WO2003074176A2 - Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion - Google Patents
Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion Download PDFInfo
- Publication number
- WO2003074176A2 WO2003074176A2 PCT/US2003/004153 US0304153W WO03074176A2 WO 2003074176 A2 WO2003074176 A2 WO 2003074176A2 US 0304153 W US0304153 W US 0304153W WO 03074176 A2 WO03074176 A2 WO 03074176A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal oxide
- catalyst composition
- group
- oxide
- molecular sieve
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 157
- 239000003054 catalyst Substances 0.000 title claims abstract description 151
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims description 72
- 230000008569 process Effects 0.000 title claims description 55
- 238000006243 chemical reaction Methods 0.000 title abstract description 25
- 238000002360 preparation method Methods 0.000 title description 2
- 150000001336 alkenes Chemical class 0.000 claims abstract description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 230000000737 periodic effect Effects 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 129
- 150000004706 metal oxides Chemical class 0.000 claims description 122
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 54
- 239000011230 binding agent Substances 0.000 claims description 34
- 239000011159 matrix material Substances 0.000 claims description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 27
- 239000001569 carbon dioxide Substances 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 4
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 18
- 239000005977 Ethylene Substances 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 20
- 229910001868 water Inorganic materials 0.000 description 20
- 239000002002 slurry Substances 0.000 description 17
- -1 titanium metal oxide Chemical class 0.000 description 16
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- 238000007792 addition Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 229910052746 lanthanum Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000001294 propane Substances 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 239000000908 ammonium hydroxide Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000008240 homogeneous mixture Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000006276 transfer reaction Methods 0.000 description 3
- 229910009112 xH2O Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 150000001255 actinides Chemical class 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- YCLAMANSVUJYPT-UHFFFAOYSA-L aluminum chloride hydroxide hydrate Chemical compound O.[OH-].[Al+3].[Cl-] YCLAMANSVUJYPT-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000002407 reforming Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- 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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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C10G45/44—Hydrogenation of the aromatic hydrocarbons
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- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the present invention relates to molecular sieve compositions and catalysts containing the same, to the synthesis of such compositions and catalysts and to the use of such compositions and catalysts in conversion processes to produce olefin(s).
- Olefms are traditionally produced from petroleum feedstocks by catalytic or steam cracking processes. These cracking processes, especially steam cracking, produce light olefm(s), such as ethylene and/or propylene, from a variety of hydrocarbon feedstocks. Ethylene and propylene are important commodity petrochemicals useful in a variety of processes for making plastics and other chemical compounds.
- oxygenates especially alcohols
- the preferred alcohol for light olefrn production is methanol and the preferred process for converting a methanol-containing feedstock into light olef ⁇ n(s), primarily ethylene and/or propylene, involves contacting the feedstock with a molecular sieve catalyst composition.
- SAPO silicoaluminophosphate
- Silicoaluminophosphate molecular sieves contain a three-dimensional microporous crystalline framework structure of [SiO 2 ], [AlO 2 ] and [PO 2 ] corner sharing tetrahedral units.
- 4,465,889 describes a catalyst composition
- a silicalite molecular sieve impregnated with a thorium, zirconium, or titanium metal oxide for use in converting methanol, dimethyl ether, or a mixture thereof into a hydrocarbon product rich in iso-C 4 compounds.
- U.S. Patent No. 6,180,828 discusses the use of a modified molecular sieve to produce methylamines from methanol and ammonia where, for example, a silicoaluminophosphate molecular sieve is combined with one or more modifiers, such as a zirconium oxide, a titanium oxide, an yttrium oxide, montmorillonite or kaolinite.
- U.S. Patent No. 5,417,949 relates to a process for converting noxious nitrogen oxides in an oxygen containing effluent into nitrogen and water using a molecular sieve and a metal oxide binder, where the preferred binder is titania and the molecular sieve is an aluminosilicate.
- EP-A-312981 discloses a process for cracking vanadium-containing hydrocarbon feed streams using a catalyst composition comprising a physical mixture of a zeolite embedded in an inorganic refractory matrix material and at least one oxide of beryllium, magnesium, calcium, strontium, barium or lanthanum, preferably magnesium oxide, on a silica-containing support material.
- Kang and Inui Effects of decrease in number of acid sites located on the external surface ofNi-SAPO-34 crystalline catalyst by the mechanochemical method, Catalysis Letters 53, pages 171-176 (1998) disclose that the shape selectivity can be enhanced and the coke formation mitigated in the conversion of methanol to ethylene over Ni-SAPO-34 by milling the catalyst with MgO, CaO, BaO or Cs 2 O on microspherical non-porous silica, with BaO being most preferred.
- WO 98/29370 discloses the conversion of oxygenates to olefins over a small pore non-zeolitic molecular sieve containing a metal selected from the group consisting of a lanthanide, an actinide, scandium, yttrium, a Group 4 metal, a Group 5 metal or combinations thereof.
- the invention resides in a catalyst composition comprising a molecular sieve and at least one oxide of a metal selected from Group 4 of the Periodic Table of Elements, wherein said metal oxide has an uptake of carbon dioxide at 100°C of at least 0.03, and typically at least 0.035, mg/m 2 of the metal oxide.
- the catalyst composition also includes at least one of a binder and a matrix material different from said metal oxide.
- the catalyst composition may also include an oxide of a metal selected from Group 2 and Group 3 of the Periodic Table of Elements.
- the Group 4 metal oxide comprises zirconium oxide and the Group 2 and/or Group 3 metal oxide comprises one or more oxides selected from calcium oxide, barium oxide, lanthanum oxide, yttrium oxide and scandium oxide.
- the molecular sieve conveniently comprises a silicoaluminophosphate.
- the invention resides in a molecular sieve catalyst composition comprising an active Group 4 metal oxide and a Group 2 and/or a
- Group 3 metal oxide a binder, a matrix material, and a silicoaluminophosphate molecular sieve.
- the invention resides in a method for making a catalyst composition, the method comprising the step of physically mixing first particles comprising a molecular sieve with second particles comprising a Group 4 metal oxide and having an uptake of carbon dioxide at 100°C of at least 0.03 mg/m 2 of the metal oxide particles.
- said second particles are produced by causing a hydrated precursor of said Group 4 metal oxide to precipitate from a solution containing ions of said metal, hydrothermally treating the hydrated precursor at a temperature of at least 80°C for up to 10 days and then calcining the hydrated precursor at a temperature in the range of from 400°C to 900°C.
- the invention is directed to a process for producing olefin(s) by converting a feedstock, such as an oxygenate, conveniently an alcohol, for example methanol, into one or more olefin(s) in the presence of a catalyst composition comprising a molecular sieve and an active Group 4 metal oxide having an uptake of carbon dioxide at 100°C of at least 0.03 mg/m 2 of the metal oxide.
- a feedstock such as an oxygenate, conveniently an alcohol, for example methanol
- the invention is directed to a process for converting a feedstock into one or more olefin(s) in the presence of a molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material and a mixture of metal oxides different from the binder and the matrix material.
- the catalyst composition has a Lifetime
- Enhancement Index greater than 1, such as greater than 1.5.
- LEI is defined herein as the ratio of the lifetime of the catalyst composition to that of the same catalyst composition in the absence of an active metal oxide.
- the invention is directed to a molecular sieve catalyst composition and to its use in the conversion of hydrocarbon feedstocks, particularly oxygenated feedstocks, into olefin(s). It has been found that combining a molecular sieve with one or more active metal oxides results in a catalyst composition with a longer lifetime when used in the conversion of feedstocks, such as oxygenates, more particularly methanol, into olefin(s).
- the resultant catalyst composition tends to yield larger amounts of the desired lower olefins, especially propylene and lower amounts of unwanted ethane and propane, together with other undesirable compounds, such as aldehydes and ketones, specifically acetaldehyde.
- the preferred active metal oxides are those having a Group 4 metal
- the catalyst composition also contains at least one oxide of a metal selected from Group 2 and/or Group 3 of the Periodic Table of Elements.
- Non-limiting examples of preferred molecular sieves particularly for use in converting an oxygenate containing feedstock into olefm(s), include framework types AEL, AFY, AEI, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON.
- the molecular sieve employed in the catalyst composition of the invention has an AEI topology or a CHA topology, or a combination thereof, most preferably a CHA topology.
- Crystalline molecular sieve materials have a 3 -dimensional, four- connected framework structure of corner-sharing [TO 4 ] tetrahedra, where T is any tetrahedrally coordinated cation, such as [SiO 4 ], [AlO 4 ] and/or [PO 4 ] tetrahedral units.
- the molecular sieves useful herein conveniently comprise a framework including [AlO 4 ] and [PO 4 ] tetrahedral units, i.e., an aluminophosphate (A1PO) molecular sieve, or [SiO 4 ], [AlO 4 ] and [PO 4 ] ] tetrahedral units, i.e., a silicoaluminophosphate (SAPO) molecular sieve.
- SAPO silicoaluminophosphate
- the molecular sieves useful herein is a silicoaluminophosphate (SAPO) molecular sieve or a substituted, preferably a metal substituted, SAPO molecular sieve.
- suitable metal substituents are an alkali metal of Group 1 of the Periodic Table of Elements, an alkaline earth metal of Group 2 of the Periodic Table of Elements, a rare earth metal of Group 3 of the Periodic Table of Elements, including the Lanthanides: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, erbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; and scandium or yttrium, a transition metal of Groups 4 to 12 of the Periodic Table of Elements, or mixtures of any of these metal species.
- the molecular sieve used herein has a pore systenm defined by an 8-membered ring of [TO 4 ] tetrahedra and has an average pore size less than 5 A, such as in the range of from 3 A to 5 A, for example from 3 A to 4.5 A, and particularly from 3.5A to 4.2A.
- Non-limiting examples of SAPO and A1PO molecular sieves useful herein include one or a combination of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. Patent No. 6,162,415), SAPO-47, SAPO-56, A1PO-5, AlPO-11, A1PO-18, A1PO-31, A1PO-34, A1PO-36, A1PO-37, A1PO-46, and metal containing molecular sieves thereof.
- molecular sieves are one or a combination of SAPO-18, SAPO- 34, SAPO-35, SAPO-44, SAPO-56, AlPO-18 and A1PO-34 and metal containing derivatives thereof, such as one or a combination of SAPO-18, SAPO-34, A1PO- 34 and AlPO-18, and metal containing derivatives thereof, and especially one or a combination of SAPO-34 and AlPO-18, and metal containing derivatives thereof.
- the molecular sieve is an intergrowth material having two or more distinct crystalline phases within one molecular sieve composition.
- intergrowth molecular sieves are described in the U.S. Patent Application Publication No. 2002-0165089 and International Publication No.
- WO 98/15496 published April 16, 1998, both of which are herein fully incorporated by reference.
- SAPO-18, AlPO-18 and RUW-18 have an AEI framework-type
- SAPO-34 has a CHA framework-type.
- the molecular sieve used herein may comprise at least one intergrowth phase of AEI and CHA framework-types, especially where the ratio of CHA framework-type to AEI framework-type, as determined by the DIFFaX method disclosed in U.S. Patent Application Publication No. 2002-0165089, is greater than 1:1.
- the molecular sieve is a silicoaluminophosphate
- the molecular sieve has a Si/Al ratio less than or equal to 0.65, such as from 0.65 to 0.10, preferably from 0.40 to 0.10, more preferably from 0.32 to 0.10, and most preferably from 0.32 to 0.15.
- Active metal oxides useful herein are those metal oxides, different from typical binders and/or matrix materials, that, when used in combination with a molecular sieve, provide benefits in catalytic conversion processes.
- Preferred active metal oxides are those metal oxides having a Group 4 metal, such as zirconium and/or hafnium, either alone or in combination with a Group 2 (for example magnesium, calcium, strontium and barium) and/or a Group 3 metal (including the Lanthanides and Actinides) oxide, (for example yttrium, scandium and lanthanum).
- the most preferred active Group 4 metal oxide is a zirconium metal oxide, either alone or in combination with calcium oxide, barium oxide, lanthanum oxide and/or yttrium oxide.
- oxides of silicon, aluminum, and combinations thereof are not preferred.
- active metal oxides are those metal oxides, different from typical binders and/or matrix materials, that, when used in combination with a molecular sieve in a catalyst composition, are effective in extending of the useful life of the catalyst composition, particularly in the conversion of a feedstock comprising methanol into one or more olefin(s). Quantification of the extension in catalyst life is determined by the Lifetime Enhancement Index (LEI) as defined by the following equation:
- Lifetime of Catalyst where the lifetime of the catalyst or catalyst composition, in the same process under the same conditions, is the cumulative amount of feedstock processed per gram of catalyst composition until the conversion of feedstock by the catalyst composition falls below some defined level, for example 10%.
- An inactive metal oxide will have little to no effect on the lifetime of the catalyst composition, or will shorten the lifetime of the catalyst composition, and will therefore have a LEI less than or equal to 1.
- active metal oxides of the invention are those metal oxides, different from typical binders and/or matrix materials, that, when used in combination with a molecular sieve, provide a molecular sieve catalyst composition that has a LEI greater than 1.
- a molecular sieve catalyst composition that has not been combined with an active metal oxide will have a LEI equal to 1.0.
- a catalyst composition can be produced having an LEI in the range of from greater than 1 to 20, such as from 1.5 to 10.
- catalyst compositions according to the invention exhibit LEI values greater than 1.1, for example in the range of from 1.2 to 15, and more particularly greater than 1.3, such as greater than 1.5, such as greater than 1.7, such as greater than 2.
- the metal oxides useful herein have an uptake of carbon dioxide at 100°C of at least 0.03 mg/m 2 of the metal oxide, such as at least 0.035 mg/m 2 of the metal oxide.
- the metal oxides useful herein will have a carbon dioxide at 100°C of less than 10 mg/m 2 of the metal oxide, such as less than 5 mg/m 2 of the metal oxide.
- the metal oxides useful herein have a carbon dioxide uptake of 0.04 to 0.2 mg/m 2 of the metal oxide.
- the temperature of the sample is then reduced to 100°C and carbon dioxide is passed over the sample, either continuously or in pulses, again until constant weight is obtained.
- the increase in weight of the sample in terms of mg/mg of the sample based on the dry weight of the sample is the amount of adsorbed carbon dioxide.
- the carbon dioxide adsorption is measured using a Mettler TGA/SDTA 851 thermogravimetric analysis system under ambient pressure.
- the metal oxide sample is dehydrated in flowing air to 500°C for one hour.
- the temperature of the sample is then reduced in flowing helium to 100°C.
- the sample is subjected to 20 separate pulses (about 12 seconds/pulse) of a gaseous mixture comprising 10-weight % carbon dioxide with the remainder being helium. After each pulse of the adsorbing gas the metal oxide sample is flushed with flowing helium for 3 minutes.
- the increase in weight of the sample in terms of mg/mg adsorbent based on the adsorbent weight after treatment at 500°C is the amount of adsorbed carbon dioxide.
- the surface area of the sample is measured in accordance with the method of Brunauer, Emmett, and Teller (BET) published as ASTM D 3663 to provide the carbon dioxide uptake in terms of mg carbon dioxide/m 2 of the metal oxide.
- BET Brunauer, Emmett, and Teller
- the active metal oxide(s) has a BET surface area of greater than 10 m 2 /g, such as greater than 10 m 2 /g to 300 m 2 /g.
- the active metal oxide(s) has a BET surface area of at least 20 m 2 /g, such as from 20 m 2 /g to 250 m 2 /g. More preferably, the active metal oxide(s) has a BET surface area of at least 25 m 2 /g, such as from 25 m 2 /g to 200 m 2 /g. In a preferred embodiment, the active metal oxide(s) includes a zirconium oxide having a BET surface area greater than 20 m 2 /g, such as greater than 25 m 2 /g and particularly greater than 30 m 2 /g
- the active metal oxide(s) can be prepared using a variety of methods.
- the active metal oxide is made from an active metal oxide precursor, such as a metal salt, such as a halide, nitrate sulfate or acetate.
- a metal salt such as a halide, nitrate sulfate or acetate.
- suitable sources of the metal oxide include compounds that form the metal oxide during calcination, such as oxychlorides and nitrates.
- Alkoxides are also suitable sources of the Group 4 metal oxide, for example zirconium n-propoxide.
- a preferred source of the Group 4 metal oxide is hydrated zirconia. The expression, hydrated zirconia, is intended to connote a material comprising zirconium atoms covalently linked to other zirconium atoms via bridging oxygen atoms, and further comprising available hydroxyl groups.
- the hydrated zirconia is hydrothermally treated under conditions that include a temperature of at least 80°C, preferably at least 100°C.
- the hydrothermal treatment typically takes place in a sealed vessel at greater than atmospheric pressure.
- a preferred mode of treatment involves the use of an open vessel under reflux conditions.
- Agitation of hydrated Group 4 metal oxide in a liquid medium for example, by the action of refluxing liquid and/or stirring, promotes the effective interaction of the hydrated oxide with the liquid medium.
- the duration of the contact of the hydrated oxide with the liquid medium is conveniently at least 1 hour, such as at least 8 hours.
- the liquid medium for this treatment typically has a pH of about 6 or greater, such as 8 or greater.
- Non-limiting examples of suitable liquid media include water, hydroxide solutions (including hydroxides of NH 4 + , Na + , K + , Mg 2+ , and Ca 2+ ), carbonate and bicarbonate solutions (including carbonates and bicarbonates of NH 4 + , Na + , K + , Mg 2+ , and Ca 2+ ), pyridine and its derivatives, and alkyl/hydroxyl amines.
- the active metal oxide is prepared, for example, by subjecting a liquid solution, such as an aqueous solution, comprising a source of ions of a Group 4 metal to conditions sufficient to cause precipitation of a hydrated precursor of the solid oxide material, such as by the addition of a precipitating reagent to the solution.
- a liquid solution such as an aqueous solution
- the precipitation is conducted at a pH above 7.
- the precipitating agent may be a base such as sodium hydroxide or ammonium hydroxide.
- a first liquid solution comprising a source of ions of a Group 4 metal can be combined with a second liquid solution comprising a source of ions of a Group 2 and/or Group 3 metal.
- This combination of two solutions can take place under conditions sufficient to cause co-precipitation of a hydrated precursor of the mixed oxide material as a solid from the solution.
- the source of ions of the Group 4 metal and the source of ions of the Group 2 and/or Group 3 metal may be combined into a single solution. This solution may then be subjected to conditions sufficient to cause co-precipitation of a hydrated precursor to the solid mixed oxide material, such as by the addition of a precipitating reagent to the solution.
- the temperature at which the solution is maintained during the precipitation is generally less than 200°C, for example in the range of from 0°C to less than 200°C.
- a particular range of temperatures for precipitation is from 20°C to 100°C.
- the resulting gel is preferably then hydrothermally treated at temperatures of at least 80°C, preferably at least 100°C.
- the hydrothermal treatment typically takes place at atmospheric pressure.
- the gel in one embodiment, is hydrothermally treated for up to 10 days, such as up to 5 days, for example up to 3 days.
- the hydrated precursor to the metal oxide(s) is then recovered, for example by filtration or centrifugation, and washed and dried.
- the resulting material can then be calcined, such as in an oxidizing atmosphere, at a temperature of at least 400°C, such as at least 500°C, for example from 600°C to 900°C, and particularly from 650°C to 800°C, to form the active metal oxide or active mixed metal oxide.
- the calcination time is typically up to 48 hours, such as for 0.5 to 24 hours, for example for 1.0 to 10 hours. In one embodiment, calcination is carried out at about 700°C for 1 to 3 hours.
- the Group 4 metal oxide and the Group 2 and/or Group 3 metal oxide are made separately and then contacted together to form the mixed metal oxide that is then contacted with the molecular sieve.
- the Group 4 metal oxide can be contacted with the molecular sieve prior to introducing the Group 2 and/or Group 3 metal oxide or alternatively, the Group 2 and/or Group 3 metal oxide can be contacted with the molecular sieve prior to introducing the Group 4 metal oxide.
- the mole ratio of the Group 4 metal oxide to the Group 3 metal oxide may be in the range of from 1000:1 to 1:1, such as from 500:1 to 2:1, preferably from 100:1 to 3:1, more preferably from 75:1 to 5:1 based on the total moles of the Group 4 and Group 3 metal oxides.
- the catalyst composition can contain from 1 to 25 %, preferably from 1 to 20 %, more preferably from 1 to 15 %, by weight of Group 3 metal based on the total weight of the mixed metal oxide, particularly where the Group 3 metal oxide is a lanthanum or yttrium metal oxide and the Group 4 metal oxide is a zirconium metal oxide.
- the mole ratio of the Group 4 metal oxide to the Group 2 metal oxide may be in the range of from 1000:1 to 1 :2, such as from 500:1 to 2:3, preferably from 100:1 to 1:1 and more preferably from 50:1 to 2:1, based on the total moles of the Group 4 and Group 2 metal oxides.
- the catalyst composition can contain from 1 to 25 %, preferably from 1 to20 % and more preferably from 1 to 15 %, by weight of Group 2 metal based on the total weight of the mixed metal oxide, particularly where the Group 2 metal oxide is calcium oxide and the Group 4 metal oxide is a zirconium metal oxide.
- the catalyst composition of the invention includes any one of the molecular sieves previously described and one or more of the active metal oxides described above, optionally with a binder and/or matrix material different from the active metal oxide(s).
- the weight ratio of the molecular sieve to the active metal oxide in the catalyst composition is in the range of from 5 weight percent to 800 weight percent, preferably from 10 weight percent to 600 weight percent, more preferably from 20 weight percent to 500 weight percent, and most preferably from 30 weight percent to 400 weight percent.
- binders that are useful in forming the catalyst composition of the invention.
- Non-limiting examples of binders that are useful alone or in combination include various types of hydrated alumina, silicas, and/or other inorganic oxide sols.
- One preferred alumina containing sol is aluminum chlorhydrol.
- the inorganic oxide sol acts like glue binding the synthesized molecular sieves and other materials such as the matrix together, particularly after thermal treatment.
- the inorganic oxide sol preferably having a low viscosity, is converted into an inorganic oxide binder component.
- an alumina sol will convert to an aluminum oxide binder following heat treatment.
- Aluminum chlorhydrol a hydroxylated aluminum based sol containing a chloride counter ion, has the general formula of Al m O n (OH) 0 Cl p *x(H 2 O) wherein m is 1 to 20, n is 1 to 8, o is 5 to 40, p is 2 to 15, and x is 0 to 30.
- the binder is Al 13 O 4 (OH) 24 Cl 7 » 12(H 2 O) as is described in G.M. Wolterman, et al., Stud. Surf. Sci. and Catal., 76, pages 105- 144 (1993).
- one or more binders are combined with one or more other alumina materials such as aluminum oxyhydroxide, ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ - alu ina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and p-alumina, aluminum trihydroxide, such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.
- alumina materials such as aluminum oxyhydroxide, ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ - alu ina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and p-alumina
- aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.
- Non-limiting examples of commercially available colloidal alumina sols include Nalco 8676 available from Nalco Chemical Co., Naperville, Illinois, and Nyacol AL20DW available from Nyacol Nano Technologies, Inc., Ashland, Massachusetts.
- the catalyst composition contains a matrix material
- this is preferably different from the active metal oxide and any binder.
- Matrix materials are typically effective in reducing overall catalyst cost, acting as thermal sinks during regeneration, densifying the catalyst composition, and increasing catalyst physical properties such as crush strength and attrition resistance.
- Non-limiting examples of matrix materials useful herein include one or more non-active metal oxides including beryllia, quartz, silica or sols, and mixtures thereof, for example silica-magnesia, silica-zirconia, silica-titania, silica- alumina and silica-alumina-thoria.
- matrix materials are natural clays such as those from the families of montmorillonite and kaolin.
- the matrix material is a clay or a clay- type composition, particularly having a low iron or titania content, and most preferably is kaolin.
- Kaolin has been found to form a pumpable, high solids content slurry, to have a low fresh surface area, and to pack together easily due to its platelet structure.
- a preferred average particle size of the matrix material, most preferably kaolin, is from 0.1 ⁇ m to 0.6 ⁇ m with a D 90 particle size distribution of less than 1 ⁇ m.
- the catalyst composition contains a binder or matrix material
- the catalyst composition typically contains from 1% to 80%, preferably from about 5% to 60%, and more preferably from 5% to 50%, by weight of the molecular sieve based on the total weight of the catalyst composition.
- the weight ratio of the binder to the matrix material is typically from 1:15 to 1:5, such as from l:10 to 1 :4, and particularly from 1:6 to 1 :5.
- the amount of binder is typically from about 2% by weight to about 30% by weight, such as from about 5% by weight to about 20% by weight, and particularly from about 7% by weight to about 15% by weight, based on the total weight of the binder, the molecular sieve and matrix material.
- the catalyst composition typically has a density in the range of from
- 0.5 g/cc to 5 g/cc such as from from 0.6 g/cc to 5 g/cc, for example from 0.7 g/cc to 4 g/cc, particularly in the range of from 0.8 g/cc to 3 g/cc.
- the molecular sieve is first synthesized and is then physically mixed with the active metal oxide, preferably in a substantially dry, dried, or calcined state. Most preferably the molecular sieve and active metal oxide are physically mixed in their calcined state. Intimate physical mixing can be achieved by any method known in the art, such as mixing with a mixer muller, drum mixer, ribbon/paddle blender, kneader, or the like. Chemical reaction between the molecular sieve and the metal oxide(s) is unnecessary and, in general, is not preferred.
- the molecular sieve is conveniently initially formulated into a catalyst precursor with the matrix and/or binder and the active metal oxide is then combined with the formulated precursor.
- the active metal oxide can be added as unsupported particles or can be added in combination with a support, such as a binder or matrix material.
- the resultant catalyst composition can then be formed into useful shaped and sized particles by well-known techniques such as spray drying, pelletizing, extrusion, and the like.
- the molecular sieve composition and the matrix material, optionally with a binder are combined with a liquid to form a slurry and then mixed to produce a substantially homogeneous mixture containing the molecular sieve composition.
- Non-limiting examples of suitable liquids include water, alcohol, ketones, aldehydes, and/or esters. The most preferred liquid is water.
- the slurry of the molecular sieve composition, binder and matrix material is then fed to a forming unit, such as spray drier, that forms Hie catalyst composition into the required shape, for example microspheres.
- a heat treatment such as calcination is usually performed.
- Typical calcination temperatures are in the range from 400°C to 1,000°C, preferably from 500°C to 800°C and more preferably from 550°C to 700°C.
- Typical calcination environments are air (which may include a small amount of water vapor), nitrogen, helium, flue gas (combustion product lean in oxygen), or any combination thereof.
- the catalyst composition is heated in nitrogen at a temperature of from 600°C to 700°C for a period of time typically from 30 minutes to 15 hours, preferably from 1 hour to about 10 hours, more preferably from about 1 hour to about 5 hours, and most preferably from about 2 hours to about 4 hours.
- the catalyst composition described above is useful in a variety of processes including cracking, of for example a naphtha feed to light olefin(s) (U.S. Patent No. 6,300,537) or higher molecular weight (MW) hydrocarbons to lower MW hydrocarbons; hydrocracking, of for example heavy petroleum and/or cyclic feedstock; isomerization, of for example aromatics such as xylene; polymerization, of for example one or more olefin(s) to produce a polymer product; reforming; hydrogenation; dehydrogenation; dewaxing, of for example hydrocarbons to remove straight chain paraffins; absorption, of for example alkyl aromatic compounds for separating out isomers thereof; alkylation, of for example aromatic hydrocarbons such as benzene and alkylbenzenes; transalkylation, of for example a combination of aromatic and polyalkylaromatic hydrocarbons; dealkylation; hydrodecylization; disproportionation, of for example
- Preferred processes include processes for converting naphtha to highly aromatic mixtures; converting light olefm(s) to gasoline, distillates and lubricants; converting oxygenates to olefin(s); converting light paraffins to olefins and/or aromatics; and converting unsaturated hydrocarbons (ethylene and/or acetylene) to aldehydes for conversion into alcohols, acids and esters.
- the most preferred process of the invention is the conversion of a feedstock to one or more olefin(s).
- the feedstock contains one or more aliphatic-containing compounds, and preferably one or more oxygenates, such that the aliphatic moiety contains from 1 to about 50 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.
- Non-limiting examples of suitable aliphatic-containing compounds include alcohols such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide, alkylamines such as methylamine, alkyl ethers such as dimethyl ether, diethyl ether and methylethyl ether, alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehydes, and various acids such as acetic acid.
- the feedstock comprises methanol, ethanol, dimethyl ether, diethyl ether or a combination thereof, more preferably methanol and/or dimethyl ether, and most preferably methanol.
- the catalyst composition of the invention is effective to convert the feedstock primarily into one or more olefin(s).
- the olefin(s) produced typically have from 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbons atoms, and most preferably are ethylene and/or propylene.
- the catalyst composition of the invention is effective to convert a feedstock containing one or more oxygenates into a product containing greater than 50 weight percent, typically greater than 60 weight percent, such as greater than 70 weight percent, and preferably greater than 80 weight percent of olefin(s) based on the total weight of hydrocarbon in the product.
- the amount of ethylene and/or propylene produced based on the total weight of hydrocarbon in the product is typically greater than 40 weight percent, for example greater than 50 weight percent, preferably greater than 65 weight percent, and more preferably greater than 78 weight percent.
- the amount ethylene produced in weight percent based on the total weight of hydrocarbon product produced is greater than 20 weight percent, such as greater than 30 weight percent, for example greater than 40 weight percent.
- the amount of propylene produced in weight percent based on the total weight of hydrocarbon product produced is greater than 20 weight percent, such as greater than 25 weight percent, for example greater than 30 weight percent, and preferably greater than 35 weight percent.
- the catalyst composition of the invention for the conversion of a feedstock comprising methanol and dimethylether to ethylene and propylene, it is found that the production of ethane and propane is reduced by greater than 10%, such as greater than 20%, for example greater than 30%, and particularly in the range of from 30% to 40% compared to a similar catalyst composition at the same conversion conditions but without the active metal oxide component(s).
- the feedstock may contain one or more diluents, which are generally non-reactive to the feedstock or molecular sieve catalyst composition and are typically used to reduce the concentration of the feedstock.
- Non-limiting examples of diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, water, essentially non-reactive paraffins (especially alkanes such as methane, ethane, and propane), essentially non-reactive aromatic compounds, and mixtures thereof.
- the most preferred diluents are water and nitrogen, with water being particularly preferred.
- the present process can be conducted over a wide range of temperatures, such as in the range of from 200°C to 1000°C, for example from 250°C to 800°C, including from 250°C to 750 °C, conveniently from 300°C to 650°C, preferably from 350°C to 600°C and more preferably from 350°C to 550°C.
- the present process can be conducted over a wide range of pressures including autogenous pressure.
- the partial pressure of the feedstock exclusive of any diluent therein employed in the process is in the range of from 0.1 kPaa to 5 MPaa, preferably from 5 kPaa to 1 MPaa, and more preferably from 20 kPaa to 500 kPaa.
- the weight hourly space velocity (WHSV), defined as the total weight of feedstock excluding any diluents per hour per weight of molecular sieve in the catalyst composition, can range from 1 hr “1 to 5000 hr “1 , preferably from 2 hr “1 to 3000 hr “1 , more preferably from 5 hr "1 to 1500 hr "1 , and most preferably from 10 hr "1 to 1000 hr “1 .
- the WHSV is at least 20 hr "1 and, where the feedstock contains methanol and/or dimethyl ether, is in the range of from 20 hr "1 to 300 hr "1 .
- the process of the invention is conveniently conducted as a fixed bed process, or more typically as a fluidized bed process (including a turbulent bed process), such as a continuous fluidized bed process, and particularly a continuous high velocity fluidized bed process.
- the process is conducted as a fluidized bed process utilizing a reactor system, a regeneration system and a recovery system.
- fresh feedstock optionally with one or more diluent(s)
- the feedstock is converted in the riser reactor(s) into a gaseous effluent that enters a disengaging vessel in the reactor system along with the coked catalyst composition.
- the coked catalyst composition is separated from the gaseous effluent within the disengaging vessel, typically with the aid of cyclones, and is then fed to a stripping zone, typically in a lower portion of the disengaging vessel.
- the coked catalyst composition is contacted with a gas, such steam, methane, carbon dioxide, carbon monoxide, hydrogen, and/or an inert gas such as argon, preferably steam, to recover adsorbed hydrocarbons from the coked catalyst composition that is then introduced into the regeneration system.
- a gas such steam, methane, carbon dioxide, carbon monoxide, hydrogen, and/or an inert gas such as argon, preferably steam, to recover adsorbed hydrocarbons from the coked catalyst composition that is then introduced into the regeneration system.
- the coked catalyst composition is contacted with a regeneration medium, preferably a gas containing oxygen, under regeneration conditions capable of burning coke from the coked catalyst composition, preferably to a level less than 0.5 weight percent based on the total weight of the coked molecular sieve catalyst composition entering the regeneration system.
- a regeneration medium preferably a gas containing oxygen
- the regeneration conditions may include temperature in the range of from 450°C to 750°C, and preferably from 550°C to 700°C.
- the regenerated catalyst composition withdrawn from the regeneration system is combined with fresh molecular sieve catalyst composition and/or re-circulated molecular sieve catalyst composition and/or feedstock and/or fresh gas or liquids, and returned to the riser reactor(s).
- the gaseous effluent is withdrawn from the disengaging system and is passed through a recovery system for separating and purifying the light olefin(s), particularly ethylene and propylene, in the gaseous effluent.
- the process of the invention forms part of an integrated process for producing light olefin(s) from a hydrocarbon feedstock, particularly methane and/or ethane.
- the first step in the process is passing the gaseous feedstock, preferably in combination with a water stream, to a syngas production zone to produce a synthesis gas stream, typically comprising carbon dioxide, carbon monoxide and hydrogen.
- the synthesis gas stream is then converted to an oxygenate containing stream generally by contacting with a heterogeneous catalyst, typically a copper based catalyst, at temperature in the range of from 150°C to 450°C and a pressure in the range of from 5 MPa to 10 MPa.
- a heterogeneous catalyst typically a copper based catalyst
- the oxygenate containing stream can be used as a feedstock in a process as described above for producing light olefin(s), such as ethylene and/or propylene.
- Non-limiting examples of this integrated process are described in EP-B-0 933 345, which is herein fully incorporated by reference.
- the olefin(s) produced are directed to one or more polymerization processes for producing various polyolefins.
- the following Examples are offered. [0082] In the Examples, LEI is defined as the ratio of the lifetime of a molecular sieve catalyst composition containing an active metal oxide(s) compared to that of the same molecular sieve in the absence of a metal oxide, defined as having an LEI of 1.
- lifetime is defined as the cumulative amount of oxygenate converted, preferably into one or more olefin(s), per gram of molecular sieve, until the conversion rate drops to about 10%) of its initial value. If the conversion has not fallen to 10% of its initial value by the end of the experiment, lifetime is estimated by linear extrapolation based on the rate of decrease in conversion over the last two data points in the experiment.
- Principal Olefin is the sum of the selectivity to ethylene and propylene.
- the "C 3 Purity” is calculated by dividing the propylene selectivity by the sum of the propylene and propane selectivities.
- the selectivities for methane, ethylene, ethane, propylene, propane, C 4 's and C 5 +'s are average selectivities weighted over the run. Note that the C 5 +'s consist only of C 5 's, C 6 's and C 7 's.
- the selectivity values do not sum to 100% in the Tables because they have been corrected for coke as is well known.
- SAPO-34 A silicoaluminophosphate molecular sieve, SAPO-34, designated as
- the resulting product formed was recovered by filtration, washed with excess water, and dried overnight at 85°C. A portion of this product, was calcined to 700°C in flowing air for 3 hours to produce an active mixed metal oxide containing a nominal 10 weight percent La (lanthanum) based on the final weight of the mixed metal oxide.
- the resulting product formed was recovered by filtration, washed with excess water, and dried overnight at 85°C. A portion of the resulting product was calcined to 700°C in flowing air for 3 hours to produce an active mixed metal oxide containing a nominal 10 weight percent Y (yttrium) based on the final weight of the mixed metal oxide.
- the carbon dioxide uptake of the oxides of Examples 1 through 8 were measured using a Mettler TGA/SDTA 851 thermogravimetric analysis system under ambient pressure.
- the metal oxide samples were first dehydrated in flowing air to about 500°C for one hour after which the uptake of carbon dioxide was measured at 100°C.
- the surface area of the samples were measured in accordance with the method of Brunauer, Emmett, and Teller (BET) to provide the carbon dioxide uptake in terms of mg carbon dioxide/m 2 of the metal oxide presented in Table 1.
- BET Brunauer, Emmett, and Teller
- the catalyst composition consisted of 40 mg MSA of Example A and 10 mg of the active zirconium oxide of Example 1.
- the catalyst composition and active mixed metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- the results of testing this catalyst composition in the process of Example B are shown in Tables 2 and 3. The results indicate that the addition of the active zirconium oxide to the catalyst bed increased the lifetime of the molecular sieve composition significantly, and decreased the amounts of undesired ethane and propane.
- the catalyst composition consisted of 40 mg MSA of Example A and 10 mg of the active mixed metal oxide containing 10 weight percent La, described in Example 2.
- the catalyst composition and active mixed metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- the results of testing this catalyst composition in the process of Example B are shown in Tables 2 and 3.
- the data in Tables 2 and 3 illustrate that by constituting 20% of the catalyst composition load with the active mixed metal oxide containing 10 weight percent La, the lifetime of the molecular sieve doubled, as indicated by its LEI value of 2.
- the catalyst consisted of 30 mg MSA of Example A and 20 mg of the active mixed metal oxide containing 10 weight percent La, as described in Example 2.
- the catalyst composition and active mixed metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- the results of testing this catalyst composition in the process of Example B are shown in Tables 2 and 3.
- the data of Tables 2 and 3 illustrate that by constituting 40% of the catalyst composition load containing 10 weight percent La, the lifetime of the SAPO-34 catalyst composition increased by 440%. Trends in selectivity for this catalyst loading are similar to those seen in Example 8.
- the catalyst composition consisted of 40 mg MSA from Example A and 10 mg of the active mixed metal oxide containing 10 weight percent Y, as described in Example 4.
- the catalyst composition and active mixed metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- Tables 2 and 3 The results of testing this catalyst composition in the process of Example B are shown in Tables 2 and 3.
- the substitution of yttrium for lanthanum has the effect of increasing the LEI even further.
- the improvements in selectivity are not as dramatic as seen with the lanthanum, with the gain in prime olefin being 1.2% on an absolute basis.
- the catalyst consisted of 40 mg MSA of Example A and 10 mg of the active mixed metal oxide containing 5 weight percent La, as described in Example 3.
- the catalyst composition and active mixed metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- Tables 2 and 3 The results of testing this catalyst composition in the process of Example B are shown in Tables 2 and 3. It will be seen that the active mixed metal oxide containing 5 weight percent lanthanum oxide seems to have a much stronger effect in increasing the LEI than the active mixed metal oxide of Example 8 containing 10 weight percent La.
- Example 16 the catalyst consisted of 40 mg MSA of Example A and 10 mg of an active mixed metal oxide containing 5 weight percent Ca, as described in Example 5.
- the catalyst composition and active mixed metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- the results of this experiment in the reactor and conditions discussed above in Example B are shown in Tables 2 and 3.
- the active mixed metal oxide containing 5 weight percent calcium oxide has increased the lifetime of the molecular sieve composition by 223%.
- the catalyst composition consisted of 40 mg MSA of Example A and 10 mg of an amorphous silica/alumina, an inactive mixed metal oxide.
- the molecular sieve catalyst composition and the inactive mixed metal oxide catalysts were well mixed, and then diluted with quartz to form the reactor bed.
- the results of testing this catalyst composition in the process of Example B are also shown in Tables 2 and 3.
- This Comparative Example 17 illustrates a reduction in LEI to a value less than 1.0 when an inactive mixed metal oxide is utilized as compared to Example 11 of the invention.
- the catalyst composition consisted of 40 mg MSA from Example A and 10 mg an active mixed metal oxide containing Ce and titania, as described in Example 6.
- the catalyst composition and active mixed metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- the results of testing this catalyst composition in the process of Example B are shown in Tables 2 and 3.
- the presence of the active mixed metal oxide increased the lifetime of the molecular sieve composition by 134%.
- the catalyst composition consisted of 40 mg MSA of Example A and 10 mg of the active hafnium metal oxide described in Example 7.
- the catalyst composition and active metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- the results of testing this catalyst composition in the process of Example B are shown in Tables 2 and 3.
- the data in Tables 2 and 3 illustrate that by constituting 20% of the catalyst composition load with the active hafnium metal oxide, the lifetime of the molecular sieve has increased by 126%. Selectivity to ethane decreased by 40% and selectivity to propane decreased by 46% suggesting that hydrogen transfer reactions have been significantly reduced.
- the catalyst composition and active mixed metal oxide were well mixed, and then diluted with quartz to form the reactor bed.
- the results of testing this catalyst composition in the process of Example B are shown in Tables 2 and 3.
- the data in Tables 2 and 3 illustrate that by constituting 20%) of the catalyst composition load with the active mixed metal oxide containing 5 weight percent La, the lifetime of the molecular sieve has increased by 150%. Selectivity to ethane decreased by 51% and selectivity to propane decreased by 51% suggesting that hydrogen transfer reactions have been significantly reduced.
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Abstract
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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EP03743671A EP1478462A2 (fr) | 2002-02-28 | 2003-02-10 | Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion |
CA002477432A CA2477432A1 (fr) | 2002-02-28 | 2003-02-10 | Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion |
AU2003225560A AU2003225560B2 (en) | 2002-02-28 | 2003-02-10 | Catalyst compositions comprising molecular sieves, their preparation and use in conversion processes |
EA200401101A EA007872B1 (ru) | 2002-02-28 | 2003-02-10 | Композиции молекулярных сит, их катализатор, их приготовление и применение в процессах превращения |
JP2003572680A JP2005518929A (ja) | 2002-02-28 | 2003-02-10 | 分子篩組成物、それらの触媒、それらの製造、及び変換法における使用 |
KR10-2004-7013384A KR20040089680A (ko) | 2002-02-28 | 2003-02-10 | 분자 체를 포함하는 촉매 조성물, 이들의 제조 방법 및전환 공정에서의 이들의 용도 |
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US36601202P | 2002-03-20 | 2002-03-20 | |
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US37469702P | 2002-04-22 | 2002-04-22 | |
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US10/215,511 | 2002-08-09 | ||
US10/215,511 US6906232B2 (en) | 2002-08-09 | 2002-08-09 | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
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WO2003074176A2 true WO2003074176A2 (fr) | 2003-09-12 |
WO2003074176A3 WO2003074176A3 (fr) | 2003-12-18 |
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PCT/US2003/004169 WO2003074177A2 (fr) | 2002-02-28 | 2003-02-10 | Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion |
PCT/US2003/003951 WO2003074175A2 (fr) | 2002-02-28 | 2003-02-10 | Compostions de tamis moleculaires, catalyseur associe et fabrication et utilisation dans des procedes de conversion |
PCT/US2003/004153 WO2003074176A2 (fr) | 2002-02-28 | 2003-02-10 | Compositions de tamis moleculaire, catalyseur de ces compositions, leur fabrication et leur utilisation dans des procedes de conversion |
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PCT/US2003/003951 WO2003074175A2 (fr) | 2002-02-28 | 2003-02-10 | Compostions de tamis moleculaires, catalyseur associe et fabrication et utilisation dans des procedes de conversion |
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EP (3) | EP1478464A2 (fr) |
JP (3) | JP2005518929A (fr) |
KR (3) | KR20040091080A (fr) |
CN (3) | CN100335172C (fr) |
AU (3) | AU2003212993A1 (fr) |
BR (1) | BR0308011A (fr) |
CA (2) | CA2477428C (fr) |
EA (3) | EA007872B1 (fr) |
MY (2) | MY139847A (fr) |
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EP1478461A2 (fr) * | 2002-02-28 | 2004-11-24 | ExxonMobil Chemical Patents Inc. | Compostions de tamis moleculaires, catalyseur associe et fabrication et utilisation dans des procedes de conversion |
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2003
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- 2003-02-10 CA CA2477428A patent/CA2477428C/fr not_active Expired - Fee Related
- 2003-02-10 WO PCT/US2003/004169 patent/WO2003074177A2/fr active Application Filing
- 2003-02-10 EP EP03743673A patent/EP1478464A2/fr not_active Withdrawn
- 2003-02-10 JP JP2003572680A patent/JP2005518929A/ja not_active Withdrawn
- 2003-02-10 KR KR10-2004-7013377A patent/KR20040091080A/ko active IP Right Grant
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- 2003-02-10 KR KR10-2004-7013384A patent/KR20040089680A/ko not_active Application Discontinuation
- 2003-02-10 AU AU2003212993A patent/AU2003212993A1/en not_active Abandoned
- 2003-02-10 JP JP2003572681A patent/JP2005518930A/ja active Pending
- 2003-02-10 EP EP03743671A patent/EP1478462A2/fr not_active Withdrawn
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- 2003-02-10 AU AU2003216248A patent/AU2003216248B2/en not_active Ceased
- 2003-02-10 EP EP03709038A patent/EP1478461A2/fr not_active Withdrawn
- 2003-02-10 JP JP2003572679A patent/JP2005518928A/ja not_active Withdrawn
- 2003-02-10 CA CA002477432A patent/CA2477432A1/fr not_active Abandoned
- 2003-02-10 KR KR10-2004-7013378A patent/KR20040089679A/ko not_active Application Discontinuation
- 2003-02-10 AU AU2003225560A patent/AU2003225560B2/en not_active Ceased
- 2003-02-10 WO PCT/US2003/003951 patent/WO2003074175A2/fr active Application Filing
- 2003-02-10 EA EA200401102A patent/EA007873B1/ru not_active IP Right Cessation
- 2003-02-10 WO PCT/US2003/004153 patent/WO2003074176A2/fr active Application Filing
- 2003-02-10 CN CNB038068079A patent/CN1327964C/zh not_active Expired - Fee Related
- 2003-02-10 BR BR0308011-0A patent/BR0308011A/pt not_active IP Right Cessation
- 2003-02-14 TW TW092103154A patent/TWI265825B/zh not_active IP Right Cessation
- 2003-02-14 TW TW092103148A patent/TWI265824B/zh not_active IP Right Cessation
- 2003-02-14 TW TW092103144A patent/TWI306780B/zh not_active IP Right Cessation
- 2003-02-21 MY MYPI20030610A patent/MY139847A/en unknown
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0312981A1 (fr) | 1987-10-19 | 1989-04-26 | Phillips Petroleum Company | Procédé de craquage |
WO1998029370A1 (fr) | 1996-12-31 | 1998-07-09 | Exxon Chemical Patents Inc. | Conversions de composes oxygenes au moyen de catalyseurs a tamis moleculaires non zeolitiques a mailles fines |
Non-Patent Citations (2)
Title |
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KANG; INUI: "Effects of decrease in number of acid sites located on the external surface ofNi-SAPO-34 crystalline catalyst by the mechanochemical method", CATALYSIS LETTERS, vol. 53, 1998, pages 171 - 176 |
See also references of EP1478462A2 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1478461A2 (fr) * | 2002-02-28 | 2004-11-24 | ExxonMobil Chemical Patents Inc. | Compostions de tamis moleculaires, catalyseur associe et fabrication et utilisation dans des procedes de conversion |
EP1478464A2 (fr) * | 2002-02-28 | 2004-11-24 | ExxonMobil Chemical Patents Inc. | Compositions de tamis moleculaires, catalyseur de celles-ci, leur preparation et utilisation dans des procedes de conversion |
WO2004045762A1 (fr) * | 2002-11-19 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Compositions catalytiques a tamis moleculaire multicomposant, leur elaboration et leur utilisation dans les reactions d'alkylation |
US7074739B2 (en) | 2002-11-19 | 2006-07-11 | Exxonmobil Chemical Patents Inc. | Multi-component molecular sieve catalyst compositions and their use in aromatics reactions |
US7276638B2 (en) | 2002-11-19 | 2007-10-02 | Exxonmobil Chemical Patents Inc. | Multi-component molecular sieve catalyst compositions and their use in aromatics reactions |
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