CN100509144C - 氧化锆挤出物 - Google Patents
氧化锆挤出物 Download PDFInfo
- Publication number
- CN100509144C CN100509144C CNB2004800025709A CN200480002570A CN100509144C CN 100509144 C CN100509144 C CN 100509144C CN B2004800025709 A CNB2004800025709 A CN B2004800025709A CN 200480002570 A CN200480002570 A CN 200480002570A CN 100509144 C CN100509144 C CN 100509144C
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- CN
- China
- Prior art keywords
- zirconia
- cobalt
- calcining
- extrudate
- elements
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 264
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 238000001354 calcination Methods 0.000 claims abstract description 59
- 239000002904 solvent Substances 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- 238000004898 kneading Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 79
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 41
- 229910017052 cobalt Inorganic materials 0.000 claims description 40
- 239000010941 cobalt Substances 0.000 claims description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 40
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 39
- 230000008569 process Effects 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229920003023 plastic Polymers 0.000 claims description 17
- 239000004033 plastic Substances 0.000 claims description 17
- 230000000737 periodic effect Effects 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 9
- 229910052768 actinide Inorganic materials 0.000 claims description 7
- 150000001255 actinides Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical group [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910021472 group 8 element Inorganic materials 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 235000013495 cobalt Nutrition 0.000 claims 9
- 150000001868 cobalt Chemical class 0.000 claims 2
- 238000001035 drying Methods 0.000 abstract description 6
- 238000001311 chemical methods and process Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 36
- 239000004215 Carbon black (E152) Substances 0.000 description 28
- 229930195733 hydrocarbon Natural products 0.000 description 28
- 150000002430 hydrocarbons Chemical class 0.000 description 28
- 239000000047 product Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000843 powder Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000002243 precursor Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- -1 oxide Chemical compound 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 238000007655 standard test method Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 101100078144 Mus musculus Msrb1 gene Proteins 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
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- WWUVJRULCWHUSA-UHFFFAOYSA-N 2MP Natural products CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003868 ammonium compounds Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 2
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- 235000015165 citric acid Nutrition 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
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- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 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
- 241000894007 species Species 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000005537 sulfoxonium group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract
一种制备煅烧的氧化锆挤出物的方法,包括如下步骤:a.制备一种可成型面坯,该步骤包括混合并揉制颗粒氧化锆与溶剂得到总固含量为50-85wt%的混合物,b.挤出所述可成型面坯形成氧化锆挤出物,和c.干燥并煅烧所述氧化锆挤出物;特征在于所述颗粒氧化锆包含不超过15wt%的非单斜晶氧化锆的氧化锆。按照本发明制备的煅烧的氧化锆挤出物表现出明显改善的压碎强度,并且适合在很多化学方法中用作催化剂或催化剂载体。
Description
技术领域
本发明涉及煅烧的氧化锆挤出物的制备及其作为催化剂或催化剂载体的用途。
背景技术
氧化锆(或二氧化锆)是一种公知的材料,已知该材料可在各种方法中用作催化剂载体或催化剂。氧化锆可以以各种成型体或成型颗粒如球型、圆柱型、环状(中空圆柱体)及不太对称的形状如细粒应用。可制备具有各种横截面形状的圆柱体,如三叶状、四叶状、星状和圆形。
成型的颗粒氧化锆可以由氧化锆粉末开始通过颗粒放大方法来制备。可以应用多种方法实现颗粒放大,如加压压实、凝聚和喷雾法。这些方法在Perry的Chemical Engineers Handbook,McGraw-HillInternational Editions(1984)ISBN 0 07-049479-7,第8-61页中有述。
加压压实在催化剂的情况下是特别合适的,这是因为其会产生强度较大的颗粒。加压压实可以通过多种方法来实施,例如挤出(其中可成型混合物通过配有合适模板的挤出机而挤出,得到圆柱状颗粒)、辊压(得到不太对称的细粒状颗粒)或压片(产生具有非常好的确定形状的颗粒)。
为了产生多孔性并增加颗粒的强度,一旦成型后,成型颗粒通常进行干燥并随后进行煅烧。在催化剂情况下,上述这些特性是特别重要的。
挤出方法通常优于压片方法,这是因为挤出的生产速率比压片的生产速率在数量级上要大好多倍。另外,压片通常产生较小的孔体积,这对催化剂的应用来说经常是一种限制。挤出方法也优于辊压方法,这是因为挤出过程所产生的颗粒具有窄得多的粒度分布。在辊压方法中,压实磨和制粒磨的组合使得颗粒材料具有较宽的粒度分布,而在催化剂领域中,这种较宽的粒度分布通常是不希望的,因为其增加了催化剂颗粒的填充床层中的分散。
因此,迄今还无法象其它材料如氧化铝一样用常规挤出设备挤出氧化锆并在煅烧后得到强度适中的载体。由于其具有较高的热稳定性及酸和碱特性,氧化锆是一种令人感兴趣的材料。因此理想的是制备具有足够强度的具有工业重要性的氧化锆挤出物。
氧化锆存在于依据通常条件而形成的多种晶体中。因此在环境温度和压力的条件下,氧化锆以一种稳定的单斜晶结构存在。在极大压力或较高温度下,例如通常在450-1000℃下,氧化锆以四角形晶体结构存在。在更高温度下,如在超过1500℃的温度下,形成一种立方体晶体相形式。对于氧化锆特性的全面讨论,参考Kirk-Othmer的"Encyclopedia of Chemical Technology",第二版,第22卷,651-655页。
EP-A-0,510,772(Shell)公开了一种制备氧化锆基催化剂挤出物的方法,该方法包括研磨氧化锆和/或氧化锆前体和溶剂的混合物,并挤出所述混合物,其中所述混合物具有20-60wt%的固含量。
EP-B-0,???716,883(BASF)公开了一种制备主要包含单斜晶氧化锆的催化剂或载体的方法。该方法包括用氨使锆盐沉积,其中向氨水溶液中加入硝酸氧锆或氯化氧锆溶液,使pH从14降低至6,并进行干燥、煅烧和压片。但是其没有给出制备氧化锆挤出物的例子。
US-A-6,034,029(BASF)公开了一种制备二氧化锆粉末的方法,所述二氧化锆粉末基本上为单斜晶的且具有较大的表面积。但其没有给出制备氧化锆挤出物的例子。
现在已经令人惊奇地发现,如果用于制备挤出物的氧化锆主要由单斜晶氧化锆组成,则会发现挤出物的强度有显著改善。
发明内容
按照本发明的一个方面,提供一种制备煅烧的氧化锆挤出物的方法,包括如下步骤:
a.制备一种可成型面坯,该步骤包括混合并揉制颗粒氧化锆与溶剂得到总固含量为50-85wt%的混合物,
b.挤出所述可成型面坯形成氧化锆挤出物,和
c.干燥并煅烧所述氧化锆挤出物;
特征在于所述颗粒氧化锆包含不超过15wt%的非单斜晶氧化锆的氧化锆。
按照本发明,还提供一种按照这里所述方法制备的煅烧的氧化锆挤出物。
相比于如下氧化锆挤出物,本发明制备的煅烧的氧化锆挤出物具有明显改善的压碎强度:由含有超过15%非单斜晶氧化锆的颗粒氧化锆制备的氧化锆挤出物,例如所述氧化锆是四角形和单斜晶氧化锆的混合物,其含有大于15wt%的四角形氧化锆,或者所述氧化锆只由四角形氧化锆组成。
具体实施方式
本发明的关键特征在于所述颗粒氧化锆含有不超过15wt%的非单斜晶氧化锆的氧化锆。因此这里的颗粒氧化锆不含有大量的非单斜晶氧化锆的氧化锆,如立方体或四角形氧化锆。优选地,颗粒氧化锆应该含有不超过约10wt%、更优选为不超过约5wt%的非单斜晶氧化锆的氧化锆。
如在R.Jenkins和R.L.Snyder的“Introduction to X-raypowder diffractometry(Chemical analysis Volume 138)”,JohnWiley & Sons,New York(1996),ISBN0-471-51339-3中所述,X-射线衍射可以用作确定氧化锆试样中四角形、单斜晶和立方体氧化锆的相对量的方法。
在这里应用的合适的颗粒氧化锆源的一个例子为DAIICHIRC-100,其由DDK Daiichi Kigenso Kagaku Kogyo Co.Ltd.,4-4-14Koraibashi Chuo-ku,Osaka 541-0043,Japan商购得到。
在本方法中第一个步骤是制备一种可成型面坯,该步包括对上述颗粒氧化锆与溶剂以及任选的添加剂进行混合且揉制得到总固含量为50-85wt%的混合物,所述总固含量优选为55-80wt%,更优选为65-75wt%。
如这里所应用,术语"溶剂"指当与颗粒氧化锆和可能存在的钴前体混合时,适合用于制备可成型面坯的任何液体。
溶剂可以为本领域中已知的任何合适的溶剂,例如水;醇如甲醇、乙醇和丙醇;酮如丙酮;醛如丙醛;和芳族稀释剂如甲苯。优选的和最方便的稀释剂为水。可以向溶剂中加入任选组分如酸和碱,以在制备可挤出面坯时用作胶溶剂。
在本发明制备的氧化锆挤出物中,以氧化锆形式存在的锆本身也可以用作催化活性组分。但如果需要的话,进行研磨的混合物也可以包含一种或多种其它的元素源来替代锆或作为除锆以外的催化活性组分,并任选与一种或多种促进剂元素一起使用。因此,混合物可以包含一种或多种选自如下的元素源:元素周期表的第IB、IIB、IIIB、IVB、VB、VIB、VIIB、VIII族元素或镧系和锕系元素。优选的催化活性组分为周期表的第VIII族元素。选自铁、钌、钴、铼、镍、钯、铂、铜和锌的元素源是特别优选的。钴、铁和镍是特别优选的催化活性元素,并且钴是最优选的。混合物也可以有利地包含周期表的第IVB族元素源,该元素可用作促进剂,特别是钛,如果需要,可以与附加的锆源一起使用。
在制备这里的氧化锆挤出物时,可以任选应用粘结剂材料。合适的粘结剂包括二氧化硅、氧化铝和二氧化钛等。
前述一种或多种元素源在溶剂中可以为可溶的也可以为不溶的。通常包括由有机酸衍生的盐,如乙酸盐、苯甲酸盐、乙醇盐(ethanoates)和丙酸盐;卤化物,例如氯化物、溴化物、碘化物和氟化物;以及其它盐如硝酸盐、氧化物、氢氧化物、碳酸盐和氯酸盐。在溶剂中不溶的物质是优选的。已经发现氢氧化物是特别优选的。
在本发明的一个优选实施方案中,颗粒氧化锆与钴前体和溶剂混合形成可成型面坯,然后使所述面坯挤出,得到位于氧化锆载体上的钴催化剂。因此本发明的另一个方面是提供一种制备煅烧钴/氧化锆的方法,包括如下步骤:
a.制备一种可成型面坯,该步骤包括混合并揉制颗粒氧化锆和钴前体与溶剂得到总固含量为50-85wt%的混合物,
b.挤出所述可成型面坯形成氧化锆/钴挤出物,和
c.干燥并煅烧所述氧化锆/钴挤出物;
特征在于所述颗粒氧化锆包含不超过15wt%的非单斜晶氧化锆的氧化锆。
本发明还提供一种通过这里所描述的方法制备的煅烧氧化锆/钴挤出物。
在这里应用的合适的钴前体包括在煅烧后在氧化锆载体上只留下钴氧化物的任何钴前体,从而最终产品的催化性能不被削弱。合适的钴前体包括氢氧化钴、乙酸钴、硝酸钴、氧化钴及其混合物,但不局限于此。在这里应用的特别优选的钴前体为氢氧化钴。
优选的是在制备氧化锆的可挤出面坯时,在混合物中包含碱性组分来用作胶溶剂。碱性化合物优选为氨、释放氨的化合物、铵化合物或有机胺。这种碱性化合物在煅烧时被脱除,不在挤出物中留存,因而不削弱最终产品的催化性能。碱性化合物最优选为铵化合物。最合适的铵化合物为氨。
在混合物中包含的碱性化合物的量应该足以使混合物中存在的氧化锆胶溶。混合物中存在的碱性化合物的量可以通过测量混合物的pH值而很容易地确定。在研磨的过程中,混合物优选具有8.0-11.5的pH值,优选为9.0-11.0。
对于制备共同研磨的氧化锆/钴可成型面坯来说,优选的是在混合物中包含用作胶溶剂的酸组分。酸化合物优选为无机酸化合物或有机酸化合物。这种酸化合物在煅烧时被脱除,不在挤出物中留存,因而不削弱最终产品的催化性能。此处应用的优选无机酸为硝酸。最合适的有机酸为柠檬酸。
为了在挤出过程中提高混合物的流动性能,可以向混合物中加入表面活性剂或聚合电解质。表面活性剂的加入会造成更光滑的挤出物质地,并会有利于挤出物产品的切割。另外,也可以提高煅烧的催化物质中微孔的形成,而这可增强产品的催化性能。合适的表面活性剂包括阳离子表面活性剂,例如脂肪胺、季铵化合物、脂族一元羧酸、乙氧基化的烷基胺、聚乙烯基吡啶、氧化锍、锍、鏻和碘鎓化合物;阴离子表面活性剂,如烷基化的芳族化合物、无环的一元羧酸、脂肪酸、磺化的芳族化合物、醇硫酸盐、醚醇硫酸盐、硫酸化的脂肪和油以及磷酸盐;以及非离子型表面活性剂,如聚亚乙基烷基酚、聚氧亚乙基醇、聚氧亚乙基烷基酰胺、多元醇、聚乙烯醇和炔属二醇。以混合物中存在的氧化锆和/或氧化锆前体的重量为基准,表面活性剂的量通常为0.5-8wt%,优选为1-5wt%。表面活性剂可以在挤出前的混合的任意阶段加入。
原则上,可以以任何顺序组合混合物的组分。但是,已经发现以如下方式制备混合物是有利的。最基本地,混合物包含氧化锆和溶剂,它们首先一起混合。如果混合物包含碱性化合物,则发现在向颗粒氧化锆中加入溶剂之前,向溶剂中加入碱性化合物是有利的。如果需要,可以加入前述的周期表中的一种或多种元素源。正如这里所讨论,优选的元素为钴。当制备共研磨的氧化锆/钴挤出物时,颗粒氧化锆和钴前体一起混合,然后加入溶剂和可能存在的酸。如果需要,表面活性剂可以在混合的任何时间内加入,优选在混合结束前加入。
混合物通常通过研磨10-120分钟而混合,优选为15-90分钟。在研磨过程中,通过研磨设备向混合物中引入能量。研磨过程应用Simpson Mixer Muller,Type LG混合器,其由Simpson TechnologiesCorporation,751 Shoreline Drive,Aurora,Illinois 60504,USA商购得到。任选地,对于揉制过程可以应用由F.Aoustin & Cie,11,Rue de Preaux BP 32,76161 Darnetal Cedex,France商购得到的AOUSTIN揉制机。
研磨过程可以在很宽的温度范围内实施,优选为15-50℃。由于在研磨过程中向混合物中输入能量的结果,研磨过程中混合物将会发生温升。研磨过程方便地在环境温度下实施。可以采用任何合适的商购研磨机。在研磨过程的终点,得到可成型面坯。
然后应用任意的常规商购挤出机挤出可成型面坯。具体地,可以应用螺杆式挤出机迫使混合物通过模板中的孔,以产生具有需要形状的催化剂挤出物。然后切割挤出形成的物料为合适的长度。
挤出物可以具有圆柱体的形状,包括中空圆柱体,也可以具有多叶或多叶在横截面上缠绕的形状,或者采取本领域中已知的任何其它形状。挤出物通常具有0.5-6mm的公称直径,优选为0.8-4mm,特别地为1-3mm。
挤出完成后,在煅烧前干燥挤出物,例如在温度为100-300℃下干燥30分钟到3小时。煅烧方便地在空气中在温度高达1000℃下实施,优选为300-1000℃,更优选为300-800℃,特别是400-600℃。挤出物的煅烧通常实施达5小时的时间段,优选为30分钟到4小时。
氧化锆挤出物的表面积优选为40-300m2/g,更优选为50-100m2/g,其通过J.Amer.Chem.Soc.,60(1938),309中所述的氮气吸附BET方法来测量。
制备后,挤出物可以实施沉积步骤,其中在挤出物上沉积一种或多种催化活性元素或促进剂元素的源。所述源可以是前文所讨论的周期表中的任意元素。当初始混合物包含给定元素源时,可以实施该元素其它源的沉积,以增加挤出物上该元素的负载。
可以通过本领域中已知的任意技术来实施催化活性元素或促进剂元素源在挤出物上的沉积。
优选的沉积技术是浸渍。通过在液体存在下使挤出物与希望元素的化合物接触而实施浸渍,其中所述液体优选为所述元素化合物的溶液形式。在浸渍中应用的合适液体包括有机液体和无机液体,水是最方便和最优选的液体。希望元素的合适化合物包括有机化合物和无机化合物,优选为在所选溶剂中可溶的化合物。应该注意的是酸或碱的加入可能有利于希望元素的合适化合物溶解。所述化合物优选为无机化合物。最优选为希望元素的硝酸盐或氢氧化物水溶液。特别优选的是希望元素的硝酸盐化合物,因为其可以以熔融态应用,从而在液体中使希望元素具有较高的浓度。
最方便地,挤出物通过在液体中浸没而与希望元素的化合物接触。挤出物优选浸没在足够体积的液体中,从而正好填充挤出物中的孔体积。
如果浸渍在单个步骤中实施,则在液体的存在下挤出物与每种希望元素的化合物同时接触。优选地,挤出物浸没在希望元素的硝酸盐或氢氧化物的水溶液中。如果浸渍在多个步骤中实施,则在第一步中,在液体的存在下挤出物与一种希望元素的化合物接触,而在随后的步骤中,在液体的存在下与其它希望元素的化合物接触。在各步中,液体可以相同也可以不同,最方便地是相同液体。
如果是单步浸渍,则在浸渍后干燥所述挤出物,而在多步浸渍中,则每次浸渍后干燥所述挤出物。挤出物的干燥条件如上文所述。优选地,干燥成每次干燥后,煅烧挤出物,煅烧条件也如前文所述。
催化活性元素在产品中存在的量可以为每100重量份氧化锆1-100重量份,优选为10-50重量份。如果存在的话,促进剂的存在量可以为每100重量份氧化锆0.1-60重量份,优选为1-10重量份。
在本发明的一个优选实施方案中,氧化锆挤出物用钴前体浸渍,然后干燥和煅烧以形成煅烧的钴浸渍氧化锆挤出物。因此,按照本发明的另一个方面,提供一种制备煅烧的钴浸渍氧化锆挤出物的方法,所述方法包括如下步骤:
a.制备一种可成型面坯,该步骤包括混合并揉制颗粒氧化锆与溶剂得到总固含量为50-85wt%的混合物,
b.挤出所述可成型面坯形成氧化锆挤出物,
c.用液体钴前体浸渍氧化锆挤出物,形成钴浸渍的氧化锆挤出物,和
d.干燥并煅烧所述钴浸渍氧化锆挤出物;
特征在于所述颗粒氧化锆包含不超过15wt%的非单斜晶氧化锆的氧化锆。
本发明还提供一种按照这里所描述的方法而制备的煅烧的钴浸渍氧化锆挤出物。
对于浸渍氧化锆挤出物来说,合适的液体钴前体包括氢氧化钴、乙酸钴、硝酸钴及其混合物的水溶液。优选的液体钴前体为硝酸钴的水溶液。另一种优选的液体钴前体为在氨中氢氧化钴的水溶液。
与用包含超过15wt%的非单斜晶氧化锆的氧化锆的颗粒氧化锆制备的煅烧的氧化锆挤出物相比,按照本发明制备的煅烧的氧化锆挤出物在强度方面表现出明显改进。对于实际应用来说,优选的是煅烧挤出物的强度大于100N/cm,其中所述强度通过挤出催化剂颗粒的径向压碎强度的标准试验方法(ASTM D6175-98)来测量。
在具有较高压碎强度的同时,按照本发明制备的煅烧的氧化锆挤出物也具有较高的孔体积,优选为0.3ml/g或更高,所述孔体积通过应用在H.L.Ritter和L.C.Drake,In.Eng.Chem.,Anal.Ed.,17(1945),782中描述的方法通过汞浸入法来测量。
这里所制备的煅烧的氧化锆挤出物也具有较高表面积,优选为50m2/g或更高,所述表面积通过J.Amer.Chem.Soc.,60(1938)309中所描述的氮气吸附BET方法来测量。
因此按照本发明的另一个方面,提供一种煅烧的氧化锆挤出物,其具有如下特性:
(a)孔体积为0.3ml/g或更大;
(b)径向压碎强度为100N/cm或更大;和
(c)表面积为50m2/g或更大。
按照本发明制备的氧化锆挤出物可以应用在任何可以应用或需要应用氧化锆基催化剂的方法中。氧化锆挤出物可以合适地用作催化剂的载体,其中所述催化剂通常在如下过程中应用:烃合成反应如费托反应、加氢转化过程如重烃油的加氢脱金属、加氢裂化和加氢脱硫、可加氢组分或烃馏分如煤油和各种类型的循环油的加氢、利用有机氢过氧化物的烯属不饱和化合物的环氧化、产生相应链烷醇的烯属不饱和化合物的水合、废气的净化、特别是含氮的含氧化合物的脱氧(denoxing)、烯烃或链烷烃的异构化、烯烃的二聚及醇脱水为烯烃。
在这里,氧化锆挤出物在由一氧化碳和氢产生(长链)烃的费-托类反应中用作催化剂载体是特别有用的。
因此,按照本发明的另一个方面,提供一种这里所制备的煅烧的氧化锆挤出物在费托反应条件下通过使一氧化碳和氢反应而制备烃的过程中用作催化剂载体的用途。
在这种反应中特别优选应用的是按照本发明制备的包含还原后具有活性的元素、及任选的一种或多种促进剂的氧化锆挤出物。在费-托合成中具体的应用是按照本发明方法制备的含有铁、镍或钴作为催化活性组分的氧化锆挤出物。钴是特别优选的。
这里所制备的氧化锆挤出物可以通过在高温和高压下使含氢气体与其接触而得到还原。通常,所述还原包括在温度为100-450℃、压力为1-200bar绝压下处理催化剂1-200小时。在还原中可以应用纯氢气,但是通常优选的是应用氢气和惰性气如氮气的混合物。混合物中存在的氢气的相对量为0.1-100vol%。
根据还原的一个优选实施方案,使催化剂在氮气气氛下达到希望的温度和压力水平。随后,催化剂与气体混合物接触,所述气体混合物仅含有少量氢气,剩余部分为氮气。在还原的过程中,气体混合物中氢气的相对量逐渐升高至达50vol%或甚至100vol%。
随后,所得的催化剂可以在高温和高压下与一氧化碳和氢气的混合物接触。反应通常在温度为125-350℃、优选为175-250℃、更优选为200-250℃、特别地为205-240℃下实施。反应压力通常为5-150bar绝压,优选为5-100bar绝压,更优选为20-100bar,特别地为40-70bar绝压。
氢和一氧化碳通常以0.7-2.5的摩尔比率进料至过程,优选为1-2。较低的氢与一氧化碳摩尔比率将会增加催化剂的C5+选择性,即增加形成C5+烃的选择性。未转化的氢和一氧化碳可以循环从而再一次与催化剂接触。按这种安排方式,与催化剂实际接触的气体中的氢与一氧化碳的摩尔比率可能会比原料气中的摩尔比率要低得多,例如为0.4-1.1。
气体小时空速("GHSV")可以在很宽范围内变化,并且通常为100-10,000,优选为100-5000,更优选为500-3500,甚至更优选为800-1600N1/1/h。术语GHSV在本领域中是公知的,其涉及每小时的气体空速,即在一小时内与每升催化剂颗粒接触的合成气体积,以N1(即在标准温度0℃和标准压力1bar(100,000Pa)下的体积)表示。在固定床催化剂的情况下,GHSV通常表示为每升催化剂床层的空速,即包括内部颗粒间的空隙。
可以应用各种类型的反应器和反应机理来实施烃的制备方法,例如应用固定床反应器或沸腾机理来实施。固定床的方案是优选的。将会理解的是催化剂颗粒的尺寸和形状可以依据其针对的反应机理而变化。对于给定的反应机理而言,本领域的熟练技术人员将会选择最合适的尺寸和形状。
另外,将会理解的是对于给定的反应器构造、反应机理或工作方案而言,本领域的熟练技术人员有能力选择最合适的条件。例如,优选的气体小时空速可能依赖于所采用的反应机理的类型。因此,如果希望用固定床方案来操作烃合成过程,则优选选择气体小时空速为500-2500 N1/1/h。
这种费-托反应的产品是烃的混合物,包括链烷烃、烯烃和含氧化合物,如醇和醛。共同研磨的氧化锆/钴挤出物和钴浸渍的氧化锆挤出物在这里特别适合于制备烯烃,特别是C11-C14烯烃,特别是当与一组优选的费-托方法条件相组合时。C11-C14烯烃对于清洁剂范畴的醇来说是特别有用的前体。
因此按照本发明的另一个方面,提供一种制备具有11-14个碳原子的较高级烯烃的方法,该方法包括在煅烧氧化锆/钴挤出物或煅烧的钴浸渍氧化锆挤出物作为催化剂存在下,在费-托反应条件下使氢和一氧化碳接触。
为了使烃产品物流中C11-C14碳馏分最大化,同时保持较高的C5+产率(至少为85%),优选的是在一定条件下实施费-托反应,使所应用的催化剂的平均"α"值为0.87-0.92,优选为0.9-0.92,特别为约0.91。已知"α"值在本领域中作为ASF-α值(Anderson-Schulz-Flory链成长因子)。正如这里所应用,平均α值是ASF链成长概率系数值,其最好地描述了所测量的C20与C39之间的烃分布,即所述值通过应用本领域熟练技术人员公知的所谓“最小二乘法”通过测量数据的统计回归得到。这里应用的和上面提到的优选范围内的"α"值比0.95-0.96范围内的值能够提供大约两倍的C11-C14馏分,同时具有相当高的C5+产率。
为了使C11-C14碳馏分的烯烃度最大化,一组优选的费-托方法条件如下:使氢气与一氧化碳以摩尔比率为1.1:1至0.4:1接触,重均床层温度为200-250℃,优选为205-240℃,压力为20-100bar,优选为40-70bar,GHSV为100-5000hr-1,优选为500-3500hr-1。
另外,为了使C11-C14馏分的烯烃度最大化,优选的是催化剂具有2.2mm或更小的平均颗粒直径,优选为1-2mm。
在氧化锆载体上催化活性钴的量优选为每100重量份氧化锆载体材料3-300重量份,更优选为10-80重量份,特别是20-60重量份。
由这里所描述的费-托反应产生的优选反应产品包含20-60wt%的C11-C14烯烃,所述比率的基准为C11-C14碳馏分的总重量。还优选的是以反应产品中烃的总重量为基准,费-托反应产品包含85%或更多的具有5个或更多个碳原子的烃。
下面通过如下实施例描述本发明。
实施例
在如下实施例中,术语烧失量(或"LOI")指当试样在炉子中在550℃处理2小时后所测量的试样的重量损失,即试样中所存在的水分的量。
实施例1(煅烧的氧化锆挤出物)
按如下步骤制备本发明的煅烧的氧化锆挤出物。使7060克商标名为DAIICHI RC-100(由DKK Daiichi Kigenso Kagaku Kogyo Co.Ltd.商购得到)、且烧失量为1.9%的氧化锆粉末与2654克水、416克氨溶液(含25wt%的氢氧化铵)、69克SUPERFLOC N100(从Cytec IndustriesB.V.,Botlekweg 175,3197 KA,Botlek-Rotterdam,The Netherlands商购得到的聚合电解质)和139克聚乙烯醇(由Kuraray SpecialtiesEuropea,GmbH,c/o Clariant Benelux N.V.,Diemerhof 36,1112XN Diemen,The Netherlands商购得到的MOWIOL8-88)混合。
应用Rietveld定量计对Daiichi粉末的X-射线分析表明:其含有92.09%的单斜晶氧化锆、7.9%的四角形氧化锆以及0.006%的立方体氧化锆;所有的数都具有+/-10%的相对准确度。用于这些测量的X-射线衍射仪器为具有如下设置的Philips PW 1800X-射线衍射计:X-射线管:铜正极;电压:40kV;电流:55mA;发散狭缝:自动;接收狭缝:细小;主光束和衍射射束中的垂直soller狭缝;衍射射束中的石墨单色器;记录范围:10-90 2θ;步长:0.025 2θ;记数时间/步频:5秒;标准试样支架的直径为20mm且深度为1.5mm。
在一个SIMPSON mix-muller Type LG(由Simpson TechnologiesCorporation商购得到)中揉制该混合物15分钟。然后在200rpm下使混合物流过一个尺寸为2"x 17"的AOUSTIN揉制机连续混合器(由F.Aoustin & Cie,11,Rue de Preaux BP 32,76161 Darnetal Cedex,France商购得到)。这样得到的面坯其测得的LOI为32.81%,并且其pH为10.3。应用2.5mm的三叶模板和1.5mm的圆柱形模板在一个2.25英寸的BONNOT挤出机中(由Bonnot Company,1520 CorporateWoods Pkwy.,Uniontown,Ohio 44685,USA商购得到)挤出面坯。挤出物在120℃下干燥1小时,然后在一个旋转烤箱中在产品温度为550℃下煅烧2小时。最终挤出物的表面积为88m2/g。孔体积为0.326ml/g。应用ASTM D6175-98的标准试验方法测量最终挤出物的径向压碎强度。结果示于下表1。
实施例2(对比例)
重复实施例1的过程,只是实施例1中应用的氧化锆粉末用如下物质的混合物替代:80%的Daiichi HC-100和20%的商标名为SEPR HC15(由Societe Europeenne des Produits Refractaires,LesMiroires,18 Rue D′Alsace,92400 Courbevoie,France商购得到)的氧化锆粉末。SEPR HC 15含有98.3wt%的四角形氧化锆和1.7wt%的单斜晶氧化锆(通过应用上文实施例1中所述相同的X-射线衍射仪器并具有相同的设置进行X-射线衍射来分析),并且其LOI为24.4%。为了使挤出面坯具有与实施例1中相似的LOI,减少所加入的水量。所得的面坯其测量的LOI为32.87%,并且其pH值为10.2。以与实施例1相同的方式实施挤出、干燥和煅烧。应用ASTM D6175-98的标准试验方法测量最终挤出物的径向压碎强度。结果示于下表1。
实施例3(对比例)
重复实施例1的过程,只是实施例1中应用的氧化锆粉末用如下物质的混合物替代:50%的Daiichi RC-100和50%的商标名为SEPR HC15(与实施例2中应用的相同)的氧化锆粉末。为了使挤出面坯具有与实施例1中相似的LOI,减少了水量。所得的面坯其测量的LOI为31.89%,并且其pH值为9.8。以与实施例1相同的方式实施挤出、干燥和煅烧。应用ASTM D6175-98的标准试验方法测量最终挤出物的径向压碎强度。结果示于下表1。
实施例4(对比例)
重复实施例1的过程,只是实施例1中应用的氧化锆粉末用氧化锆粉末SEPR HC 15(与实施例2中应用的相同)替代。为了使挤出面坯具有与实施例1中相似的LOI,减少所加入的水量。所得的面坯其测量的LOI为31.89%,并且其pH值为9.8。以与实施例1相同的方式实施挤出、干燥和煅烧。应用ASTM D6175-98的标准试验方法测量最终挤出物的径向压碎强度。结果示于下表1。
实施例5(对比例)
重复实施例1的过程,只是实施例1中应用的氧化锆粉末用氧化锆粉末SEPR HC 15(与实施例2中应用的相同)替代,其中SEPR HC15在加入到挤出混合物之前已在400℃进行了煅烧。所述粉末由四角形(98.3%)和单斜晶(1.7%)氧化锆的混合物组成,其组成通过X-射线衍射(应用上文实施例1中所述相同的X-射线衍射仪器和设置)进行分析,并且其LOI为3.2%。为了使挤出面坯具有与实施例1中相似的LOI,减少所加入的水量。所得的面坯其测量的LOI为33.75%,并且其pH值为9.8。以与实施例1相同的方式实施挤出、干燥和煅烧。应用ASTMD6175-98的标准试验方法测量最终挤出物的径向压碎强度。结果示于下表1。
实施例6(对比例)
重复实施例1的过程,只是实施例1中应用的氧化锆粉末用氧化锆粉末MEL XZO 880/1(由MEL Chemicals,Clifton Junction,P.O.Box 6,Swinton,M27 8LS,Manchester,UK商购得到)替代。该粉末由100%的四角形氧化锆组成,其组成通过X-射线衍射(应用上文实施例1中所述相同的X-射线衍射仪器和设置)进行分析,并且其LOI为1.9%。为了使挤出面坯具有与实施例1中相似的LOI,减少所加入的水量。所得的面坯其测量的LOI为48.5%,并且其pH值为9.3。以与实施例1相同的方式(只是仅用2.5mm的圆柱形模板)实施挤出、干燥和煅烧。应用ASTM D6175-98的标准试验方法测量最终挤出物的径向压碎强度。结果示于下表1。
表1:
表1中提供的数据清楚地表明:与应用四角形氧化锆或单斜晶和四角形氧化锆的混合物而制备的煅烧的氧化锆挤出物相比,应用基本由单斜晶氧化锆(如92.09%)组成的氧化锆粉末制得的煅烧的氧化锆挤出物具有明显更高的压碎强度。
实施例7(在不加酸或碱的情况下制备煅烧的氧化锆挤出物)
将商标名为DAIICHI RC-100(同实施例1中所应用的)、LOI为5.3%的264克氧化锆粉末与90克5wt%的聚乙烯醇水溶液(商标名为MOWIOL 18-88)混合。这种混合物在由Werner & Pfleiderer,Stuttgart,Germany提供的Sigma(Z-blade)kneader type LUK 0.5中揉制2分钟。向混合物中加入2.5克SUPERFLOC N100,并持续混合5分钟。然后向混合物中加入8克水,并继续混合30分钟。这样得到的面坯其测量的LOI为31.5%,并且其pH为8.4。应用一个1英寸单螺杆针式挤出机(由Bonnot Company提供)应用1.6mm的三叶状模板挤出该面坯。挤出物在120℃干燥1小时,然后在一个静置的烤箱中在产品温度为550℃下煅烧2小时。最终挤出物的孔体积为0.312ml/g,并且其表面积为55m2/g。最终挤出物的径向压碎强度为233N/cm。该实施例表明:在本发明的制备方法中,应用酸或碱并不是必须的。因此,当酸或碱对催化剂产生有害影响时,在制备挤出物的过程中可以避免酸或碱的应用。
实施例8(煅烧的钴浸渍氧化锆挤出物)
重复实施例1的过程,只是应用1.0mm的三叶状模板挤出所述面坯。挤出物在120℃下干燥1小时,然后在一个旋转烤箱中在产品温度为550℃下煅烧2小时。重复该过程,并使两次的产品混合。最终产品的表面积为60.5m2/g,孔体积为0.352ml/g,并且其径向压碎强度为154N/cm,其中所述表面积通过J.Amer.Chem.Soc.,60(1938)309中所描述的氮吸附BET方法来测量,所述孔体积通过H.L.Ritter和L.C.Drake,In.Eng.Chem.,Anal.Ed.,17(1945)782中所描述的汞浸入方法来测量,而所述径向压碎强度应用实施例1中应用的相同试验方法来测量。
使10250克所得的挤出物加热至60℃,并用温度为60℃的6938克熔融硝酸钴溶液浸渍2分钟,在该过程中浸渍物的平均温度为约60℃。浸渍后的挤出物在120℃下干燥,并在产品温度为445℃下在一个旋转炉中煅烧。最终挤出物的钴含量为11.45wt%(通过X-射线荧光测量),表面积为48m2/g(通过J.Amer.Chem.Soc.,60(1938)309中所描述的氮吸附BET方法来测量),并且径向压碎强度为188N/cm,其应用实施例1中应用的相同试验方法来测量。
实施例9(煅烧的共研磨钴/氧化锆挤出物)
使18749克氧化锆DAIICHI RC-100粉末与8091克氢氧化钴混合。干的粉末在Simpson混合研磨机中混合。向该混合物中加入5729克5wt%的聚乙烯醇(MOWIOL 18-88)水溶液、210.5克固体聚乙烯醇(MOWIOL 18-88)、255克柠檬酸和2802克水。该混合物在SIMPSON混合研磨机中揉制36分钟。然后加入505克SUPERFLOC N100,并且再继续混合5分钟。这样得到的面坯所测的LOI为31.8%,并且其pH值为7.8。该面坯应用2.25英寸的BONNOT挤出机应用1.0mm三叶状模板挤出。挤出物在120℃下干燥4小时,然后在一个旋转烤箱中在产品温度为550℃下煅烧1小时。重复该过程并混合两次的产品。最终产品的强度为113N/cm。
实施例10
按照实施例8和9制备的挤出物通过还原被转化为活性的费-托催化剂,随后经受如下费-托反应条件。
将一个含有为固定床形式的催化剂颗粒的微流反应器加热至温度280℃,并用连续流动的氮气加压至1bar绝压的压力。催化剂用氮气和氢气的混合物原位还原24小时。在还原过程中,混合物中氢的相对量从0vol%逐渐升高至100vol%。尾气中的水含量保持为低于3000ppmw。
还原后,通过在H2/CO比率为1.1:1下引入氢气和一氧化碳的混合物而实施烃的制备。GHSV、反应温度(按重均床层温度表示)和压力按表2所示的设定。操作40小时后,确定如下量:空时产率(STY),以每小时每升催化剂颗粒(包括颗粒间的空隙)的烃产品克数表示;对含有5个或更多个碳原子的烃的选择性(C5+选择性),以总烃产品的wt%表示;对含有11-14个碳原子的烃的选择性(C11-C14选择性),以总烃产品的wt%表示;以及对含有15-20个碳原子的烃的选择性(C15-C20选择性),以总烃产品的wt%表示。结果在下表2中给出。
表2:
实施例8的催化剂 | 实施例9的催化剂 | |
温度,℃ | 231 | 227 |
压力,bar绝压 | 51 | 52 |
GHSV,NL/(1.hr) | 1200 | 1200 |
STY,g/(1.hr) | 148 | 151 |
C5+选择性,wt% | 88 | 87 |
C11-C14选择性,wt% | 9 | 9 |
C15-C20选择性,wt% | 13 | 13 |
表2所述结果表明:按照本发明所制备的Co/Zr催化剂在烃的费-托合成中可以成功地用作催化剂。
实施例11
在下列实施例中,对上文按照实施例8制备的催化剂和两种具有不同组成且制备方法不同的其它催化剂(催化剂A和B)进行比较。催化剂A是载带在二氧化硅载体上的钴催化剂,该催化剂具有促进剂元素氧化锆,并且按EP-A-428223的实施例11制备。催化剂B为载带在二氧化钛载体上的钴催化剂,该催化剂具有促进剂元素锰,并按W099/34917中描述的通用方法制备,即应用110.5g二氧化钛粉末(商标名为P25,由Degussa商购得到)、51.4g商购得到的Mn/Co比率(%原子/原子)为5.6的MnCo(OH)x共沉积物制备。该混合物通过揉制30分钟而压实。应用Bonnot挤出机使混合物成型。将挤出物(1.7mm的三叶状)在120℃下干燥2小时,并在550℃煅烧2小时。所得的挤出物含有20wt%的Co、1wt%的Mn和71.1wt%的TiO2。
按照上文实施例10相同的方式通过还原使这三种催化剂转化为活性的费-托催化剂。
还原后,按H2/CO比率为1.1:1引入氢和一氧化碳的混合物实施烃的制备。GHSV、反应温度(按重均床层温度表示)和压力按表3所示的设定。操作120小时后,确定如下量:空时产率(STY),以每小时每升催化剂颗粒(包括颗粒间的空隙)的烃产品克数表示;对含有5个或更多个碳原子的烃的选择性(C5+选择性),以总烃产品的wt%表示;对含有11-14个碳原子的烃的选择性(C11-C14选择性),以总烃产品的wt%表示;以及C11-14烃产品的烯烃度,以C11-C14烃产品的wt%表示。结果在下表3中给出。
表3:
实施例8的催化剂 | 催化剂A(比较) | 催化剂B(比较) | |
H<sub>2</sub>/CO原料比率 | 1.1 | 1.1 | 1.1 |
原料气中的氦含量[vol%] | 15 | 15 | 15 |
温度,℃ | 221 | 221 | 222 |
压力,bar绝压 | 60 | 60 | 58 |
GHSV,NL/(1.hr) | 1200 | 1200 | 1200 |
STY,g/(1.hr) | 152 | 115 | 170 |
C5+选择性,wt% | 81 | 73 | 87 |
C11-C14选择性,wt% | 11.6 | 9.3 | 9.2 |
C11-C14烯烃度,wt% | 31 | 19 | 19 |
C20-C39,α | 0.91 | 0.93 | 0.94 |
表3的结果表明:与基于其它类型的载体(如二氧化硅和二氧化钛)并应用不同方法制备的钴催化剂相比,按本发明实施例8制备的催化剂得到明显改善的C11-C14烯烃产率。
实施例12
在如下反应中应用煅烧的固体酸氧化锆催化剂:硫化氢与2-甲基-1-戊烯反应生成相应的硫醇并随后生成相应的硫醚。
应用实施例7中描述的方法制备氧化锆挤出物,只是应用1mm的三叶状模板。干燥和煅烧与实施例7中所述相同。应用上文所述BET表面积方法测得挤出物的表面积为57.7m2/g。所测的氧化锆的骨架密度为5.41g/ml,并且所测的主体密度为1.15g/ml。所测的孔体积为0.316ml/g。通过使挤出物在450℃保持2小时而确定挤出物的水分含量。热处理造成的重量减少占1.03%。取出244g挤出物,随后用硫酸浸渍。用四份75ml的硫酸将300ml 1M的硫酸浸渍入取出的氧化锆挤出物中。在每次浸渍步骤后,通过应用硅油浴提升温度至150℃而在真空下干燥所述挤出物。通过用pH值为2的乙酸萃取挤出物而确定氧化锆挤出物的硫酸盐含量。萃取液的硫酸盐含量通过用氢氧化钠滴定而确定。干燥的挤出物的硫酸含量被确定为7.7wt%。在450℃下煅烧2小时后,硫酸盐的含量降低为3.4wt%。
这样制备的煅烧固体酸催化剂在硫化氢与2-甲基-1-戊烯的反应中应用,生成相应的硫醇并随后生成相应的硫醚。用催化剂填充直径为4cm的圆柱形反应器。催化剂床层的高度为约10cm。每小时12.5NI的含500ppmv硫化氢的氮气物流与每分钟9ml的主要含芳烃的液体物流一起向上流过催化剂床层,所述芳烃如由Shell以商标名SHELLSOL A 100商购得到的。环境温度下硫化氢的转化率为80-90%。在超过一个月的时间内转化率均保持相同的水平。转化率没有达到100%的事实是由于硫化氢不能有效地从气相传递入液相。除了异-戊烯与硫化氢的反应外,也发生低聚物的形成反应。
这些实施例表明:本发明的氧化锆挤出物表现出非常好的压碎强度,并且适合在很多化学方法中用作催化剂或催化剂载体。
Claims (16)
1.制备煅烧的氧化锆挤出物的方法,该挤出物含有锆和一种或多种选自元素周期表的第IB、IIB、IIIB、IVB、VB、VIB、VIIB、VIII族或镧系和锕系元素的其它元素,所述方法包括如下步骤:
a.制备一种可成型面坯,该步骤包括混合并揉制颗粒氧化锆及一种或多种选自元素周期表的第IB、IIB、IIIB、IVB、VB、VIB、VIIB、VIII族或镧系和锕系元素的其它元素的源与溶剂得到总固含量为50-85wt%的混合物,
b.挤出所述可成型面坯形成氧化锆挤出物,该挤出物含有锆和一种或多种选自元素周期表的第IB、IIB、IIIB、IVB、VB、VIB、VIIB、VIII族或镧系和锕系元素的其它元素,和
c.干燥并煅烧在步骤b中形成的氧化锆挤出物;
特征在于所述颗粒氧化锆包含不超过15wt%的非单斜晶氧化锆的氧化锆。
2.权利要求1的方法,其中一种或多种其它元素选自元素周期表第VIII族元素。
3.权利要求1或2的方法,其中一种或多种其它元素选自钴、铁和镍。
4.权利要求1或2的方法,其中一种或多种其它元素是钴。
5.权利要求4的方法,其中所述钴的源选自氢氧化钴、乙酸钴、硝酸钴、氧化钴及其混合物。
6.权利要求1或2的方法,其中所述颗粒氧化锆包含不超过10wt%的非单斜晶氧化锆的氧化锆。
7.按权利要求1-6任一项的方法制备的煅烧的氧化锆挤出物。
8.按权利要求4-6任一项的方法制备的煅烧的氧化锆/钴挤出物。
9.制备煅烧的氧化锆挤出物的方法,该挤出物含有用一种或多种选自元素周期表的第IB、IIB、IIIB、IVB、VB、VIB、VIIB、VIII族或镧系和锕系元素的其它元素浸渍的锆,所述方法包括如下步骤:
a.制备一种可成型面坯,该步骤包括混合并揉制颗粒氧化锆与溶剂得到总固含量为50-85wt%的混合物,
b.挤出所述可成型面坯形成氧化锆挤出物,
c.在液体存在下用一种或多种选自元素周期表的第IB、IIB、IIIB、IVB、VB、VIB、VIIB、VIII族或镧系和锕系元素的其它元素的化合物浸渍所述氧化锆挤出物,形成用一种或多种选自元素周期表的第IB、IIB、IIIB、IVB、VB、VIB、VIIB、VIII族或镧系和锕系元素的其它元素浸渍的氧化锆挤出物,和
d.干燥并煅烧在步骤c中形成的氧化锆挤出物;
特征在于所述颗粒氧化锆包含不超过15wt%的非单斜晶氧化锆的氧化锆。
10.权利要求9的方法,其中一种或多种其它元素选自元素周期表第VIII族元素。
11.权利要求9或10的方法,其中一种或多种其它元素选自钴、铁和镍。
12.权利要求9或10的方法,其中一种或多种其它元素是钴。
13.权利要求12的方法,其中所述钴的源选自钴盐的水溶液,所述钴盐选自硝酸钴、乙酸钴、氢氧化钴及其混合物。
14.按照权利要求9-13中任一项的方法制备的煅烧的氧化锆挤出物。
15.按照权利要求12或13的方法制备的煅烧的钴浸渍的氧化锆挤出物。
16.制备具有11-14个碳原子的高级烯烃的方法,包括在权利要求8的煅烧的氧化锆/钴挤出物或权利要求15的煅烧的钴浸渍氧化锆挤出物作为催化剂存在下,在费-托反应条件下使氢和一氧化碳接触。
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MY143120A (en) * | 2003-02-20 | 2011-03-15 | Shell Int Research | A process for the preparation of detergent compounds |
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WO2009071863A2 (fr) * | 2007-11-30 | 2009-06-11 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Poudre nanometrique |
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US8859828B2 (en) * | 2009-03-02 | 2014-10-14 | Clariant Corporation | Conversion of sugar, sugar alcohol, or glycerol to valuable chemicals using a promoted zirconium oxide supported catalyst |
US20110301021A1 (en) * | 2009-03-02 | 2011-12-08 | Sud-Chemie Inc. | Promoted zirconium oxide catalyst support |
JP2012136516A (ja) * | 2010-12-08 | 2012-07-19 | Idemitsu Kosan Co Ltd | オレフィンの製造方法 |
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EP3024572A1 (en) | 2013-06-27 | 2016-06-01 | Clariant Corporation | Manganese oxide-stabilized zirconia catalyst support materials |
US20150314274A1 (en) * | 2014-05-02 | 2015-11-05 | Clariant Corporation | Metal oxide-stabilized zirconium oxide ceramic materials |
GB201518996D0 (en) * | 2015-10-27 | 2015-12-09 | Magnesium Elektron Ltd | Zirconia-based compositions for use as three-way catalysts |
CN107297206A (zh) | 2016-04-14 | 2017-10-27 | 巴斯夫公司 | 用于稀燃压缩天然气发动机的氧化催化剂 |
US10618042B1 (en) | 2017-05-31 | 2020-04-14 | University Of South Florida | Mixed metal oxide extrudate catalyst |
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