WO2004096439A1 - Spherical catalysts to convert hydrocarbons to light olefins - Google Patents
Spherical catalysts to convert hydrocarbons to light olefins Download PDFInfo
- Publication number
- WO2004096439A1 WO2004096439A1 PCT/US2003/009564 US0309564W WO2004096439A1 WO 2004096439 A1 WO2004096439 A1 WO 2004096439A1 US 0309564 W US0309564 W US 0309564W WO 2004096439 A1 WO2004096439 A1 WO 2004096439A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- ofthe
- propylene
- weight
- zeolite
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 35
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 238000011069 regeneration method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 230000008929 regeneration Effects 0.000 description 16
- -1 polyethylene Polymers 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 6
- 239000000017 hydrogel Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003349 gelling agent Substances 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 230000007420 reactivation Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005662 Paraffin oil Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 150000003463 sulfur Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100305864 Alteromonas mediterranea (strain DSM 17117 / CIP 110805 / LMG 28347 / Deep ecotype) rph2 gene Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910003953 H3PO2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 101100135363 Yarrowia lipolytica (strain CLIB 122 / E 150) RIM101 gene Proteins 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- RDXABLXNTVBVML-UHFFFAOYSA-N diethoxyphosphanyl diethyl phosphite Chemical compound CCOP(OCC)OP(OCC)OCC RDXABLXNTVBVML-UHFFFAOYSA-N 0.000 description 1
- ZUKLAAHCPUBQLQ-UHFFFAOYSA-N diethylphosphinous acid Chemical compound CCP(O)CC ZUKLAAHCPUBQLQ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical class PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical group S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/16—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "moving bed" method
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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 converting a hydrocarbon feed to light olefins, especially to propylene and ethylene.
- the present invention relates to conversion of a hydrocarbon stream containing C4 to Cg olefins and/or paraffins, through the use of a spherical catalyst consisting of silicalite with a non-acidic binder, to propylene and ethylene.
- a spherical catalyst consisting of silicalite with a non-acidic binder
- propylene is largely derived from selected petroleum feed materials by procedures such as steam cracking, which also produce high quantities of other materials.
- procedures such as steam cracking, which also produce high quantities of other materials.
- propylene which result in uncertainties in feed supplies, rapidly escalating raw material costs and similar situations, which are undesirable from a commercial standpoint.
- Propylene a light olefin consisting of three carbon atoms wherein two ofthe carbon atoms are joined by a double bond, has a great number of commercial applications, particularly in the manufacture of polypropylene, isopropyl alcohol, propylene oxide, cumene, synthetic glycerol, acrylonitrile and oxo alcohols.
- a recently developed process for improved production of propylene is described in US-A-6,222,087 BI in which a catalyst containing ZSM-5 and/or ZSM-11, having an initial silica-to-alumina molar ratio of over 300, as well as containing phosphorus, is contacted with an olefin feed.
- the phosphorus is a part ofthe catalyst and the C3 yield is described to be as much as 90% propylene or even more.
- US-A-6,313,366 BI a process for producing propylene from a naphtha stream comprising contacting the naphtha feed with a crystalline zeolite at the appropriate process conditions, including adding a feed of single ring aromatics to increase the propylene yield.
- a spherical catalyst prepared by an oil drop method is described in US-A-6,143,941 BI. In that patent, the catalyst is used for the processing of Cg aromatics to increase the concentration of a particular xylene isomer.
- An object ofthe present invention is to provide a catalyst that converts a higher proportion of a hydrocarbon feed of C4 to Cg olefins to propylene and to ethylene.
- a further object ofthe present invention is to produce a sufficiently high proportion of propylene to propane to eliminate the need for a separate propylene/propane separation step for the production of chemical grade propylene.
- the feed contains from 40 to 80 wt-% olefins and from 20 to 60 wt-% paraffins or other hydrocarbons.
- the present invention comprises a process for producing propylene comprising the steps of contacting an olefin feed containing between 40 and 80 wt-% olefins, with the majority ofthe rest ofthe feed being paraffins, with a catalyst to form a cracked product, the catalyst comprising 30 to 80 wt-% of a crystalline zeolite, the reaction conditions including a temperature from 500° to 650°C, a hydrocarbon partial pressure of 70 to 280 kPa, a liquid hourly space velocity (LHSV) of between 5 and 40 hr"l, and wherein propylene comprises at least 90 mol-% ofthe total C3 products and ethylene comprises at least 90 mol-% ofthe total C2 products.
- LHSV liquid hourly space velocity
- the cracking ofthe olefins is preferably carried out in a moving-bed reaction zone wherein feed and catalyst are contacted at effective olefin cracking conditions.
- a carbonaceous material i.e. coke — is deposited on the catalyst.
- the carbonaceous deposit material has the effect of reducing the number of active sites on the catalyst, which thereby affects the yield.
- coked catalyst is withdrawn from the reaction zone and regenerated to remove at least a portion ofthe carbonaceous material and returned to the reaction zone.
- the regenerated catalyst will contain 0 to 1 wt-% and more preferably from 0 to 0.5 wt-% carbon.
- the present invention relates to a catalyst for converting light olefins to propylene and ethylene, comprising 30 to 80% by weight MFI-type zeolite and 20 to 70% by weight of a non-acidic binder selected from the group consisting of AIPO4, Si ⁇ 2 and Zr ⁇ 2, and wherein said zeolite has an Si/Al2 molar ratio offro 300 to 600.
- the present invention relates to a process for producing propylene comprising passing a feed stream comprising C ,to C Q olefins into a reaction zone and contacting said feed with an oil dropped spherical catalyst to form a cracked product, wherein said catalyst comprises 30 to 80% by weight MFI-type zeolite and 20 to 70% by weight of a non-acidic AIPO4 binder.
- the present invention comprises a process for producing propylene comprising the steps of contacting an olefin feed containing between 40 and 80 wt-% olefins and between 20 and 60 wt-% paraffins with a catalyst to form a cracked product, the catalyst comprising 30 to 80 wt-% of a crystalline zeolite, the reaction conditions including a temperature from 500° to 650°C, an LHSV of between 5 and 40 hr 1, and wherein propylene comprises at least 90 mol-% ofthe total C3 products.
- the term "liquid hourly space velocity" is defined herein as the volume of liquid feed per hour divided by the volume ofthe catalyst bed, where the same units are used for both volumes and the liquid volume ofthe feed defined in accordance with standard conditions.
- the reactor section employed in the present invention is ofthe type usually associated with catalyst-regeneration options known to those of ordinary skill in the art, such as: (1) a semi-regenerative unit containing fixed-bed reactors maintains operating severity by increasing temperature, eventually shutting the unit down for catalyst regeneration and reactivation; (2) a swing-reactor unit, in which individual fixed-bed reactors are serially isolated by manifolding arrangements as the catalyst become deactivated and the catalyst in the isolated reactor is regenerated and reactivated while the other reactors remain on-stream; (3) continuous regeneration of catalyst withdrawn from a moving-bed reactor, with reactivation and substitution ofthe reactivated catalyst, permitting higher operating severity by maintaining high catalyst activity through regeneration cycles of a few days; (4) a hybrid system with semi-regenerative and continuous-regeneration provisions in the same unit or (5) a fluidized bed reactor.
- the preferred embodiment ofthe present invention utilizes continuous regeneration of catalyst withdrawn from a moving-bed reactor. A constant amount of catalyst is removed from the bottom ofthe catalyst bed in the reactor to
- Process conditions that are employed include temperatures from 500° to 650°C, preferably from 540° to 600°C, hydrocarbon partial pressures from 70 to 280 kPa, preferably from 140 to 245 kPa and an LHSV of between 5 and 40 hr"l, preferably between 10 and 20 hr"l .
- steam is not introduced with the olefin stream into the reaction. It is preferred that the feed residence time in the reaction zone be less than 5 seconds, for example from 1 to 2 seconds.
- the preferred catalyst used in the present invention consists of 30 to 80% by weight of a high silica MFI-type zeolite, also known as silicalite, with a molar Si/Al2 ratio of 300 to 600, preferably between 400 and 500, and 20 to 70% by weight of a non- acidic binder comprising amorphous aluminum phosphate, formed by sol-gel methods and having a 1:1 atomic ratio of Al/P.
- Silicalite is a hydrophobic crystalline silica molecular sieve. Silicalite is disclosed and claimed in US- A-4,061,724 BI and US-A-4, 104,294 BI to Grose et al, incorporated herein by reference.
- Silicalite differs from other zeolites in that silicalite does not exhibit appreciable ion exchange properties as AIO4 tetrahedra do not comprise a portion ofthe crystalline silica framework.
- the binder serves the purpose of maintaining the shape of the catalyst particles.
- the binder may be incorporated with the zeolite in any acceptable manner known to those skilled in the art. Examples of such incorporation techniques include sol- gel oil-dropping, pillings, nodulizing, marumerization, spray drying, extrusion, or any combination of these techniques.
- the preferred shape ofthe catalyst is spherical particles, which are preferably formed by the sol-gel oil dropping methods as described below. Spherical particles have good resistance to attrition and are well suited to a moving-bed type reactor with continuous regeneration of catalyst withdrawn from the reactor. In hydrocarbon reactions, the catalysts gradually deactivate due to coke formation on the catalyst. A spherical shaped catalyst can be readily moved from the reactor through a regeneration section and back to the moving bed, allowing for both continuous reaction and continuous regeneration ofthe catalyst.
- silicalite zeolite used in the catalyst may be calcined, acid-washed, ion- exchanged or steamed prior to being combined with the binder and formed into the spherical catalyst shape. Such modifications may be made as known to one skilled in the art.
- a non-acidic binder is used, such as AIPO4, Si ⁇ 2 or Zr ⁇ 2-
- the preferred binder is AIPO4 with a stoichiometric ratio of Al/P.
- This formulation results in a binder with essentially no acidity and thereby avoids potential undesirable reactions that could lower selectivity, stability and product purity.
- it is formed from water-soluble Al and P compounds.
- the phosphorus may be incorporated with the alumina in any acceptable manner known to those skilled in the art. Examples of such incorporation techniques include pillings, nodulizing, marumerization, spray drying, extrusion, or any combination of these techniques.
- One preferred method of preparing this phosphorus-containing alumina is the gelation of a hydrosol precursor in accordance with the well-known oil drop method.
- a phosphorus compound is added to an alumina hydrosol to form a phosphorus-containing alumina hydrosol.
- Representative phosphorus-containing compounds which may be utilized in the present invention include: H3PO4, H3PO2, H3PO3, (NE ⁇ PO ( E ⁇ HPO K3PO4, K2HPO4, KH2 p ⁇ 4 > Na 3 PO 4 , Na 2 HPO 4 , NaH 2 PO 4 , PX 3 , RPX 2 , R2PX, R3P, X3PO, (XO) 3 PO, (XO) 3 P, R3PO, R3PS, RPO 2 , RPS 2 , RP(O)(OX) 2 , RP(S)(SX) 2 ,
- R3P phosphines such as butyl phosphine, and tertiary phosphine oxides R3PO, such as tributylphosphine oxide, the tertiary phosphine sulfides, R3PS, the primary, RP(O)(OX)2, and secondary, R2P(O)OX, phosphonic acids such as benzene phosphonic acid, the corresponding sulfur derivatives such as RP(S)(SX)2 and R2P(S)SX, the esters ofthe phosphonic acids such as dialkyl phosphonate, (RO)2P(O)H, dialkyl alkyl phosphonates, (RO)2P(O)R, and alkyl dialkyl-phosphinates, (RO)P(O)R2; phosphinous acids, R2POX, such as diethylphosphinous acid
- Corresponding sulfur derivatives may also be employed including (RS)2P(S)H, (RS) 2 P(S)R, (RS)P(S)R 2 , R 2 PSX, (RS)P(SX) 2 , (RS) 2 PSX, (RS) 3 P, (RS)PR 2 and (RS)2PR.
- phosphite esters include trimethylphosphite, triethylphosphite, diisopropylphosphite, butylphosphite, and pyrophosphites such as tetraethylpyrophosphite.
- the alkyl groups in the mentioned compounds preferably contain one to four carbon atoms.
- Suitable phosphorus-containing compounds include ammonium hydrogen phosphate, the phosphorus halides such as phosphorus trichloride, bromide, and iodide, alkylphosphorodichloridites, (RO)PCl2, dialkylphosphorochloridites, (RO)2PCl, dialkylphosphinochloridites, R2PCI, alkyl alkylphosphonochloridates,
- the alumina hydrosol is typically prepared by digesting aluminum in aqueous hydrochloric acid and/or aluminum chloride solution at reflux temperature, usually from 80° to 105°C, and reducing the chloride compound concentration ofthe resulting aluminum chloride solution by the device of maintaining an excess ofthe aluminum reactant in the reaction mixture as a neutralizing agent.
- the alumina hydrosol is an aluminum chloride hydrosol, variously referred to as an aluminum oxychloride hydroxol, aluminum hydroxychloride hydrosol, and the like, such as is formed when utilizing aluminum metal as a neutralizing agent in conjunction with an aqueous aluminum chloride solution.
- the aluminum chloride is prepared to contain aluminum in from a 0.70:1 to 1.5:1 weight ratio with the chloride compound content thereof.
- the phosphorus compound is mixed with a gelling agent before admixing with the alumina hydrosol. It is preferred that said alumina hydrosol contain the active catalytic component ofthe first or second discrete catalyst. Commingling ofthe alumina hydrosol, containing said active catalytic component, with the phosphorus-gelling agent mixture is effected by any suitable means. The resultant admixture is dispersed as droplets in a suspending medium, e.g. oil, under conditions effective to transform said droplets into hydrogel particles.
- a suspending medium e.g. oil
- the gelling agent is typically a weak base which, when mixed with the hydrosol, will cause the mixture to set to a gel within a reasonable time.
- the hydrosol is typically coagulated by utilizing ammonia as a neutralizing or setting agent.
- the ammonia is furnished by an ammonia precursor, which is added to the hydrosol.
- the precursor is suitably hexamethylenetetramme (HMT), or urea, or mixtures thereof, although other weakly basic materials, which are substantially stable at normal temperatures, but decompose to form ammonia with increasing temperature, may be suitably employed. It has been found that equal volumes ofthe hydrosol and of the HMT solution to alumina sol solution are satisfactory, but it is understood that this may vary somewhat.
- Aging ofthe hydrogel is suitably accomplished over a period of from 1 to 24 hours, preferably in the oil suspending medium, at a temperature of from 60° to 150°C or more and at a pressure to maintain the water content ofthe hydrogel spheres in a substantially liquid phase.
- the aging ofthe hydrogel can also be carried out in an aqueous NH3 solution at 95°C for a period up to 6 hours.
- the hydrogel spheres may be washed with water containing ammonia.
- the phosphorus-containing alumina component ofthe two discrete catalysts ofthe present invention may also contain minor proportions of other well-known inorganic oxides such as silica, titanium dioxide, zirconium dioxide, tin oxide, germanium oxide, chromium oxide, beryllium oxide, vanadium oxide, cesium oxide, hafnium oxide, zinc oxide, iron oxide, cobalt oxide, magnesia, boria, thoria and the like materials which can be added to the hydrosol prior to dropping.
- other well-known inorganic oxides such as silica, titanium dioxide, zirconium dioxide, tin oxide, germanium oxide, chromium oxide, beryllium oxide, vanadium oxide, cesium oxide, hafnium oxide, zinc oxide, iron oxide, cobalt oxide, magnesia, boria, thoria and the like materials which can be added to the hydrosol prior to dropping.
- a preferred method for producing the catalyst involves the following procedure: Silicalite powder, aluminum hydroxychloride solution (containing 12 to 14 wt-% Al) and 85 wt-% phosphoric acid are weighed out in appropriate amounts to make a formulation containing (volatile-free basis) 67% silicalite and 33% aluminum phosphate (1:1 Al/P atomic ratio) by weight.
- the silicalite is dispersed in water by appropriate means with stirring, milling or other means to form a concentrated slurry (about 45 wt-%).
- the Al sol and H3PO4 are cooled, diluted with water and mixed to form an AIPO4 solution with 5 to 7 wt-% Al.
- the silicalite slurry and AIPO4 solution are then mixed, along with a solution of a gelling agent, HMT, which releases NH3 on heating.
- HMT a gelling agent
- the amount of HMT added corresponds to 100 to 150 mol-% ofthe CI content ofthe aluminum hydroxychloride that is used.
- the mixture is then fed through a vibrating perforated disc or tube to form droplets, which are directed into a heated paraffin oil column, resulting in formation of rigid spherical particles of silicalite- AIPO4 gel.
- the gelled particles are collected at the bottom ofthe column, aged for several hours in hot paraffin oil and then washed with a heated dilute aqueous NH3 solution.
- the washed spheres are then dried and calcined, to form the final spherical catalyst particles.
- the order of mixing of most ofthe components is not critical.
- an equivalent catalyst can be formed by first mixing the silicate slurry with the Al sol, mixing the H3PO4 with the HMT solution and water and then combining these to form the dropping mixture.
- the silicalite slurry, H3PO4, HMT solution and water may be combined simultaneously to form the dropping mixture.
- the resulting product is silicalite bound with amorphous AIPO4.
- the catalysts are contained in a fixed-bed system or a moving-bed system with associated continuous catalyst regeneration, whereby catalyst may be continuously withdrawn, regenerated and returned to the reactors.
- catalyst-regeneration options known to those of ordinary skill in the art, such as: (1) a semi-regenerative unit containing fixed-bed reactors maintains operating severity by increasing temperature, eventually shutting the unit down for catalyst regeneration and reactivation; (2) a swing-reactor unit, in which individual fixed-bed reactors are serially isolated by manifolding arrangements as the catalyst become deactivated and the catalyst in the isolated reactor is regenerated and reactivated while the other reactors remain on- stream; (3) continuous regeneration of catalyst withdrawn from a moving-bed reactor, with reactivation and return to the reactors ofthe reactivated catalyst as described herein; or (4) a hybrid system with semi-regenerative and continuous-regeneration provisions in the same zone.
- the preferred embodiment ofthe present invention is a moving-bed reactor with a continuous catalyst regeneration section.
- a portion ofthe coked catalyst is withdrawn from the reaction zone and regenerated to remove the carbonaceous material.
- it can be desirable to substantially remove the carbonaceous material e.g. to less than 1 wt-%.
- regeneration conditions can be varied depending upon catalyst used and the type of contaminant material present upon the catalyst prior to its regeneration. The details concerning the conditions for regeneration are known to those skilled in the art and need not be further disclosed herein.
- the ethylene comprises at least 90 mol-% ofthe C2 products and the propylene comprises at least 90 mol-% ofthe C3 products.
- a zeolite- water suspension is prepared by addition ofthe silicalite (a calcined, steamed and acid- washed silicalite, with an Si/Al2 molar ratio of 500, 139g, volatile- free) to water (120g) with stirring. The resulting mixture is then circulated through a bead mill for 5 to 20 minutes. Meanwhile, a solution is prepared containing water (45g), HMT (70g of a 42 wt-% solution) and H3PO4 (62.5g of 85 wt-% acid). Finally, a solution of aluminum chlorohydrate is weighed out (120g, 12.2 wt-% Al, 13.9 wt-% CI).
- the spheres are then drained of oil, transferred into a vertical washing column and washed for 1 to 4 hours at 90° to 100°C in a continuous flow of water containing 0.01 to 0.5 wt-% NH3.
- the washed spheres are drained, oven-dried for 1 to 20 hours at 90° to 100°C and oven-calcined in air at 500° to 650°C for 1 to 20 hours.
- the preparation yields 190g (volatile-free) ofthe final spherical catalyst.
- Example 1 The preparation is carried out as in Example 1, except that the water/HMT/H3PO4 solution is added with stirring to the aluminum chlorohydrate solution to form a solution of AIPO4.
- the water-silicalite suspension is then added and the resulting mixture is used to form the catalyst using the same procedure and conditions as in Example 1. This gives about the same yield of catalyst and the resulting catalyst shows equivalent performance to those prepared as in Example 1.
- pilot plant consists of three main sections: feed delivery, reactor zone, and products separation and analysis section.
- a hydrocarbon feed from charger is directed to a pump, which pressurizes and delivers feed to a capillary; the feed rate being controlled by the capillary inlet/outlet pressure difference. The feed rate is measured by the decrease in charger weight. It is also possible to add hydrogen, nitrogen, or other appropriate gases or mixtures thereof to the main hydrocarbon feed with a desired feed/diluent ratio. After the feed pressure is being lowered to close to process conditions
- the feed enters a pre-heating zone which allows liquid component(s) to vaporize and it is heated to 400°C.
- the preheated feed then enters a stainless steel reactor, filled with 15 to 50 cc of catalyst and spacers (such as quartz wool, ceramic balls, etc), located below and above catalyst bed.
- the reactor is also equipped with a thermowell with a moving thermocouple inside it. The reactor internal diameter is varied to maintain the catalyst bed thickness of 12 cm, thus allowing accurate measurement of temperature profile across the bed.
- Reaction products are analyzed by online gas chromatograph, located close to the reactor outlet. Liquid products are condensed from a gas into a receiver, placed onto a balance and cooled to 0°C.
- the volume and composition of remaining gas products are measured by a wet test meter and yet another gas chromatograph, thus allowing calculation ofthe molecular weight ofthe gas and therefore its weight. Summation of weight of liquid products with weight of gas products enables one to mass balance the plant very well, with weight recoveries being 100+/-3% most ofthe time.
- One ofthe advantages ofthe invention is that the catalyst is not air or moisture sensitive and does not require a special pre-treatment.
- a catalyst prepared in accordance with procedure described in Example 1, but having different silicalite to binder ratio of 60/40, was tested according to a procedure similar to that of Example 3, using C4 to C ⁇ paraffins-olefins blend. Hydrocarbon feed was diluted with 5 mol % of hydrogen. The results are provided in
- Light olefins resulting from the preferred process may be used as feeds for processes such as oligomerization, polymerization and related processes (hereinafter "polymerization") to form macromolecules.
- Such light olefins may be polymerized both alone and in combination with other species, in accordance with polymerization methods known in the art.
- Propylene and ethylene are preferred polymerization feeds.
- Polypropylene and polyethylene are preferred polymerization products made therefrom. Depending upon the intended end use application ofthe ethylene and propylene, they may be used directly in certain reactions or they may be upgraded prior to their use in the desired application.
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03714446A EP1603668A1 (en) | 2003-03-27 | 2003-03-27 | Spherical catalysts to convert hydrocarbons to light olefins |
AU2003218444A AU2003218444A1 (en) | 2003-03-27 | 2003-03-27 | Spherical catalysts to convert hydrocarbons to light olefins |
PCT/US2003/009564 WO2004096439A1 (en) | 2003-03-27 | 2003-03-27 | Spherical catalysts to convert hydrocarbons to light olefins |
CNA038262258A CN1761521A (en) | 2003-03-27 | 2003-03-27 | Spherical catalyst for light olefin conversion from hydrocarbon |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2003/009564 WO2004096439A1 (en) | 2003-03-27 | 2003-03-27 | Spherical catalysts to convert hydrocarbons to light olefins |
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WO2004096439A1 true WO2004096439A1 (en) | 2004-11-11 |
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PCT/US2003/009564 WO2004096439A1 (en) | 2003-03-27 | 2003-03-27 | Spherical catalysts to convert hydrocarbons to light olefins |
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EP (1) | EP1603668A1 (en) |
CN (1) | CN1761521A (en) |
AU (1) | AU2003218444A1 (en) |
WO (1) | WO2004096439A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1700635A1 (en) * | 2005-03-10 | 2006-09-13 | ExxonMobil Chemical Patents Inc. | Catalyst composition |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4605637A (en) * | 1983-02-14 | 1986-08-12 | Mobil Oil Corporation | Hydrothermal activation of acid zeolites with aluminum phosphates |
EP0496226A1 (en) * | 1991-01-22 | 1992-07-29 | W.R. Grace & Co.-Conn. | Catalytic compositions |
WO1999046043A1 (en) * | 1998-03-11 | 1999-09-16 | Exxon Chemical Patents Inc. | Zeolite catalyst activity enhancement by aluminum phosphate and phosphorus |
EP1002577A1 (en) * | 1998-11-06 | 2000-05-24 | Enichem S.p.A. | Process for the preparation of catalysts based on MFI-type zeolite |
US6239056B1 (en) * | 1998-12-17 | 2001-05-29 | Uop Llc | Selective aromatics disproportionation process |
-
2003
- 2003-03-27 WO PCT/US2003/009564 patent/WO2004096439A1/en not_active Application Discontinuation
- 2003-03-27 EP EP03714446A patent/EP1603668A1/en not_active Withdrawn
- 2003-03-27 CN CNA038262258A patent/CN1761521A/en active Pending
- 2003-03-27 AU AU2003218444A patent/AU2003218444A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4605637A (en) * | 1983-02-14 | 1986-08-12 | Mobil Oil Corporation | Hydrothermal activation of acid zeolites with aluminum phosphates |
EP0496226A1 (en) * | 1991-01-22 | 1992-07-29 | W.R. Grace & Co.-Conn. | Catalytic compositions |
WO1999046043A1 (en) * | 1998-03-11 | 1999-09-16 | Exxon Chemical Patents Inc. | Zeolite catalyst activity enhancement by aluminum phosphate and phosphorus |
EP1002577A1 (en) * | 1998-11-06 | 2000-05-24 | Enichem S.p.A. | Process for the preparation of catalysts based on MFI-type zeolite |
US6239056B1 (en) * | 1998-12-17 | 2001-05-29 | Uop Llc | Selective aromatics disproportionation process |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1700635A1 (en) * | 2005-03-10 | 2006-09-13 | ExxonMobil Chemical Patents Inc. | Catalyst composition |
Also Published As
Publication number | Publication date |
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AU2003218444A1 (en) | 2004-11-23 |
CN1761521A (en) | 2006-04-19 |
EP1603668A1 (en) | 2005-12-14 |
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