CA2877956A1 - High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses - Google Patents
High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses Download PDFInfo
- Publication number
- CA2877956A1 CA2877956A1 CA2877956A CA2877956A CA2877956A1 CA 2877956 A1 CA2877956 A1 CA 2877956A1 CA 2877956 A CA2877956 A CA 2877956A CA 2877956 A CA2877956 A CA 2877956A CA 2877956 A1 CA2877956 A1 CA 2877956A1
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- active composition
- reforming
- catalyst
- Prior art date
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- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000002407 reforming Methods 0.000 title claims abstract description 56
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 23
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 29
- 239000001569 carbon dioxide Substances 0.000 title description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 34
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims description 52
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims 2
- 239000010987 cubic zirconia Substances 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000571 coke Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000005470 impregnation Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- -1 platinum metals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910004625 Ce—Zr Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 150000003002 phosphanes Chemical class 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
-
- 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
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
- B01J23/63—Platinum group metals with rare earths or actinides
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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
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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Abstract
The invention relates to a catalytic high-pressure process for CO2 reforming of hydrocarbons, preferably methane, in the presence of iridium-containing active masses, and also a preferred active mass in which Ir is present in finely divided form on zirconium dioxide-containing support material. Preferably, the predominant fraction of the zirconium dioxide has a cubic and/or tetragonal structure and, more preferably, the zirconium dioxide is stabilized with at least one doping element. In the process according to the invention, reforming gas at a pressure which is greater than 5 bar, preferably greater than 10 bar, and more preferably greater than 20 bar, and at a temperature which is in the range from 600 to 1200°C, preferably in the range from 850 to 1100°C, and particularly preferably in the range from 850 to 950°C, is brought into contact and reacted to form synthesis gas. The process according to the invention is carried out using a reforming gas that contains only small amounts of steam, or is completely steam-free. The process is characterized in that the formation of coke on the catalyst is greatly restricted when the process is being carried out, as a result of which the process can be carried out over a long time period without in this case significant losses in activity occurring.
Description
High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses _ Description The present invention relates to a high-pressure process for the carbon dioxide reforming of hydrocarbons using iridium-comprising active compositions. The utilization of carbon dioxide as reagent in chemical processes is of great economic and industrial importance in order to reduce the emission of carbon dioxide into the atmosphere.
Numerous scientific publications and patents relate to the preparation of synthesis gas. It is known that noble metal-comprising catalysts can be used for the carbon dioxide reforming of methane (also known as dry reforming).
In the following part, an overview of the prior art in the field of carbon dioxide reforming of methane is given.
An overview of carbon dioxide reforming of methane is given in a publication by Bradford et al. (M.C.J. Bradford, M.A. Vannice; Cataly. Rev. - Sci. Eng., 41(1) (1999) p. 1 -42).
US 6,749,828 B1 discloses a catalyst in which ruthenium has been deposited on zirconium dioxide or a ruthenium salt has been added in order to precipitate zirconium-comprising species. The catalyst leads to high yields in the conversion of reforming gas comprising carbon dioxide. In addition, only small amounts of carbonaceous deposits are formed on the catalyst. The experimental examples describe catalysis tests carried out at pressures of 0.98 bar and 4.9 bar. In one test (i.e. example 6), the temperatures were 1000 C. Otherwise, the tests were carried out at temperatures of from 780 to 800 C. Furthermore, it is disclosed that the catalytic tests were carried out in the presence of steam, with a steam/carbon ratio of from 0.1 to 10 being considered to be typical and a steam/carbon ratio of from 0.4 to 4 being preferred.
Numerous scientific publications and patents relate to the preparation of synthesis gas. It is known that noble metal-comprising catalysts can be used for the carbon dioxide reforming of methane (also known as dry reforming).
In the following part, an overview of the prior art in the field of carbon dioxide reforming of methane is given.
An overview of carbon dioxide reforming of methane is given in a publication by Bradford et al. (M.C.J. Bradford, M.A. Vannice; Cataly. Rev. - Sci. Eng., 41(1) (1999) p. 1 -42).
US 6,749,828 B1 discloses a catalyst in which ruthenium has been deposited on zirconium dioxide or a ruthenium salt has been added in order to precipitate zirconium-comprising species. The catalyst leads to high yields in the conversion of reforming gas comprising carbon dioxide. In addition, only small amounts of carbonaceous deposits are formed on the catalyst. The experimental examples describe catalysis tests carried out at pressures of 0.98 bar and 4.9 bar. In one test (i.e. example 6), the temperatures were 1000 C. Otherwise, the tests were carried out at temperatures of from 780 to 800 C. Furthermore, it is disclosed that the catalytic tests were carried out in the presence of steam, with a steam/carbon ratio of from 0.1 to 10 being considered to be typical and a steam/carbon ratio of from 0.4 to 4 being preferred.
2 US 2005/0169835 Al discloses a process in which reforming gas is reacted with carbon dioxide and methane over a catalyst comprising more than 50% by weight of silicon carbide in the beta form as support material. Apart from the silicon carbide support material, the catalyst can further comprise noble metals or nickel in a proportion of from 0.1 to 10% as active components. Possible noble metals are Rh, Ru, Pt or Ir and mixtures thereof.
US 5,753,143 discloses a catalytic process for the reforming of carbon dioxide in the presence of methane, with the process being able to be carried out in the absence of steam. A zeolite having Rh as active component is disclosed as catalyst.
US 7,166,268 B2 discloses a steam reforming process for preparing hydrogen or synthesis gas, in which the catalyst comprises a crystalline alumina comprising Ce02 as support and ruthenium and cobalt as active components are distributed on the support. The process can also be used for the carbon dioxide reforming of hydrocarbons.
EP 1 380 341 discloses a process for the reforming of hydrocarbons by means of a steam reforming process. The active components are elements selected from the group consisting of Ru, Pt, Rh, Pd, Ir and Ni. The support for the active components comprises alumina and from 5 to 95% by weight of manganese oxide.
US 7,309,480 B2 discloses and claims a catalyst for producing hydrogen which comprises a catalyst support comprising monoclinic zirconium oxide on which Ir is present in dispersed form.
One of the objects of the invention was to provide a catalytic process for the production of synthesis gas, which has a high energy efficiency compared to the processes known in the prior art. A further object was to provide a catalytic process by means of which carbon dioxide can be chemically converted. The object of the invention relates to both the development of a suitable catalyst and
US 5,753,143 discloses a catalytic process for the reforming of carbon dioxide in the presence of methane, with the process being able to be carried out in the absence of steam. A zeolite having Rh as active component is disclosed as catalyst.
US 7,166,268 B2 discloses a steam reforming process for preparing hydrogen or synthesis gas, in which the catalyst comprises a crystalline alumina comprising Ce02 as support and ruthenium and cobalt as active components are distributed on the support. The process can also be used for the carbon dioxide reforming of hydrocarbons.
EP 1 380 341 discloses a process for the reforming of hydrocarbons by means of a steam reforming process. The active components are elements selected from the group consisting of Ru, Pt, Rh, Pd, Ir and Ni. The support for the active components comprises alumina and from 5 to 95% by weight of manganese oxide.
US 7,309,480 B2 discloses and claims a catalyst for producing hydrogen which comprises a catalyst support comprising monoclinic zirconium oxide on which Ir is present in dispersed form.
One of the objects of the invention was to provide a catalytic process for the production of synthesis gas, which has a high energy efficiency compared to the processes known in the prior art. A further object was to provide a catalytic process by means of which carbon dioxide can be chemically converted. The object of the invention relates to both the development of a suitable catalyst and
3 the development of a suitable reforming process.
The objects mentioned here and further objects which are not mentioned here are achieved by provision of a reforming process and a catalyst for the reforming of hydrocarbons, preferably methane, in the presence of CO2; firstly the catalyst according to the invention and then the reforming process of the invention will be described in more detail below.
I. Reforming catalyst The invention relates to a catalyst for the CO2 reforming of hydrocarbons, preferably methane, having an active composition which comprises at least iridium as active component and zirconium dioxide-comprising support material, wherein a) the Ir content based on the zirconium dioxide-comprising active composition is in the range 0.01-10% by weight, preferably 0.05-5% by weight and more preferably 0.1-1% by weight, and b) the zirconium dioxide in the zirconium dioxide-comprising support material is, according to X-ray-diffractometric analysis, predominantly present in the cubic and/or tetragonal structural form, where the proportion of cubic and/or tetragonal phase is > 50% by weight, more preferably > 70% by weight and in particular >
90% by weight.
In a preferred embodiment of the catalyst of the invention, the zirconium dioxide-comprising active composition has a specific surface area of > 5 m2/g, preferably > 20 m2/g, more preferably 50 m2/g and in particular >80 m2/g. The determination of the specific surface area of the catalyst was carried out by gas adsorption using the BET method (ISO 9277:1995).
The objects mentioned here and further objects which are not mentioned here are achieved by provision of a reforming process and a catalyst for the reforming of hydrocarbons, preferably methane, in the presence of CO2; firstly the catalyst according to the invention and then the reforming process of the invention will be described in more detail below.
I. Reforming catalyst The invention relates to a catalyst for the CO2 reforming of hydrocarbons, preferably methane, having an active composition which comprises at least iridium as active component and zirconium dioxide-comprising support material, wherein a) the Ir content based on the zirconium dioxide-comprising active composition is in the range 0.01-10% by weight, preferably 0.05-5% by weight and more preferably 0.1-1% by weight, and b) the zirconium dioxide in the zirconium dioxide-comprising support material is, according to X-ray-diffractometric analysis, predominantly present in the cubic and/or tetragonal structural form, where the proportion of cubic and/or tetragonal phase is > 50% by weight, more preferably > 70% by weight and in particular >
90% by weight.
In a preferred embodiment of the catalyst of the invention, the zirconium dioxide-comprising active composition has a specific surface area of > 5 m2/g, preferably > 20 m2/g, more preferably 50 m2/g and in particular >80 m2/g. The determination of the specific surface area of the catalyst was carried out by gas adsorption using the BET method (ISO 9277:1995).
4 It is particularly advantageous for the iridium to be present in finely dispersed form on the zirconium dioxide support, since a high catalytic activity is achieved at a low content of Ir in this way.
In a preferred embodiment of the catalyst of the invention, the Ir is present on the zirconium dioxide-comprising support and the latter is doped with further elements. For doping the zirconium dioxide support, preference is given to selecting elements from the group of the rare earths (i.e. from the group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), group Ila (i.e. from the group consisting of Mg, Ca, Sr, Ba), group IVa (i.e.
from the group consisting of Si), group IVb (i.e. from the group consisting of Ti, Hf), group Vb (i.e. from the group consisting of V, Nb, Ta) of the Periodic Table and oxides thereof.
Further doping elements can be, inter alia: platinum metals such as Pt, Pd, Ru, Rh, base metals such as Ni, Co and Fe, other metals such as Mn or other promoters known to those skilled in the art.
If the catalyst comprises one or more doping elements from the group of the rare earths in addition to Ir and zirconium dioxide, the proportion by weight of doping elements based on the total weight of the catalyst is in the range from 0.01 to 80% by weight, preferably in the range from 0.1 to 50% by weight and in particular in the range from 1.0 to 30% by weight.
Without restricting the invention by theoretical considerations, it is assumed that the doping of the active composition with one or more of the abovementioned elements leads to stabilization of the tetragonal or cubic phase of the zirconium dioxide. Furthermore, it can be presumed that the ion-conducting properties or redox properties of the zirconium dioxide support are influenced by doping.
The influence of these properties on the activity of the catalyst for the reforming of methane in the presence of CO2 at high temperatures, high pressures and very low steam-to-methane ratios appear to be significant.
In a particularly preferred embodiment, the active composition according to the invention comprises not only iridium and zirconium dioxide but also yttrium as further doping element, with the yttrium being present in oxidic form. The yttrium oxide content based on Zr02 is preferably in the range from 0.01-80% by weight,
In a preferred embodiment of the catalyst of the invention, the Ir is present on the zirconium dioxide-comprising support and the latter is doped with further elements. For doping the zirconium dioxide support, preference is given to selecting elements from the group of the rare earths (i.e. from the group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), group Ila (i.e. from the group consisting of Mg, Ca, Sr, Ba), group IVa (i.e.
from the group consisting of Si), group IVb (i.e. from the group consisting of Ti, Hf), group Vb (i.e. from the group consisting of V, Nb, Ta) of the Periodic Table and oxides thereof.
Further doping elements can be, inter alia: platinum metals such as Pt, Pd, Ru, Rh, base metals such as Ni, Co and Fe, other metals such as Mn or other promoters known to those skilled in the art.
If the catalyst comprises one or more doping elements from the group of the rare earths in addition to Ir and zirconium dioxide, the proportion by weight of doping elements based on the total weight of the catalyst is in the range from 0.01 to 80% by weight, preferably in the range from 0.1 to 50% by weight and in particular in the range from 1.0 to 30% by weight.
Without restricting the invention by theoretical considerations, it is assumed that the doping of the active composition with one or more of the abovementioned elements leads to stabilization of the tetragonal or cubic phase of the zirconium dioxide. Furthermore, it can be presumed that the ion-conducting properties or redox properties of the zirconium dioxide support are influenced by doping.
The influence of these properties on the activity of the catalyst for the reforming of methane in the presence of CO2 at high temperatures, high pressures and very low steam-to-methane ratios appear to be significant.
In a particularly preferred embodiment, the active composition according to the invention comprises not only iridium and zirconium dioxide but also yttrium as further doping element, with the yttrium being present in oxidic form. The yttrium oxide content based on Zr02 is preferably in the range from 0.01-80% by weight,
5 more preferably 0.1-50% by weight and even more preferably 1.0-30% by weight.
Doping with yttrium leads to stabilization of the cubic or tetragonal phase of Zr02.
In a further and preferred embodiment, the active composition according to the invention comprises not only iridium and zirconium dioxide but additionally two elements from the group of the rare earths as doping elements. The content of doping elements based on the content of Zr02 is preferably in the range 0.01-80% by weight, more preferably 0.1-50% by weight and even more preferably 1.0-30% by weight. Particular preference is given to using lanthanum (La) and cerium (Ce) as doping elements.
Doping with lanthanum and cerium leads to stabilization of the cubic or tetragonal phase of Zr02 resembling the stabilization by yttrium, with La-Zr oxide, Ce-Zr oxide and Ce-La-Zr oxide phases being able to be partially formed. In the catalyst of the invention, the total proportion of the cubic and tetragonal zirconium dioxide-comprising phase based on zirconium dioxide present is preferably >
60% by weight, more preferably > 70% by weight and even more preferably > 80% by weight.
It has surprisingly been found that the catalysts according to the invention in which the iridium has been deposited on zirconium dioxide and the zirconium dioxide predominantly has a tetragonal and/or cubic structure display significantly greater operating lives and improved resistance to formation of carbonaceous deposits than corresponding catalysts which have other noble metal-comprising active components and corresponding catalysts in which iridium-comprising species are in contact with zirconium dioxide which has a monoclinic structure.
Very particular preference is given to catalysts according to the invention which comprise Ir/Zr02 active compositions in which the zirconium dioxide is doped with yttrium or doped with lanthanum and/or cerium.
Doping with yttrium leads to stabilization of the cubic or tetragonal phase of Zr02.
In a further and preferred embodiment, the active composition according to the invention comprises not only iridium and zirconium dioxide but additionally two elements from the group of the rare earths as doping elements. The content of doping elements based on the content of Zr02 is preferably in the range 0.01-80% by weight, more preferably 0.1-50% by weight and even more preferably 1.0-30% by weight. Particular preference is given to using lanthanum (La) and cerium (Ce) as doping elements.
Doping with lanthanum and cerium leads to stabilization of the cubic or tetragonal phase of Zr02 resembling the stabilization by yttrium, with La-Zr oxide, Ce-Zr oxide and Ce-La-Zr oxide phases being able to be partially formed. In the catalyst of the invention, the total proportion of the cubic and tetragonal zirconium dioxide-comprising phase based on zirconium dioxide present is preferably >
60% by weight, more preferably > 70% by weight and even more preferably > 80% by weight.
It has surprisingly been found that the catalysts according to the invention in which the iridium has been deposited on zirconium dioxide and the zirconium dioxide predominantly has a tetragonal and/or cubic structure display significantly greater operating lives and improved resistance to formation of carbonaceous deposits than corresponding catalysts which have other noble metal-comprising active components and corresponding catalysts in which iridium-comprising species are in contact with zirconium dioxide which has a monoclinic structure.
Very particular preference is given to catalysts according to the invention which comprise Ir/Zr02 active compositions in which the zirconium dioxide is doped with yttrium or doped with lanthanum and/or cerium.
6 In further embodiments, the active compositions according to the invention which are used for the process of the invention additionally comprise promoters and/or further metal cations which further increase the efficiency of the catalysts.
In a preferred embodiment, the catalyst of the invention or the active composition comprises at least one noble metal-comprising promoter from the group consisting of Pt, Rh, Pd, Ru, Au, where the proportion of noble metal-comprising promoters based on the catalyst is 0.01-5% by weight and more preferably in the range 0.1-3% by weight.
In a further preferred embodiment, the catalyst comprises at least one base metal-comprising promoter from the group consisting of Ni, Co, Fe, Mn, Mo, W, where the proportion of base metal-comprising promoters based on the weight of the catalyst is in the range 0.1-50% by weight, preferably in the range 0.5-30%
by weight and more preferably in the range 1-20% by weight.
In a further embodiment, the catalyst additionally comprises a proportion of further metal cations which are preferably selected from the group consisting of Mg, Ca, Sr, Ba, Ga, Be, Cr, Mn, with Ca and Mg being particularly preferred.
The components present in the catalyst of the invention, i.e. the abovementioned noble metals, alkaline earth metals, doping elements, promoters and support materials, can be present in elemental and/or oxidic form.
It should be noted that the invention is not intended to be restricted to the combinations and value ranges indicated in the description, but other combinations of the components within the limits of the main claim are also conceivable and possible.
The catalyst of the invention can be produced by impregnation coating of the support material with the individual components. In a further and advantageous embodiment of the production process, the active components are applied to pulverulent support material which is subsequently at least partially kneaded and
In a preferred embodiment, the catalyst of the invention or the active composition comprises at least one noble metal-comprising promoter from the group consisting of Pt, Rh, Pd, Ru, Au, where the proportion of noble metal-comprising promoters based on the catalyst is 0.01-5% by weight and more preferably in the range 0.1-3% by weight.
In a further preferred embodiment, the catalyst comprises at least one base metal-comprising promoter from the group consisting of Ni, Co, Fe, Mn, Mo, W, where the proportion of base metal-comprising promoters based on the weight of the catalyst is in the range 0.1-50% by weight, preferably in the range 0.5-30%
by weight and more preferably in the range 1-20% by weight.
In a further embodiment, the catalyst additionally comprises a proportion of further metal cations which are preferably selected from the group consisting of Mg, Ca, Sr, Ba, Ga, Be, Cr, Mn, with Ca and Mg being particularly preferred.
The components present in the catalyst of the invention, i.e. the abovementioned noble metals, alkaline earth metals, doping elements, promoters and support materials, can be present in elemental and/or oxidic form.
It should be noted that the invention is not intended to be restricted to the combinations and value ranges indicated in the description, but other combinations of the components within the limits of the main claim are also conceivable and possible.
The catalyst of the invention can be produced by impregnation coating of the support material with the individual components. In a further and advantageous embodiment of the production process, the active components are applied to pulverulent support material which is subsequently at least partially kneaded and
7 extruded.
It is also possible for different production processes to be combined with one another and, for example, only part of the active components to be applied to and kneaded with the pulverulent support material. For example, a combination of kneading and extrusion is also possible in order firstly to bring part of the starting components into contact and subsequently carry out the deposition of the remaining components by means of impregnation coating.
The process for producing the active compositions according to the invention is not restricted in any way, but it is instead possible to use quite different process steps. Thus, the term of application is not to be considered as a restriction for the purposes of the present disclosure and in respect of the active components.
The term application thus also comprises contacting of starting components, the active components and zirconium-comprising species. The zirconium-comprising species can also be present as precursor materials which are converted into the material according to the invention only during the synthesis process.
For example, production of the active composition by coprecipitation of active component and zirconium-comprising species in combination with a thermal treatment process is not ruled out. In the case of such a synthesis process, it is possible for the zirconium-comprising species to be converted into the zirconium dioxide having the cubic and/or tetragonal structure only during the thermal treatment. Further examples for synthesis processes are flame-pyrolytic processes or plasma processes.
In this context, it may also be said that application of active components in the sense of impregnation onto the zirconium dioxide-comprising support material is particularly preferred when the zirconium dioxide within the support material is already present in the cubic and/or tetragonal structural form.
To apply the active components to the support, preference is given to metal compounds which are soluble in solvents. Solvents which are preferably used
It is also possible for different production processes to be combined with one another and, for example, only part of the active components to be applied to and kneaded with the pulverulent support material. For example, a combination of kneading and extrusion is also possible in order firstly to bring part of the starting components into contact and subsequently carry out the deposition of the remaining components by means of impregnation coating.
The process for producing the active compositions according to the invention is not restricted in any way, but it is instead possible to use quite different process steps. Thus, the term of application is not to be considered as a restriction for the purposes of the present disclosure and in respect of the active components.
The term application thus also comprises contacting of starting components, the active components and zirconium-comprising species. The zirconium-comprising species can also be present as precursor materials which are converted into the material according to the invention only during the synthesis process.
For example, production of the active composition by coprecipitation of active component and zirconium-comprising species in combination with a thermal treatment process is not ruled out. In the case of such a synthesis process, it is possible for the zirconium-comprising species to be converted into the zirconium dioxide having the cubic and/or tetragonal structure only during the thermal treatment. Further examples for synthesis processes are flame-pyrolytic processes or plasma processes.
In this context, it may also be said that application of active components in the sense of impregnation onto the zirconium dioxide-comprising support material is particularly preferred when the zirconium dioxide within the support material is already present in the cubic and/or tetragonal structural form.
To apply the active components to the support, preference is given to metal compounds which are soluble in solvents. Solvents which are preferably used
8 include, inter alia, the following: water, acidic or alkaline aqueous solutions, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ketones such as acetone or methyl ethyl ketone, aromatic solvents such as toluene or xylenes, aliphatic solvents such as cyclohexane or n-hexane, ethers and polyethers such as tetrahydrofuran, diethyl ether or diglyme, esters such as methyl acetate or ethyl acetate.
As metal compounds, particular preference is given to using soluble salts, complexes or metal-organic compounds. Examples of salts are, inter alia, halides, carbonyls, acetates, nitrates, carbonates. Examples of complexes are, inter alia, bipyridyl complexes, acetonitrile complexes, carbonyl complexes, complexes with amino acids or amines, complexes with polyols or polyacids, complexes with phosphanes. Examples of metal-organic compounds are, inter alia, acetylacetonates, alkoxides, amides, alkyl compounds, cyclopentadienyls and cycloalkanes.
Furthermore, sols comprising colloidal particles in metallic or oxidic form are also used as starting materials. Such colloidal particles can be stabilized by means of stabilizing agents and/or special treatment methods, for example by means of surface-active agents.
In a preferred embodiment, the catalyst has an active composition comprising an yttrium-stabilized zirconium dioxide and an iridium-comprising active component, where the iridium-comprising active component is present in finely divided form and the iridium- comprising particles have a size of < 30 nm, preferably < 20 nm and more preferably < 10 nm.
The present invention also provides a process for producing the catalyst of the invention, in which at least one noble metal, particularly preferably iridium, is applied to the support material comprising cubic and/or tetragonal zirconium dioxide and at least one doping element selected from the group of rare earths, particularly preferably yttrium.
As metal compounds, particular preference is given to using soluble salts, complexes or metal-organic compounds. Examples of salts are, inter alia, halides, carbonyls, acetates, nitrates, carbonates. Examples of complexes are, inter alia, bipyridyl complexes, acetonitrile complexes, carbonyl complexes, complexes with amino acids or amines, complexes with polyols or polyacids, complexes with phosphanes. Examples of metal-organic compounds are, inter alia, acetylacetonates, alkoxides, amides, alkyl compounds, cyclopentadienyls and cycloalkanes.
Furthermore, sols comprising colloidal particles in metallic or oxidic form are also used as starting materials. Such colloidal particles can be stabilized by means of stabilizing agents and/or special treatment methods, for example by means of surface-active agents.
In a preferred embodiment, the catalyst has an active composition comprising an yttrium-stabilized zirconium dioxide and an iridium-comprising active component, where the iridium-comprising active component is present in finely divided form and the iridium- comprising particles have a size of < 30 nm, preferably < 20 nm and more preferably < 10 nm.
The present invention also provides a process for producing the catalyst of the invention, in which at least one noble metal, particularly preferably iridium, is applied to the support material comprising cubic and/or tetragonal zirconium dioxide and at least one doping element selected from the group of rare earths, particularly preferably yttrium.
9 As process for applying the active components to the support material, it is possible to use all processes which are known to a person skilled in the art in the field of catalyst production. Mention may be made here by way of example of impregnation with an impregnation solution, impregnation to pore volume, spraying-on of the impregnation solution, washcoating and precipitation. In the case of impregnation to pore volume, a defined amount of impregnation solution which is sufficient for filling the pore volume of the support material and leaves the support material with the appearance of a dry state is added to the support material.
In an advantageous embodiment, the active component, and also optionally the promoters and further metal cations, is firstly applied at least partly to a pulveru lent support material, kneaded and subsequently extruded. Kneading and extrusion of the support material together with the active components is carried out using apparatuses known to those skilled in the art.
The production of shaped bodies from pulverulent raw materials can be carried out by methods known to those skilled in the art, for example tableting, aggregation or extrusion, as described, inter alia, in Handbook of Heterogeneous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp 414-417.
Auxiliaries can be added to the synthesis system. The addition of auxiliaries can be carried out, for example, during shaping or during application of the active component to the support. Auxiliaries which can be used are, for example, binders, lubricants and/or solvents. The auxiliaries added to the synthesis system are then converted by thermal treatment into the other constituents which can form additional components. The additional components are generally oxidic materials, some of which may function as bonding sites and thereby contribute to increasing the mechanical stability of the shaped body or of the individual particles. The binders can, for example, comprise species comprising aluminum hydroxide, silicon hydroxide or magnesium hydroxide.
The iridium-comprising active composition can also have been applied to a support, monolith or honeycomb body. The monolith or honeycomb body can comprise metal or ceramic. The molding of the active composition or the application of the active composition to a support or support bodies is of great technical importance for the fields of application of the catalyst of the invention.
Depending on particle size and reactor packing, the shape of the particles has an 5 effect on the pressure drop brought about by the fixed catalyst bed.
A characteristic of the process of the invention for the reforming of hydrocarbons, preferably methane, in the presence of CO2 is that it is possible to use Zr02-comprising active compositions which have a relatively low content of Ir and nevertheless have a high catalytic efficiency. Thus, it is also possible, for
In an advantageous embodiment, the active component, and also optionally the promoters and further metal cations, is firstly applied at least partly to a pulveru lent support material, kneaded and subsequently extruded. Kneading and extrusion of the support material together with the active components is carried out using apparatuses known to those skilled in the art.
The production of shaped bodies from pulverulent raw materials can be carried out by methods known to those skilled in the art, for example tableting, aggregation or extrusion, as described, inter alia, in Handbook of Heterogeneous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp 414-417.
Auxiliaries can be added to the synthesis system. The addition of auxiliaries can be carried out, for example, during shaping or during application of the active component to the support. Auxiliaries which can be used are, for example, binders, lubricants and/or solvents. The auxiliaries added to the synthesis system are then converted by thermal treatment into the other constituents which can form additional components. The additional components are generally oxidic materials, some of which may function as bonding sites and thereby contribute to increasing the mechanical stability of the shaped body or of the individual particles. The binders can, for example, comprise species comprising aluminum hydroxide, silicon hydroxide or magnesium hydroxide.
The iridium-comprising active composition can also have been applied to a support, monolith or honeycomb body. The monolith or honeycomb body can comprise metal or ceramic. The molding of the active composition or the application of the active composition to a support or support bodies is of great technical importance for the fields of application of the catalyst of the invention.
Depending on particle size and reactor packing, the shape of the particles has an 5 effect on the pressure drop brought about by the fixed catalyst bed.
A characteristic of the process of the invention for the reforming of hydrocarbons, preferably methane, in the presence of CO2 is that it is possible to use Zr02-comprising active compositions which have a relatively low content of Ir and nevertheless have a high catalytic efficiency. Thus, it is also possible, for
10 example, to achieve high conversions using active compositions which have, for example, only 1% by weight or less than 1% by weight of Ir.
CO2 reforming process The present invention provides a catalytic high-pressure process for the carbon dioxide reforming of hydrocarbons, preferably methane, to produce synthesis gas, wherein:
(i) the 002-comprising reforming gas is brought into contact with an iridium-comprising active composition, where the total content of hydrocarbons, preferably CH4, and CO2 in the reforming gas is greater than 80% by volume, preferably greater than 85% by volume and more preferably greater than 90% by volume, (ii) the pressure of the reforming gas on contacting with the active composition is in the range 5-500 bar, preferably in the range from 10 to 250 bar and more preferably in the range from 20 to 100 bar, and the temperature of the reforming gas on contacting with the active composition is in the range from 600 to 1200 C, preferably in the range from 850 to 1100 C and in particular in the range from 850 to 950 C, (iii) the GHSV in the process is in the range from 500 to 100 000 h-1, preferably in the range from 500 to 50 000 h-1,
CO2 reforming process The present invention provides a catalytic high-pressure process for the carbon dioxide reforming of hydrocarbons, preferably methane, to produce synthesis gas, wherein:
(i) the 002-comprising reforming gas is brought into contact with an iridium-comprising active composition, where the total content of hydrocarbons, preferably CH4, and CO2 in the reforming gas is greater than 80% by volume, preferably greater than 85% by volume and more preferably greater than 90% by volume, (ii) the pressure of the reforming gas on contacting with the active composition is in the range 5-500 bar, preferably in the range from 10 to 250 bar and more preferably in the range from 20 to 100 bar, and the temperature of the reforming gas on contacting with the active composition is in the range from 600 to 1200 C, preferably in the range from 850 to 1100 C and in particular in the range from 850 to 950 C, (iii) the GHSV in the process is in the range from 500 to 100 000 h-1, preferably in the range from 500 to 50 000 h-1,
11 (iv) the synthesis gas produced has an H2/C0 ratio in the range from 0.4 to 1.8, more preferably in the range from 0.5 to 1.4 and in particular in the range from 0.8 to 1.2.
In a preferred embodiment of the process, the iridium is present in combination with zirconium dioxide in the iridium-comprising active composition and the Ir content based on Zr02 is in the range 0.01-10% by weight, preferably 0.05-5%
by weight and more preferably 0.1-1% by weight.
In a preferred embodiment of the process, the active composition comprises zirconium dioxide as support material, where the zirconium dioxide predominantly has a cubic and/or tetragonal structure and the proportion of cubic and/or tetragonal phase is > 50% by weight, more preferably > 70% by weight and in particular > 90% by weight.
A characteristic of the catalyst of the invention and the process of the invention is a high activity in respect of the carbon dioxide reforming of hydrocarbons, preferably methane, in the presence of CO2. A further characteristic of the process of the invention is the excellent resistance to formation of carbonaceous deposits under very severe reaction conditions. With regard to the severe reaction conditions, particular mention may be made of a high pressure and temperature resistance at low steam-to-carbon ratios (S/C). The technical effect brought about thereby results in high operating lives of the catalyst when carrying out the process of the invention.
In a further preferred embodiment, the active composition comprises not only iridium and zirconium dioxide but also at least one doping element selected from the group of rare earths (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), particularly preferably yttrium, where the content based on Zr02 is in the range 0.01-80% by weight, preferably 0.1-50% by weight and more preferably 1.0-30% by weight.
In order to increase the performance properties in the reforming reaction, the . .
In a preferred embodiment of the process, the iridium is present in combination with zirconium dioxide in the iridium-comprising active composition and the Ir content based on Zr02 is in the range 0.01-10% by weight, preferably 0.05-5%
by weight and more preferably 0.1-1% by weight.
In a preferred embodiment of the process, the active composition comprises zirconium dioxide as support material, where the zirconium dioxide predominantly has a cubic and/or tetragonal structure and the proportion of cubic and/or tetragonal phase is > 50% by weight, more preferably > 70% by weight and in particular > 90% by weight.
A characteristic of the catalyst of the invention and the process of the invention is a high activity in respect of the carbon dioxide reforming of hydrocarbons, preferably methane, in the presence of CO2. A further characteristic of the process of the invention is the excellent resistance to formation of carbonaceous deposits under very severe reaction conditions. With regard to the severe reaction conditions, particular mention may be made of a high pressure and temperature resistance at low steam-to-carbon ratios (S/C). The technical effect brought about thereby results in high operating lives of the catalyst when carrying out the process of the invention.
In a further preferred embodiment, the active composition comprises not only iridium and zirconium dioxide but also at least one doping element selected from the group of rare earths (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), particularly preferably yttrium, where the content based on Zr02 is in the range 0.01-80% by weight, preferably 0.1-50% by weight and more preferably 1.0-30% by weight.
In order to increase the performance properties in the reforming reaction, the . .
12 catalyst used in the process of the invention can additionally comprise noble metal-comprising promoters, base metal-comprising promoters and also further metal cations.
The noble metal promoters are selected from the group consisting of Pt, Rh, Pd, Ru, Au, where the proportion of noble metal-comprising promoters, based on the weight of the catalyst, is in the range 0.01-5% by weight and more preferably in the range 0.1-3% by weight.
The base metal-comprising promoters are selected from the group consisting of Ni, Co, Fe, Mn, Mo, W, where, based on the weight of the catalyst, the proportion of base metal-comprising promoters based on the weight of the catalyst is in the range 0.1-50% by weight, preferably in the range 0.5-30% by weight and more preferably in the range 1-20% by weight.
The metal cations are preferably one or more elements selected from the group consisting of Mg, Ca, Sr, Ga, Be, Cr and Mn, with particular preference being given to Ca and/or Mg.
Another advantage of the process of the invention is that the process of the invention can be carried out using a feed fluid having small amounts of steam or no steam at all. In a preferred embodiment, the steam/carbon ratio in the reforming gas is less than 0.2, more preferably less than 0.1 and even more preferably less than 0.05.
In addition, it is even possible in connection with the process of the invention and in particular embodiments even preferred for a reforming gas which is largely water-free or comprises no water to be used.
Carrying out the process of the invention at low water contents offers the advantage of a high energetic efficiency of the process and simplification of the process flow diagram of a plant in which the process of the invention is utilized.
When carrying out the process of the invention, the iridium-comprising active
The noble metal promoters are selected from the group consisting of Pt, Rh, Pd, Ru, Au, where the proportion of noble metal-comprising promoters, based on the weight of the catalyst, is in the range 0.01-5% by weight and more preferably in the range 0.1-3% by weight.
The base metal-comprising promoters are selected from the group consisting of Ni, Co, Fe, Mn, Mo, W, where, based on the weight of the catalyst, the proportion of base metal-comprising promoters based on the weight of the catalyst is in the range 0.1-50% by weight, preferably in the range 0.5-30% by weight and more preferably in the range 1-20% by weight.
The metal cations are preferably one or more elements selected from the group consisting of Mg, Ca, Sr, Ga, Be, Cr and Mn, with particular preference being given to Ca and/or Mg.
Another advantage of the process of the invention is that the process of the invention can be carried out using a feed fluid having small amounts of steam or no steam at all. In a preferred embodiment, the steam/carbon ratio in the reforming gas is less than 0.2, more preferably less than 0.1 and even more preferably less than 0.05.
In addition, it is even possible in connection with the process of the invention and in particular embodiments even preferred for a reforming gas which is largely water-free or comprises no water to be used.
Carrying out the process of the invention at low water contents offers the advantage of a high energetic efficiency of the process and simplification of the process flow diagram of a plant in which the process of the invention is utilized.
When carrying out the process of the invention, the iridium-comprising active
13 component is subjected to severe physical and chemical stress since the process is carried out at a temperature in the range from 600 to 1200 C, preferably from 850 to 1100 C and more preferably in the range from 850 to 950 C, with the process pressure being in the range from 5 to 500 bar, preferably in the range from 10 to 250 bar and more preferably in the range from 20 to 100 bar.
Although the process is carried out under very severe process conditions, deposition of carbonaceous material on the catalyst can be largely ruled out due to the specific properties of the material according to the invention, which also represents an advantage of the process of the invention.
Owing to the low level of carbonaceous deposits, the process of the invention can be carried on over a long period of time, which is once again advantageous in terms of process efficiency.
III. Examples To illustrate the invention, a number of examples of the production and use of the reforming catalysts of the invention are presented. In addition, comparative examples which correspond to the prior art and thus do not have the features according to the invention are described.
1. Production of the iridium-comprising catalysts 2.
To produce the catalyst (S2) according to the invention, 198 g of yttrium-stabilized zirconium dioxide were impregnated with an aqueous iridium chloride solution. To produce the iridium chloride solution, 3.84 g of IrC14*H20 were firstly dissolved in 20 ml of distilled water and the solution was made up with water.
The amount of water was selected in such a way that 90% of the free pore volume of the support oxide could be filled with the solution. The free pore volume was 0.2 cm3/g. The yttrium-stabilized zirconium dioxide had an yttrium oxide content (Y203) of 8% by weight and was present as crushed material having a particle size in the range 0.5-1.0 mm.
Although the process is carried out under very severe process conditions, deposition of carbonaceous material on the catalyst can be largely ruled out due to the specific properties of the material according to the invention, which also represents an advantage of the process of the invention.
Owing to the low level of carbonaceous deposits, the process of the invention can be carried on over a long period of time, which is once again advantageous in terms of process efficiency.
III. Examples To illustrate the invention, a number of examples of the production and use of the reforming catalysts of the invention are presented. In addition, comparative examples which correspond to the prior art and thus do not have the features according to the invention are described.
1. Production of the iridium-comprising catalysts 2.
To produce the catalyst (S2) according to the invention, 198 g of yttrium-stabilized zirconium dioxide were impregnated with an aqueous iridium chloride solution. To produce the iridium chloride solution, 3.84 g of IrC14*H20 were firstly dissolved in 20 ml of distilled water and the solution was made up with water.
The amount of water was selected in such a way that 90% of the free pore volume of the support oxide could be filled with the solution. The free pore volume was 0.2 cm3/g. The yttrium-stabilized zirconium dioxide had an yttrium oxide content (Y203) of 8% by weight and was present as crushed material having a particle size in the range 0.5-1.0 mm.
14 The crushed material composed of stabilized support oxide was placed in an impregnation drum and spray-impregnated with the iridium chloride solution while rotating the drum. After impregnation, the material was rotated for a further minutes and subsequently dried at 120 C in a convection drying oven for 5 16 hours. Calcination of the dried material was carried out at 550 C for two hours.
The iridium-comprising catalyst S2 obtained in this way had an iridium content of 1.0 g of iridium per 100 g of catalyst.
3. Production of comparative platinum catalyst 4.
The platinum-comprising comparative catalyst CE5 was produced by the same process as the iridium catalyst S2 using a cerium/lanthanum-doped zirconium dioxide as support oxide. The support oxide had a free pore volume of 0.21 cm3/g and a rare earth content of La oxide and Ce oxide of 22% by weight.
100 g of support oxide in the form of crushed material having a particle size in the range from 0.5 to 1.0 mm were used for impregnation. To carry out the impregnation, 6.37 g of platinum nitrate salt (comprising 15.7% by weight of platinum) were dissolved in water and the solution was subsequently sprayed onto the support oxide in a spray drum. The comparative catalyst CE5 obtained after impregnation had a Pt content of 1.0 g of Pt/100 g of catalyst.
A summary of the active compositions examined is shown in table 1. All active compositions shown in the table were produced in the laboratory by means of an impregnation process using a rotating impregnation drum.
Figure 1 shows the X-ray diffraction pattern recorded on catalyst sample S2 before the reductive treatment. In the upper part of the figure, there is an enlargement of the angle range from 25 2theta to 65 2theta to highlight the reflections which can be assigned to the iridium-comprising phase.
Figure 2 shows the X-ray diffraction pattern recorded on catalyst sample S3 in the unreduced form, in which no reflections of an iridium oxide-comprising phase are to be found.
The determination of the average particle size of the iridium particles was carried out by evaluation of the X-ray diffraction patterns. In catalyst sample S2, which was loaded with 1% by weight of iridium (stabilized by yttrium), the iridium oxide particles (Ir02) had an average crystallite size of 8.0 nm. An evaluation of the 5 XRD data shown in figure 1 followed. Here, the iridium particles were present in the oxidic form since XRD analyses of the catalysts in the unreduced form have been carried out. Evaluation of the diffraction pattern shown in figure 2 indicated that no iridium oxide phase could be detected. This demonstrates that the iridium particles are smaller than 1 or 2 nm, since otherwise corresponding reflections 10 would have to be able to be found in the XRD.
The XRD analyses were carried out by means of a D8 Advance Series 2 from Bruker/AXS using a CuK-alpha source (having a wavelength of 0.154 nm at 40 kV and 40 mA) and theta-2theta geometry (Bragg-Brentano geometry) in the
The iridium-comprising catalyst S2 obtained in this way had an iridium content of 1.0 g of iridium per 100 g of catalyst.
3. Production of comparative platinum catalyst 4.
The platinum-comprising comparative catalyst CE5 was produced by the same process as the iridium catalyst S2 using a cerium/lanthanum-doped zirconium dioxide as support oxide. The support oxide had a free pore volume of 0.21 cm3/g and a rare earth content of La oxide and Ce oxide of 22% by weight.
100 g of support oxide in the form of crushed material having a particle size in the range from 0.5 to 1.0 mm were used for impregnation. To carry out the impregnation, 6.37 g of platinum nitrate salt (comprising 15.7% by weight of platinum) were dissolved in water and the solution was subsequently sprayed onto the support oxide in a spray drum. The comparative catalyst CE5 obtained after impregnation had a Pt content of 1.0 g of Pt/100 g of catalyst.
A summary of the active compositions examined is shown in table 1. All active compositions shown in the table were produced in the laboratory by means of an impregnation process using a rotating impregnation drum.
Figure 1 shows the X-ray diffraction pattern recorded on catalyst sample S2 before the reductive treatment. In the upper part of the figure, there is an enlargement of the angle range from 25 2theta to 65 2theta to highlight the reflections which can be assigned to the iridium-comprising phase.
Figure 2 shows the X-ray diffraction pattern recorded on catalyst sample S3 in the unreduced form, in which no reflections of an iridium oxide-comprising phase are to be found.
The determination of the average particle size of the iridium particles was carried out by evaluation of the X-ray diffraction patterns. In catalyst sample S2, which was loaded with 1% by weight of iridium (stabilized by yttrium), the iridium oxide particles (Ir02) had an average crystallite size of 8.0 nm. An evaluation of the 5 XRD data shown in figure 1 followed. Here, the iridium particles were present in the oxidic form since XRD analyses of the catalysts in the unreduced form have been carried out. Evaluation of the diffraction pattern shown in figure 2 indicated that no iridium oxide phase could be detected. This demonstrates that the iridium particles are smaller than 1 or 2 nm, since otherwise corresponding reflections 10 would have to be able to be found in the XRD.
The XRD analyses were carried out by means of a D8 Advance Series 2 from Bruker/AXS using a CuK-alpha source (having a wavelength of 0.154 nm at 40 kV and 40 mA) and theta-2theta geometry (Bragg-Brentano geometry) in the
15 reflection mode. The measurements were carried out over the measurement range: 5-80 (2theta), 0.02 steps at 4.8 seconds/step. The structure analysis software TOPAS (Bruker AXS) was used for determining the average crystallite sizes of the individual phases.
Catalytic studies The catalytic studies on the reforming of a hydrocarbon-comprising gas in the presence of CO2 were carried out by means of a catalyst test set-up equipped with six reactors connected in parallel. To prepare for the studies, the individual reactors were each charged with 20 ml of catalyst samples.
An overview of the catalytic studies carried out is shown in tables 2 and 3.
Firstly, the reactors charged with the catalysts were heated in a controlled manner under a carrier gas atmosphere from 25 C to the target temperature. Nitrogen was used as carrier gas. (It is conceivable to carry out heating in the presence of a reducing gas atmosphere.) A heating rate of 10 C/min was selected for heating the reactors. After the reactors with the catalysts had been maintained at the target temperature in the stream of nitrogen for 0.5 h, they were supplied with the
Catalytic studies The catalytic studies on the reforming of a hydrocarbon-comprising gas in the presence of CO2 were carried out by means of a catalyst test set-up equipped with six reactors connected in parallel. To prepare for the studies, the individual reactors were each charged with 20 ml of catalyst samples.
An overview of the catalytic studies carried out is shown in tables 2 and 3.
Firstly, the reactors charged with the catalysts were heated in a controlled manner under a carrier gas atmosphere from 25 C to the target temperature. Nitrogen was used as carrier gas. (It is conceivable to carry out heating in the presence of a reducing gas atmosphere.) A heating rate of 10 C/min was selected for heating the reactors. After the reactors with the catalysts had been maintained at the target temperature in the stream of nitrogen for 0.5 h, they were supplied with the
16 reforming gas.
In the catalytic studies, the individual samples were subjected to a sequence of different test conditions. In the first two test conditions of the sequence, the catalysts were maintained at 950 C and the water vapor content of the reforming gas was reduced stepwise from 10% by volume to 0% by volume. In the tables below, the studies carried out at 950 C in the presence of 10% by volume and 0% by volume of water vapor are denoted by the suffixes c1 and c2 (i.e. c1 corresponds to 10% by volume of water vapor at 950 C and c2 corresponds to 0% by volume of water vapor at 950 C). The samples tested at 850 C in the presence of 0% by volume of water vapor are denoted by the suffix c3 in table 3.
In the case of the test conditions in the presence of 10% by volume of water vapor (c1), the samples were subjected to a lower space velocity that in the case of test conditions in the absence of water vapor in the feed fluid (c2 and c3).
All catalytic studies were carried out in the presence of 5% by volume of argon as internal standard; this was added to the feed fluid for analytical reasons in order to monitor the recovery rates of material.
The test conditions selected here were so demanding in terms of the physicochemical conditions that it was possible to achieve high conversions and stable performance properties over a prolonged period of time only by means of the catalyst samples according to the invention (table 2). This can be seen from the fact that the comparative samples CE1, CE3 and CE4, in which the iridium was present on alpha-aluminum oxide and in which the iridium loadings were in the range from 0.5 to 2% by weight, were completely deactivated or coked within a few hours at 10% by volume of H20 in the feed. Similarly rapid deactivation or coking in the presence of 10% by volume of H20 in the feed was also observed for the comparative sample CE2 in which 1% by weight of iridium was present on an undoped monoclinic zirconium dioxide. The comparative sample CE5, which had 1% by weight of Pt and otherwise the same composition of the remaining components as Si and S4, displayed stable performance properties at 850 C
and 10% by volume of H20 in the feed but deactivated very severely over a period of 43 hours, after which the water content was reduced to 0% by volume
In the catalytic studies, the individual samples were subjected to a sequence of different test conditions. In the first two test conditions of the sequence, the catalysts were maintained at 950 C and the water vapor content of the reforming gas was reduced stepwise from 10% by volume to 0% by volume. In the tables below, the studies carried out at 950 C in the presence of 10% by volume and 0% by volume of water vapor are denoted by the suffixes c1 and c2 (i.e. c1 corresponds to 10% by volume of water vapor at 950 C and c2 corresponds to 0% by volume of water vapor at 950 C). The samples tested at 850 C in the presence of 0% by volume of water vapor are denoted by the suffix c3 in table 3.
In the case of the test conditions in the presence of 10% by volume of water vapor (c1), the samples were subjected to a lower space velocity that in the case of test conditions in the absence of water vapor in the feed fluid (c2 and c3).
All catalytic studies were carried out in the presence of 5% by volume of argon as internal standard; this was added to the feed fluid for analytical reasons in order to monitor the recovery rates of material.
The test conditions selected here were so demanding in terms of the physicochemical conditions that it was possible to achieve high conversions and stable performance properties over a prolonged period of time only by means of the catalyst samples according to the invention (table 2). This can be seen from the fact that the comparative samples CE1, CE3 and CE4, in which the iridium was present on alpha-aluminum oxide and in which the iridium loadings were in the range from 0.5 to 2% by weight, were completely deactivated or coked within a few hours at 10% by volume of H20 in the feed. Similarly rapid deactivation or coking in the presence of 10% by volume of H20 in the feed was also observed for the comparative sample CE2 in which 1% by weight of iridium was present on an undoped monoclinic zirconium dioxide. The comparative sample CE5, which had 1% by weight of Pt and otherwise the same composition of the remaining components as Si and S4, displayed stable performance properties at 850 C
and 10% by volume of H20 in the feed but deactivated very severely over a period of 43 hours, after which the water content was reduced to 0% by volume
17 (table 3).
In contrast to the comparative examples, the catalysts according to the invention of examples S1 to S4, which were used in combination with the process of the invention and were tested in the presence of 10% by volume and finally 0% by volume of water vapor, displayed no deactivation and a very high conversion of CO2 and CH4.
It is remarkable that the catalysts according to the invention displayed a high catalytic activity under the very demanding conditions and maintained this even after a very long period of more than 485 hours (cumulative), as can clearly be seen from the test results for catalyst S3 (table 4).
After the catalytic tests, the catalysts removed from the reactors were subjected to analyses to determine the amount of carbonaceous material. It was found that the catalysts according to the invention had no carbonaceous deposits even after the catalysis tests. This demonstrated the high carbonation resistance of the catalysts of the invention.
In all studies on Si to S4, a synthesis gas having an H2/C0 ratio of 5 1 was produced. The lower the water vapor content in the reforming gas, the higher is the conversion of CO2 relative to the conversion of CH4. Particularly in dry reforming, the synthesis gas had an H2/C0 ratio of less than 0.9 and sometimes also less than 0.8.
In contrast to the comparative examples, the catalysts according to the invention of examples S1 to S4, which were used in combination with the process of the invention and were tested in the presence of 10% by volume and finally 0% by volume of water vapor, displayed no deactivation and a very high conversion of CO2 and CH4.
It is remarkable that the catalysts according to the invention displayed a high catalytic activity under the very demanding conditions and maintained this even after a very long period of more than 485 hours (cumulative), as can clearly be seen from the test results for catalyst S3 (table 4).
After the catalytic tests, the catalysts removed from the reactors were subjected to analyses to determine the amount of carbonaceous material. It was found that the catalysts according to the invention had no carbonaceous deposits even after the catalysis tests. This demonstrated the high carbonation resistance of the catalysts of the invention.
In all studies on Si to S4, a synthesis gas having an H2/C0 ratio of 5 1 was produced. The lower the water vapor content in the reforming gas, the higher is the conversion of CO2 relative to the conversion of CH4. Particularly in dry reforming, the synthesis gas had an H2/C0 ratio of less than 0.9 and sometimes also less than 0.8.
18 Table 1 shows a summary of the composition of the active compositions tested and the metal content.
Metal content Stabilizer content Sample Support Stabilizer [% by wt.] [% by wt. as oxide]
Si 2 Zr02 Ce, La 22 S2 1 Zr02 Y 8 S3 0.1 Zr02 Y 8 S4 0.1 Zr02 Ce, La 22 CE2 1 Zr02 CE3 0.5 A1203 CE5 1 (Pt) Zr02 Ce, La 22 Table 2 shows the chemical constitution of the product stream obtained in the CO2 reformation of CH4 under different experimental conditions in respect of the water vapor content. The reforming gas used had an equimolar ratio of CH4 and CO2 and 5% by volume of argon as internal standard. All experiments were carried out at a temperature of 950 C and a reactor pressure of 20 bar. The values denoted by "start" were recorded immediately at the beginning of each experiment; the values denoted by "end" were recorded after a TOS (time on stream) of 43 hours. The notation (*) indicates that carbonaceous deposits were formed on the samples after lowering of the water vapor content and led to blockage/malfunction of the reactor.
. .
Metal content Stabilizer content Sample Support Stabilizer [% by wt.] [% by wt. as oxide]
Si 2 Zr02 Ce, La 22 S2 1 Zr02 Y 8 S3 0.1 Zr02 Y 8 S4 0.1 Zr02 Ce, La 22 CE2 1 Zr02 CE3 0.5 A1203 CE5 1 (Pt) Zr02 Ce, La 22 Table 2 shows the chemical constitution of the product stream obtained in the CO2 reformation of CH4 under different experimental conditions in respect of the water vapor content. The reforming gas used had an equimolar ratio of CH4 and CO2 and 5% by volume of argon as internal standard. All experiments were carried out at a temperature of 950 C and a reactor pressure of 20 bar. The values denoted by "start" were recorded immediately at the beginning of each experiment; the values denoted by "end" were recorded after a TOS (time on stream) of 43 hours. The notation (*) indicates that carbonaceous deposits were formed on the samples after lowering of the water vapor content and led to blockage/malfunction of the reactor.
. .
19 cony. cony. cony. cony. H2/C0 H2/C0 Sample (start) (end) (start) (end) (start) (end) [oh] [0/0] [oh] [0/0]
Si_c1 80 80 80 80 0.9 0.9 S2_c1 82 82 83 83 0.9 0.9 S3_c1 82 80 82 82 0.9 0.9 S4_c1 82 82 84 84 0.9 0.9 CE1_c1 70 13 71 9 1.0 2.8 CE2_c1 70 59 74 67 0.9 0.9 CE3_c1 75 33 80 45 1.0 0.75 CE4_c1 76 13 80 9 1.0 2.5 c1: feed gas: 0F14:CO2:H20:Ar = 42.5:42.5:10:5 (% by vol.); T = 950 C, p = 20 bar Si_c2 73 75 85 87 0.8 0.8 52_c2 75 75 88 88 0.8 0.8 S3_c2 35 35 45 51 0.6 0.5 CE1_c2 22 0* 19 0* / /
CE2_c2 20 0* 15 0* / /
0E3_c2 20 0* 18 0* / /
0E4_c2 15 0* 11 0* / /
c2: feed gas: CH4:002:H20:Ar = 47.5:47.5:0:5 (% by vol.); T = 950 C, p = 20 bar Table 3 shows the results achieved in the studies on catalyst samples S2 and CE5 under test conditions c3. The values denoted by "start" were recorded immediately at the beginning of each experiment; the "end" values were recorded after a TOS (time on stream) of 43 hours. The catalytic measurements were carried out at 850 C.
cony. cony. cony. cony. H2/C0 H2/C0 Sample (start) (end) (start) (end) (start) (end) [ /0] [%]
S2_c3 55 55 73 73 0.7 0.7 CE5_c3 50 35 64 51 0.7 0.4 Table 4 shows the results obtained in the study on catalyst sample S3 after a TOS (time on stream) of 235 h and 254 h under test conditions c1 (10% by volume of H20) and c2 (0% by volume of H20). The catalytic measurements 5 were carried out at a temperature of 950 C and a pressure of 20 bar.
CH4 cony. CO2 cony. H2/C0 TOS
Sample [h]
S3_c1 80 82 0.9 235 S3_c2 58 79 0.7 254
Si_c1 80 80 80 80 0.9 0.9 S2_c1 82 82 83 83 0.9 0.9 S3_c1 82 80 82 82 0.9 0.9 S4_c1 82 82 84 84 0.9 0.9 CE1_c1 70 13 71 9 1.0 2.8 CE2_c1 70 59 74 67 0.9 0.9 CE3_c1 75 33 80 45 1.0 0.75 CE4_c1 76 13 80 9 1.0 2.5 c1: feed gas: 0F14:CO2:H20:Ar = 42.5:42.5:10:5 (% by vol.); T = 950 C, p = 20 bar Si_c2 73 75 85 87 0.8 0.8 52_c2 75 75 88 88 0.8 0.8 S3_c2 35 35 45 51 0.6 0.5 CE1_c2 22 0* 19 0* / /
CE2_c2 20 0* 15 0* / /
0E3_c2 20 0* 18 0* / /
0E4_c2 15 0* 11 0* / /
c2: feed gas: CH4:002:H20:Ar = 47.5:47.5:0:5 (% by vol.); T = 950 C, p = 20 bar Table 3 shows the results achieved in the studies on catalyst samples S2 and CE5 under test conditions c3. The values denoted by "start" were recorded immediately at the beginning of each experiment; the "end" values were recorded after a TOS (time on stream) of 43 hours. The catalytic measurements were carried out at 850 C.
cony. cony. cony. cony. H2/C0 H2/C0 Sample (start) (end) (start) (end) (start) (end) [ /0] [%]
S2_c3 55 55 73 73 0.7 0.7 CE5_c3 50 35 64 51 0.7 0.4 Table 4 shows the results obtained in the study on catalyst sample S3 after a TOS (time on stream) of 235 h and 254 h under test conditions c1 (10% by volume of H20) and c2 (0% by volume of H20). The catalytic measurements 5 were carried out at a temperature of 950 C and a pressure of 20 bar.
CH4 cony. CO2 cony. H2/C0 TOS
Sample [h]
S3_c1 80 82 0.9 235 S3_c2 58 79 0.7 254
Claims (15)
1. A catalyst for the CO2 reforming of hydrocarbons having an active composition which comprises an iridium- comprising active component and zirconium dioxide-comprising support material, wherein a) the iridium content based on the content of active composition is in the range 0.01-10% by weight, preferably 0.05-5% by weight and more preferably 0.1-1% by weight, and b) the zirconium dioxide in the zirconium dioxide-comprising support material predominantly has a cubic and/or tetragonal structural form, where the proportion of cubic and/or tetragonal phase is > 50% by weight, more preferably > 70% by weight and in particular > 90% by weight.
2. The catalyst for the CO2 reforming of hydrocarbons according to claim 1, wherein the zirconium dioxide-comprising support comprises additional components, and the proportion of the tetragonal and/or cubic zirconium dioxide based on the total weight of the support is > 80% by weight, preferably > 90% by weight and more preferably > 95% by weight.
3. The catalyst for the CO2 reforming of hydrocarbons according to claim 1 or 2, wherein the zirconium dioxide-comprising active composition has a specific surface area of > 5 m2/g, preferably > 10 m2/g, more preferably > 20 m2/g, even more preferably > 50 m2/g and in particular > 80 m2/g.
4. The catalyst for the CO2 reforming of hydrocarbons having an active composition according to any of claims 1 to 3, wherein the active composition comprises a dopant with one or more elements selected from the group of the rare earths (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), group Ila (Mg, Ca, Sr, Ba), group IVb (Ti, Hf), group Vb (V, Nb, Ta) and/or silicon, where the proportion of doping elements based on the amount of active composition is in the range 0.01-80% by weight, preferably in the range 0.1-50% by weight and in particular in the range 1.0-30% by weight.
5. The catalyst for the CO2 reforming of hydrocarbons having an active composition according to any of claims 1 to 4, wherein the active composition comprises a dopant with one or more elements from the group of the rare earths (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), where the proportion of doping elements based on the proportion of active composition is in the range 0.01-80% by weight, preferably in the range 0.1-50% by weight and in particular in the range 1.0-30% by weight.
6. The catalyst for the CO2 reforming of hydrocarbons having an active composition according to any of claims 1 to 5, wherein the support material comprises yttrium as doping element or the support material comprises La and/or Ce as doping elements.
7. The catalyst for the CO2 reforming of hydrocarbons having an active composition according to any of claims 1 to 6, wherein the active composition comprises at least one noble metal-comprising promoter selected from the group consisting of Pt, Rh, Pd, Ru, Au, which is present in an amount in the range 0.01-5% by weight, more preferably in the range 0.1-3% by weight.
8. The catalyst for the CO2 reforming of hydrocarbons having an active composition according to any of claims 1 to 7, wherein the active composition comprises at least one base metal-comprising promoter selected from the group consisting of Ni, Co, Fe, Mn, Mo and W, which is present in an amount in the range 0.1-50% by weight, more preferably in the range 0.5-30% by weight and more preferably in the range 1-20% by weight.
9. The catalyst for the CO2 reforming of hydrocarbons having an active composition according to any of claims 1 to 8, wherein the active composition comprises at least further metal cation species, where the metal cation species are preferably selected from the group consisting of Mg, Ca, Sr, Ga, Be, Cr, Mn, more preferably from the group consisting of Ca and/or Mg.
10. A high-pressure process for the CO2 reforming of hydrocarbons, preferably methane, to produce synthesis gas by bringing reforming gas into contact with catalyst which comprises an iridium- comprising active composition, wherein, (i) the total content of hydrocarbons, preferably CH4, and CO2 in the reforming gas is greater than 80% by volume, preferably greater than 85% by volume and more preferably greater than 90% by volume, (ii) the pressure of the reforming gas on contacting with the active composition is in the range 5-500 bar, preferably in the range from 10 to 250 bar and more preferably in the range from 20 to 100 bar, and the temperature of the reforming gas on contacting with the active composition is in the range from 600 to 1200°C, preferably in the range from 850 to 1100°C and in particular in the range from 850 to 950°C, (iii) the GHSV in the process is in the range from 500 to 100 000 h-1, preferably in the range from 500 to 50 000 h-1, (iv) the synthesis gas produced has an H2/CO ratio in the range from 0.4 to 1.8, more preferably in the range from 0.5 to 1.4 and in particular in the range from 0.8 to 1.2.
11. The high-pressure process according to claim 10, wherein the iridium-comprising active composition is present in combination with ZrO2, where the Ir content based on ZrO2 is in the range 0.01-10% by weight, preferably 0.05-5% by weight and more preferably 0.1-1% by weight, and/or the zirconium dioxide in the zirconium dioxide-comprising support material predominantly has a cubic and/or tetragonal structure, where the proportion of cubic and/or tetragonal phase is > 50% by weight, more preferably >
70% by weight and in particular > 90% by weight.
70% by weight and in particular > 90% by weight.
12. The high-pressure process according to claim 10 or claim 11, wherein the active composition comprising the iridium-comprising ZrO2 according to claim 1 comprises at least one element from the group of the rare earths, with the rare earth element preferably being selected from the group consisting of Ce and/or La and more preferably the stabilizing element being Y.
13. The high-pressure process according to any of claims 10-12, wherein the reforming gas comprises only small amounts of H2O, with the steam/carbon ratio in the reforming gas being less than 0.2, more preferably less than 0.1 and even more preferably 0.05.
14. The high-pressure process according to any of claims 10-13, wherein the iridium-comprising active composition is provided with promoters.
15. The high-pressure process according to any of claims 10-14, wherein the reforming gas used is free of H2O.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12174258 | 2012-06-29 | ||
| EP12174258.9 | 2012-06-29 | ||
| PCT/EP2013/063455 WO2014001423A1 (en) | 2012-06-29 | 2013-06-27 | High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses |
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| CA2877956A1 true CA2877956A1 (en) | 2014-01-03 |
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| CA2877956A Abandoned CA2877956A1 (en) | 2012-06-29 | 2013-06-27 | High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses |
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| EP (1) | EP2866930A1 (en) |
| JP (1) | JP2015525668A (en) |
| KR (1) | KR20150028329A (en) |
| CN (1) | CN104619413A (en) |
| CA (1) | CA2877956A1 (en) |
| RU (1) | RU2015102717A (en) |
| WO (1) | WO2014001423A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016087976A1 (en) * | 2014-12-01 | 2016-06-09 | Sabic Global Technologies B.V. | Synthesis of trimetallic nanoparticles by homogeneous deposition precipitation, and application of the supported catalyst for carbon dioxide reforming of methane |
| WO2020015894A1 (en) | 2018-07-17 | 2020-01-23 | Omnagen Limited | Carbon dioxide conversion using combined fuel cell and electrolysis cell |
| US11618015B2 (en) | 2016-08-05 | 2023-04-04 | Korea Advanced Institute Of Science And Technology | Dry reforming catalyst using metal oxide support, and method for preparing synthetic gas by using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6212065B2 (en) * | 2015-03-02 | 2017-10-11 | 株式会社ノリタケカンパニーリミテド | Ceria zirconia composite oxide particles and production method thereof |
| CN107405602B (en) * | 2015-03-05 | 2020-08-21 | 国际壳牌研究有限公司 | Methane oxidation catalyst, method of making and method of using the same |
| ES2898788T3 (en) | 2016-08-31 | 2022-03-08 | Shell Int Research | Process for preparing a methane oxidation catalyst |
| DK3507008T3 (en) | 2016-08-31 | 2021-11-22 | Shell Int Research | PROCEDURE FOR PREPARING A METHANE OXIDIZATION CATALYST |
| CN108940381A (en) * | 2017-05-27 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of tetragonal phase zirconium oxide carrier, the catalyst containing the carrier and its application in the reaction of methane dry reforming |
| CN109718799A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
| RU2719176C1 (en) * | 2019-09-13 | 2020-04-17 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Synthetic gas production method |
| CN114713223A (en) * | 2021-01-04 | 2022-07-08 | 中国科学院大连化学物理研究所 | Method for preparing tetragonal-phase zirconia in one step, copper-based supported catalyst and application thereof |
| WO2024003354A1 (en) | 2022-07-01 | 2024-01-04 | Basf Se | Cobalt-based catalyst for the conversion of hydrocarbons to synthesis gas |
| WO2024003347A1 (en) | 2022-07-01 | 2024-01-04 | Basf Se | Cobalt- and strontium-based catalyst for the conversion of hydrocarbons to synthesis gas |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5753143A (en) | 1996-03-25 | 1998-05-19 | Northwestern University | Process for the CO2 reforming of methane in the presence of rhodium zeolites |
| WO1999064150A1 (en) | 1998-06-09 | 1999-12-16 | Idemitsu Kosan Co., Ltd. | Catalyst and process for reforming hydrocarbon |
| CZ20004900A3 (en) * | 1998-06-30 | 2001-08-15 | Shell Internationale Research Maatschappij B. V. | Catalyst and partial catalytic oxidation process by making use of two catalytically active metals |
| JP4159874B2 (en) | 2000-11-08 | 2008-10-01 | 出光興産株式会社 | Hydrocarbon reforming catalyst and hydrocarbon reforming method using the same |
| JP4409833B2 (en) * | 2001-03-29 | 2010-02-03 | 出光興産株式会社 | Hydrocarbon reforming catalyst and method for producing the same, and hydrocarbon reforming method using the catalyst |
| FR2864528B1 (en) | 2003-12-31 | 2006-12-15 | Total France | PROCESS FOR TREATING METHANE / CARBON DIOXIDE MIXTURES |
| US7309480B2 (en) | 2004-04-16 | 2007-12-18 | H2Gen Innovations, Inc. | Catalyst for hydrogen generation through steam reforming of hydrocarbons |
| GB0510514D0 (en) * | 2005-05-24 | 2005-06-29 | Johnson Matthey Plc | Steam reforming |
| WO2008135581A1 (en) * | 2007-05-08 | 2008-11-13 | Basf Se | Iridium catalysts for converting hydrocarbons in the presence of water vapour and especially for the steam dealkylation of alkyl-substituted aromatic hydrocarbons |
| CN101289166B (en) * | 2008-06-13 | 2011-09-14 | 清华大学 | Process and device for preparing H2 and CO by co-transformation of CH4 and CO2 |
-
2013
- 2013-06-27 EP EP13733270.6A patent/EP2866930A1/en not_active Withdrawn
- 2013-06-27 WO PCT/EP2013/063455 patent/WO2014001423A1/en active Application Filing
- 2013-06-27 RU RU2015102717A patent/RU2015102717A/en unknown
- 2013-06-27 CN CN201380044868.5A patent/CN104619413A/en active Pending
- 2013-06-27 KR KR1020157002325A patent/KR20150028329A/en not_active Application Discontinuation
- 2013-06-27 JP JP2015519083A patent/JP2015525668A/en active Pending
- 2013-06-27 CA CA2877956A patent/CA2877956A1/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016087976A1 (en) * | 2014-12-01 | 2016-06-09 | Sabic Global Technologies B.V. | Synthesis of trimetallic nanoparticles by homogeneous deposition precipitation, and application of the supported catalyst for carbon dioxide reforming of methane |
| US11618015B2 (en) | 2016-08-05 | 2023-04-04 | Korea Advanced Institute Of Science And Technology | Dry reforming catalyst using metal oxide support, and method for preparing synthetic gas by using same |
| WO2020015894A1 (en) | 2018-07-17 | 2020-01-23 | Omnagen Limited | Carbon dioxide conversion using combined fuel cell and electrolysis cell |
| US12068511B2 (en) | 2018-07-17 | 2024-08-20 | Omnagen Limited | Carbon dioxide conversion using combined fuel cell and electrolysis cell |
Also Published As
| Publication number | Publication date |
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| WO2014001423A1 (en) | 2014-01-03 |
| RU2015102717A (en) | 2016-08-20 |
| CN104619413A (en) | 2015-05-13 |
| KR20150028329A (en) | 2015-03-13 |
| JP2015525668A (en) | 2015-09-07 |
| EP2866930A1 (en) | 2015-05-06 |
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