EP1583717A4 - Molecular sieve ssz-63 - Google Patents
Molecular sieve ssz-63Info
- Publication number
- EP1583717A4 EP1583717A4 EP03814852A EP03814852A EP1583717A4 EP 1583717 A4 EP1583717 A4 EP 1583717A4 EP 03814852 A EP03814852 A EP 03814852A EP 03814852 A EP03814852 A EP 03814852A EP 1583717 A4 EP1583717 A4 EP 1583717A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- oxide
- hydrocarbon
- conditions
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 63
- 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 63
- 238000000034 method Methods 0.000 claims abstract description 174
- 239000003054 catalyst Substances 0.000 claims abstract description 128
- -1 N-cyclodecyl-N-methyl-pyrrolidinium cation Chemical class 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000010457 zeolite Substances 0.000 claims description 84
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 83
- 229930195733 hydrocarbon Natural products 0.000 claims description 82
- 150000002430 hydrocarbons Chemical class 0.000 claims description 81
- 229910052751 metal Inorganic materials 0.000 claims description 75
- 239000002184 metal Substances 0.000 claims description 75
- 229910021536 Zeolite Inorganic materials 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 62
- 239000004215 Carbon black (E152) Substances 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 37
- 150000001336 alkenes Chemical class 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 238000006317 isomerization reaction Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 20
- 238000002441 X-ray diffraction Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 150000002736 metal compounds Chemical class 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000008096 xylene Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004523 catalytic cracking Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000010687 lubricating oil Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000002178 crystalline material Substances 0.000 claims description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000010936 titanium Chemical group 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 150000003738 xylenes Chemical class 0.000 claims description 7
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 230000029936 alkylation Effects 0.000 claims description 6
- 238000005804 alkylation reaction Methods 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 150000002790 naphthalenes Chemical class 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 238000006384 oligomerization reaction Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- 230000002152 alkylating effect Effects 0.000 claims description 3
- 230000003606 oligomerizing effect Effects 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 description 22
- 239000000377 silicon dioxide Substances 0.000 description 20
- 150000002739 metals Chemical class 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 11
- 239000000499 gel Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- SJGOXJVCQSFSAD-UHFFFAOYSA-M 1-cyclodecyl-1-methylpyrrolidin-1-ium;hydroxide Chemical compound [OH-].C1CCCCCCCCC1[N+]1(C)CCCC1 SJGOXJVCQSFSAD-UHFFFAOYSA-M 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010555 transalkylation reaction Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- RKGFMCZDUDNPOZ-UHFFFAOYSA-M 1-cyclodecyl-1-methylpyrrolidin-1-ium;iodide Chemical compound [I-].C1CCCCCCCCC1[N+]1(C)CCCC1 RKGFMCZDUDNPOZ-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- JYZFALNLDFOLIG-UHFFFAOYSA-N 1-cyclodecylpyrrolidine Chemical compound C1CCCN1C1CCCCCCCCC1 JYZFALNLDFOLIG-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 150000002081 enamines Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
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- 238000002407 reforming Methods 0.000 description 2
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- 238000004626 scanning electron microscopy Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
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- GYHQJCFKQZOTBN-UHFFFAOYSA-N trisodium;borate;decahydrate Chemical class O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]B([O-])[O-] GYHQJCFKQZOTBN-UHFFFAOYSA-N 0.000 description 2
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- PBWHJRFXUPLZDS-UHFFFAOYSA-N (1-Ethylpropyl)benzene Chemical compound CCC(CC)C1=CC=CC=C1 PBWHJRFXUPLZDS-UHFFFAOYSA-N 0.000 description 1
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- NMUWSGQKPAEPBA-UHFFFAOYSA-N 1,2-dibutylbenzene Chemical compound CCCCC1=CC=CC=C1CCCC NMUWSGQKPAEPBA-UHFFFAOYSA-N 0.000 description 1
- LRJOXARIJKBUFE-UHFFFAOYSA-N 1,2-diethyl-3-methylbenzene Chemical compound CCC1=CC=CC(C)=C1CC LRJOXARIJKBUFE-UHFFFAOYSA-N 0.000 description 1
- WSBLPEUGKJUOFS-UHFFFAOYSA-N 1-(cyclodecen-1-yl)pyrrolidine Chemical compound C1CCCN1C1=CCCCCCCCC1 WSBLPEUGKJUOFS-UHFFFAOYSA-N 0.000 description 1
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- GKGTVJOYFGUPSA-UHFFFAOYSA-N 2,4-dimethylpentan-3-ylbenzene Chemical compound CC(C)C(C(C)C)C1=CC=CC=C1 GKGTVJOYFGUPSA-UHFFFAOYSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
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- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
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- 239000000017 hydrogel Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000079 presaturation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- 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
-
- 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
- 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
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
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- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
Definitions
- the present invention relates to new crystalline molecular sieve SSZ-63, a method for preparing SSZ-63 using N-cyclodecyl-N-methyl-pyrrolidinium cation as a structure directing agent and the use of SSZ-63 in catalysts for, e.g., hydrocarbon conversion reactions.
- crystalline molecular sieves and zeolites are especially useful in applications such as hydrocarbon conversion, gas drying and separation.
- New zeolites may contain novel internal pore architectures, providing enhanced selectivities in these processes.
- Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina.
- Crystalline borosilicates are usually prepared under similar reaction conditions except that boron is used in place of aluminum. By varying the synthesis conditions and the composition of the reaction mixture, different zeolites can often be formed.
- the present invention is directed to a family of crystalline molecular sieves with unique properties, referred to herein as "molecular sieve SSZ-63" or simply “SSZ-63".
- SSZ-63 is obtained in its silicate, aluminosilicate, titanosilicate, germanosilicate, vanadosilicate or borosilicate form.
- silicate refers to a molecular sieve having a high mole ratio of silicon oxide relative to aluminum oxide, preferably a mole ratio greater than 100, including molecular sieves comprised entirely of silicon oxide.
- aluminosilicate refers to a molecular sieve containing both alumina and silica and the term “borosilicate” refers to a molecular sieve containing oxides of both boron and silicon.
- a molecular sieve having a mole ratio greater than about 15 of (1) an oxide of a first tetravalent element to (2) an oxide of a trivalent element, pentavalent element, second tetravalent element different from said first tetravalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table II.
- a molecular sieve having a mole ratio greater than about 15 of (1) an oxide selected from silicon oxide, germanium oxide and mixtures thereof to (2) an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof and having, after calcination, the X-ray diffraction lines of Table II below.
- the mole ratio of the first oxide or mixture of first oxides to the second oxide can be infinity, i.e., there is no second oxide in the molecular sieve.
- the molecular sieve is an all-silica molecular sieve or a germanosilicate.
- the present invention further provides such a molecular sieve having a composition, as synthesized and in the anhydrous state, in terms of mole ratios as follows: YO 2 /W c O d 15 - 00 M 2 ⁇ /YO 2 0.01 - 0.03 Q/YO 2 0.02 - 0.05 wherein Y is silicon, germanium or a mixture thereof; W is aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures thereof; c is 1 or 2; d is 2 when c is 1 (i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W is trivalent or 5 when W is pentavalent); M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; n is the valence of M (i.e., 1 or 2); and Q is N-cyclodecyl-N-methyl- pyrrolidin
- a molecular sieve prepared by thermally treating a zeolite having a mole ratio of an oxide selected from silicon oxide, germanium oxide and mixtures thereof to an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof greater than about 15 at a temperature of from about 200°C to about 800°C, the thus-prepared zeolite having the X-ray diffraction lines of Table II.
- the present invention also includes this thus-prepared molecular sieve which is predominantly in the hydrogen form, which hydrogen form is prepared by ion exchanging with an acid or with a solution of an ammonium salt followed by a second calcination.
- Also provided in accordance with the present invention is a method of preparing a crystalline material comprising (1) an oxide of a first tetravalent element and (2) an oxide of a trivalent element, pentavalent element, second tetravalent element which is different from said first tetravalent element, or mixture thereof and having mole ratio of the first oxide to the second oxide greater than 15, said method comprising contacting under crystallization conditions sources of said oxides and a structure directing agent comprising N-cyclodecyl-N-methyl-pyrrolidinium cation.
- the method of this invention can be used to synthesize crystalline materials having, after calcination, the X-ray diffraction lines of Table II, as well as crystalline materials having the BE A* crystal structure.
- a process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with a catalyst comprising the zeolite of this invention.
- the zeolite may be predominantly in the hydrogen form. It may also be substantially free of acidity.
- a hydrocracking process comprising contacting a hydrocarbon feedstock under hydrocracking conditions with a catalyst comprising the zeolite of this invention, preferably predominantly in the hydrogen form.
- This invention also includes a dewaxing process comprising contacting a hydrocarbon feedstock under dewaxing conditions with a catalyst comprising the zeolite of this invention, preferably predominantly in the hydrogen form.
- the present invention also includes a process for improving the viscosity index of a dewaxed product of waxy hydrocarbon feeds comprising contacting the waxy hydrocarbon feed under isomerization dewaxing conditions with a catalyst comprising the zeolite of this invention, preferably predominantly in the hydrogen form.
- the present invention further includes a process for producing a C 20+ lube oil from a C 20+ olefin feed comprising isomerizing said olefin feed under isomerization conditions over a catalyst comprising the zeolite of this invention.
- the zeolite may be predominantly in the hydrogen form.
- the catalyst may contain at least one Group VLTI metal.
- a process for catalytically dewaxing a hydrocarbon oil feedstock boiling above about 350°F and containing straight chain and slightly branched chain hydrocarbons comprising contacting said hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pressure of about 15-3000 psi with a catalyst comprising the zeolite of this invention, preferably predominantly in the hydrogen form.
- the catalyst may contain at least one Group VIII metal.
- the catalyst may be a layered catalyst comprising a first layer comprising the zeolite of this invention, and a second layer comprising an aluminosilicate zeolite which is more shape selective than the zeolite of said first layer.
- the first layer may contain at least one Group VIII metal.
- Also included in the present invention is a process for preparing a lubricating oil which comprises hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil, and catalytically dewaxing said effluent comprising hydrocracked oil at a temperature of at least about 400°F and at a pressure of from about 15 psig to about 3000 psig in the presence of added hydrogen gas with a catalyst comprising the zeolite of this invention.
- the zeolite may be predominantly in the hydrogen form.
- the catalyst may contain at least one Group VIII metal.
- a process for isomerization dewaxing a raff ⁇ nate comprising contacting said raffinate in the presence of added hydrogen with a catalyst comprising the zeolite of this invention.
- the raffinate may be bright stock, and the zeolite may be predominantly in the hydrogen form.
- the catalyst may contain at least one Group VIII metal.
- Also included in this invention is a process for increasing the octane of a hydrocarbon feedstock to produce a product having an increased aromatics content
- a hydrocarbonaceous feedstock which comprises normal and slightly branched hydrocarbons having a boiling range above about 40°C and less than about 200°C, under aromatic conversion conditions with a catalyst comprising the zeolite of this invention made substantially free of acidity by neutralizing said zeolite with a basic metal.
- a catalyst comprising the zeolite of this invention made substantially free of acidity by neutralizing said zeolite with a basic metal.
- the zeolite contains a Group VIII metal component.
- a catalytic cracking process comprising contacting a hydrocarbon feedstock in a reaction zone under catalytic cracking conditions in the absence of added hydrogen with a catalyst comprising the zeolite ofthis invention, preferably predominantly in the hydrogen form. Also included in this invention is such a catalytic cracking process wherein the catalyst additionally comprises a large pore crystalline cracking component.
- This invention further provides an isomerization process for isomerizing C 4 to C 7 hydrocarbons, comprising contacting a feed having normal and slightly branched C 4 to C hydrocarbons under isomerizing conditions with a catalyst comprising the zeolite ofthis invention, preferably predominantly in the hydrogen form.
- the zeolite may be impregnated with at least one Group Vffi metal, preferably platinum.
- the catalyst may be calcined in a steam/air mixture at an elevated temperature after impregnation of the Group VIII metal.
- a process for alkylating an aromatic hydrocarbon which comprises contacting under alkylation conditions at least a molar excess of an aromatic hydrocarbon with a C 2 to C 20 olefin under at least partial liquid phase conditions and in the presence of a catalyst comprising the zeolite of this invention, preferably predominantly in the hydrogen form.
- the olefin may be a C 2 to C 4 olefin, and the aromatic hydrocarbon and olefin may be present in a molar ratio of about 4:1 to about 20:1, respectively.
- the aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene or mixtures thereof.
- a process for transalkylating an aromatic hydrocarbon which comprises contacting under transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the presence of a catalyst comprising the zeolite ofthis invention, preferably predominantly in the hydrogen form.
- the aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon may be present in a molar ratio of from about 1 : 1 to about 25 : 1 , respectively.
- the aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof, and the polyalkyl aromatic hydrocarbon may be a dialkylbenzene.
- this invention is a process to convert paraffins to aromatics which comprises contacting paraffins under conditions which cause paraffins to convert to aromatics with catalyst comprising the zeolite ofthis invention, said catalyst comprising gallium, zinc, or a compound of gallium or zinc.
- a process for isomerizing olefins comprising contacting said olefin under conditions which cause isomerization of the olefin with a catalyst comprising the zeolite ofthis invention.
- a process for isomerizing an isomerization feed comprising an aromatic C 8 stream of xylene isomers or mixtures of xylene isomers and ethylbenzene, wherein a more nearly equilibrium ratio of ortho-, meta- and para-xylenes is obtained, said process comprising contacting said feed under isomerization conditions with a catalyst comprising the zeolite ofthis invention.
- the present invention further provides a process for oligomerizing olefins comprising contacting an olefin feed under oligomerization conditions with a catalyst comprising the zeolite of this invention.
- This invention also provides a process for converting oxygenated hydrocarbons comprising contacting said oxygenated hydrocarbon with a catalyst comprising the zeolite ofthis invention under conditions to produce liquid products.
- the oxygenated hydrocarbon may be a lower alcohol.
- a process for the production of higher molecular weight hydrocarbons from lower molecular weight hydrocarbons comprising the steps of: (a) introducing into a reaction zone a lower molecular weight hydrocarbon- containing gas and contacting said gas in said zone under C 2+ hydrocarbon synthesis conditions with the catalyst and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon; and (b) withdrawing from said reaction zone a higher molecular weight hydrocarbon-containing stream.
- an improved process for the reduction of oxides of nitrogen contained in a gas stream in the presence of oxygen comprising contacting the gas stream with a zeolite, the improvement comprising using as the zeolite a zeolite having a mole ratio greater than about 15 of an oxide of a first tetravalent element to an oxide of a second tetravalent element different from said first tetravalent element, trivalent element, pentavalent element or mixture thereof and having, after calcination, the X-ray diffraction lines of Table II.
- the zeolite may contain a metal or metal ions (such as cobalt, copper or mixtures thereof) capable of catalyzing the reduction of the oxides of nitrogen, and may be conducted in the presence of a stoichiometric excess of oxygen.
- the gas stream is the exhaust stream of an internal combustion engine.
- the term "large pore” means having an average pore size diameter greater than about 6.0 Angstroms, preferably from about 6.5 Angstroms to about 7.5 Angstroms. While not wishing to be bound by any theory, it is believed that the crystal structure of SSZ-63 consists of two polymorphs of zeolite beta. Typical zeolite beta (BEA*) has a crystal structure consisting of about a 50/50 combination of two polymorphs, polymorph A and polymorph B. It is believed that the crystal structure of SSZ-63 consists of about 60-70% of a beta polymorph referred to herein as beta-C (Higgins) with the remainder being beta polymorph B. Beta polymorph C (Higgins) is different from beta polymorph C.
- beta-C beta-C
- Beta polymorph C Higgins
- polymorph C has been postulated in the literature, but it is believed that polymorph C (Higgins) has heretofore not been made.
- a discussion of polymorph C (Higgins) can be found in Higgins et al, "The framework Topology of Zeolite Beta", Zeolites, 1988, vol. 8, pp.446-452, with a correction at Higgins et al., "The Framework Topology of Zeolite Beta - A Correction", Zeolites. 1989, vol. 9, p. 358.
- SDA structure directing agent
- SSZ-63 is prepared by contacting an active source of one or more oxides selected from the group consisting of monovalent element oxides, divalent element oxides, trivalent element oxides, tetravalent element oxides and pentavalent elements with the N-cyclodecyl-N-methyl-pyrrolidinium cation SDA.
- SSZ-63 is prepared from a reaction mixture having the composition shown in Table A below.
- YO 2 /W a O b > 15 30 - 70 OH- YO 2 0.10 - 0.50 0.20 - 0.30 Q/YO 2 0.05 - 0.50 0.10 - 0.20 M 2 n /YO 2 0.02 - 0.40 0.10 - 0.25 H 2 O/YO 2 30 - 80 35 - 45
- Y, W, Q, M and n are as defined above, and a is 1 or 2, and b is 2 when a is 1 (i.e., W is tetravalent) and b is 3 when a is 2 (i.e., W is trivalent).
- SSZ-63 is prepared by a process comprising: (a) preparing an aqueous solution containing sources of at least one oxide capable of forming a crystalline molecular sieve and a N-cyclodecyl-N-methyl- pyrrolidinium cation having an anionic counterion which is not detrimental to the formation of SSZ-63; (b) maintaining the aqueous solution under conditions sufficient to form crystals of SSZ-63; and (c) recovering the crystals of SSZ-63.
- SSZ-63 may comprise the crystalline material and the SDA in combination with metallic and non-metallic oxides bonded in tetrahedral coordination through shared oxygen atoms to form a cross-linked three dimensional crystal structure.
- the metallic and non-metallic oxides comprise one or a combination of oxides of a first tetravalent element(s), and one or a combination of a trivalent element(s), pentavalent element(s), second tetravalent element(s) different from the first tetravalent element(s) or mixture thereof.
- the first tetravalent element(s) is preferably selected from the group consisting of silicon, germanium and combinations thereof. More preferably, the first tetravalent element is silicon.
- the trivalent element, pentavalent element and second tetravalent element (which is different from the first tetravalent element) is preferably selected from the group consisting of aluminum, gallium, iron, boron, titanium, indium, vanadium and combinations thereof. More preferably, the second trivalent or tetravalent element is aluminum or boron.
- Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, aluminum colloids, aluminum oxide coated on silica sol, hydrated alumina gels such as Al(OH) 3 and aluminum compounds such as A1C1 3 and Al (SO ) 3 .
- Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicates, and silica hydroxides. Boron, as well as gallium, germanium, titariium, indium, vanadium and iron, can be added in forms corresponding to their aluminum and silicon counterparts.
- a source zeolite reagent may provide a source of aluminum or boron. In most cases, the source zeolite also provides a source of silica. The source zeolite in its dealuminated or deboronated form may also be used as a source of silica, with additional silicon added using, for example, the conventional sources listed above.
- a source zeolite reagent as a source of alumina for the present process is more completely described in U.S. Patent No. 5,225,179, issued July 6, 1993 to Nakagawa entitled “Method of Making Molecular Sieves", the disclosure of which is incorporated herein by reference.
- an alkali metal hydroxide and/or an alkaline earth metal hydroxide such as the hydroxide of sodium, potassium, lithium, cesium, rubidium, calcium, and magnesium, is used in the reaction mixture; however, this component can be omitted so long as the equivalent basicity is maintained.
- the SDA may be used to provide hydroxide ion.
- the alkali metal cation or alkaline earth cation may be part of the as-synthesized crystalline oxide material, in order to balance valence electron charges therein.
- the reaction mixture is maintained at an elevated temperature until the crystals of the SSZ-63 are formed.
- the hydrothermal crystallization is usually conducted under autogenous pressure, at a temperature between 100°C and 200°C, preferably between 135°C and 160°C.
- the crystallization period is typically greater than 1 day and preferably from about 3 days to about 20 days.
- the molecular sieve is prepared using mild stirring or agitation.
- the SSZ-63 crystals can be allowed to nucleate spontaneously from the reaction mixture.
- the use of SSZ-63 crystals as seed material can be advantageous in decreasing the time necessary for complete crystallization to occur.
- seeding can lead to an increased purity of the product obtained by promoting the nucleation and/or formation of SSZ-63 over any undesired phases.
- SSZ-63 crystals are added in an amount between 0.1 and 10% of the weight of silica used in the reaction mixture.
- the crystals are water- washed and then dried, e.g., at 90°C to 150°C for from 8 to 24 hours, to obtain the as-synthesized SSZ-63 crystals.
- the drying step can be performed at atmospheric pressure or under vacuum.
- SSZ-63 as prepared has a mole ratio of an oxide selected from silicon oxide, germanium oxide and mixtures thereof to an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide, vanadium oxide and mixtures thereof greater than about 15; and has, after calcination, the X-ray diffraction lines of Table II below.
- SSZ-63 further has a composition, as synthesized (i.e., prior to removal of the SDA from the SSZ-63) and in the anhydrous state, in terms of mole ratios, shown in Table B below.
- SSZ-63 can be made essentially aluminum free, i.e., having a silica to alumina mole ratio of ⁇ . A method of increasing the mole ratio of silica to alumina is by using standard acid leaching or chelating treatments.
- essentially aluminum-free SSZ-63 can be synthesized directly using essentially aluminum-free silicon sources as the main tetrahedral metal oxide component, if boron is also present.
- the boron can then be removed, if desired, by treating the borosilicate SSZ- 63 with acetic acid at elevated temperature ( as described in Jones et al., Chem. Mater., 2001, 13, 1041-1050) to produce an all-silica version of SSZ-63.
- SSZ-63 can also be prepared directly as a borosilicate. If desired, the boron can be removed as described above and replaced with metal atoms by techniques known in the art to make, e.g.,, an aluminosilicate version of SSZ-63.
- SSZ-63 can also be prepared directly as an aluminosilicate.
- Lower silica to alumina ratios may also be obtained by using methods which insert aluminum into the crystalline framework.
- aluminum insertion may occur by thermal treatment of the zeolite in combination with an alumina binder or dissolved source of alumina. Such procedures are described in U.S. Patent No. 4,559,315, issued on December 17, 1985 to Chang et al. It is believed that SSZ-63 is comprised of a new framework structure or topology which is characterized by its X-ray diffraction pattern. SSZ-63, as-synthesized, has a crystalline structure whose X-ray powder diffraction pattern exhibit the characteristic lines shown in Table I and is thereby distinguished from other molecular sieves . TABLE I
- the X-ray patterns provided are based on a relative intensity scale in which the strongest line in the X-ray pattern is assigned a value of 100: W(weak) is less than 20; M(medium) is between 20 and 40; S(strong) is between 40 and 60; VS(very strong) is greater than 60.
- Table IA shows the X-ray powder diffraction lines for as-synthesized SSZ-63 including actual relative intensities.
- Table IIA shows the X-ray powder diffraction lines for calcined SSZ-63 including actual relative intensities.
- the molecular sieve produced by exchanging the metal or other cations present in the molecular sieve with various other cations yields essentially the same diffraction pattern, although again, there may be minor shifts in the interplanar spacing and variations in the relative intensities of the peaks. Notwithstanding these minor perturbations, the basic crystal lattice remains unchanged by these treatments.
- Crystalline SSZ-63 can be used as-synthesized, but preferably will be thermally treated (calcined). Usually, it is desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or any desired metal ion.
- the molecular sieve can be leached with chelating agents, e.g., EDTA or dilute acid solutions, to increase the silica to alumina mole ratio.
- the molecular sieve can also be steamed; steaming helps stabilize the crystalline lattice to attack from acids.
- the molecular sieve can be used in intimate combination with hydrogenating components, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as palladium or platinum, for those applications in which a hydrogenation-dehydrogenation function is desired.
- Metals may also be introduced into the molecular sieve by replacing some of the cations in the molecular sieve with metal cations via standard ion exchange techniques (see, for example, U.S. Patent Nos. 3,140,249 issued July 7, 1964 to Plank et al.; 3,140,251 issued July 7, 1964 to Plank et al.; and 3,140,253 issued July 7, 1964 to Plank et al.).
- Typical replacing cations can include metal cations, e.g., rare earth, Group IA, Group IIA and Group VIII metals, as well as their mixtures.
- cations of metals such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe are particularly preferred.
- the hydrogen, ammonium, and metal components can be ion-exchanged into the SSZ-63.
- the SSZ-63 can also be impregnated with the metals, or the metals can be physically and intimately admixed with the SSZ-63 using standard methods known to the art. Typical ion-exchange techniques involve contacting the synthetic molecular sieve with a solution containing a salt of the desired replacing cation or cations.
- the molecular sieve is typically washed with water and dried at temperatures ranging from 65°C to about 200°C. After washing, the molecular sieve can be calcined in air or inert gas at temperatures ranging from about 200°C to about 800°C for periods of time ranging from 1 to 48 hours, or more, to produce a catalytically active product especially useful in hydrocarbon conversion processes. Regardless of the cations present in the synthesized form of SSZ-63, the spatial arrangement of the atoms which form the basic crystal lattice of the molecular sieve remains essentially unchanged. SSZ-63 can be formed into a wide variety of physical shapes.
- the molecular sieve can be in the form of a powder, a granule, or a molded product, such as extradate having a particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen.
- the SSZ-63 can be extruded before drying, or, dried or partially dried and then extruded.
- SSZ-63 can be composited with other materials resistant to the temperatures and other conditions employed in organic conversion processes.
- matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides.
- Hydrocarbon Conversion Processes SSZ-63 zeolites are useful in hydrocarbon conversion reactions. Hydrocarbon conversion reactions are chemical and catalytic processes in which carbon containing compounds are changed to different carbon containing compounds. Examples of hydrocarbon conversion reactions in which SSZ-63 are expected to be useful include hydrocracking, dewaxing, catalytic cracking and olefin and aromatics formation reactions.
- the catalysts are also expected to be useful in other petroleum refining and hydrocarbon conversion reactions such as isomerizing n-paraffins and naphthenes, polymerizing and oligomerizing olefinic or acetylenic compounds such as isobutylene and butene-1, reforming, isomerizing polyalkyl substituted aromatics (e.g., m-xylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of benzene, xylenes and higher methylbenzenes and oxidation reactions.
- isomerizing n-paraffins and naphthenes polymerizing and oligomerizing olefinic or acetylenic compounds such as isobutylene and butene-1
- reforming isomerizing polyalkyl substituted aromatics (e.g., m-xylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of
- SSZ-63 catalysts may have high selectivity, and under hydrocarbon conversion conditions can provide a high percentage of desired products relative to total products.
- SSZ-63 zeolites can be used in processing hydrocarbonaceous feedstocks.
- Hydrocarbonaceous feedstocks contain carbon compounds and can be from many different sources, such as virgin petroleum fractions, recycle petroleum fractions, shale oil, liquefied coal, tar sand oil, synthetic paraffins from NAO, recycled plastic feedstocks and, in general, can be any carbon containing feedstock susceptible to zeolitic catalytic reactions.
- the feed can contain metal or be free of metals, it can also have high or low nitrogen or sulfur impurities. It can be appreciated, however, that in general processing will be more efficient (and the catalyst more active) the lower the metal, nitrogen, and sulfur content of the feedstock.
- the conversion of hydrocarbonaceous feeds can take place in any convenient mode, for example, in fluidized bed, moving bed, or fixed bed reactors depending on the types of process desired.
- the formulation of the catalyst particles will vary depending on the conversion process and method of operation.
- Other reactions which can be performed using the catalyst ofthis invention containing a metal, e.g., a Group VIII metal such platinum, include hydrogenation-dehydrogenation reactions, denitrogenation and desulfurization reactions.
- the following table indicates typical reaction conditions which may be employed when using catalysts comprising SSZ-63 in the hydrocarbon conversion reactions ofthis invention. Preferred conditions are indicated in parentheses.
- Hydrocracking Using a catalyst which comprises SSZ-63, preferably predominantly in the hydrogen form, and a hydrogenation promoter, heavy petroleum residual feedstocks, cyclic stocks and other hydrocrackate charge stocks can be hydrocracked using the process conditions and catalyst components disclosed in the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753.
- the hydrocracking catalysts contain an effective amount of at least one hydrogenation component of the type commonly employed in hydrocracking catalysts.
- the hydrogenation component is generally selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIII, including the salts, complexes and solutions containing such.
- the hydrogenation catalyst is preferably selected from the group of metals, salts and complexes thereof of the group consisting of at least one of platinum, palladium, rhodium, iridiurn, ruthenium and mixtures thereof or the group consisting of at least one of nickel, molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof.
- the hydrogenation catalyst is present in an effective amount to provide the hydrogenation function of the hydrocracking catalyst, and preferably in the range of from 0.05 to 25% by weight.
- Dewaxing SSZ-63 preferably predominantly in the hydrogen form, can be used to dewax hydrocarbonaceous feeds by selectively removing straight chain paraffins.
- the viscosity index of the dewaxed product is improved (compared to the waxy feed) when the waxy feed is contacted with SSZ-63 under isomerization dewaxing conditions.
- the catalytic dewaxing conditions are dependent in large measure on the feed used and upon the desired pour point.
- Hydrogen is preferably present in the reaction zone during the catalytic dewaxing process.
- the hydrogen to feed ratio is typically between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel), preferably about 1000 to about 20,000 SCF/bbl.
- Typical feedstocks include light gas oil, heavy gas oils and reduced crudes boiling above about 350°F.
- a typical dewaxing process is the catalytic dewaxing of a hydrocarbon oil feedstock boiling above about 350°F and containing straight chain and slightly branched chain hydrocarbons by contacting the hydrocarbon oil feedstock in the presence of added hydrogen gas at a hydrogen pressure of about 15-3000 psi with a catalyst comprising SSZ-63 and at least one Group VIII metal.
- the SSZ-63 hydrodewaxing catalyst may optionally contain a hydrogenation component of the type commonly employed in dewaxing catalysts. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for examples of these hydrogenation components.
- the hydrogenation component is present in an effective amount to provide an effective hydrodewaxing and hydroisomerization catalyst preferably in the range of from about 0.05 to 5% by weight.
- the catalyst may be run in such a mode to increase isomerization dewaxing at the expense of cracking reactions.
- the feed may be hydrocracked, followed by dewaxing. This type of two stage process and typical hydrocracking conditions are described in U.S. Patent No. 4,921 ,594, issued May 1 , 1990 to Miller, which is incorporated herein by reference in its entirety.
- SSZ-63 may also be utilized as a dewaxing catalyst in the form of a layered catalyst.
- the catalyst comprises a first layer comprising zeolite SSZ-63 and at least one Group VIII metal, and a second layer comprising an aluminosilicate zeolite which is more shape selective than zeolite SSZ-63.
- the use of layered catalysts is disclosed in U.S. Patent No. 5,149,421, issued September 22, 1992 to Miller, which is incorporated by reference herein in its entirety.
- the layering may also include a bed of SSZ-63 layered with a non-zeolitic component designed for either hydrocracking or hydro finishing.
- SSZ-63 may also be used to dewax raffinates, including bright stock, under conditions such as those disclosed in U. S. Patent No.
- hydrofinishing mild hydrogenation
- the hydro finishing step can be performed either before or after the dewaxing step, and preferably after.
- Hydrofinishing is typically conducted at temperatures ranging from about 190°C to about 340°C at pressures from about 400 psig to about 3000 psig at space velocities (LHSV) between about 0.1 and 20 and a hydrogen recycle rate of about 400 to 1500 SCF/bbl.
- the hydrogenation catalyst employed must be active enough not only to hydrogenate the olefins, diolefins and color bodies which may be present, but also to reduce the aromatic content. Suitable hydrogenation catalyst are disclosed in U. S. Patent No. 4,921,594, issued May 1, 1990 to Miller, which is incorporated by reference herein in its entirety.
- the hydrofinishing step is beneficial in preparing ah acceptably stable product (e.g., a lubricating oil) since dewaxed products prepared from hydrocracked stocks tend to be unstable to air and light and tend to form sludges spontaneously and quickly.
- Lube oil may be prepared using SSZ-63.
- a C o + lube oil may be made by isomerizing a C 20+ olefin feed over a catalyst comprising SSZ-63 in the hydrogen form and at least one Group VIII metal.
- the lubricating oil may be made by hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil, and catalytically dewaxing the effluent at a temperature of at least about 400°F and at a pressure of from about 15 psig to about 3000 psig in the presence of added hydrogen gas with a catalyst comprising SSZ-63 in the hydrogen form and at least one Group VIII metal.
- Aromatics Formation SSZ-63 can be used to convert light straight run naphthas and similar mixtures to highly aromatic mixtures.
- normal and slightly branched chained hydrocarbons preferably having a boiling range above about 40°C and less than about 200°C, can be converted to products having a substantial higher octane aromatics content by contacting the hydrocarbon feed with a catalyst comprising SSZ-63.
- the conversion catalyst preferably contains a Group VIII metal compound to have sufficient activity for commercial use.
- Group VIII metal compound as used herein is meant the metal itself or a compound thereof.
- the Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium or tin or a mixture thereof may also be used in conjunction with the Group VIII metal compound and preferably a noble metal compound. The most preferred metal is platinum.
- the amount of Group VIII metal present in the conversion catalyst should be within the normal range of use in reforming catalysts, from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent. It is critical to the selective production of aromatics in useful quantities that the conversion catalyst be substantially free of acidity, for example, by neutralizing the zeolite with a basic metal, e.g., alkali metal, compound. Methods for rendering the catalyst free of acidity are known in the art. See the aforementioned U.S.
- Catalytic Cracking Hydrocarbon cracking stocks can be catalytically cracked in the absence of hydrogen using SSZ-63, preferably predominantly in the hydrogen form.
- SSZ-63 When SSZ-63 is used as a catalytic cracking catalyst in the absence of hydrogen, the catalyst may be employed in conjunction with traditional cracking catalysts, e.g., any aluminosilicate heretofore employed as a component in cracking catalysts.
- these are large pore, crystalline aluminosilicates.
- these traditional cracking catalysts are disclosed in the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No 5,316,753.
- TC traditional cracking catalyst
- the relative weight ratio of the TC to the SSZ-63 is generally between about 1:10 and about 500: 1 , desirably between about 1:10 and about 200:1, preferably between about 1:2 and about 50:1, and most preferably is between about 1 : 1 and about 20: 1.
- the novel zeolite and/or the traditional cracking component may be further ion exchanged with rare earth ions to modify selectivity.
- the cracking catalysts are typically employed with an inorganic oxide matrix component.
- the present catalyst is highly active and highly selective for isomerizing C 4 to C 7 hydrocarbons.
- the activity means that the catalyst can operate at relatively low temperature which thermodynamically favors highly branched paraffins. Consequently, the catalyst can produce a high octane product.
- the high selectivity means that a relatively high liquid yield can be achieved when the catalyst is run at a high octane.
- the present process comprises contacting the isomerization catalyst, i.e., a catalyst comprising SSZ-63 in the hydrogen form, with a hydrocarbon feed under isomerization conditions.
- the feed is preferably a light straight run fraction, boiling within the range of 30°F to 250°F and preferably from 60°F to 200°F.
- the hydrocarbon feed for the process comprises a substantial amount of C 4 to C 7 normal and slightly branched low octane hydrocarbons, more preferably C 5 and C 6 hydrocarbons.
- hydrogen is added to give a hydrogen to hydrocarbon ratio (H 2 /HC) of between 0.5 and 10 H 2 /HC, more preferably between 1 and 8 H 2 /HC. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No.
- a low sulfur feed is especially preferred in the present process.
- the feed preferably contains less than 10 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm sulfur.
- acceptable levels can be reached by hydrogenating the feed in a presaturation zone with a hydrogenating catalyst which is resistant to sulfur poisoning. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for a further discussion of this hydrodesulfurization process. It is preferable to limit the nitrogen level and the water content of the feed.
- the conversion catalyst preferably contains a Group VIII metal compound to have sufficient activity for commercial use.
- Group VIII metal compound as used herein is meant the metal itself or a compound thereof.
- the Group VIII noble metals and their compounds, platinum, palladium, and iridium, or combinations thereof can be used. Rhenium and tin may also be used in conjunction with the noble metal. The most preferred metal is platinum.
- Alkylation and Transalkylation SSZ-63 can be used in a process for the alkylation or transalkylation of an aromatic hydrocarbon.
- the process comprises contacting the aromatic hydrocarbon with a C 2 to C 16 olefin alkylating agent or a polyalkyl aromatic hydrocarbon transalkylating agent, under at least partial liquid phase conditions, and in the presence of a catalyst comprising SSZ-63.
- SSZ-63 can also be used for removing benzene from gasoline by alkylating the benzene as described above and removing the alkylated product from the gasoline.
- the SSZ-63 zeolite should be predominantly in its hydrogen ion form. It is preferred that, after calcination, at least 80% of the cation sites are occupied by hydrogen ions and/or rare earth ions.
- suitable aromatic hydrocarbon feedstocks which may be alkylated or transalkylated by the process of the invention include aromatic compounds such as benzene, toluene and xylene. The preferred aromatic hydrocarbon is benzene.
- naphthalene or naphthalene derivatives such as dimethylnaphthalene
- Mixtures of aromatic hydrocarbons may also be employed.
- Suitable olefins for the alkylation of the aromatic hydrocarbon are those containing 2 to 20, preferably 2 to 4, carbon atoms, such as ethylene, propylene, butene-1, trans-butene-2 and cis-butene-2, or mixtures thereof.
- pentenes are desirable.
- the preferred olefins are ethylene and propylene. Longer chain alpha olefins may be used as well.
- the transalkylating agent is a polyalkyl aromatic hydrocarbon containing two or more alkyl groups that each may have from 2 to about 4 carbon atoms.
- suitable polyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkyl aromatic hydrocarbons, such as diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene), di-isopropylbenzene, di-isopropyltoluene, dibutylbenzene, and the like.
- Preferred polyalkyl aromatic hydrocarbons are the dialkyl benzenes.
- a particularly preferred polyalkyl aromatic hydrocarbon is di-isopropylbenzene.
- reaction conditions are as follows.
- the aromatic hydrocarbon feed should be present in stoichiometric excess. It is preferred that molar ratio of aromatics to olefins be greater than four-to-one to prevent rapid catalyst fouling.
- the reaction temperature may range from 100°F to 600°F, preferably 250°F to 450°F.
- the reaction pressure should be sufficient to maintain at least a partial liquid phase in order to retard catalyst fouling. This is typically 50 psig to 1000 psig depending on the feedstock and reaction temperature.
- Contact time may range from 10 seconds to 10 hours, but is usually from 5 minutes to an hour.
- the weight hourly space velocity (WHS V), in terms of grams (pounds) of aromatic hydrocarbon and olefin per gram (pound) of catalyst per hour, is generally within the range of about 0.5 to 50.
- the molar ratio of aromatic hydrocarbon will generally range from about 1 : 1 to 25 : 1 , and preferably from about 2:1 to 20:1.
- the reaction temperature may range from about 100°F to 600°F, but it is preferably about 250°F to 450°F.
- the reaction pressure should be sufficient to maintain at least a partial liquid phase, typically in the range of about 50 psig to 1000 psig, preferably 300 psig to 600 psig.
- the weight hourly space velocity will range from about 0.1 to 10.
- the zeolite will contain a catalyst metal or metal oxide wherein said metal is selected from the group consisting of Groups IB, IIB, VIII and IIIA of the Periodic Table.
- the metal is gallium, niobium, indium or zinc in the range of from about 0.05 to 5% by weight.
- Xylene Isomerization SSZ-63 may also be useful in a process for isomerizing one or more xylene isomers in a C 8 aromatic feed to obtain ortho-, meta-, and para-xylene in a ratio approaching the equilibrium value.
- xylene isomerization is used in conjunction with a separate process to manufacture para-xylene.
- a portion of the para-xylene in a mixed C 8 aromatics stream may be recovered by crystallization and centrifugation. The mother liquor from the crystallizer is then reacted under xylene isomerization conditions to restore ortho-, meta- and para-xylenes to a near equilibrium ratio.
- part of the ethylbenzene in the mother liquor is converted to xylenes or to products which are easily separated by filtration.
- the isomerate is blended with fresh feed and the combined stream is distilled to remove heavy and light by-products.
- the resultant C 8 aromatics stream is then sent to the crystallizer to repeat the cycle.
- isomerization in the vapor phase is conducted in the presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene (e.g., ethylbenzene).
- the catalyst should comprise about 0.1 to 2.0 wt.% of a hydrogenation/dehydrogenation component selected from Group VIII (of the Periodic Table) metal component, especially platinum or nickel.
- Group VIII metal component is meant the metals and their compounds such as oxides and sulfides.
- the isomerization feed may contain 10 to 90 wt. of a diluent such as toluene, trimethylbenzene, naphthenes or paraffins.
- Oligomerization It is expected that SSZ-63 can also be used to oligomerize straight and branched chain olefins having from about 2 to 21 and preferably 2-5 carbon atoms.
- the oligomers which are the products of the process are medium to heavy olefins which are useful for both fuels, i.e., gasoline or a gasoline blending stock and chemicals.
- the oligomerization process comprises contacting the olefin feedstock in the gaseous or liquid phase with a catalyst comprising SSZ-63.
- the zeolite can have the original cations associated therewith replaced by a wide variety of other cations according to techniques well known in the art. Typical cations would include hydrogen, ammonium and metal cations including mixtures of the same. Of the replacing metallic cations, particular preference is given to cations of metals such as rare earth metals, manganese, calcium, as well as metals of Group II of the Periodic Table, e.g., zinc, and Group VIII of the Periodic Table, e.g., nickel.
- the zeolite have a fairly low aromatization activity, i.e., in which the amount of aromatics produced is not more than about 20% by weight. This is accomplished by using a zeolite with controlled acid activity [alpha value] of from about 0.1 to about 120, preferably from about 0.1 to about 100, as measured by its ability to crack n-hexane. Alpha values are defined by a standard test known in the art, e.g., as shown in U.S. Patent No. 3,960,978 issued on June 1, 1976 to Givens et al. which is incorporated totally herein by reference.
- Such zeolites may be obtained by steaming, by use in a conversion process or by any other method which may occur to one skilled in this art.
- Condensation of Alcohols SSZ-63 can be used to condense lower aliphatic alcohols having 1 to 10 carbon atoms to a gasoline boiling point hydrocarbon product comprising mixed aliphatic and aromatic hydrocarbon.
- the process disclosed in U.S. Patent No. 3,894,107, issued July 8, 1975 to Butter et al. describes the process conditions used in this process, which patent is incorporated totally herein by reference.
- the catalyst may be in the hydrogen form or may be base exchanged or impregnated to contain ammonium or a metal cation complement, preferably in the range of from about 0.05 to 5% by weight.
- the metal cations that may be present include any of the metals of the Groups I through VIII of the Periodic Table. However, in the case of Group IA metals, the cation content should in no case be so large as to effectively inactivate the catalyst, nor should the exchange be such as to eliminate all acidity. There may be other processes involving treatment of oxygenated substrates where a basic catalyst is desired. Methane Upgrading Higher molecular weight hydrocarbons can be formed from lower molecular weight hydrocarbons by contacting the lower molecular weight hydrocarbon with a catalyst comprising SSZ-63 and a metal or metal compound capable of converting the lower molecular weight hydrocarbon to a higher molecular weight hydrocarbon.
- Examples of such reactions include the conversion of methane to C 2+ hydrocarbons such as ethylene or benzene or both.
- Examples of useful metals and metal compounds include lanthanide and or actinide metals or metal compounds.
- SSZ-63 may be used for the catalytic reduction of the oxides of nitrogen in a gas stream.
- the gas stream also contains oxygen, often a stoichiometric excess thereof.
- the SSZ-63 may contain a metal or metal ions within or on it which are capable of catalyzing the reduction of the nitrogen oxides. Examples of such metals or metal ions include copper, cobalt, platinum, iron, chromium, manganese, nickel, zinc, lanthanum, palladium, rhodium and mixtures thereof.
- One example of such a process for the catalytic reduction of oxides of nitrogen in the presence of a zeolite is disclosed in U.S. Patent No.
- the catalytic process is the combustion of carbon monoxide and hydrocarbons and the catalytic reduction of the oxides of nitrogen contained in a gas stream, such as the exhaust gas from an internal combustion engine.
- the zeolite used is metal ion- exchanged, doped or loaded sufficiently so as to provide an effective amount of catalytic copper or copper ions within or on the zeolite, h addition, the process is conducted in an excess of oxidant, e.g., oxygen.
- the anion (X " ) associated with the cation may be any anion which is not detrimental to the formation of the zeolite.
- Representative anions include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and the like. Hydroxide is the most preferred anion.
- SDA structure-directing agent N-cyclodecyl-N-methyl-pyrrolidinium cation was synthesized according to the procedure described below (see Scheme 1).
- the filtrate was concentrated at reduced pressure on a rotary evaporator to yield 32 gm (96%) of the expected enamine (1-cyclodec-l-enyl-pyrrolidine) as a reddish oily substance. 1H-NMR and 13 C-NMR spectra were acceptable for the desired product.
- the enamine was reduced to the corresponding amine (N-cyclodecyl-pyrrolidine) in quantitative yield via catalytic hydrogenation in the presence of 10% Pd on activated carbon at hydrogen pressure of 55 PSI in ethanol.
- Borosilicate SSZ-63 was determined from its unique XRD pattern, and by transmission electron microscopy analysis Example 3 Conversion of Borosilicate SSZ-63 to Aluminosilicate SSZ-63 Borosilicate SSZ-63 synthesized as described in Example 2 above and calcined as shown in Example 17 below was suspended in IM solution of aluminum nitrate nonahydrate (15 ml of IM Al(NO 3 ) 3 .9H 2 O soln./l gm zeolite). The suspension was heated at reflux for 48 hours. The mixture was then filtered and the collected solids were thoroughly rinsed with water and air-dried overnight. The solids were further dried in an oven at 120° C for 2 hours.
- IM solution of aluminum nitrate nonahydrate 15 ml of IM Al(NO 3 ) 3 .9H 2 O soln./l gm zeolite
- Example 4 Synthesis of Germanosilicate SSZ-63 A 23 cc Teflon liner was charged with 4.85 gm of 0.61M aqueous solution of N-cyclodecyl-N-methyl-pyrrolidinium hydroxide (3 mmol SDA), 1.25 gm of IM aqueous solution of NaOH (1.25 mmol NaOH) and 5.8 gm of de-ionized water. To this mixture, 0.25 gm of GeO 2 (2.39 mmol) was added and stirred until completely dissolved. To this solution, 0.7 gm of CAB-O-SIL M-5 ® (-11.4 mmol SiO 2 ) was added and thoroughly stirred by hand.
- the resulting gel was capped off and placed in a Parr steel autoclave and heated in an oven at about 160° C while tumbling at about 43 rpm.
- the reaction was monitored by periodically monitoring the pH of the gel, and by looking for crystal growth using scanning electron microscopy (SEM). Once the crystallization was completed, after heating for six days, the starting reaction gel turned into a clear liquid layer and a fine powdery precipitate.
- the mixture was filtered through a fritted-glass funnel. The collected solids were thoroughly washed with water and, then, rinsed with acetone (-20 ml) to remove any organic residues. The solids were allowed to air-dry over night and, then, dried in an oven at 120° C for one hour. The reaction afforded 0.73 gram of SSZ-63.
- Example 17 Calcination of SSZ-63
- the material from Example 3 is calcined in the following manner.
- a thin bed of material is heated in a muffle furnace from room temperature to 120°C at a rate of 1 °C per minute and held at 120°C for three hours.
- the temperature is then ramped up to 540°C at the same rate and held at this temperature for five hours, after which it is increased to 594°C and held there for another five hours.
- a 50/50 mixture of air and nitrogen is passed over the SSZ-63 at a rate of 20 standard cubic feet per minute during heating.
- Example 18 NEU Exchange Ion exchange of calcined SSZ-63 material is performed using NH 4 NO 3 to convert the SSZ-63 from its Na + form to the NUV " form, and, ultimately, the ⁇ form.
- NH 4 NO 3 is slurried in water at a ratio of 25-50:1 water to SSZ-63.
- the exchange solution is heated at 95°C for two hours and then filtered. This procedure can be repeated up to three times. Following the final exchange, the SSZ- 63 is washed several times with water and dried.
- This NH + form of SSZ-63 can then be converted to the H + form by calcination (as described in Example 17) to 540°C.
- Example 19 Constraint Index Determination
- the hydrogen form of the SSZ-63 of Example 2 (after treatment according to Examples 17, 3 and 18) is pelletized at 2-3 KPSL crushed and meshed to 20-40, and then > 0.50 gram is calcined at about 540°C in air for four hours and cooled in a desiccator. 0.50 Gram is packed into a 3/8 inch stainless steel tube with alundum on both sides of the molecular sieve bed. A Lindburg furnace is used to heat the reactor tube. Helium is introduced into the reactor tube at 10 cc/min. and at atmospheric pressure.
- the reactor is heated to about 315°C, and a 50/50 (w/w) feed of n-hexane and 3-methylpentane is introduced into the reactor at a rate of 8 ⁇ l/min. Feed delivery is made via a Brownlee pump. Direct sampling into a gas chromatograph begins after ten minutes of feed introduction. The Constraint Index value is calculated from the gas chromatographic data using methods known in the art. SSZ-63 has a Constraint Index of 1.1 after 10 minutes at 315 °C with 87.7% feed conversion. The Constraint Index dropped with time on stream (0.6 at 100 minutes) suggesting that SSZ-63 is a large pore molecular sieve.
- Example 20 Hydrocracking of n-Hexadecane
- a sample of SSZ-63 as prepared in Example 2 was treated as in Examples 17, 3 and 18. Then a sample was slurried in water and the pH of the slurry was adjusted to a pH of -10 with dilute ammonium hydroxide. To the slurry was added a solution of Pd(NH ) 4 (NO 3 ) 2 at a concentration which would provide 0.5 wt. % Pd with respect to the dry weight of the molecular sieve sample. This slurry was stirred for 48 hours at 100°C. After cooling, the slurry was filtered through a glass frit, washed with de-ionized water, and dried at 100°C.
- the catalyst was then calcined slowly up to 482°C in air and held there for three hours.
- the calcined catalyst was pelletized in a Carver Press and crushed to yield particles with a 20/40 mesh size range.
- Sized catalyst (0.5 g) was packed into a inch OD tubing reactor in a micro unit for n-hexadecane hydroconversion.
- the table below gives the run conditions and the products data for the hydrocracking test on n-hexadecane. After the catalyst was tested with n-hexadecane, it was titrated using a solution of butyl amine in hexane. The temperature was increased and the conversion and product data evaluated again under titrated conditions. The results shown in the table below show that SSZ-63 is effective as a hydrocracking catalyst.
- Example 21 Argon Adsorption Analysis SSZ-63 has a micropore volume of 0.22 cc/gm based on argon adsorption isotherm at 87.6 K recorded on ASAP 2010 equipment from Micromerities.
- the low- pressure dose was 3.00 cm 3 /g (STP) with 15-s equilibration interval.
- the argon adsorption isotherm was analyzed using the density function theory (DFT) formalism and parameters developed for activated carbon slits by Olivier (Porous Mater., 1995, 2, 9) using the Saito Foley adaptation of the Horvarth-Kawazoe formalism (Microporous Materials, 1995, 3, 531) and the conventional t-plot method (J. Catalysis, 1965, 4, 319). Analogous measurements were made with nitrogen using the Digisorb system.
- DFT density function theory
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US10/329,600 US6776973B2 (en) | 2002-12-26 | 2002-12-26 | Using molecular sieve SSZ-63 for reduction of oxides of nitrogen in a gas stream |
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US10/329,963 US6827843B2 (en) | 2002-12-26 | 2002-12-26 | Hydrocarbon conversion using molecular sieve SSZ-63 |
US329939 | 2002-12-26 | ||
PCT/US2003/040199 WO2004060794A2 (en) | 2002-12-26 | 2003-12-17 | Molecular sieve ssz-63 |
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WO2007001934A2 (en) * | 2005-06-23 | 2007-01-04 | Chevron U.S.A. Inc. | Molecular sieve ssz-56 composition of matter and synthesis thereof |
JP5208763B2 (en) * | 2005-12-27 | 2013-06-12 | シェブロン ユー.エス.エー. インコーポレイテッド | Molecular sieve SSZ-73 |
JP7104298B2 (en) | 2018-02-06 | 2022-07-21 | 東ソー株式会社 | New zeolite and hydrocarbon adsorbent containing it |
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2003
- 2003-12-17 WO PCT/US2003/040199 patent/WO2004060794A2/en active Application Filing
- 2003-12-17 JP JP2004565546A patent/JP2006512273A/en not_active Ceased
- 2003-12-17 EP EP03814852A patent/EP1583717A4/en not_active Withdrawn
- 2003-12-17 AU AU2003300993A patent/AU2003300993A1/en not_active Abandoned
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US4544538A (en) * | 1982-07-09 | 1985-10-01 | Chevron Research Company | Zeolite SSZ-13 and its method of preparation |
WO1998029336A1 (en) * | 1996-12-31 | 1998-07-09 | Chevron U.S.A. Inc. | Zeolite ssz-48 |
EP1148027A1 (en) * | 1998-12-22 | 2001-10-24 | Consejo Superior De Investigaciones Cientificas | Itq-7 zeolite |
US20020182145A1 (en) * | 1999-07-29 | 2002-12-05 | Camblor Fernandez Miguel Angel | Zeolite ITQ-10 |
WO2001092155A1 (en) * | 2000-05-31 | 2001-12-06 | Chevron U.S.A. Inc. | Zeolite ssz-53 |
US6461580B1 (en) * | 2001-07-13 | 2002-10-08 | Chevron U.S.A. Inc. | Using zeolite SSZ-58 for reduction of oxides of nitrogen in a gas stream |
US6464956B1 (en) * | 2001-07-13 | 2002-10-15 | Chevron U.S.A. Inc. | Zeolite SSZ-59 composition of matter and synthesis thereof |
Also Published As
Publication number | Publication date |
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WO2004060794A3 (en) | 2004-11-04 |
EP1583717A2 (en) | 2005-10-12 |
JP2006512273A (en) | 2006-04-13 |
AU2003300993A8 (en) | 2004-07-29 |
WO2004060794A2 (en) | 2004-07-22 |
AU2003300993A1 (en) | 2004-07-29 |
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