugt im Bereich von 0,1 bis 50 Gew.-% und insbesondere bevorzugt im Bereich von 1 ,0 bis 30 Gew.-%. In a preferred embodiment, the catalyst used according to the invention is characterized in that the Ir and / or Rh on a carrier, advantageously a zirkoni umdioxidhaltigen carrier, is present and this doped with further elements. For the doping of the carrier, it is preferable to use elements from the group of rare earths (ie from the group Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). , Group IIa (ie from the group Mg, Ca, Sr, Ba,), Group IVa (ie from the group Si), Group IVb (ie from the group Ti, Hf), Group Vb (ie from the group V, Nb , Ta) of the periodic table or their oxides. If the catalyst also contains one or more doping elements in addition to the iridium and / or rhodium and optionally zirconium dioxide, then the proportion by weight of doping elements, in particular rare earth doping elements, based on the total weight of the catalyst is in the range from 0.01 to 80 Wt .-%, preferably in the range of 0.1 to 50 wt .-% and particularly preferably in the range of 1, 0 to 30 wt .-%.
Vorteilhaft ist der erfindungsgemäß-verwendete Katalysator dadurch gekennzeichnet, dass dieser neben Iridium und/oder Rhodium und einem Trägermaterial, vorteilhaft Zirkoniumdioxid, Yttrium als weiteres Dotierungselement enthält, wobei das Yttrium in oxidischer Form vorliegt. Bevorzugt liegt der Yttriumoxid-Gehalt bezogen auf das Gesamtgewicht des Katalysators, im Bereich von 0,01 - 80 Gew.-%, vorzugsweise von 0,1 - 50 Gew.-% und weiter bevorzugt von 1 ,0 - 30 Gew.-%. Advantageously, the catalyst used according to the invention is characterized in that it contains iridium and / or rhodium and a support material, advantageously zirconium dioxide, yttrium as a further doping element, wherein the yttrium is present in oxidic form. Preferably, the yttria content based on the total weight of the catalyst, in the range of 0.01 to 80 wt .-%, preferably from 0.1 to 50 wt .-% and more preferably from 1, 0 to 30 wt .-% ,
In einer weiteren und bevorzugten Ausführungsform ist der erfindungsgemäß-verwendete Katalysator dadurch gekennzeichnet, dass dieser neben Iridium und/oder Rhodium und einem Trägermaterial, vorteilhaft Zirkoniumdioxid, zusätzlich ein oder mehrere, bevorzugt zwei, Elemente aus der Gruppe der Seltenen Erden als Dotierungselemente enthält. Bevorzugt liegt der Gehalt
an Dotierungselementen in Bezug auf das Gesamtgewicht des Katalysators, im Bereich von 0,01 - 80 Gew.-%, vorzugsweise von 0,1 - 50 Gew.-% und weiter bevorzugt von 1 ,0 - 30 Gew.- %. Besonders bevorzugt werden Lanthan (La) und Cer (Ce) als Dotierungselemente eingesetzt. Insbesondere bevorzugt sind diejenigen erfindungsgemäß-verwendeten Katalysatoren, die Ir/Zr02- und/oder Rh/ZrC"2- Aktivmassen enthalten, bei denen das Zirkoniumdioxid eine Dotierung mit Yttrium und/oder eine Dotierung mit Lanthan und/oder Cer aufweist. In a further and preferred embodiment, the catalyst used according to the invention is characterized in that, in addition to iridium and / or rhodium and a support material, preferably zirconium dioxide, additionally contains one or more, preferably two, elements from the group of rare earths as doping elements. The content is preferably to doping elements with respect to the total weight of the catalyst, in the range of 0.01-80 wt.%, preferably 0.1-50 wt.%, and more preferably 1-30 wt.%. Particular preference is given to using lanthanum (La) and cerium (Ce) as doping elements. Particular preference is given to those catalysts used according to the invention which comprise Ir / ZrO 2 and / or Rh / ZrC 2 active compositions in which the zirconium dioxide has a doping with yttrium and / or a doping with lanthanum and / or cerium.
In weiteren Ausgestaltungsformen enthalten die erfindungsgemäßen-verwendeten Aktivmas- sen, die für das erfindungsgemäße Verfahren eingesetzt werden, auch Promotoren und/oder weitere Metallkationen, die die Effizienz der Katalysatoren weiter steigern. In further embodiments, the active compounds used according to the invention which are used for the process according to the invention also contain promoters and / or further metal cations, which further increase the efficiency of the catalysts.
Weitere Dotierungselemente können unter anderem sein: edelmetallhaltige Promotoren, nicht edelmetallhaltige Promotoren und weitere Metallkationen: Other doping elements may include, but are not limited to: noble metal promoters, non-noble metal promoters, and other metal cations:
In einer bevorzugten Ausführungsform enthält der erfindungsgemäß-verwendete Katalysator, beziehungsweise die Aktivmasse, zumindest einen edelmetallhaltigen Promotor aus der Gruppe Pt, Pd, Ru, Au, wobei der Anteil an edelmetallhaltigen Promotoren in Bezug auf das Gesamtgewicht des Katalysators einen Anteil von 0,01 - 5 Gew.-% und weiter bevorzugt im Bereich von 0,1 - 3 Gew.-% aufweisen. In a preferred embodiment, the catalyst used according to the invention or the active composition contains at least one noble metal-containing promoter from the group Pt, Pd, Ru, Au, where the proportion of noble metal-containing promoters in relation to the total weight of the catalyst is 0.01. 5 wt .-% and more preferably in the range of 0.1 to 3 wt .-% have.
In einer weiter bevorzugten Ausführungsform enthält der erfindungsgemäß-verwendete Katalysator zumindest einen nichtedelmetallhaltigen Promotor aus der Gruppe Ni, Co, Fe, Mn, Mo, W, wobei der Anteil an nichtedelmetallhaltigen Promotoren bezogen auf das Gesamtgewicht des Katalysators im Bereich von 0,1 - 50 Gew.-%, bevorzugt im Bereich von 0,5 - 30 Gew.-% und weiter bevorzugt im Bereich 1 - 20 Gew.-% liegt. In a further preferred embodiment, the catalyst used according to the invention comprises at least one non-noble metal-containing promoter from the group Ni, Co, Fe, Mn, Mo, W, the fraction of non-noble metal-containing promoters being in the range from 0.1 to 50 based on the total weight of the catalyst Wt .-%, preferably in the range of 0.5 to 30 wt .-% and more preferably in the range 1-20 wt .-% is.
In einer weiteren Ausführungsform umfasst der erfindungsgemäß-verwendete Katalysator auch einen Anteil an weiteren Metallkationen, die vorzugsweise aus der Gruppe Mg, Ca, Sr, Ba, Ga, Be, Cr, Mn ausgewählt sind, wobei Ca und/oder Mg besonders bevorzugt sind. In a further embodiment, the catalyst used according to the invention also comprises a proportion of further metal cations, which are preferably selected from the group Mg, Ca, Sr, Ba, Ga, Be, Cr, Mn, with Ca and / or Mg being particularly preferred.
Die in dem erfindungsgemäß-verwendeten Katalysator vorliegenden Komponenten, d.h. die genannten Edelmetalle, Erdalkalimetalle, Dotierungselemente, Promotoren und Trägermaterialien können in elementarer und/oder oxydischer Form vorliegen. The components present in the catalyst used in the present invention, i. the said noble metals, alkaline earth metals, doping elements, promoters and support materials can be present in elemental and / or oxidic form.
Es ist zu berücksichtigen, dass die Erfindung nicht auf die in der Beschreibung angegebenen Kombinationen und Wertebereiche beschränkt sein soll, sondern die Komponenten auch in anderen Kombinationen in den Grenzen des Hauptanspruchs denkbar und auch möglich sein können.
Als Verfahren zum Aufbringen der Aktivkomponenten auf das Trägermaterial können alle Verfahren eingesetzt werden, die dem Fachmann auf dem Gebiet der Katalysatorherstellung bekannt sind (siehe z.B. Haber et al.„Manual of methods and procedures for catalyst characteri- zation" in Pure & Appl. Chem., Vol. 67, Nos 8/9, pp. 1257-1306, 1995). Beispielhaft seien hier das Tränken mit Imprägnierlösung, das Tränken auf Porenvolumen, das Aufsprühen der Imprägnierlösung, das Washcoating und die Ausfällung genannt. Die Herstellung von Formkörpern aus pulverförmigen Rohstoffen kann durch dem Fachmann bekannte Methoden, wie beispielsweise Tablettierung, Aggregation oder Extrusion erfolgen, wie sie u. a. im Handbook of Heterogeneous Catalysis, Vol. 1 , VCH Verlagsgesellschaft Weinheim, 1997, S. 414-417 be- schrieben sind, erfolgen. It should be noted that the invention should not be limited to the combinations and ranges of values specified in the description, but the components may also be conceivable and also possible in other combinations within the limits of the main claim. As methods for applying the active components to the support material, it is possible to use all methods which are known to the person skilled in the art of catalyst preparation (see, for example, Haber et al., "Manual of methods and procedures for catalyst characterization" in Pure & Appl , Vol. 67, Nos 8/9, pp. 1257-1306, 1995), examples being impregnation with impregnating solution, impregnation with pore volume, spraying of the impregnating solution, washcoating and precipitation powdery raw materials can be carried out by methods known to those skilled in the art, such as tableting, aggregation or extrusion, as described, inter alia, in the Handbook of Heterogenous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp. 414-417.
Die iridiumhaltige und/oder rhodiumhaltige Aktivmasse kann auch auf einem Träger, Monolith oder Wabenkörper aufgetragen vorliegen. Der Monolith oder Wabenkörper kann aus Metall o- der Keramik bestehen. Die Abformung der Aktivmasse beziehungsweise die Aufbringung der Aktivmasse auf einem Träger beziehungsweise Trägerkörpern ist von großer technischer Bedeutung für die Anwendungsgebiete des erfindungsgemäß-verwendeten Katalysators. Je nach Partikelgröße und Reaktorpackung wirken sich die Form der Partikel auf den Druckabfall aus, der durch das Katalysatorfestbett hervorgerufen wird. Die Abformung kann nach allen Verfahren durchgeführt werden, die dem Fachmann auf dem Gebiet der Katalysatorherstellung bekannt sind (siehe z.B. Deutschmann, O., Knözinger, H., Kochloefl, K. and Turek, T. 201 1. Heterogeneous Catalysis and Solid Catalysts, 2. Development and Types of Solid Catalysts. Ullmann's Encyclopedia of Industrial Chemistry). The iridium-containing and / or rhodium-containing active composition may also be applied to a carrier, monolith or honeycomb body. The monolith or honeycomb body may be made of metal or ceramic. The molding of the active composition or the application of the active composition on a carrier or carrier bodies is of great industrial significance for the fields of application of the catalyst used according to the invention. Depending on the particle size and reactor packing, the shape of the particles affect the pressure drop caused by the fixed catalyst bed. Impression may be carried out by any method known to those skilled in the art of catalyst preparation (see, eg, Deutschmann, O., Knözinger, H., Kochloefl, K. and Turek, T. 201. 1. Heterogeneous Catalysis and Solid Catalysts, 2. Development and Types of Solid Catalysts, Ullmann's Encyclopedia of Industrial Chemistry).
Die vorliegende Erfindung betrifft ferner ein katalytisches Verfahren zur Kohlenstoffdioxid-Hyd- rierung zu Kohlenstoffmonoxid, d.h. zur Herstellung von Synthesegas, das dadurch gekennzeichnet ist, dass: The present invention further relates to a catalytic process for the carbon dioxide hydrogenation to carbon monoxide, i. for the production of synthesis gas, characterized in that:
(i) das CO2- und H2-haltiges Eduktgas mit einer iridiumhaltigen und/oder rhodiumhaltigen Katalysator in Kontakt gebracht wird, (i) the CO 2 and H 2 -containing educt gas is brought into contact with an iridium-containing and / or rhodium-containing catalyst,
(ii) der Druck des Eduktgases beim Inkontaktbringen mit dem Katalysator im Bereich von 1 bis 100 barabs und die Temperatur des Eduktgases beim Inkontaktbringen mit dem Katalysator im Bereich von 20 bis 1400°C liegt, (iii) die GHSV des Verfahrens einen Wert im Bereich von 1000 bis 1000000 r1 besitzt, (ii) the pressure of the reactant gas in contacting with the catalyst is in the range of 1 to 100 bar a bs and the temperature of the educt gas in contacting with the catalyst is in the range of 20 to 1400 ° C, (iii) the GHSV of the process has a value in the range of 1,000 to 1,000,000 r 1 ,
(iv) das erzeugte Synthesegas ein H2/CO-Verhältnis im Bereich von 0,1 bis 10, weiter bevorzugt im Bereich von 1 bis 4 und insbesondere bevorzugt im Bereich von 1 ,5 bis 3 aufweist. Vorteilhaft ist das molare Verhältnis von Eduktgases H2/C02 im Bereich von 0,1 bis 20, bevorzugt 0,3 bis 10, weiter bevorzugt 1 bis 7, insbesondere 2 bis 5.
Vorteilhaft weist das Eduktgas folgende Zusammensetzung auf: Der Molanteil von C02 liegt vorteilhaft im Bereich von 1 bis 90 %, bevorzugt von 3 bis 75 %, weiter bevorzugt von 10 bis 60 %, insbesondere von 20 bis 50%. Der Molanteil von H2 liegt vorteilhaft im Bereich von 1 bis 99 %, bevorzugt von 10 bis 90 %, weiter bevorzugt von 20 bis 85 %, insbesondere von 40 bis 80%. Der Molanteil von CH4 liegt vorteilhaft im Bereich von 0 bis 30 %, bevorzugt von 0 bis 20 %, weiter bevorzugt 0 bis 15 %, weiter bevorzugt 0 bis 10 %, insbesondere von 0 bis 5 %. Der Molanteil von N2 liegt vorteilhaft im Bereich von 0 bis 80 %, bevorzugt von 0 bis 20 %, insbesondere von 0 bis 5%. Der Molanteil von 02 liegt vorteilhaft im Bereich von 0 bis 5 %, bevorzugt von 0 bis 2 %, weiter bevorzugt von 0 bis 1 %, insbesondere von 0 bis 0,5%. Der Molanteil von H20 liegt vorteilhaft im Bereich von 0 bis 99 %, bevorzugt von 0 bis 90 %, weiter bevorzugt von 0 bis 40 %, weiter bevorzugt 0 bis 20 %, weiter bevorzugt 0 bis 15 %, weiter bevorzugt 0 bis 10 %, insbesondere 0 bis 5 %. (iv) the synthesis gas produced has a H 2 / CO ratio in the range of 0.1 to 10, more preferably in the range of 1 to 4, and most preferably in the range of 1, 5 to 3. The molar ratio of educt gas H2 / CO 2 in the range from 0.1 to 20, preferably from 0.3 to 10, more preferably from 1 to 7, in particular from 2 to 5, is advantageous. Advantageously, the educt gas has the following composition: The molar fraction of CO 2 is advantageously in the range from 1 to 90%, preferably from 3 to 75%, more preferably from 10 to 60%, in particular from 20 to 50%. The molar fraction of H 2 is advantageously in the range from 1 to 99%, preferably from 10 to 90%, more preferably from 20 to 85%, in particular from 40 to 80%. The molar fraction of CH4 is advantageously in the range from 0 to 30%, preferably from 0 to 20%, more preferably 0 to 15%, more preferably 0 to 10%, in particular from 0 to 5%. The molar fraction of N 2 is advantageously in the range from 0 to 80%, preferably from 0 to 20%, in particular from 0 to 5%. The molar fraction of O 2 is advantageously in the range from 0 to 5%, preferably from 0 to 2%, more preferably from 0 to 1%, in particular from 0 to 0.5%. The molar fraction of H 2 O is advantageously in the range from 0 to 99%, preferably from 0 to 90%, more preferably from 0 to 40%, more preferably 0 to 20%, further preferably 0 to 15%, further preferably 0 to 10%, in particular 0 to 5%.
Vorteilhaft liegt der Druck des Eduktgases beim Inkontaktbringen mit dem Katalysator im Be- reich von 3 bis 60 barabs, insbesondere bei 10 bis 30 barabs. The pressure of the educt gas when contacting with the catalyst is advantageously in the range from 3 to 60 bar a bs, in particular from 10 to 30 bar a bs.
Vorteilhaft liegt die Temperatur des Eduktgases beim Inkontaktbringen mit dem Katalysator im Bereich von 600 bis 1300°C liegt, bevorzugt von 750 bis 1200°C, insbesondere von 850 bis 1200°C. Advantageously, the temperature of the educt gas when it comes into contact with the catalyst is in the range from 600 to 1300 ° C., preferably from 750 to 1200 ° C., in particular from 850 to 1200 ° C.
Vorteilhaft liegt die GHSV des Verfahrens im Bereich von 2000 bis 700000 hr1, bevorzugt von 5000 bis 500000 hr1, insbesondere von 10000 bis 300000 hr1. Advantageously, the GHSV of the process is in the range from 2000 to 700,000 hr.sup.- 1 , preferably from 5000 to 500,000 hr.sup.- 1 , in particular from 10,000 to 300,000 hr.sup.- 1 .
Das erfindungsgemäße Verfahren kann vorteilhaft als ATR-Verfahren (Autothermal Reforming), wie z.B. in Reimert, et al. ,201 1. Gas Production, 2. Processes. Ullmann's Encyclopedia of In- dustrial Chemistry. beschrieben, durchgeführt werden. Im Fall eines ATR-Verfahrens wird somit zusätzlich zum Eduktgas Sauerstoff eingebracht. The process according to the invention can be advantageously used as an ATR process (autothermal reforming), such as, for example, in Reimert, et al. , 201 1. Gas Production, 2. Processes. Ullmann's Encyclopedia of Industrial Chemistry. described be performed. In the case of an ATR process, oxygen is thus introduced in addition to the educt gas.
Ein Kennzeichen des erfindungsgemäßen Verfahrens zur Hydrierung von Kohlenstofffdioxid, gegebenenfalls in Gegenwart von Kohlenwasserstoffen, vorteilhaft Methan, und/oder Wasser, ist, dass Zr02-haltige Aktivmassen verwendet werden können, die einen relativ geringen Gehalt an Iridium und/oder Rhodium aufweisen und trotzdem eine hohe katalytische Effizienz aufweisen. So ist es beispielsweise auch möglich, hohe Umsätze mit Aktivmassen zu erzielen, die beispielsweise nur 1 Gew.-% oder weniger als 1 Gew.-% Iridium und/oder Rhodium aufweisen. A characteristic of the process according to the invention for the hydrogenation of carbon dioxide, if appropriate in the presence of hydrocarbons, advantageously methane, and / or water, is that ZrO 2 -containing active compositions can be used which have a relatively low content of iridium and / or rhodium and nevertheless one have high catalytic efficiency. For example, it is also possible to achieve high conversions with active compositions which, for example, have only 1% by weight or less than 1% by weight of iridium and / or rhodium.
Ein weiteres Kennzeichen ist, dass im erfindungsgemäßen Verfahren unter Einsatz von leicht herstellbaren geträgerten Katalysatoren vergleichbare Performance gezeigt werden konnte wie im Stand der Technik unter Einsatz von aufwendig herzustellenden Vollkatalysatoren. Ferner konnte die gute Performance auch bei hohen Lasten, z.B. bei einer GHSV von 80.000 hr1, er- reicht werden.
Als Vorteil des erfindungsgemäßen Verfahrens ist auch zu nennen, dass das erfindungsgemäße Verfahren mit einem Eduktfluid durchgeführt werden kann, das geringe Mengen an Wasserdampf aufweist. In einer bevorzugten Ausführungsform ist der Wasserdampf/Kohlenstoffdioxid-Anteil im Eduktgas kleiner als 0,2, weiter bevorzugt kleiner 0,1 und noch weiter bevorzugt kleiner 0,05. Another characteristic is that comparable performance could be shown in the process according to the invention using easily prepared supported catalysts as in the prior art using complex catalysts to be produced in a complicated manner. Furthermore, the good performance could be, for example, at a GHSV of 80,000 hr 1, ER enough even at high loads. It should also be mentioned as an advantage of the process according to the invention that the process according to the invention can be carried out with a reactant fluid which has small amounts of water vapor. In a preferred embodiment, the water vapor / carbon dioxide content in the educt gas is less than 0.2, more preferably less than 0.1, and even more preferably less than 0.05.
Die Durchführung des erfindungsgemäßen Verfahrens bei geringen Wassergehalten bietet den Vorteil der hohen energetischen Effizienz des Verfahrens sowie der Vereinfachung des Verfahrensschemas einer Anlage, in der das erfindungsgemäße Verfahren genutzt wird. The implementation of the method according to the invention at low water contents offers the advantage of the high energy efficiency of the process and the simplification of the process scheme of a plant in which the inventive method is used.
Bei der Durchführung des erfindungsgemäßen Verfahrens ist die iridiumhaltige und/oder rhodi- umhaltige Aktivkomponente einer starken physikalischen und chemischen Belastung ausgesetzt, da das Verfahren bei einer Temperatur im Bereich von 600 bis 1300 "Cdurchgeführt wird, wobei der Prozessdruck im Bereich von 5 bis 500 bar, vorzugsweise im Bereich von 10 bis 250 bar und weiter vorzugweise im Bereich von 20 bis 100 bar liegt. Obwohl das Verfahren durch sehr rauhe Prozessbedingungen gekennzeichnet ist, kann die Koksabscheidung auf dem Katalysator weitgehend durch die spezifischen Eigenschaften des erfindungsgemäßen Materiales ausgeschlossen werden, was auch einen Vorteil des erfindungsgemäßen Verfahrens darstellt. Mittels des erfindungsgemäßen Verfahrens ist es möglich, den Prozess bei drastischen Prozessbedingungen, insbesondere bei hohen Temperaturen und hohen Lasten, durchzuführen, ohne dass hierbei eine signifikante Menge an Koks auf dem Katalysator abgeschieden wird. Als signifikante Koksabscheidung wird im Rahmen der Erfindung eine Abscheidung von über 2 Gew.-% Koks auf dem Katalysator betrachtet, typischerweise machen sich Koksablagerungen oberhalb dieses Wertes durch einen starken Anstieg im Druckabfall bemerkbar. Bevorzugt liegt die Koksablagerung bei < 2 Gew.-% Kohlenstoffgehalt in Bezug auf den eingesetzten Katalysator, besonders bevorzugt < 1 Gew.-%, weiter bevorzugt < 0,5 Gew.-%, insbesondere < 0,2 Gew.-%. Aufgrund der sehr hohen thermischen Stabilität und der Betriebsbeständigkeit unter Druck bei Drücken von 5 bis 40 bar des Katalysators kann dieser über lange Prozesslaufzeiten, mehrere tausend Stunden, hinweg eingesetzt werden. In carrying out the process according to the invention, the iridium-containing and / or rhodium-containing active component is exposed to a strong physical and chemical load, since the process is carried out at a temperature in the range of 600 to 1300 "C, the process pressure in the range of 5 to 500 bar , preferably in the range of 10 to 250 bar, and more preferably in the range of 20 to 100. Although the process is characterized by very harsh process conditions, coke deposition on the catalyst can be largely excluded by the specific properties of the material of the invention, as well By means of the method according to the invention it is possible to carry out the process under drastic process conditions, in particular at high temperatures and high loads, without a significant amount of coke being deposited on the catalyst In the context of the invention, significant coke deposition is considered to be a separation of more than 2% by weight of coke on the catalyst, coke deposits above this value typically being noticeable by a sharp increase in the pressure drop. Preferably, the coke deposit is <2 wt .-% carbon content with respect to the catalyst used, more preferably <1 wt .-%, more preferably <0.5 wt .-%, in particular <0.2 wt .-%. Due to the very high thermal stability and the operational stability under pressure at pressures of 5 to 40 bar of the catalyst this can be used over long process times, several thousand hours away.
Beispiele Examples
Um die Erfindung näher zu illustrieren, werden mehrere Beispiele für die Herstellung und Ver- wendung der erfindungsgemäßen Katalysatoren zur Hydrierung dargestellt. In Ergänzung hierzu werden Vergleichsbeispiele aus dem Stand der Technik gezeigt. To further illustrate the invention, several examples of the preparation and use of the hydrogenation catalysts of this invention are presented. In addition, comparative examples from the prior art are shown.
A. Herstellung der Katalysatoren A. Preparation of the catalysts
A.1 . Herstellung des Srlro.-iAln.gOig-Y Hexaaluminats nach dem Stand der Technik, WO A.1. Preparation of Srlro.-iAln.gOig-Y hexaaluminate according to the prior art, WO
2013/135710
Der Katalysator S1 wurde analog dem Stand der Technik, WO 2013/135710 und Äquivalenten hierzu, hergestellt: 2013/135710 The catalyst S1 was prepared analogously to the prior art, WO 2013/135710 and equivalents thereof:
Die entsprechende Menge an Sr(N 0.3)2 (4,344g mit einer Reinheit von 99,7 Gew.-%) wurde in 250 ml Dl-Wasser unter Rühren in einem 500 ml-Becherglas gelöst. Die entsprechende Menge an IrC 'xh O -Lösung (4096, 9μΙ_ mit c = 0,5mol/L) wurde der Lösung von Sr(NOs)2 zugesetzt. Eine Dispersion der AI-Quelle (15,462g Disperal mit 42,51 wt% AI) wurde dieser Lösung zugesetzt, woraufhin sich eine Suspension gebildet hat. Diese Suspension wurde für 30 Minuten zur Homogenisierung gerührt. Die Suspension wurde tropfenweise in flüssigem Stickstoff blitzgefroren. Die gefrorenen Tröpfchen wurden bei -10 C und 2,56 mbar gefriergetrocknet. The corresponding amount of Sr (N 0.3) 2 (4.344 g with a purity of 99.7% by weight) was dissolved in 250 ml DI water with stirring in a 500 ml beaker. The appropriate amount of IrC'xhO solution (4096, 9μΙ_ with c = 0.5 mol / L) was added to the solution of Sr (NOs) 2. A dispersion of the AI source (15.462 g Disperal with 42.51 wt% AI) was added to this solution, whereupon a suspension has formed. This suspension was stirred for 30 minutes for homogenization. The suspension was flash frozen dropwise in liquid nitrogen. The frozen droplets were freeze-dried at -10 C and 2.56 mbar.
Das gefriergetrocknete Pulver wurde unter Luft kalziniert, um die Nitrate und Chlore zu zersetzen. Die Heizrate betrug 1 K / min. Die Probe wurde auf 150 C, 250 C und 350 C erwärmt bei einer Verweilzeit von je 1 Stunde bei der erreichten Temperatur. Die endgültige Kalzinierungs- temperatur betrug 450 C und die Verweilzeit wiederum 1 Stunde, anschließend wurde auf Umgebungstemperatur abgekühlt. The freeze-dried powder was calcined in air to decompose the nitrates and chlorides. The heating rate was 1 K / min. The sample was heated to 150 C, 250 C and 350 C with a residence time of 1 hour at the temperature reached. The final calcination temperature was 450 C and the residence time was again 1 hour, then cooled to ambient temperature.
Die vorkalzinierte Probe wurde einem Formgebungsverfahren unterzogen. Es wurden 3 Gew.- % Graphit der Probe zugesetzt und intensiv vermischt. Die Mischung wurde mit einem Korsch XP1 Pelletierer im Automatikbetrieb pelletiert. Das Peiletierwerkzeug hatte einen Durchmesser von 13 mm und die aufgebrachte Kraft zum Aufnehmen von Pellets mit einer Höhe von 2 mm war 40 kN. Die Pellets wurden zerkleinert und auf 315-500 pm gesiebt. The precalcined sample was subjected to a molding process. 3% by weight of graphite was added to the sample and mixed thoroughly. The mixture was pelletized with a Korsch XP1 pelletizer in automatic mode. The direction finding tool had a diameter of 13 mm and the applied force for picking up pellets with a height of 2 mm was 40 kN. The pellets were crushed and sieved to 315-500 pm.
Die zerkleinerte und gesiebte Probe (315-500 pm) wurde einer endgültigen Kalzinierung unter Luft unterzogen, um das Graphit zu entfernen und um die gewünschte Hexaaluminatphase zu bilden. Die endgültige Kalziniertemperatur betrug 1400 C mit einer Heizrate von 5 K / min und einer Verweilzeit von 2 Stunden. The crushed and sieved sample (315-500 pm) was subjected to final calcination in air to remove the graphite and to form the desired hexaaluminate phase. The final calcination temperature was 1400 C with a heating rate of 5 K / min and a residence time of 2 hours.
A.2. Herstellung des Garnet-Materials, Y2.68Nio.32AI5Oi2, nach dem Stand der Technik, A.2. Preparation of the Garnet Material, Y2.68Nio.32AI 5 Oi2, According to the Prior Art,
W015135968 Der Katalysator S2 wurde gemäß der Beschreibung in WO 15/135968 A1 hergestellt. W015135968 Catalyst S2 was prepared as described in WO 15/135968 A1.
A.3. Herstellung der Pd- und Pt-Katalysatoren nach dem Stand der Technik, US 201 1/0105630 A.3. Preparation of Pd and Pt catalysts of the prior art, US 201 1/0105630
Die Katalysator S3 und S4 wurden analog dem Stand der Technik, US 201 1/0105630, via Im- prägnierverfahren hergestellt: The catalysts S3 and S4 were prepared analogously to the prior art, US 201 1/0105630, via impregnation process:
10g Al203-Trägermaterial mit einer Partikelgröße von 315-500 pm wurde in einer runden Porzellanschale mit einem Durchmesser von 10 cm abgewogen. Die Höhe der Trägerschicht überschritt den Wert von 5 mm nicht. Die Imprägnierlösung aus 1281 pL einer 0.199 molar wässrigen IrC Lösung und 1919 L DI Wasser, siehe Tabelle I, wurde über eine 0,5 ml-Pipette zu dem
Trägermaterial gegeben, der mit einem Shaker (Probenschüttler Heidolph Titramax 100) in Bewegung gehalten wurde. Der imprägnierte Träger wurde ferner mit einem Spatel gemischt und vor der Trocknung für 30 Minuten bei Umgebungsbedingungen gealtert. Die Trocknung erfolgte in einem Trockenofen bei 80 C für 16 Stunden. Die getrocknete Probe wurde wie folgt unter Luft (6 I / min) in einem Ofen (Nabertherm TH120 / 12) kalziniert: Heizrate von 1 K / min bis zu einer Temperatur von 250 °C, Verweilzeit von 1 h, Heizrate von 5K / min bis zu einer Temperatur von 400 C, Verweilzeit von 4h, anschließen Abkühlen auf Umgebungstemperatur. 10 g Al 2 O 3 support material with a particle size of 315-500 pm was weighed in a round 10 cm diameter porcelain dish. The height of the carrier layer did not exceed the value of 5 mm. The impregnation solution of 1281 pL of a 0.199 molar aqueous IrC solution and 1919 L DI water, see Table I, was added via a 0.5 ml pipette to the Carrier material which was kept in motion with a shaker (Heidolph Titramax 100 sample shaker). The impregnated carrier was further mixed with a spatula and aged at ambient conditions for 30 minutes prior to drying. The drying took place in a drying oven at 80 C for 16 hours. The dried sample was calcined in air (6 l / min) in an oven (Nabertherm TH120 / 12) as follows: heating rate of 1 K / min up to a temperature of 250 ° C, residence time of 1 h, heating rate of 5 K / min up to a temperature of 400 C, residence time of 4 h, then cool to ambient temperature.
Tabelle I: Metallsalz-Lösungen
Table I: Metal salt solutions
A.4 Übersicht der Katalysatoren aus dem Stand der Technik In der Tabelle II sind die Katalysatoren aus dem Stand der Technik zusammengefasst. A.4 Overview of the Catalysts of the Prior Art Table II summarizes the catalysts of the prior art.
Tabelle II: Liste der Katalysatoren aus dem Stand der Technik Table II: List of prior art catalysts
10 g Trägermaterial (siehe Tabelle III) mit einer Partikelgröße von 315-500 μπι wurde in einer runden Porzellanschale mit einem Durchmesser von 10 cm abgewogen. Die Höhe der Träger- schicht überschritt den Wert von 5 mm nicht. Ein Imprägnierlösung (siehe Tabelle IV) wurde über eine 0,5 ml-Pipette zu dem Trägermaterial gegeben, der mit einem Shaker (Probenschüttler Heidolph Titramax 100) in Bewegung gehalten wurde. Der imprägnierte Träger wurde ferner mit einem Spatel gemischt und vor der Trocknung für 30 Minuten bei Umgebungsbedingungen gealtert. 10 g of carrier material (see Table III) with a particle size of 315-500 μπι was weighed in a round porcelain dish with a diameter of 10 cm. The height of the carrier layer did not exceed the value of 5 mm. An impregnation solution (see Table IV) was added via a 0.5 ml pipette to the support material which was kept in motion with a shaker (Heidolph Titramax 100 sample shaker). The impregnated carrier was further mixed with a spatula and aged at ambient conditions for 30 minutes prior to drying.
Die Trocknung erfolgte in einem Trockenofen bei 80 C für 16 Stunden. Die getrocknete Probe wurde wie folgt unter Luft (6 I / min) in einem Ofen (Nabertherm TH120 / 12) kalziniert: Heizrate von 1 K / min bis zu einer Temperatur von 250 0 C, Verweilzeit von 1 h, Heizrate von 5K / min bis zu einer Temperatur von 400 0 C, Verweilzeit von 4h, anschließen Abkühlen auf Umgebungstemperatur.
Tabelle III: Liste der verwendeten Trägermaterialien The drying took place in a drying oven at 80 C for 16 hours. The dried sample was calcined as follows under air (6 I / min) in a furnace (Nabertherm TH120 / 12): heating rate of 1 K / min up to a temperature of 250 0 C, residence time of 1 hour, heating rate of 5K / min up to a temperature of 400 0 C, residence time of 4h, then cool to ambient temperature. Table III: List of carrier materials used
Tabelle IV: Liste der verwendeten Imprägnierlösungen
In der Tabelle V sind die erfindungsgemäß-verwendeten Katalysatoren zusammengefasst. Tabelle V: Liste der erfindungsgemäß-verwendeten Ir- und Rh-Katalysatoren Table IV: List of impregnating solutions used Table V summarizes the catalysts used according to the invention. Table V: List of Ir and Rh catalysts used in the invention
A5.1 Beispielhafte Detailbeschreibung der Herstellung des Katalysators E1 , (0,5wt. % Ir auf Ce,La,Zr,AI Mischoxid) A5.1 Exemplary detailed description of the preparation of the catalyst E1, (0.5 wt% Ir on Ce, La, Zr, Al mixed oxide)
Die Bestimmung des Glühverlusts (LOI) ist ein entscheidender Punkt bei der Herstellung von imprägnierten Katalysatoren mit einer klar definierten Metallbeladung. The determination of the loss on ignition (LOI) is a crucial point in the production of impregnated catalysts with a well-defined metal loading.
Der verwendete Träger hatte einen LOI von 2.43%. The carrier used had an LOI of 2.43%.
Berechnung: Calculation:
Träger, um den Glühverlust korrigiert: 10g - 10g*0,0243 = 9,757g Carrier to correct the loss on ignition: 10g - 10g * 0.0243 = 9.777g
Absolutes Gewicht des Iridium-haltigen Katalysators: 9,757 * 1 ,005 Beladung von Iridium im Katalysator: 9,806g - 9,757g = 0,049g
Iridium Beladung: 0,049g/9,806g = 0,0049969 = 0,4996% Absolute weight of the iridium-containing catalyst: 9.757 * 1.005 loading of iridium in the catalyst: 9.806g - 9.757g = 0.049g Iridium loading: 0.049g / 9.806g = 0.0049969 = 0.4996%
Berechnung des Volumens der benötigten IrC Lösung Calculation of the volume of IrC solution needed
mir = Mir * Clr * V|r ~> V|r = ΓΠ|Γ / (M|r * C|r) me = Mir * Clr * V | r ~ > V | r = ΓΠ | Γ / (M | r * C | r )
V,r = 0,049g / (192,217g*mor1 * 0,199g*mol-1) = 0,001281 L V, r = 0.049g / (192.217g * mor 1 * 0.199g * mol- 1 ) = 0.001281L
Die Imprägnierung wurde als 100% incipient wetness impregnation (100% ICW) durchgeführt (Anfeuchtungsimprägnierung) unter Verwendung einer Lösung aus DI Wasser mit einer 0.199molar IrC Lösung. Die Wasseraufnahme des gebrauchten Katalysators war 320μίΛ}. Absolutes Volumen (beinhaltend DI Wasser und IrCIs Lösung): 10g * 320M-Jg = 3200μί Volume DI Wasser: 3200μί - 1281 μί = 1919μί The impregnation was carried out as 100% incipient wetness impregnation (100% ICW) (moistening impregnation) using a solution of DI water with a 0.199 molar IrC solution. The water uptake of the used catalyst was 320μίΛ}. Absolute volume (including DI water and IrCI solution): 10g * 320M-Jg = 3200μί Volume DI Water: 3200μί - 1281 μί = 1919μί
B. Katalytische Testung B. Catalytic Testing
B.1 Katalytische Performance der Katalysatoren in der Kohlenstoffdioxid-Hydrierung (Reversen Wassergas Shift Reaktion) mit und ohne Methan im Eduktgasstrom B.1 Catalytic performance of the catalysts in the carbon dioxide hydrogenation (reverse water gas shift reaction) with and without methane in the reactant gas stream
Tabelle 1 : Testprotokoll des katalytischen Screenings Table 1: Test Protocol of Catalytic Screening
Phase Laufzeit [h] Temp. Druck GHSV H2-IN C02- CH4-IN Ar- IN Phase Runtime [h] Temp. Pressure GHSV H2-IN C02- CH4-IN Ar-IN
[°C] [bar] [h-1] [vol.%] IN [vol.%] [vol.%] [° C] [bar] [h-1] [vol.%] IN [vol.%] [Vol.%]
[vol.%] [Vol.%]
I 24 750 10 30000 63.33 31 .67 0 5 I 24 750 10 30000 63.33 31 .67 0 5
II 24 750 10 30000 71 .25 23.75 0 5 II 24 750 10 30000 71 .25 23.75 0 5
III 24 750 10 30000 54.29 27.14 13.57 5 III 24 750 10 30000 54.29 27.14 13.57 5
IV 24 750 10 40000 47.75 23.75 23.75 4,75 IV 24 750 10 40000 47.75 23.75 23.75 4.75
V 24 750 10 40000 38 38 19 5 V 24 750 10 40000 38 38 19 5
VI 24 750 10 40000 63.33 31 .67 0 5
VI 24 750 10 40000 63.33 31 .67 0 5
Tabelle 2: Zusammenfassung von Wasserstoffumsatz, Kohlenstoffdioxidumsatz, sowie Methanausbeute (ohne Methan im Eduktgas) bzw. Methanumsatz (bei Methan im Eduktgas) der Katalysatoren S1-S4 (Stand der Technik), E1-E6 (erfindungsgemäß) der Phase I - VI der Tabelle 1 Table 2: Summary of hydrogen conversion, carbon dioxide conversion, and methane yield (without methane in the educt gas) or methane conversion (methane in educt gas) of the catalysts S1-S4 (prior art), E1-E6 (according to the invention) of the phase I - VI of the table 1
Es wurde bei allen Katalysatoren keine Kohlenstoffabscheidung beobachtet. No carbon deposition was observed with all catalysts.
Tabelle 4: Testprotokoll des katalytischen Screenings der Katalysatoren E1 , E4 und E8 Table 4: Test protocol of the catalytic screening of catalysts E1, E4 and E8
Phase Laufzeit Temp. Druck GHSV H2-IN C02- CH4- H20- Ar- IN N2-IN Phase Runtime Temp. Pressure GHSV H2-IN C02- CH4- H20- Ar- IN N2-IN
[ ] [°C] [bar] [h-1] [vol.%] IN IN IN [vol.%] [vol.%] [] [° C] [bar] [h-1] [vol.%] IN IN IN [vol.%] [Vol.%]
[vol.%] [vol.%] [vol.%] [vol.%] [vol.%] [vol.%]
I 24 750 20 30000 71.25 23.75 0 0 5 0 I 24 750 20 30000 71.25 23.75 0 0 5 0
II 24 850 20 30000 71.25 23.75 0 0 5 0 II 24 850 20 30000 71.25 23.75 0 0 5 0
III 24 950 20 30000 71.25 23.75 0 0 5 0 III 24 950 20 30000 71.25 23.75 0 0 5 0
IV 24 950 20 40000 71.25 23.75 0 0 5 0 IV 24 950 20 40000 71.25 23.75 0 0 5 0
V 24 950 20 40000 63.33 31 .67 0 0 5 0 V 24 950 20 40000 63.33 31 .67 0 0 5 0
VI 24 950 20 40000 51.09 19.35 8.12 16.44 5 0 VI 24 950 20 40000 51.09 19.35 8.12 16.44 5 0
VII 24 950 20 40000 66.27 22.1 6.63 0 5 0VII 24 950 20 40000 66.27 22.1 6.63 0 5 0
VI II 24 950 20 40000 71.25 23.75 0 0 5 0
Tabelle 5: Zusammenfassung von Wasserstoffumsatz, Kohlenstoffdioxidumsatz, sowie Methanausbeute (ohne Methan im Eduktgas) bzw. Methanumsatz (bei Methan im Eduktgas) der Katalysatoren E1 (0.5wt. % lr@Ce,La,Zr,AI-oxide), E4 (0.5wt. % lr@Ce auf Zr02) und E8 (0.5wt. %lr@35%Mg065%AI203) der Phase I - VIII der Tabelle 4 VI II 24 950 20 40000 71.25 23.75 0 0 5 0 Table 5: Summary of hydrogen conversion, carbon dioxide conversion, and methane yield (without methane in the educt gas) or methane conversion (methane in the reactant gas) of the catalysts E1 (0.5wt.% Lr @ Ce, La, Zr, Al-oxides), E4 (0.5 wt.% lr @ Ce on ZrO 2) and E8 (0.5 wt% lr @ 35% Mg 065% Al 2 O 3) of phase I-VIII of Table 4
Alle verwendeten Träger für die Katalysatoren E1 , E4 und E8 zeigten eine gute, vergleichbare Performance; auch bei erhöhten Temperaturen und erhöhten Drücken.
Tabelle 6: Testprotokoll des katalytischen Screenings der Katalysatoren E4, E5 und E7 All supports used for the catalysts E1, E4 and E8 showed good, comparable performance; even at elevated temperatures and elevated pressures. Table 6: Test protocol of the catalytic screening of catalysts E4, E5 and E7
Phase Laufzeit Temp. Druck GHSV H2-IN C02- CH4- H20- Ar- IN N2-IN Phase Runtime Temp. Pressure GHSV H2-IN C02- CH4- H20- Ar- IN N2-IN
[ ] [°C] [bar] [h-1] [vol.%] IN IN IN [vol.%] [vol.%] [] [° C] [bar] [h-1] [vol.%] IN IN IN [vol.%] [Vol.%]
[vol.%] [vol.%] [vol.%] [vol.%] [vol.%] [vol.%]
I 24 950 20 80000 71 .25 23.75 0 0 5 0 I 24 950 20 80000 71 .25 23.75 0 0 5 0
II 24 950 20 80000 51 .09 19.35 8.12 16.44 5 0 II 24 950 20 80000 51 .09 19.35 8.12 16.44 5 0
III 24 950 20 80000 71 .25 23.75 0 0 5 0 III 24 950 20 80000 71 .25 23.75 0 0 5 0
IV 24 850 20 80000 71 .25 23.75 0 0 5 0 IV 24 850 20 80000 71 .25 23.75 0 0 5 0
V 24 750 20 80000 71 .25 23.75 0 0 5 0 V 24 750 20 80000 71 .25 23.75 0 0 5 0
VI 48 750 20 80000 51 .09 19.35 8.12 16.44 5 0 VI 48 750 20 80000 51 .09 19.35 8.12 16.44 5 0
VII 48 750 20 70000 51 .09 19.35 8.12 16.44 5 0VII 48 750 20 70000 51 .09 19.35 8.12 16.44 5 0
VIII 48 750 20 60000 51 .09 19.35 8.12 16.44 5 0 VIII 48 750 20 60000 51 .09 19.35 8.12 16.44 5 0
IX 48 750 20 50000 51 .09 19.35 8.12 16.44 5 0 IX 48 750 20 50000 51 .09 19.35 8.12 16.44 5 0
X 48 750 20 40000 51 .09 19.35 8.12 16.44 5 0 X 48 750 20 40000 51 .09 19.35 8.12 16.44 5 0
XI 24 950 20 80000 51 .09 19.35 8.12 16.44 5 0 XI 24 950 20 80000 51 .09 19.35 8.12 16.44 5 0
XII 24 950 20 80000 54.5 45.5 0 0 0 0 XII 24 950 20 80000 54.5 45.5 0 0 0 0
XIII 24 950 20 80000 31.0 44.0 20.0 0 5 0
XIII 24 950 20 80000 31.0 44.0 20.0 0 5 0
Tabelle 7: Zusammenfassung von Wasserstoffumsatz, Kohlenstoffdioxidumsatz, sowie Methanausbeute (ohne Methan im Eduktgas) bzw. Methanumsatz (bei Methan im Eduktgas) der Katalysatoren E4 (0.5 Gew.-% Ir), E5 (0.05 Gew.-% Ir) and E7 (0.1 Gew.-% Ir) der Phase I - XI II der Table 6 Table 7: Summary of hydrogen conversion, carbon dioxide conversion, and methane yield (without methane in the educt gas) or methane conversion (methane in educt gas) of the catalysts E4 (0.5% by weight Ir), E5 (0.05% by weight Ir) and E7 ( 0.1% by weight Ir) of phase I-XI II of Table 6
Umsatz / Ausbeute [%] E4 E7 E5 Conversion / yield [%] E4 E7 E5
Phase Umsatz C02 [%] 78 79 78 Phase Sales C0 2 [%] 78 79 78
I Umsatz H2 [%] 30 32 30 I Sales H 2 [%] 30 32 30
Ausbeute CH4 [%] 4 5 5 Yield CH 4 [%] 4 5 5
Phase Umsatz C02 [%] 63 61 62 Phase Sales C0 2 [%] 63 61 62
II Umsatz H2 [%] -4 1 2 II Sales H 2 [%] -4 1 2
Umsatz CH4 [%] 57 45 44 Sales CH 4 [%] 57 45 44
Phase Umsatz C02 [%] 78 78 78 Phase Sales C0 2 [%] 78 78 78
III Umsatz H2 [%] 29 30 29 III Sales H 2 [%] 29 30 29
Ausbeute CH4 [%] 4 5 5 Yield CH 4 [%] 4 5 5
Phase Umsatz C02 [%]] 75 74 74 Phase Sales C0 2 [%]] 75 74 74
IV Umsatz H2 [%] 36 36 35 IV Sales H 2 [%] 36 36 35
Ausbeute CH4 [%] 1 1 12 1 1 Yield CH 4 [%] 1 1 12 1 1
Phase Umsatz. C02 [%] 70 71 71 Phase sales. C0 2 [%] 70 71 71
V Umsatz H2 [%] 45 43 40 V turnover H 2 [%] 45 43 40
Ausbeute CH4 [%] 18 20 18 Yield CH 4 [%] 18 20 18
Phase Umsatz C02 [%] 73 73 74 Phase Sales C0 2 [%] 73 73 74
VI Umsatz H2 [%] 45 44 42 VI Sales H 2 [%] 45 44 42
Ausbeute CH4 [%] -21 -21 -18 Yield CH 4 [%] -21 -21 -18
Phase Umsatz C02 [%] 54 54 52 Phase Sales C0 2 [%] 54 54 52
VII Umsatz H2 [%] 27 28 24 VII Sales H 2 [%] 27 28 24
Ausbeute CH4 [%] 9 9 6 Yield CH 4 [%] 9 9 6
Phase Umsatz C02 [%] 55 54 53 Phase Sales C0 2 [%] 55 54 53
VI II Umsatz H2 [%] 28 27 24 VI II Sales H 2 [%] 28 27 24
Ausbeute CH4 [%] 8 9 7 Yield CH 4 [%] 8 9 7
Phase Umsatz C02 [%] 56 56 55 Phase Sales C0 2 [%] 56 56 55
IX Umsatz H2 [%] 28 28 26 IX turnover H 2 [%] 28 28 26
Ausbeute CH4 [%] 8 10 8 Yield CH 4 [%] 8 10 8
Phase Umsatz C02 [%] 56 57 58 Phase Sales C0 2 [%] 56 57 58
X Umsatz H2 [%] 27 30 28 X Sales H 2 [%] 27 30 28
9 10 8 9 10 8
Ausbeute CH4 [%]
Phase Umsatz C02 [%] 65 64 64Yield CH 4 [%] Phase Sales C0 2 [%] 65 64 64
XI Umsatz H2 [%] -1 2 3 XI conversion H 2 [%] -1 2 3
Umsatz CH4 [%] 51 42 40 Sales CH 4 [%] 51 42 40
Phase Umsatz C02 [%] 59 59 59 Phase Sales C0 2 [%] 59 59 59
XII Umsatz H2 [%] 49 50 49 XII conversion H 2 [%] 49 50 49
Ausbeute CH4 [%] 1 1 1 Yield CH 4 [%] 1 1 1
Phase Umsatz C02 [%] 63 58 56 Phase Sales C0 2 [%] 63 58 56
XI II Umsatz H2 [%] -23 -4 0 XI II Sales H 2 [%] -23 -4 0
Umsatz CH4 [%] 56 43 38 Performance der Katalysatoren E4, E5 und E9 ist vergleichbar, auch bei einer Beladung lediglich 0.05 Gew.-% Ir.
Conversion CH 4 [%] 56 43 38 Performance of the catalysts E4, E5 and E9 is comparable, even at a loading of only 0.05% by weight Ir.
Claims
Patentansprüche claims
Verfahren zur Kohlenstoffdioxid-Hydrierung, dadurch gekennzeichnet, dass Kohlenstoffdioxid mit Wasserstoff in Gegenwart eines Katalysators umgesetzt wird, wobei der Katalysator ein Trägermaterial und eine Aktivmasse aufweist, wobei als Trägermaterialien Ce-, La-, Zr-, AI-, Ti-, Ca-, Si-, Mg-Oxide, SiC, MgAI-Spinelle, Sr-Aluminate, La-, Ba-, Sr-Hexa- Aluminate und/oder Mischungen hieraus eingesetzt werden, und die Aktivmasse mindestens Iridium und/oder Rhodium als Aktivkomponente enthält, wobei der Iridium- Gehalt in einem Bereich von 0,005 bis 2 Gew.-% und der Rhodium- Gehalt zwischen 0,005 bis < 1 Gew.-% in Bezug auf das Gesamtgewicht des Katalysators liegt und die Temperatur der Eduktgase, Kohlenstoffdioxid mit Wasserstoff, beim Inkontaktbringen mit der Aktivmasse im Bereich von 600 bis 1300°C liegt. A process for the hydrogenation of carbon dioxide, which comprises reacting carbon dioxide with hydrogen in the presence of a catalyst, the catalyst comprising a support material and an active composition, the support materials being Ce, La, Zr, Al, Ti, Ca. , Si, Mg oxides, SiC, MgAI spinels, Sr aluminates, La, Ba, Sr hexa aluminates and / or mixtures thereof, and the active composition contains at least iridium and / or rhodium as active component, wherein the iridium content in a range of 0.005 to 2 wt .-% and the rhodium content between 0.005 to <1 wt .-% with respect to the total weight of the catalyst and the temperature of the educt gases, carbon dioxide with hydrogen, in contacting with the active composition in the range of 600 to 1300 ° C.
Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass der Rhodium- Gehalt in Bezug auf das Gesamtgewicht des Katalysators in einem Bereich von 0,005 bis 0,75 Gew.- % liegt. A method according to claim 1, characterized in that the rhodium content in relation to the total weight of the catalyst in a range of 0.005 to 0.75% by weight.
Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass der Iridium- Gehalt in Bezug auf das Gesamtgewicht des Katalysators in einem Bereich von 0,005 bis 1 ,5 Gew.-% liegt. A method according to claim 1, characterized in that the iridium content in relation to the total weight of the catalyst is in a range of 0.005 to 1, 5 wt .-%.
Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Edukt- gas einen Molanteil von Kohlenstoffdioxid von 10 bis 60 % und einen Molanteil von Wasserstoff von 10 bis 90 % aufweist und der Molanteil von Methan im Eduktgas zwischen 0 bis 20 % liegt. Method according to one of claims 1 to 3, characterized in that the reactant gas has a molar fraction of carbon dioxide of 10 to 60% and a molar fraction of hydrogen of 10 to 90% and the molar ratio of methane in the educt gas between 0 to 20% ,
Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als Trägermaterialien Zirkoniumdioxid, Titandioxid und/oder Aluminate eingesetzt werden. Method according to one of claims 1 to 4, characterized in that zirconium dioxide, titanium dioxide and / or aluminates are used as support materials.
Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Iridium und/oder Rhodium in fein verteilter Form auf dem Träger bzw. in der Aktivmasse vorliegt. Method according to one of claims 1 to 5, characterized in that the iridium and / or rhodium in finely divided form on the carrier or in the active composition.
Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die iridium- haltigen und/oder rhodiumhaltigen Partikel eine Größe im Bereich von 1 bis 100 nm aufweisen. Method according to one of claims 1 to 6, characterized in that the iridium-containing and / or rhodium-containing particles have a size in the range of 1 to 100 nm.
Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die iridium- haltigen und/oder rhodiumhaltigen Partikel eine Größe im Bereich von 1 bis 10 nm aufwei sen.
Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass als Dotierungselemente des Trägermaterials Siliziumdioxid, Yttrium, Lanthan und/oder Cer eingesetzt werden. 10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass der Katalysator Iridium als Aktivkomponente enthält. Method according to one of claims 1 to 7, characterized in that the iridium-containing and / or rhodium-containing particles have a size in the range of 1 to 10 nm aufwei sen. Method according to one of claims 1 to 8, characterized in that are used as doping elements of the support material silicon dioxide, yttrium, lanthanum and / or cerium. 10. The method according to any one of claims 1 to 9, characterized in that the catalyst contains iridium as an active component.
Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass: Method according to one of claims 1 to 10, characterized in that:
(i) das CO2- und h -haltiges Eduktgas in Gegenwart eines Katalysators umgesetzt wird, wobei der Katalysator eine Aktivmasse aufweist, die mindestens Iridium und/oder Rhodium als Aktivkomponente enthält, wobei der Iridium-und/oder Rhodium- Gehalt in Bezug auf das Gesamtgewicht des Katalysators in einem Bereich von 0,005 - 2 Gew.-% liegt, (I) the CO2 and h-containing educt gas is reacted in the presence of a catalyst, wherein the catalyst has an active composition which contains at least iridium and / or rhodium as the active component, wherein the iridium and / or rhodium content with respect to Total weight of the catalyst is in a range of 0.005 - 2 wt .-%,
(ii) der Druck des Eduktgases beim Inkontaktbringen mit dem Katalysator im Bereich von 1 bis 100 barabs und die Temperatur des Eduktgases beim Inkontaktbringen mit der Aktivmasse im Bereich von 20 bis 1400°C liegt, (ii) the pressure of the educt gas when it is brought into contact with the catalyst is in the range from 1 to 100 bar a bs and the temperature of the educt gas when it is brought into contact with the active mass is in the range from 20 to 1400 ° C,
(iii) die GHSV des Verfahrens einen Wert im Bereich von 1000 bis 1000000 hr1 besitzt,(iii) the GHSV of the process has a value in the range 1000 to 1000000 hr 1 ,
(iv) das erzeugte Synthesegas ein H2/CO-Verhältnis im Bereich von 0,1 bis 10 aufweist. (iv) the synthesis gas produced has an H 2 / CO ratio in the range of 0.1 to 10.
Verfahren nach Anspruch 1 1 , dadurch gekennzeichnet, dass der Druck des Eduktgases beim Inkontaktbringen mit dem Katalysator im Bereich von 3 bis 60 barabS und die Temperatur des Eduktgases beim Inkontaktbringen mit der Aktivmasse im Bereich von 600 bis 1300°C liegt, die GHSV des Verfahrens einen Wert im Bereich von 10000 bis 500000 hr1 besitzt und das erzeugte Synthesegas ein h /CO-Verhältnis im Bereich von 1 bis 4 aufweist. A method according to claim 1 1, characterized in that the pressure of the educt gas when contacting with the catalyst in the range of 3 to 60 bar a b S and the temperature of the reactant gas in contacting with the active composition in the range of 600 to 1300 ° C, the GHSV of the process has a value in the range of 10,000 to 500,000 hr 1 and the synthesis gas produced has a h / CO ratio in the range of 1 to 4.
Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass der Druck des Eduktgases beim Inkontaktbringen mit dem Katalysator im Bereich von 10 bis 30 barabS und die Temperatur des Eduktgases beim Inkontaktbringen mit der Aktivmasse im Bereich von 850 bis 1200°C liegt, die GHSV des Verfahrens einen Wert im Bereich von 10000 bis 300000 hr1 besitzt und das erzeugte Synthesegas ein H2/CO-Verhältnis im Bereich von 1 ,5 bis 3 aufweist.
A method according to claim 12, characterized in that the pressure of the reactant gas in contacting with the catalyst in the range of 10 to 30 bar a b S and the temperature of the reactant gas in contacting with the active composition in the range of 850 to 1200 ° C, the GHSV of the method has a value in the range of 10,000 to 300,000 hr 1 and the synthesis gas produced has an H2 / CO ratio in the range of 1, 5 to 3.
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