CN1283522A - 多组分催化剂 - Google Patents
多组分催化剂 Download PDFInfo
- Publication number
- CN1283522A CN1283522A CN00122547A CN00122547A CN1283522A CN 1283522 A CN1283522 A CN 1283522A CN 00122547 A CN00122547 A CN 00122547A CN 00122547 A CN00122547 A CN 00122547A CN 1283522 A CN1283522 A CN 1283522A
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- CN
- China
- Prior art keywords
- catalyst
- carrier
- lanthanum
- preferred
- platinum
- 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.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 9
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 9
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 5
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000002243 precursor Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- 238000001354 calcination Methods 0.000 description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 12
- 239000001294 propane Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 6
- 235000013847 iso-butane Nutrition 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- -1 rare earth compound Chemical class 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 230000019612 pigmentation Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 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
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000010424 alunite Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- YKIAZARODMJWBV-UHFFFAOYSA-N formic acid;lanthanum Chemical compound [La].OC=O YKIAZARODMJWBV-UHFFFAOYSA-N 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- KGDJAQAMSDMZCD-UHFFFAOYSA-M hydrogen carbonate lanthanum(3+) oxygen(2-) Chemical compound C([O-])(O)=O.[O-2].[La+3] KGDJAQAMSDMZCD-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B01J35/613—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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Abstract
本发明公开了一种多组分催化剂,其包含载负于氧化锆载体上的a)铂和锡,b)镓、铟、钴和/或锗,c)根据需要,还含钪、钇和/或镧,和d)根据需要,还含碱金属和/或碱土金属,所述的氧化锆载体如果需要的话还包含SiO2、Al2O3和/或TiO2。
Description
本发明涉及一种多组分催化剂,其包含载负于氧化锆载体上的a)铂和锡,b)镓、铟、钴和/或锗,c)根据需要,加钪、钇和/或镧,和d)根据需要,加碱金属和/或碱土金属,所述的氧化锆载体如果需要的话还包含SiO2、Al2O3和/或TiO2。
US-A-5,220,091描述了一种催化剂,其包含Pt/Sn作为在Zn尖晶石载体上的活性组分,用于采用蒸气作为稀释剂进行的低级烃分子,如异丁烷的脱氢,这些催化剂的性能还需要进行改进,其原因在于,尽管进料用蒸气进行了高度稀释(比例=4∶1),但是,在高达600℃的反应温度下仅能达到相对较纸的转化率和选择性。同样地,改善的意义还体现在催化剂的操作寿命上,因为这些催化剂仅在运行7个小时后就需要进行再生。
US-A-4,788,371公开了Pt/Sn/Cs/Al2O3催化剂,其用于在蒸气存在下(例如蒸气/丙烷比例为10∶1)下进行烃脱氢反应。尽管高度稀释,但也仅达到21%的较纸转化率。
WO-A-94/29021公开了一种催化剂,该催化剂基于镁和铝的混合氧化物与元素周期表第Ⅷ族的贵金属、第Ⅳa族的金属以及选择性的第Ⅰa族的碱金属,用于例如比例为8∶7∶1∶5的H2O/丙烷/H2/N2的气体混合物脱氢。这些催化剂的工业应用缺陷是它们的硬度较低,使其在工业上难以使用。进而,这些催化剂的性能,特别是在低反应温度下的性能还需要改进。其它缺点是,操作过程复杂,需要在进料中加入氢气,并且混入氮气以进一步稀释来保证其性能。
本发明的目的是改善上述缺陷。
业已发现,上述目的可通过一种下述的新型改进多组分催化剂来实现,所述催化剂包含载负于氧化锆载体上的
a)铂和锡,
b)镓、铟、钴和/或锗,
c)根据需要,还含钪、钇和/或镧,和
d)根据需要,还含碱金属和/或碱土金属,所述的氧化锆载体如果需要的话还包含SiO2、Al2O3和/或TiO2。
本发明的催化剂可以使用通过煅烧转化成氧化物的锆氧化物的前体来制造。这些可通过公知的方法生产,例如,采用溶胶-凝胶法、盐沉淀法、相应酸的脱水法、干混法、浆液法或喷雾干燥法。例如,ZrO2载体可通过下述方法生产:首先,通过适宜的含锆前体进行沉淀,制备一种富含水的式ZrO2(xH2O的锆氧化物。适宜的锆前体例如为Zr(NO3)4、ZrOCl2或ZrCl4。沉淀过程中加入碱,如NaOH、KOH、Na2CO3和NH3,如EP-A-849 224所述。
为了生产具有特殊孔半径分布的ZrO2,可在ZrO2中加入能够通过煅烧部分或完全除去的各种聚合物从而形成孔半径限定于一定范围内的孔。例如,可通过简单的机械混合或通过在喷雾干燥器中进行喷雾干燥以使两种组分混合。
业已发现,加入聚乙烯基吡咯烷酮(PVP)对于生产具有两种孔半径分布方式的ZrO2是特别有用的。如果在生产步骤中向ZrO2前体中加入PVP,在煅烧后可形成200-5000mm的大孔。使用PVP的另一个优点是,载体更容易成型。因此,当在120℃下干燥的新沉淀出的含水ZrO2·xH2O中加入聚乙烯基吡咯烷酮和甲酸时,易于生产出具有优异机械性质的挤出物。
除了纯ZrO2外,也可以采用锆的混合氧化物作为载体。这些混合氧化物可进一步包含钛、硅或铝的氧化物作为附加组分。业已发现,采用以ZrO2计,包含0.5-10wt%SiO2的ZrO2·xSiO2混合氧化物,和包含0.5-10wt%SiO2及0.5-60wt% Al2O3的ZrO2·xAl2O3·xSiO2混合氧化物是特别有益的。
混合氧化物例如可通过共沉淀法、前体干混法或结合喷雾法制备。在制备ZrO2·xSiO2混合氧化物时,特别有用的方法是采用具有通式ZrO2·XH2O的锆化合物与含SiO2的溶胶(如LudoxTM)进行的结合喷雾法。在将该混合物干燥后,加入Al2O3,例如AlOOH(勃姆石)形式的前体。一起涅合后,通过煅烧可获得混合氧化物载体。
本发明的催化剂载体在煅烧后通常有更高的BET表面积。该BET表面积通常为40-250m2/g,优选50-200m2/g,特别优选70-150m2/g,本发明催化剂的孔体积通常为0.2-0.8ml/g,优选0.25-0.5ml/g。本发明催化剂的平均孔半径(由Hg测孔仪测量)为3-20nm,优选4-15nm。
载体的煅烧优选在涂敷了活性组分后进行,煅烧温度为400-700℃,优选500-650℃,特别优选560-620℃。煅烧温度应至少与采用本发明催化剂进行脱氢反应的反应温度一样高。
载体可掺杂入碱性化合物,掺杂过程可在载体形成过程中进行,例如通过共沉淀法,或者随后进行,例如通过用碱金属化合物或碱土金属化合物或过渡族Ⅲ的化合物或稀土金属化合物浸渍混合氧化物。特别适宜的掺杂剂为钾、铯和镧。
按照本发明,通常采用适宜的金属盐前体浸渍法以涂敷脱氢活性组分铂以及至少一种选自镓、铟、锗和/或钴。但是,也可通过其它方法来涂敷脱氢活性组分而不采用浸渍法,例如,将金属盐前体喷雾至载体上。适宜的金属盐前体例如为适宜金属的硝酸盐、乙酸盐和氯化物,也可以采用金属的配合物阴离子。优选采用铂,如H2PtCl6或Pt(NO3)2。双金属组分镓、铟、锗和钴的适宜的金属盐前体例如为相应金属的硝酸盐、乙酸盐和氯化物,也可以采用金属的配合物阴离子。
优选采用镓,如Ga(NO3)3·xH2O,铟,如In(NO3)3·xH2O,锗,如GeCl4和钴,如C0(CH3COO)2。双金属组分可与铂组分一起以相同的溶液进行涂敷,也可以在涂敷铂组分之前涂敷,或在涂敷铂组分之后涂敷。优选铂组分和双金属组分在某一溶剂中进行结合涂敷。适用于金属盐前体的溶剂为水和有机溶剂。特别有用的是低级醇如甲醇和乙醇。
适宜的前体为由公知方法制备的相应金属的溶胶,例如在稳定剂,如PVP存在下用还原剂还原金属盐。该技术在DE-A-195 00 366中有详细描述。
催化剂在反应器中可设置成固体床,或者例如可以流化床形式使用,并可具有适宜的形状。适宜的形状例如为颗粒(粉碎物料)、丸粒、整体料、球体或挤出物(柱形、马车轮形、星形、环形)。
碱金属、碱土金属或过渡族Ⅲ金属或稀土金属或锌的含量通常为0-20wt%,优选0.1-15wt%,特别优选0.3-10wt%。所用碱金属和碱土金属前体一般是通过锻烧可转化成相应氧化物的化合物,适宜前体例子为碱金属和碱土金属的氢氧化物、碳酸盐、草酸盐、乙酸盐或混合羟基碳酸盐。
如果载体附加并专有地掺杂有过渡族Ⅲ的金属,则在此情形下,也应使用那些可通过煅烧转化成相应氧化物的化合物。如果采用镧,适宜的前体例如为碳酸氧化镧(lanthanum oxide carbonate)、La(OH)3,La3(CO3)2,La(NO3)3或包含有机阴离子的镧化合物,例如乙酸镧、甲酸镧或草酸镧。
存在于本发明催化剂中的铂的含量通常为0.05-5wt%,优选0.1-1wt%,特别优选0.2-0.5wt%。存在于本发明催化剂中的选自镓、铟、锗和/或钴的一种或多种元素的含量通常为0.05-5wt%,优选0.1-1wt%,特别优选0.2-0.5wt%。
丙烷的脱氢通常在下述反应条件下进行:反应温度300-800℃,优选450-700℃,压力为0.1-100巴,优选0.1-40巴,GHSV(气体小时空速)100-10,000h-1,优选500-2000h-1。除了被脱氢的烃外,进料还包含稀释剂,如CO2、N2、稀有气体和/或蒸气。
本发明催化剂的具体特征是,它们在蒸气存在下的烃脱氢反应中具有活性,因此,可以利用其相应的优点,如解除平衡限制,碳沉积形成减少及操作时间延长。
如果需要的话,可在烃进料中加入氢气,在此情形下,氢气与烃的比例通常为0.1至100,优选1至20。采用本发明的催化剂进行的烃脱氢反应优选在不加入氢气的条件下进行。
除了连续加入气体特别是蒸气外(通入蒸汽减小反应中的碳沉积),也有可能通过通入氢气或空气不时地再生催化剂。再生过程的温度为300-900℃,优选400-800℃,采用游离氧化剂,优选采用空气,或者在还原气氛下进行再生,优选包含氢气。再生可以低于大气压、大气压或高于大气压的压力下进行。优选压力范围为0.5-100巴。
采用本发明的催化剂进行的脱氢反应适用的烃例如为C2-C16-烃,如乙烷、正丙烷、正丁烷、异丁烷、正戊烷、异戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷、正十一烷、正十二烷、正十三烷、正十四烷、正十五烷、正十六烷,优选C2-C8烃,如乙烷、、正丙烷、正丁烷、异丁烷、正戊烷、异戊烷、正己烷、正庚烷、正辛烷,特别优选C2-C4烃,如乙烷、正丙烷、正丁烷和异丁烷,特别是丙烷和异丁烷。
丙烯为一种人们看着的产品,特别是可用于合成聚丙烯或用于合成功能化单体和其聚合产物。丙烷脱氢是代替轻油进行蒸气裂解生产丙烯的方法。
异丁烯也是一种重要产品,其特别适用于生产MTBE(甲基叔丁基醚)。其可用作(尤其在美国)燃料添加剂以增加辛烷值。异丁烯可通过与制丙烯类似的方法经异丁烷脱氢生产。
实施例
催化剂生产
实施例1
采用ULTRA-TURRAXTMT50(来自Ika),将ZrO2含量为89.8%的4835.82g的ZrO2·xH2O在12升水中成浆并粉碎。向悬浮液中加入SiO2含量为47.6%的SiO2溶胶(LudoxTM)330.84g。将喷雾浆液在NIRO喷雾器中喷雾干燥,固体/水比例为1∶3.7,在顶部温度为350℃,出口温度为105-110℃,喷雾压力在28,000rpm下为5.2巴的条件下,得到一种白色粉末。将喷雾干燥的粉末在600℃下煅烧2小时。再将1416.5g喷雾干燥后的粉末与400g的PuralTM SCF(勃姆石,灼烧损失为25%)混合,再加入25g的浓HNO3(65%),捏合2.5小时。将捏合后的混合物采用活塞式挤出机在50巴下挤出,形成3mm的固体挤出物。切割硬度为51N/挤出物(SA=22N)。
将88g已粉碎至1.6-2mm的载体用下述溶液浸渍:1.2063g的SnCl2·2H2O和0.6748g的H2PtCl6·6H2O以及1.1157g的Co·CH3COO)4·4H2O在524ml乙醇中的溶液。减压下除去上清液,将残余物在100℃下煅烧15小时,随后在560℃下煅烧3小时。随后,将其用下述溶液浸渍:0.6595g的CsNO3和1.1633g的KNO3在219ml水中的溶液。将催化剂在100℃下干燥15小时,再在560℃下煅烧3小时。
催化剂的BET表面积为95m2/g。汞测孔法测得的孔体积为0.37m1/g,计算出的孔面积为91m2/g,平均孔半径为18.6nm。
催化剂的组成如表1所示。
实施例2
重复实施例1的过程,只是在粉碎的载体浸渍过程中采用1.62g的Ga(NO3)3w 9H2O代替Co(CH3COO)2·4H2O。
催化剂的BET表面积为93m2/g。汞测孔法测得的孔体积为0.36ml/g,计算出的孔面积为95m2/g,平均孔半径为17.7nm。
催化剂的组成如表1所示。
实施例3
重复实施例1的过程,只是在粉碎的载体浸渍过程中采用0.797g的GeCl4代替Co(CH3COO)2·4H2O。
催化剂的BET表面积为94m2/g。汞测孔法测得的孔体积为0.36ml/g,计算出的孔面积为94m2/g,平均孔半径为17.8nm。
催化剂的组成如表1所示。
实施例4
重复实施例1的过程,只是在粉碎的载体的浸渍过程中采用0.919g的In(NO3)3·5H2O代替Co(CH3COO)2·4H2O。
催化剂的BET表面积为94m2/g。汞测孔法测得的孔体积为0.36ml/g,计算出的孔面积为95m2/g,平均孔半径为18.3nm。
催化剂的组成如表1所示。
比较例
为进行比较,生产如WO-A-94/29021的实施例1所述的催化剂(Pt/Sn/Cs/Mg(Al)O)。
催化剂实验
将20ml催化剂安装于管式反应器中,反应器的内径为22mm。催化剂用氢气在580℃下处理30分钟,然后置于80%氮气和20%空气的混合物(贫空气)中,随后用纯氮气冲洗15分钟,用氢气还原30分钟,使20标准升/小时的丙烷(99.5%纯度)和H2O以摩尔比丙烷/蒸气1∶1通过反应器。压力为1.5巴,GHSV值为1000h-1。反应产物用气相色谱法进行分析。
实施例1-4和比较例的结果示于表1。
表1:实施例1-4的催化剂和比较例的催化剂在丙烷脱氢中的性能*
转化率[%] | 选择性[%] | |||||||||||
实施例 | Pt[%] | Sn[%] | Met[%] | K[%] | Cs[%] | ZrO2[%] | Al2O3[%] | SiO2[%] | 1小时后 | 17小时后 | 1小时后 | 17小时后 |
1 | 0.3 | 0.6 | 0.3Co | 0.5 | 0.5 | 75.6 | 19.5 | 2.7 | 44 | 36 | 80 | 90 |
2 | 0.3 | 0.6 | 0.3Ga | 0.5 | 0.5 | 75.6 | 19.5 | 2.7 | 41 | 36 | 83 | 93 |
3 | 0.3 | 0.6 | 0.3Ge | 0.5 | 0.5 | 75.6 | 19.5 | 2.7 | 41 | 34 | 82 | 84 |
4 | 0.3 | 0.6 | 0.3In | 0.5 | 0.5 | 75.6 | 19.5 | 2.7 | 41 | 37 | 83 | 88 |
0.3 | 0.6 | --- | --- | 0.5 | --- | --- | --- | 33 | 29 | 92 | 95 |
*)实验条件:20ml催化剂,颗粒粒径=1.6-2mm;580℃;丙烷/H2O 1∶1(mol/mol);20丙烷标准升/小时;GHSV=1000h-1;1.5巴。
**)比较催化剂:Pt/Sn/Cs/Mg(Al)O来自WO-A-94/29021的实施例1。
Claims (5)
1、一种多组分催化剂,其包含载负于氧化锆载体上的
a)铂和锡,
b)镓、铟、钴和/或锗,
c)根据需要,还含钪、钇和/或镧,和
d)根据需要,还含碱金属和/或碱土金属,所述载体如果需要的话还包含SiO2、Al2O3和/或TiO2。
2、根据权利要求1的多组分催化剂,其包含载负于载体上的
a)0.05-2wt%的铂和0.05-5wt%锡,
b)0.05-5wt%的镓、铟、钴和/或锗,
c)0-5wt%的钪、钇和/或镧,和
d)0-10wt%的碱金属和/或碱土金属。
3、根据权利要求1或2的多组分催化剂,其包含0-5wt%的镧作为c)组分,和0.1-5wt%的钾和/或铯作为d)组分。
4、权利要求1-3任一项的催化剂在C2-C16烃的脱氢反应中的用途。
5、一种C2-C16烃脱氢的方法,在权利要求1-4任一项的催化剂存在下,并在蒸气存在或不存在下进行。
Applications Claiming Priority (2)
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DE19937106.7 | 1999-08-06 | ||
DE19937106A DE19937106A1 (de) | 1999-08-06 | 1999-08-06 | Multikomponenten-Katalysatoren |
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CN1283522A true CN1283522A (zh) | 2001-02-14 |
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ID=7917411
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CN00122547A Pending CN1283522A (zh) | 1999-08-06 | 2000-08-07 | 多组分催化剂 |
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EP (1) | EP1074299A3 (zh) |
CN (1) | CN1283522A (zh) |
DE (1) | DE19937106A1 (zh) |
NO (1) | NO20003933L (zh) |
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-
1999
- 1999-08-06 DE DE19937106A patent/DE19937106A1/de not_active Withdrawn
-
2000
- 2000-07-12 EP EP00115123A patent/EP1074299A3/de not_active Withdrawn
- 2000-08-03 NO NO20003933A patent/NO20003933L/no unknown
- 2000-08-07 CN CN00122547A patent/CN1283522A/zh active Pending
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Also Published As
Publication number | Publication date |
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NO20003933D0 (no) | 2000-08-03 |
DE19937106A1 (de) | 2001-02-08 |
EP1074299A2 (de) | 2001-02-07 |
NO20003933L (no) | 2001-02-07 |
EP1074299A3 (de) | 2001-02-21 |
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