CN102711979A - 包括担载的钴和低含量碱土金属的费-托催化剂,及其制备方法和在制备烃中的应用 - Google Patents
包括担载的钴和低含量碱土金属的费-托催化剂,及其制备方法和在制备烃中的应用 Download PDFInfo
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- CN102711979A CN102711979A CN2010800607423A CN201080060742A CN102711979A CN 102711979 A CN102711979 A CN 102711979A CN 2010800607423 A CN2010800607423 A CN 2010800607423A CN 201080060742 A CN201080060742 A CN 201080060742A CN 102711979 A CN102711979 A CN 102711979A
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- Prior art keywords
- catalyst
- described method
- cobalt
- alkaline
- metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 185
- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 60
- 150000001342 alkaline earth metals Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 54
- 229910017052 cobalt Inorganic materials 0.000 title claims description 53
- 239000010941 cobalt Substances 0.000 title claims description 53
- 229930195733 hydrocarbon Natural products 0.000 title claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 17
- 238000000034 method Methods 0.000 claims abstract description 133
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000012545 processing Methods 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 77
- 239000007789 gas Substances 0.000 claims description 76
- 239000011575 calcium Substances 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 40
- 229910052791 calcium Inorganic materials 0.000 claims description 39
- 239000012876 carrier material Substances 0.000 claims description 39
- 229910052783 alkali metal Inorganic materials 0.000 claims description 37
- 150000001340 alkali metals Chemical class 0.000 claims description 37
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- 239000003426 co-catalyst Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 19
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- 238000005470 impregnation Methods 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052596 spinel Inorganic materials 0.000 claims description 11
- 239000011029 spinel Substances 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical group [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- -1 cobalt (VI) ammonium salt Chemical compound 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical group CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000009970 fire resistant effect Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- 150000001869 cobalt compounds Chemical class 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- ZIZHEHXAMPQGEK-UHFFFAOYSA-N dirhenium decacarbonyl Chemical group [Re].[Re].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] ZIZHEHXAMPQGEK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 239000012779 reinforcing material Substances 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 description 25
- 239000012535 impurity Substances 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 231100000419 toxicity Toxicity 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
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- 150000003281 rhenium Chemical class 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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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
- B01J23/005—Spinels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- 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
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Abstract
一种用于制备费-托催化剂的方法,其中,在载体自身以及加工条件中最大限度地减少碱土金属的存在量,以提供碱土金属的含量小于2000ppm的催化剂。
Description
技术领域
在商业上,用含有活性金属铁(Fe)或钴(Co)的催化剂催化费-托(Fischer-Tropsch,FT)反应,费-托反应用于合成气体的转化,合成气体是CO和氢气的混合物,事实上还可能含有惰性组分(如,CO2、氮气和甲烷)。但是,铁催化剂表现出显著的变换反应(shift reaction),除CO2之外,从CO和蒸汽生成更多的氢气。因此,铁催化剂最适用于H2/CO比(<1.2)较低的合成气体,例如,来自煤或其它重质烃原料的合成气体,其中的比例大大低于费-托反应的消耗率(2.0-2.1)。
本发明涉及钴基催化剂,特别涉及具有担载的钴基(supported Co-based)催化剂。通过费-托合成可制备多种产物,但使用担载的钴的情况下,主要产物为可进一步升级为柴油和石化石油脑等产物的长链烃。副产物可包括烯烃和含氧化物。
背景技术
一般来说,活性费-托金属分散在固态多孔载体上。因此,一大部分的Co暴露为可发生反应的表面原子。载体可为氧化铝、二氧化钛或氧化硅,但一般来说,其他氧化物,例如,氧化锆、氧化镁、氧化硅-氧化铝、各种铝酸盐、沸石及碳,以及它们的混合物都曾被使用过。有时载体含有改性组分的成分,例如,硅、镧、钛和锆的化合物。
为了提高催化剂的性能,例如,在进行费-托合成之前,通常添加不同的助催化剂(铼、钌、铂、铱及其他过渡金属均可有益),来促进氧化钴还原为钴金属。另外,助催化剂可为碱金属或碱土金属。已经发现,一定量的碱金属(K、Na、Cs、Rb、Li、Cs)对钴担载的催化剂的催化性能有显著的影响。US4880763(Eri等人)报道了,在催化剂中添加碱可增加产物的平均分子量,通过Schulz-Flory中α值的增加来表明。但是,随着碱含量的增加,其活性降低。因此,对于任何特定情况,都存在一个平衡所需平均产物分子量与催化剂活性的最佳碱的含量。在WO2006/010936A1中,Rytter和Eri描述了Na对钴催化剂的影响。发现在0-500ppm,对活性有明显的负面影响。
Luo和Davis(Fischer-Tropsch synthesis:Group II alkali-earth metal promotedcatalysts,Appl.Catal.A 246(2003)171)比较了在连续搅拌釜式反应器(Continuous Stirred Tank Reactor,CSTR)中,碱土金属(其中的钙)与铁基催化剂对费-托合成性能上的影响。他们发现,作为助催化剂的钙的添加对费-托合成和水煤气变换反应(water-gas shift reaction)的活性具有负面影响。但是,Ca产生的FTS阿尔法值(链增长几率)比无助催化剂的催化剂高。
在工业生产中,在将合成气体(合成气;可能含有其他气体,例如,CO2、CH4、轻质烃、蒸汽、N2等的H2和CO的气体混合物)转化成烃的费-托工艺中使用费-托催化剂。合成气体可以多种方式制备,例如,自热重整(autothermalreforming,ATR)、甲烷蒸汽转化(MSR)(有时也称为管式转化)、部分氧化(POx)、催化部分氧化(CPO)和气化。后者主要用于除天然气之外的其他原料,一般为煤或生物质。还可对这些工艺进行组合和优化,如,组合转化、热交换转化、紧凑式转化和气热转化。
合成气生成后,在余热锅炉(WHB)(也称为过程气体冷却器)中对气体进行频繁冷却,且可使用过热器从气体中进一步提取能量,以提高所生成的蒸汽的温度。在气体进入费-托反应器之前,可使用保护床清除气体中的杂质(例如,氨、硫和各种羰基化合物)。在合成气体的生成和清除过程中,通常使用耐火或陶瓷材料。这些材料可由各种金属氧化物的混合物组成。目前已经发现的是必须特别谨慎的使用这些材料的组合。
在催化剂手册(Catalyst Handbook(催化剂手册),第二版,M.V.Twigg,编者,Wolfe Publishing,,London(伦敦),1989)中,第77-81页对杂质的毒性进行了描述。但是,没有描述钙对加氢裂化催化剂的影响,而仅描述了钠的影响。此外,也未描述从合成气或气体净化段的材料的携带污染率(carryover)。目前已经发现的是,必须十分注意避免这种携带污染率的发生。通过存在的蒸汽可增强通过合成气的携带污染率。在2008年4月20-23日于莫斯科进行的2008氮+合成气大会的纪要中,卡塔尔化肥公司(Qatar Fertilizer Company)的R.Stevens和U.R.Desai对生成合成气所使用的特定材料进行了说明。这些材料包括用于二段转化炉(ATR)上部的含有0.7wt%NaO的氧化铝块、铝酸钠、NaAl11O18和含有17wt%CaO的陶瓷内衬(环形)。
发明内容
总体来讲,本发明的目的在于提供一种改进的担载的钴基费-托催化剂。此外,本发明的目的在于避免XTL设备运行过程中发生的催化剂污染,XTL为GTL(天然气制油)、BTL(生物质制油)或CTL(煤制油)。污染会导致催化性能的降低,特别是活性下降,从而需要在其他必要之前更换催化剂。
根据本发明的一个方面,提供了一种用于费-托合成反应的催化剂的制备方法,包括以下步骤:
采用选自碱土金属的含量小于1000ppm的氧化铝、二氧化钛、氧化锆、沸石、含碳材料以及它们的混合物的初始多孔载体材料;
用钴源浸渍初始载体材料,这将有助于在最终催化剂中的附加碱土金属含量小于1000ppm;以及
在至少200℃的温度下热处理浸渍后的载体材料,以获得氧化钴催化剂;
由此,最终催化剂的碱土金属含量小于2000ppm。
钴催化剂的制备需要用钴前体溶液浸渍载体,两者均可为杂质来源。水是常选的溶剂。水通常包含大量的矿物质,如钙、镁和钠。为了符合医疗、药理、化工应用的要求,通常需要对这些元素进行控制。方法包括蒸馏、过滤、水软化、反渗透、超滤、分子汽提(molecular stripping)、去离子作用和碳处理。
总体来说,本发明针对于使得费-托催化剂不受有害组分(如,碱金属和碱土金属)影响下的使用。
已经证明,催化剂包含的碱土金属或碱金属的量应为10-2000ppm,优选为20-1000ppm,更优选为20-400ppm。因此,重要的是,原料气中的这些金属的含量相应地较低。可进行简化计算,假定平均运行时间为10000小时(即,更换催化剂之间的总时间为20000小时),每小时每千克催化剂的烃产物的产量为1.0kg,通过费-托催化剂吸收了所有碱金属或碱土金属。惊人地,这意味着合成气原料中的碱金属或碱土金属的重量含量应低至100ppb(相对于合成气中的千克CO),以使催化剂中的含量低于2000ppm。换句话说,在未转化气体的循环操作中,合成气体(通常称为补给气体)中包含的碱金属或碱土金属的平均含量应为0.1-100ppb,优选为0.5-50ppb,更优选为0.5-20ppb。
这种碱金属或碱土金属的毒性通常作为运行中的故障或扰乱产生,在较短时间(如10-1000小时)内,催化剂活性表现出急剧下降。因此,在这段时间内具有增强毒性的碱金属或碱土金属的含量应保持在5ppb-100ppm之间,优选10ppb-50ppm之间,更优选10ppb-20ppm之间。此外,除工艺用水和补给水的含量之外,选择任何陶瓷内衬(ceramic lining)、转化炉催化剂(reformercatalyst)和保护床材料的期间应严格控制碱金属和碱土金属。
通过控制碱金属和碱土金属的量来实现性能的提高。碱土金属为那些元素周期表中第二族中的元素,且本发明特指钙和镁,以及第一族中的钠和钾。
优选地,热处理步骤为在200-600℃温度下的煅烧步骤。载体材料可选自氧化铝、氧化硅、二氧化钛、氧化锆(zicinia)、氧化镁和沸石及类沸石材料(zeolitelike materials)、多种形式的碳包括任何无定形或结晶形式的碳纳米纤维和碳管,及其它们的混合物和反应产物,以及可选地改性。氧化铝可为γ-氧化铝、任何过渡型氧化铝、α-氧化铝、勃姆石、氢氧化铝或它们的混合物。
用于载体的氧化铝的最优选的制备方法为醇盐法,因为该方法可提供高纯度。还可采用沉淀法,如果采用该方法,应用过量的水多次洗涤沉淀氧化铝,以去除各种杂质(如碱金属、碱土金属和硫酸盐)。所使用的水中上述杂质的量不应高于20ppm。洗涤之后,优选对氧化铝进行干燥,在200-600℃的优化温度下进行煅烧。
优选地,初始氧化铝载体材料包括稳定剂,稳定剂优选包括镧。
浸渍步骤可包括熔融浸渍、离子交换、沉积/沉淀,或更优选地,初湿浸渍法。在采用初湿法的情况下,溶剂可为有机溶剂,或更优选水。可有一个以上的浸渍步骤。
人们惊奇地发现,一些碱土金属对使用钴催化剂的费-托合成产生不良影响。特别地,采用初湿浸渍的量为100ppm(mg/l)的Ca对催化剂的活性具有明显的负面影响。大量的钙(200-1000ppm)具有很强的不利影响。这些量对于许多生水(自来水)源来说并非异常。例如,硬水中含有80-120ppm的Ca。
在浸渍以及本发明任何其他过程步骤中使用水时,水通过某种可确保碱土金属的限度符合规定的方式进行处理。优选地,水为蒸馏水或去离子水。
优选地,浸渍步骤包括初湿处理,在初湿处理中,将钴金属的水溶液与改性氧化铝载体材料混合,直到充满孔隙,随后在煅烧之前,干燥浸渍载体材料。优选地,浸渍所使用的水溶液的量比所测量的催化剂载体的孔隙体积大0.2-2倍。
优选地,该方法还包括用助催化剂对初始氧化铝载体材料进行浸渍或共浸。优选地,助催化剂包括铂或铼。铂助催化剂的优选0.001-0.5wt%,更优选0.01-0.1wt%。对于Re,优选0.01-5wt%,更优选0.1-1.0wt%。
优选地,助催化剂为铼时,铼源优选选自高铼酸(HReO4)、高铼酸铵、卤化铼和羰基铼。
钴源可选自硝酸钴(Co(NO3)2)、碳酸钴、钴(VI(hexa))铵盐和有机钴化合物。在煅烧步骤之后,优选活化氧化铝担载的催化剂材料。
优选地,在80-120℃的温度下,干燥浸渍载体。优选在200-600℃的温度下进行后续的煅烧。
在煅烧步骤之后,优选活化氧化铝担载的催化剂材料。
活化步骤可包括将基本一部分的催化活性金属化合物还原成金属,其可通过用还原气体(如氢气和/或一氧化碳,可选的与惰性气体混合)处理催化剂材料来进行。还原可在250-500℃,优选300-450℃的活化温度下进行。
在用钴源浸渍载体之前,可对载体材料进行改性。这可通过用能与载体材料形成尖晶石化合物(通式(X)(Y)2O4,其中X和Y为阳离子)的二价金属源先浸渍载体材料来完成。
在热处理之后向氧化铝中添加二价金属化合物可生成尖晶石化合物,随后尖晶石化合物可构成一部分或全部载体。二价金属可包括钴、镍、镁或锌,但也可使用其他能形成尖晶石的元素。热处理可在高达900℃的温度下进行,以便于生成尖晶石,但对于特定用途,900-1400℃的温度,一般950-1250℃是有利的。
因此,二价金属优选为锌、钴、镁或镍,以及可包括对应硝酸盐的合适源。在使用合适溶剂的一个或多个浸渍步骤中散开(deployed)二价金属,其中合适溶剂可为有机溶剂,或更优选水。
如同上述后续钴浸渍步骤一样,优选地,溶剂中的碱土金属含量小于20ppm,且优选为蒸馏水或去离子水。优选地,二价金属源使得在氧化钴催化剂中的附加碱土金属的含量小于500ppm,优选小于300ppm,更优选小于100ppm。
在浸渍之后,干燥、清洗(如果需要)载体材料,并在一个或多个步骤中至多为600℃的温度下煅烧,以基本分解二价金属源,以形成二价金属氧化物,或其化合物。此后,可在600-900℃的温度下进行高温煅烧,以形成尖晶石。如果要求载体的强度特别高,最后的煅烧甚至可在更高温度(900-1400℃),优选950-1250℃下进行。
如上所述,用二价金属进行的这种处理生成的改性载体材料,随后可用钴浸渍。这种高温处理会降低载体的孔隙率,以使改性载体的表面积低于80m2/g,一般为30-70m2/g,孔隙体积小于0.5ml/g,一般为0.15-0.4ml/g。虽然较高的表面积有利于钴的担载和分散、较高的孔隙体积有助于浸渍,但与初始载体相比,改性载体的物理和化学鲁棒性大大增加,所获得的值完全可以接受。
还需要最大程度的降低最终催化剂中存在的碱金属,碱金属为元素周期表中第一族中的元素。因此,优选地,载体材料中碱金属的含量小于200ppm,处理过程中使用的任何水中碱金属的含量小于50ppm,由此,最终催化剂中碱金属的含量小于250ppm。
本发明还涉及根据本发明的方法制备的催化剂材料。
本发明还延伸至在费-托合成反应中这种催化剂的使用,例如浆态鼓泡床反应器中进行。这种情况下,H2和CO被提供给反应器中浆液,该浆液包括液体中的悬浮的催化剂,该液体包括H2和CO的反应产物,该催化剂通过提供浆液的气体的运动至少部分的在浆液中维持悬浮。
本发明还涉及一种生成烃的方法,包括:在反应器中,在担载的钴基催化剂的存在下,对H2和CO气体进行费-托合成反应,其中,将包括H2和CO的补给合成气体从合成气发生器中导入到系统中,所述补给合成气体包含的碱土金属或碱金属的含量小于100ppb。
碱土金属和/或碱金属的含量可为例如0.1-100ppb,优选为0.5-50,更优选为0.5-20ppb。碱土金属可为钙,且碱金属可为钠。
优选地,该反应为三相反应,其中,反应物为气态,产物至少部分为液态,催化剂为固态,并且该反应在浆态鼓泡床反应器中进行。这种情况下,H2和CO可被提供给在反应器中的提供浆液,该浆液包括含有H2和CO的反应产物的液体中的悬浮的催化剂,该催化剂通过提供浆液的气体的运动至少部分的在浆液中维持悬浮。
优选地,在合成气体进行费-托合成反应之前,将补给合成气体通过材料保护床,该材料保护床用于吸收合成气体流中碱金属和碱土金属的组分。优选地,保护床包括金属氧化物,如氧化铝、氧化硅、氧化硅-氧化铝或沸石,或镁或氧化锌,或担载在金属氧化物材料上的废催化剂或失活催化剂。另外,保护床包括活性碳或碳纳米纤维或碳管。
一般来说,反应温度为190-250℃,优选200-230℃。一般来说,反应压力为10-60巴,优选15-30巴。
一般来说,提供给费-托合成反应器的气体的H2/CO比为1.1-2.2,优选1.5-1.95。一般来说,反应器中的表观气速(superficial gas velocity)为5-60cm/s,优选20-40cm/s。
随后可对费-托合成反应的产物进行后处理。后处理可包括脱蜡、加氢异构化、加氢裂化、及其组合。
本发明还涉及一种用于生成上述烃的方法,其中,催化剂根据本发明的方法进行制备。上述方法的优选和可选的特征也适用于本发明的该实施例。
通过使用包含较低浓度的碱土金属和/或碱金属的原料,来控制合成气体中碱土金属或碱金属的含量。在生产合成气体中,水或蒸汽可作为反应物导入或再导入,且采用选自蒸馏、过滤、水软化、反渗透、超滤、分子汽提、去离子作用和碳处理的一个或多个过程进行清洁。
在合成气体生产、运输以及费-托转化中,暴露在工艺流中的反应器、管道和设备的内衬可由不释放碱土金属或碱金属的材料制成。反应器的内衬可为耐火或陶瓷内衬,或一种耐酸钢。
烃类生产工厂中,在开始烃生产之前,在合成气体生产和运输以及其转化成烃中,所涉及暴露在工艺流中的反应器、催化剂、以及管道或其他设备的表面可通过从这些表面上去除碱金属或碱土金属物质来进行清洁。例如,可使用蒸汽或水清洁所述表面。
附图说明
本发明可以多种方式实施,下文将在以下非限制性示例中对其进行说明,其中:
图1显示了A、B和C系列中催化剂的图形数据。
具体实施方式
催化剂的制备
对于所有系列的催化剂,制备方法中都使用高纯度的化学品和溶剂。
A系列
假定还原催化剂中的钴被完全还原的情况下计算,A系列催化剂中的额定含量为:20wt%的Co、0.5wt%的Re和0-1000ppm的Ca。通过XRF或ICP确定的实际金属担载可相差10%,如,对于额定担载为20wt%的催化剂,还原催化剂总重量中钴的实际含量可在18与22wt%之间变化。通过用含有硝酸钴六水合物、高铼酸和硝酸钙四水合物的水溶液,一步初湿共渍(incipient wetnessco-impregnation)γ-Al2O3载体(BET表面积=182m2/g,孔隙体积=0.73cm3/g)来制备催化剂。
在110℃的温度下,干燥新制备的催化剂3个小时。在干燥期间,第一个小时内每15分钟搅拌一次催化剂,后两个小时内每30分钟搅拌一次。浸渍和干燥之后,在300℃下,煅烧样品16个小时。
B系列
假定还原催化剂中的钴被完全还原的情况下计算,B系列催化剂中的额定含量为:20wt%的Co、0.5wt%的Re和0-1000ppm的Ca。
通过用含有硝酸钙四水合物的水溶液,一步初湿浸渍γ-Al2O3载体(BET表面积=182m2/g,孔隙体积=0.73cm3/g)来制备载体。在110℃的温度下,干燥载体3个小时。在干燥期间,第一个小时内每15分钟搅拌一次载体,后两个小时内每30分钟搅拌一次。浸渍和干燥之后,在900℃下,煅烧改性载体10个小时。
通过用含有硝酸钴六水合物和高铼酸的水溶液,一步初湿共浸含Ca载体(BET表面积=107m2/g,孔隙体积=0.68cm3/g)来制备催化剂。以与A系列相同的方式对催化剂进行干燥。最后在300℃下,煅烧催化剂16个小时。
C系列
假定还原催化剂中的钴被完全还原的情况下计算,C系列催化剂中的额定含量为:20wt%的Co和0.5wt%的Re。另外,催化剂还含有来自氧化铝生成过程的200或700ppm的Ca。
通过用含有硝酸钴六水合物和高铼酸的水溶液,一步初湿共浸含Ca载体(BET表面积=107m2/g,孔隙体积=0.68cm3/g)来制备催化剂。在110℃的温度下,干燥载体3个小时。在干燥期间,第一个小时内每15分钟搅拌一次载体,后两个小时内每30分钟搅拌一次。最后在300℃下,煅烧催化剂16个小时。
D系列
假定还原催化剂中的钴被完全还原的情况下计算,D系列催化剂中的额定含量为:20wt%的Co、0.5wt%的Re和0或500ppm的Ca。通过用含有硝酸钴六水合物、高铼酸和硝酸钙四水合物的水溶液,一步初湿共浸SiO2载体来制备催化剂。浸渍、干燥和煅烧程序与A系列相同。
E系列
假定还原催化剂中的钴被完全还原的情况下计算,E系列催化剂中的额定含量为:12wt%的Co、0.3wt%的Re和0或400ppm的Ca或Mg。在所有情况下,催化剂载体基本为Ni-尖晶石。通过对初始γ-氧化铝载体进行硝酸镍水合物的一步初湿浸渍,随后通过在400-500℃内的固定温度下干燥和煅烧,得到在氧化镍中氧化铝形式的载体。随后在1000-1200℃下的回转煅烧炉中,高温处理该氧化物载体10-30分钟,得到改性载体,且一项分析显示,Ca的含量为29ppm,Mg为18ppm,相比随后浸渍过程中添加的400ppm,这两个量较小。改性载体的孔隙体积为0.23ml/g,表面积为50m2/g。
通过对改性载体在水溶液中进行钴和铼盐共浸,且随后进行干燥和煅烧来制备催化剂,且得到氧化物形式的催化剂。随后通过硝酸盐溶液的初湿浸渍将Ca或Mg小心地添加到该氧化物催化剂中,随后在110℃下干燥3个小时。干燥期间,第一个小时内每15分钟搅拌一次载体,后两个小时内每30分钟搅拌一次。最后在300℃下,煅烧并入有Mg或Ca的催化剂16个小时。
氢气的化学吸附
在40℃下,用Micromeritics ASAP 2010装置记录氢气的吸附等温线。在350℃下,氢气氛中原位还原样品16个小时。温度从室温以1K/min增加到350℃。以20至510mmHg的压力间隔对吸附等温线进行记录。通过将等温线的直线部分外推为零压力而进行计算化学吸附氢的量。为了计算钴的表面积,假定两个钴位置被一个氢分子覆盖,且一个钴原子的面积为6.62-10-22m2。
催化剂试验
在具有四个平行的固定床反应器的实验装置中进行固定床试验。将粒级为53-90微米的1g催化剂颗粒与20g惰性SiC混合。在加入比例为2∶1的氢气和CO的混合物之前,350℃下,在氢气中原位还原16个小时。在210℃和20巴的总压力下对蒸汽操作20个小时之后,调整空间速度,以在100小时之后获得45-50%的CO推定的转化率。这对于在相同转化率下进行选择性和活性的比较是非常重要的,因为反应中生成的蒸汽量对催化剂性能有深刻影响。
结果
A系列
表1给出了A系列的催化剂的费-托合成性能。这种情况下,将Ca小心地添加到催化剂中,并将结果与不添加钙的情况相比较。显而易见的是,随着钙含量的增加,相对活性大大降低。1000ppmCa的添加(0.1wt%)可将活性降低50%。但是,在实验误差范围内,非原位测量的所有催化剂的钴表面积(m2/g催化剂)相似。Ca不仅影响催化剂的相对活性,还影响C5+的选择性;如表1所示,Ca的添加会降低C5+的选择性。因此,Ca对活性和选择性均有不利影响。
表1.A系列催化剂的性质和催化数据。总体包含20wt%的Co、0.5wt%的Re和0-1000ppm的Ca。Ca与钴和铼共浸渍。
催化剂 | 钙含量(ppm) | 钴表面积(m2/g) | 相对活性 | 相对C5+选择性 |
A1 | 0 | 12.4 | 1.48 | 0.929 |
A2 | 100 | 1.30 | 0.914 | |
A3 | 500 | 0.92 | 0.918 | |
A4 | 1000 | 13.2 | 0.75 | 0.910 |
如上所述,钙可来源于补给合成气体中的杂质,且明显地,这种杂质的沉积将对催化剂性能产生负面影响。在表2中,假定操作持续10000小时(即,更换催化剂之间的时间总共为20000小时),生产率为1.0kg HC/每kg催化剂,合成气体中存在的钙完全被催化剂吸收。如表2所示,合成气体中50ppbCa的浓度使活性下降了50%。
表2.A系列催化剂的性质和催化数据。模拟从合成气体吸收钙的情况。总体含有20wt%Co、0.5wt%Re。
B系列
表3显示了B系列催化剂的催化数据。对于这些催化剂,将钙添加到载体中。在钙前体溶液浸渍γ-Al2O3载体后,干燥样品,随后在1173K下煅烧10个小时。因此,大多数钙都可能以铝酸钙的形式存在。但是,如同A系列催化剂的情况,钙对催化剂的活性不利。添加Ca时,C5+选择性也会降低。
表3.B系列催化剂的性质和催化数据。总体包含20wt%的Co、0.5wt%和0-1000ppm的Ca。Ca添加到载体中。
C系列
C系列催化剂的钙含量来自制备过程。因此,在这些催化剂中不添加外部的Ca。与A和B系列相似,随着钙浓度的增加,活性和C5+选择性降低(表4)。
表4.C系列催化剂的性质和催化数据。总体包含20wt%Co、0.5wt%Re和0-700ppm Ca。Ca为氧化铝中固有,含量为200至700ppm,将结果与氧化铝中无Ca存在的情况相比较。
图1中的图为A系列至C系列中催化剂测试所获得的数据的图示,显示了催化剂活性如何随着试验催化剂中钙浓度的增加而降低。C1系列测试结果中获得的C1催化剂(Ca浓度为200ppm)的活性值同等较低可能是由催化剂载体中钙的固有分散和其他杂质的未知性质和浓度造成的。
D系列
表5给出了D系列催化剂的费-托合成性能。通过与钴和铼在氧化硅载体上共浸渍,小心地将Ca添加到催化剂中,并将结果与未添加钙的情况相比较。同样,对于这些催化剂,相对活性随着钙含量的增加大大降低。Ca的添加也会降低C5+选择性。但是,通过比较表1和表5中500ppm Ca的结果,惊奇的是,氧化铝比氧化硅对碱土金属(尤其是钙)的毒性具有更大的鲁棒性。因此,相比氧化硅,氧化铝是更优选的载体材料。
表5.D系列催化剂的性质和催化数据。总体包含20wt%Co、0.5wt%Re和0-500ppm Ca。在氧化硅载体上将Ca与钴和铼共浸渍。
催化剂 | 钙含量(ppm) | 相对活性 | 相对C5+选择性 |
D1 | 0 | 1.36 | 0.957 |
D2 | 500 | 0.44 | 0.951 |
E系列
表6给出了E系列催化剂的费-托合成性能。这种情况下,载体基本为Ni-尖晶石,且通过在水溶液中共浸渍钴和铼盐,随后进行干燥和煅烧而制备催化剂,生成氧化物形式的催化剂。然后,通过浸渍将Ca或Mg小心地添加到该氧化物催化剂中。同样,对于这些催化剂,相对活性随着钙或镁含量的增加大大降低,但对于镁,程度较低。
注意,向催化剂添加杂质元素与将杂质通过补给合成气体引入、随后由催化剂吸收的情况(见表2,合成气体中含有25ppb钙)非常相似。
表6.D系列催化剂的性质和催化数据。总体包含12wt%Co、0.3wt%Re和0-500ppm Ca或Mg。在氧化物催化剂上对后者进行浸渍。
催化剂 | 钙或镁含量(ppm) | 相对活性 | 相对C5+选择性 |
E1 | 0 | 0.96 | 0.915 |
E2 | 400(Ca) | 0.49 | 0.894 |
E3 | 400(Mg) | 0.76 | 0.908 |
将钙作为催化剂的毒物添加时,需要钙分布在催化剂的有效表面。对于含有500ppm Ca的Co/Re/γ-氧化铝催化剂,该面积为135m2/g,而对于Co/Re/NiAL2O4催化剂,该面积为46m2/g。因此,可以预计,对后一种催化剂的毒性影响更强,例如,强135/46=2.9倍。但是,相比400ppm Ca使Co/Re/NiAL2O4的活性降低41%,500ppm Ca使得Co/Re/γ-氧化铝的活性降低37%,换句话说,有中等差异。因此,我们观察到,对于给定的表面积,含有尖晶石载体的催化剂对于毒性具有更大的鲁棒性。这一观点同样适用于,如果我们用钴担载的不同(20和12%)或钴表面积不同的两种催化剂来替代总表面积的不同的两种催化剂。再次说明,尖晶石催化剂对于每Co担载的的钙毒性具有更大的鲁棒性。
Claims (95)
1.一种用于制备费-托合成反应的催化剂的方法,包括以下步骤:
采用选自碱土金属的含量小于1000ppm的氧化铝、二氧化钛、氧化锆、沸石、含碳材料及它们的混合物的初始多孔载体材料;
用钴源浸渍所述初始载体材料,这有助于在最终催化剂中的附加碱土金属含量小于1000ppm;以及
在至少200℃的温度下热处理所述浸渍后的载体材料,以获得氧化钴催化剂;
由此,所述最终催化剂的碱土金属含量小于2000ppm。
2.根据权利要求1所述的方法,其中,所述热处理的步骤为在200-600℃温度下的煅烧步骤。
3.根据权利要求1或2所述的方法,其中,在所述热处理的步骤之前,在至少100℃的温度下,所述浸渍后的载体材料进行干燥步骤。
4.根据前述权利要求中任一项所述的方法,其中,所述热处理在多个步骤中进行。
5.根据前述权利要求中任一项所述的方法,其中,所述载体材料为多种形式的碳,包括任何无定形或结晶形式的碳纳米纤维和碳管,以及它们的混合物和反应产物,以及可选地改性或与其他载体材料混合,所述其他载体材料还可选地包括粘合剂。
6.根据权利要求1-4中任一项所述的方法,其中,所述载体材料为γ-氧化铝、任何过渡型氧化铝、α-氧化铝、勃姆石、氢氧化铝或它们的混合物。
7.根据权利要求1-4或6中任一项所述的方法,其中,所述载体材料为氧化铝,并通过沉淀法或醇盐法制备。
8.根据权利要求6或7所述的方法,其中,所述载体材料为γ-氧化铝,并通过将温度加热到400-800℃而制备。
9.根据前述权利要求中任一项所述的方法,其中,所述初始载体材料的碱土金属含量小于500ppm。
10.根据权利要求1-8中任一项所述的方法,其中,所述初始载体材料的碱土金属含量为5-1000ppm,优选为10-500ppm,更优选为10-200ppm。
11.根据前述权利要求中任一项所述的方法,其中,所述碱土金属为钙或镁。
12.根据前述权利要求中任一项所述的方法,其中,在所述初始载体材料中并入稳定剂。
13.根据权利要求12所述的方法,其中,所述稳定剂为镧。
14.根据前述权利要求中任一项所述的方法,其中,所述浸渍的步骤包括初湿处理。
15.根据权利要求14所述的方法,其中,在所述初湿处理中,将钴金属化合物的水溶液与所述载体材料混合,直到充满孔隙,随后在煅烧之前,干燥所述浸渍后的载体材料。
16.根据权利要求15所述的方法,其中,所述浸渍使用的水溶液的量是所述催化剂载体测得的孔隙体积的0.05-2倍。
17.根据前述权利要求中任一项所述的方法,其中,钴源选自硝酸钴(Co(NO3)2)、碳酸钴、钴(VI)铵盐和有机钴化合物。
18.根据权利要求15-17中任一项所述的方法,其中,使用的水为蒸馏水或去离子水。
19.根据前述权利要求中任一项所述的方法,包括用助催化剂浸渍或共浸所述初始氧化铝载体材料。
20.根据权利要求19所述的方法,其中,所述助催化剂包括铂或铼。
21.根据权利要求20所述的方法,其中,所述氧化物催化剂中的所述助催化剂为铂,含量为0.001-0.5wt%,优选为0.01-0.1wt%。
22.根据权利要求20所述的方法,其中,所述氧化物催化剂中的所述助催化剂为铼,含量为0.01-5wt%,优选为0.1-1.0wt%。
23.根据权利要求20所述的方法,其中,所述助催化剂为铼,且铼源选自高铼酸(HReO4)、高铼酸铵、卤化铼和羰基铼。
24.根据权利要求14-18中任一项所述的方法,其中,在80-120℃的温度干燥所述浸渍后的载体材料。
25.根据权利要求19-24中任一项所述的方法,其中,在钴和所述助催化剂浸渍的步骤中,使得在所述氧化钴催化剂中碱土金属的含量小于1000ppm。
26.根据权利要求19-25中任一项所述的方法,其中,在钴和所述助催化剂浸渍的步骤中,使得在所述氧化钴催化剂中碱土金属的含量在5-1000ppm之,优选10-500ppm,更优选10-200ppm。
27.根据前述权利要求中任一项所述的方法,其中,在所述煅烧步骤之后,活化所述氧化铝担载的催化剂材料。
28.根据权利要求27所述的方法,其中,所述活化的步骤包括将基本一部分的催化活性金属化合物还原成金属,且所述步骤通过用还原气体,例如氢气和/或一氧化碳,可选地将还原气体与惰性气体混合处理所述催化剂材料来进行。
29.根据权利要求28所述的方法,其中,所述还原在250-500℃,优选300-450℃的活化温度下进行。
30.根据前述权利要求中任一项所述的方法,其中,在用钴源浸渍所述载体之前,所述载体材料用能形成尖晶石的二价金属处理以进行改性,以与所述载体材料形成尖晶石。
31.根据前述权利要求中任一项所述的方法,其中,在钴浸渍步骤之前,所述多孔载体材料用二价金属处理以进行改性,所述改性载体材料的比表面积低于80m2/g,优选为30-70m2/g。
32.根据前述权利要求中任一项所述的方法,其中,在钴浸渍步骤之前,所述多孔载体材料用二价金属处理以进行改性,所述改性载体材料的孔隙体积低于0.5ml/g。
33.根据权利要求30-32中任一项所述的方法,其中,所述二价金属为镍或锌,或它们的混合物。
34.根据权利要求33所述的方法,其中,镍源为硝酸镍,和/或锌源为硝酸锌。
35.根据权利要求30-34中所述的方法,其中,在使用溶剂的一个或多个浸渍步骤中散开所述二价金属,由所述浸渍步骤使得所述氧化钴催化剂的碱土金属的含量小于500ppm。
36.根据权利要求35所述的方法,其中,在使用溶剂的一个或多个浸渍步骤中散开所述二价金属,由所述浸渍步骤使得所述氧化钴催化剂的碱土金属的含量5-500ppm,优选5-300ppm,更优为5-100ppm。
37.根据权利要求35或36所述的方法,其中,所述溶剂为蒸馏水或去离子水。
38.根据权利要求35-37中任一项所述的方法,其中,所述浸渍步骤包括初湿处理。
39.根据权利要求35-37中任一项所述的方法,其中,所述浸渍步骤包括沉淀/沉积步骤。
40.根据权利要求30-40中任一项所述的方法,其中,所述二价金属并入载体材料中,以形成尖晶石,从而形成改性载体材料。
41.根据权利要求40所述的方法,其中,所述载体材料作为悬浮前体分散在液体媒介物中,将能与载体前体形成尖晶石化合物的二价金属源添加到液体中,随后所述载体材料的前体形成并入有二价金属源的多孔固体颗粒,从而生成改性载体材料。
42.根据权利要求41所述的方法,其中,所述固体颗粒通过喷雾干燥生成。
43.根据权利要求30-42中任一项所述的方法,其中,对并入有二价金属的所述载体材料进行清洗、干燥以及在至多为600℃的温度下煅烧,以分解二价金属化合物源,从而基本生成二价金属氧化物。
44.根据权利要求43所述的方法,其中,对所述改性载体材料在600-900℃的高温下煅烧以形成尖晶石化合物。
45.根据权利要求43或44所述的方法,其中,对所述改性载体材料进行高温煅烧以增强材料,所述高温为900-1400℃,优选950-1100℃。
46.根据权利要求38-45中任一项所述的方法,其中,所述形成改性载体材料的过程使得所述氧化钴催化剂中碱土金属的含量小于1000ppm。
47.根据权利要求46所述的方法,其中,所述形成改性载体材料的过程使得所述氧化钴催化剂中碱土金属的含量在10-1000ppm,优选20-500ppm。
48.一种用于费-托合成反应的催化剂,所述催化剂根据前述权利要求任一项所述的方法制备,并且包括多孔载体材料,活性钴含量占所述催化剂的总重量的5-60wt%,假定钴完全还原为钴金属,碱土金属含量小于1000ppm。
49.根据权利要求48所述的催化剂,其中,所述载体材料为γ-氧化铝,可通过添加氧化铝尖晶石,例如镍氧化铝尖晶石进行改性。
50.根据权利要求48或49所述的催化剂,进一步包括作为稳定剂的镧,其中,基于所述催化剂的重量,所述镧的含量可至多为3wt%。
51.根据权利要求48-50中任一项所述的催化剂,其中,所述钴的含量为10-30wt%。
52.根据权利要求48-51中任一项所述的催化剂,进一步包括作为助催化剂的铼,其中,基于所述催化剂的重量,所述助催化剂的含量可为0.01-5wt%。
53.根据权利要求48-52中任一项所述的催化剂,所述催化剂具有至少为0.2ml/g的孔隙体积,和/或至少为20m2/g的比表面积。
54.一种用于生成烃的方法,包括:在反应器中,在担载的钴基催化剂的存在下,H2和CO气体进行费-托合成反应,其中,在所述合成反应中导入包括H2和CO的补给合成气体,且所述补给合成气体包含小于100ppb的碱土金属或碱金属。
55.根据权利要求54所述的方法,其中,所述补给合成气体包括0.1-100ppb,优选0.5-50,更优选0.5-20ppb的碱土金属或碱金属。
56.根据权利要求54或55所述的方法,其中,所述碱土金属为钙,和/或所述碱金属为钠。
57.根据权利要求54-56中任一项所述的方法,其中,在所述合成气体进行费-托合成反应之前,将所述补给合成气体通过材料保护床,所述材料保护床用于吸收所述合成气体流中碱金属和碱土金属的组分。
58.根据权利要求57所述的方法,其中,所述保护床由金属氧化物组成。
59.根据权利要求58所述的方法,其中,所述金属氧化物选自氧化铝、氧化硅、氧化硅-氧化铝或沸石。
60.根据权利要求58所述的方法,其中,所述金属氧化物选自氧化镁或氧化锌。
61.根据权利要求57所述的方法,其中,所述保护床材料选自活性碳或碳纳米纤维或碳管。
62.根据权利要求58所述的方法,其中,所述保护床材料由担载在金属氧化物材料上的废催化剂或失活催化剂组成。
63.根据权利要求62所述的方法,其中,所述金属氧化物材料为含氧化铝的载体。
64.根据权利要求57-63中任一项所述的方法,其中,所述保护床材料具有较高的比表面积。
65.根据权利要求64所述的方法,其中,所述比表面积高于75m2/g,优选高于150m2/g。
66.根据权利要求57-65中任一项所述的方法,其中,所述保护床材料的孔隙率高于0.15cm3/g,优选高于0.3cm3/g。
67.根据权利要求54-66中任一项所述的方法,其中,所述反应为三相反应,其中,所述反应物为气态,所述产物至少部分为液态,所述催化剂为固态,以及其中,所述反应在浆态鼓泡床反应器中进行。
68.根据权利要求67所述的方法,其中,所述H2和CO被提供给所述反应器中浆液,所述浆液包括液体中的悬浮的所述催化剂,所述液体包括所述H2和CO的所述反应产物,所述催化剂通过提供给浆液的气体的运动至少部分在浆液中维持悬浮。
69.根据权利要求68所述的方法,其中,所述反应温度为190-250℃,优选200-230℃,所述反应压力为10-60巴,优选为15-30巴。
70.根据权利要求54-69任一项所述的方法,其中,提供给所述费-托合成反应器的气体的H2/CO比为1.1-2.2,优选1.5-1.95。
71.根据权利要求54-70中任一项所述的方法,其中,反应器中的表观气体速度为5-60cm/s,优选20-40cm/s。
72.根据权利要求54-71中任一项所述的方法,其中,随后对所述费-托合成反应的产物进行后处理,所述后处理可包括脱蜡和/或加氢异构化和/或加氢裂化。
73.根据权利要求54-72中任一项所述的方法,其中,所述催化剂包括多孔载体材料;含量为所述催化剂的总重量的5-60wt%的活性钴;假定钴完全还原为钴金属,碱土金属的含量小于1000ppm。
74.根据权利要求73所述的方法,其中,所述载体材料为γ-氧化铝,可通过添加氧化铝尖晶石,例如镍氧化铝尖晶石进行改性。
75.根据权利要求73或74所述的方法,其中,所述催化剂进一步包括作为稳定剂的镧,其中,基于所述催化剂的重量,所述镧的含量可高达3wt%。
76.根据权利要求73-75中任一项所述的方法,其中,所述催化剂中所述钴的含量为10-30wt%。
77.根据权利要求73-76中任一项所述的方法,其中,所述催化剂进一步包括作为助催化剂的铼,其中,基于所述催化剂的重量,所述助催化剂的含量可为0.01-5wt%。
78.根据权利要求73-77中任一项所述的方法,其中,所述催化剂具有至少为0.2ml/g的孔隙体积,和/或至少为20m2/g的比表面积。
79.一种用于生成烃的方法,包括:在反应器中,在催化剂的存在下,对H2和CO气体进行费-托合成反应,所述催化剂根据权利要求1-47任一项所述的方法制备。
80.根据权利要求79所述的方法,其中,在所述合成反应中导入包括H2和CO的补给合成气体,所述补给合成气体包含小于100ppb的碱土金属或碱金属。
81.根据权利要求79或80所述的方法,其中,所述补给合成气体包括0.1-100ppb,优选为0.5-50,更优选为0.5-20ppb的碱土金属或碱金属。
82.根据权利要求80或81所述的方法,其中,所述碱土金属为钙,和/或所述碱金属为钠。
83.根据权利要求80至82中任一项所述的方法,其中,在所述合成气体进行费-托合成反应之前,将所述补给合成气体通过材料保护床,所述材料保护床用于吸收所述合成气体流中碱金属和碱土金属的组分。
84.根据权利要求79-83中任一项所述的方法,其中,所述反应为三相反应,其中,所述反应物为气态,所述产物至少部分为液态,所述催化剂为固态,以及其中,所述反应在浆态鼓泡床反应器中进行。
85.根据权利要求84所述的方法,其中,所述H2和CO被提供给所述反应器中浆液,所述浆液包括液体中的悬浮的所述催化剂,所述液体包括所述H2和CO的所述反应产物,所述催化剂通过提供给浆液的气体的运动至少部分的在浆液中维持悬浮。
86.根据权利要求85所述的方法,其中,所述反应温度为190-250℃,优选200-230℃,所述反应压力为10-60巴,优选15-30巴。
87.根据权利要求79-86中任一项所述的方法,其中,提供给所述费-托合成反应器的气体的H2/CO比为1.1至2.2,优选1.5-1.95。
88.根据权利要求79-87中任一项所述的方法,其中,所述反应器中的表观气速为5-60cm/s,优选20-40cm/s。
89.根据权利要求79-88中任一项所述的方法,其中,随后对所述费-托合成反应的产物进行后处理,所述后处理可包括脱蜡和/或加氢异构化和/或加氢裂化。
90.根据权利要求54-89中任一项所述的方法,其中,通过使用包含较低浓度的碱土金属和/或碱金属的原料,来控制所述合成气体中所述碱土金属或碱金属的含量。
91.根据权利要求90所述的方法,其中,在生成所述合成气体中,水或蒸汽作为反应物被导入或被再导入,其中,这种反应物采用选自蒸馏、过滤、水软化、反渗透、超滤、分子汽提、去离子作用和碳处理的一个或多个过程进行清洁。
92.根据权利要求54-91任一项所述的方法,其中,在所述合成气体的生成、运输和费-托转化中,暴露在工艺流中的反应器、管道和设备的内衬由不释放碱土金属或碱金属的材料制成。
93.根据权利要求92所述的方法,其中,所述内衬为耐火或陶瓷内衬。
94.根据权利要求54-93中任一项所述的方法,其中,烃类生产厂中,在烃生产开始之前,在合成气体生成和运输及其转化成烃的过程中,暴露在工艺流中的反应器、催化剂、管道或其他设备的表面通过从这些表面上去除碱金属或碱土金属物质来进行清洁。
95.根据权利要求54-94中任一项所述的方法,其中,使用蒸汽或水清洁所述表面。
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PCT/GB2010/002111 WO2011061484A2 (en) | 2009-11-18 | 2010-11-16 | Fischer-tropsch synthesis |
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CN103769109A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 一种合成气转化催化剂及其制备方法和应用 |
CN103769098A (zh) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | 一种合成气转化催化剂及其制备方法和应用 |
CN103769109B (zh) * | 2012-10-24 | 2015-12-16 | 中国石油化工股份有限公司 | 一种合成气转化催化剂及其制备方法和应用 |
CN104148101A (zh) * | 2013-05-13 | 2014-11-19 | 中国科学院大连化学物理研究所 | 一种甲烷无氧直接制烯烃的方法及其催化剂 |
CN104148101B (zh) * | 2013-05-13 | 2016-12-28 | 中国科学院大连化学物理研究所 | 一种甲烷无氧直接制烯烃的方法及其催化剂 |
CN112533697A (zh) * | 2018-06-05 | 2021-03-19 | 沙特基础全球技术有限公司 | 铁-镁二氧化硅负载的催化剂、其制备方法及其用途 |
CN111905741A (zh) * | 2019-05-07 | 2020-11-10 | 国家能源投资集团有限责任公司 | 氧化铝负载的钴基费托合成催化剂及其制备方法 |
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US20130012606A1 (en) | 2013-01-10 |
US10040054B2 (en) | 2018-08-07 |
GB2475492B (en) | 2014-12-31 |
EP2501470A2 (en) | 2012-09-26 |
GB2475492A (en) | 2011-05-25 |
WO2011061484A3 (en) | 2011-07-07 |
WO2011061484A2 (en) | 2011-05-26 |
GB0920226D0 (en) | 2010-01-06 |
JP2013511383A (ja) | 2013-04-04 |
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