WO2022132866A1 - A process for producing alpha-olefins - Google Patents
A process for producing alpha-olefins Download PDFInfo
- Publication number
- WO2022132866A1 WO2022132866A1 PCT/US2021/063457 US2021063457W WO2022132866A1 WO 2022132866 A1 WO2022132866 A1 WO 2022132866A1 US 2021063457 W US2021063457 W US 2021063457W WO 2022132866 A1 WO2022132866 A1 WO 2022132866A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- ligand
- methyl
- oligomerization
- olefins
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000004711 α-olefin Substances 0.000 title claims abstract description 29
- 239000003446 ligand Substances 0.000 claims abstract description 96
- 239000001257 hydrogen Substances 0.000 claims abstract description 90
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 90
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- -1 hydroxo Chemical group 0.000 claims abstract description 55
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 53
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 32
- 125000000524 functional group Chemical group 0.000 claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005977 Ethylene Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 19
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims description 30
- 239000011737 fluorine Substances 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000003426 co-catalyst Substances 0.000 claims description 18
- 150000001993 dienes Chemical class 0.000 claims description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 18
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 3
- IKQUUYYDRTYXAP-UHFFFAOYSA-N 3-methylpenta-1,4-diene Chemical compound C=CC(C)C=C IKQUUYYDRTYXAP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 150000001336 alkenes Chemical class 0.000 description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 13
- 239000012535 impurity Substances 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 239000012018 catalyst precursor Substances 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- SMSVUYQRWYTTLI-UHFFFAOYSA-L 2-ethylhexanoate;iron(2+) Chemical compound [Fe+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SMSVUYQRWYTTLI-UHFFFAOYSA-L 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- UWZODPYTQSSIEQ-UHFFFAOYSA-N 2-tert-butyloxaluminane Chemical compound CC(C)(C)[Al]1CCCCO1 UWZODPYTQSSIEQ-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel 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
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KEFOZNJTQPJEOB-UHFFFAOYSA-N pyridine-2,3-diimine Chemical group N=C1C=CC=NC1=N KEFOZNJTQPJEOB-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- FQMMZTDQJFUYSA-UHFFFAOYSA-N triheptylalumane Chemical compound CCCCCCC[Al](CCCCCCC)CCCCCCC FQMMZTDQJFUYSA-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the invention relates to a process for producing alpha-olefins from an ethylene feed using specific iron-ligand complex catalyst systems.
- Linear alpha olefins are a valuable comonomer for linear low-density polyethylene and high-density polyethylene.
- Such olefins are also valuable as a chemical intermediate in the production of plasticizer alcohols, fatty acids, detergent alcohols, polyalphaolefins, oil field drilling fluids, lubricant oil additives, linear alkylbenzenes, alkenylsuccinic anhydrides, alkyldimethylamines, dialkylmethylamines, alpha-olefin sulfonates, internal olefin sulfonates, chlorinated olefins, linear mercaptans, aluminum alkyls, alkyldiphenylether disulfonates, and other chemicals.
- US 6,683,187 describes a bis(arylimino)pyridine ligand, catalyst precursors and catalyst systems derived from this ligand for ethylene oligomerization to form linear alpha olefins.
- the patent teaches the production of linear alpha olefins with a Schulz-Flory oligomerization product distribution. In such a process, a wide range of oligomers are produced, and the fraction of each olefin can be determined by calculation on the basis of the K-factor.
- the K-factor is the molar ratio of (C n +2)/C n , where n is the number of carbons in the linear alpha olefin product.
- alpha olefins are commonly used as comonomers in the production of polyethylene.
- the catalysts used for manufacturing polyethylene can be poisoned by impurities in the feed, including by dienes present in the comonomer.
- the invention provides a process for producing alpha-olefins comprising contacting an ethylene feed with an oligomerization catalyst system in an oligomerization reaction zone under ohgomerization conditions to produce a product stream comprising alpha-olefins wherein the oligomerization catalyst system comprises an iron-ligand complex wherein the ligand comprises a bis-aryliminepyridine compound of formula (III): wherein R 4 , R 5 , R 8 and R 12 are methyl; R 13 and R 17 are hydrogen; and R 1 -R 3 , R 9 -R 11 , R 14 -R 16 are selected from hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- formula (III) wherein R 4 , R 5 , R 8 and R 12 are methyl; R 13 and R 17 are hydrogen; and R 1 -R 3 , R 9 -R 11 , R 14 -R 16 are selected from hydrogen, optionally substituted hydrocarbyl
- the invention further provides a process for producing alpha-olefins comprising contacting an ethylene feed with an oligomerization catalyst system in an oligomerization reaction zone under oligomerization conditions wherein the oligomerization catalyst system comprises an iron-ligand complex wherein the ligand comprises a compound of formula (V):
- R 8 and R 12 are methyl; R 18 and R 21 are hydrogen; and R 1 - R 5 , R 9 -R 11 , R 19 -R 20 are selected from hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- the process comprises converting an olefin feed into a higher oligomer product stream by contacting the feed with an oligomerization catalyst system and a co-catalyst in an oligomerization reaction zone under oligomerization conditions.
- an ethylene feed may be contacted with an iron-ligand complex and modified methyl aluminoxane under oligomerization conditions to produce a product slate of alpha olefins having a specific k-factor.
- the olefin feed to the process comprises ethylene.
- the feed may also comprise olefins having from 3 to 8 carbon atoms.
- the ethylene may be pretreated to remove impurities, especially impurities that impact the reaction, product quality or damage the catalyst.
- the ethylene may be dried to remove water.
- the ethylene may be treated to reduce the oxygen content of the ethylene. Any pretreatment method known to one of ordinary skill in the art can be used to pretreat the feed.
- the oligomerization catalyst system may comprise one or more oligomerization catalysts as described further herein.
- the oligomerization catalyst is a metal-ligand complex that is effective for catalyzing an oligomerization process.
- the ligand may comprise a bis(arylimino)pyridine compound, a bis(alkylimino)pyridine compound or a mixed aryl-alkyl iminopyridine compound.
- the ligand comprises a pyridine bis(imine) group.
- the ligand may be a bis(aryltmino)pyridine compound having the structure of Formula I.
- R 1 , R 2 and R 3 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- R 4 and R 5 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- R 6 and R 7 are each independently an aryl group as shown in Formula II. The two aryl groups ( R 6 and R 7 ) on one ligand may be the same or different.
- R 8 , R 9 , R 10 , R 11 , R 12 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano, an inert functional group, fluorine, or chlorine. Any two of R 1 -R 3 , and R 9 -R 11 vicinal to one another taken together may form a ring. R 12 may be taken together with R 11 , R 4 or R 5 to form a ring. R 2 and R 4 or R 3 and R 5 may be taken together to form a ring.
- a hydrocarbyl group is a group containing only carbon and hydrogen.
- the number of carbon atoms in this group is preferably in the range of from 1 to 30.
- An optionally substituted hydrocarbyl is a hydrocarbyl group that optionally contains one or more “inert” heteroatom-containing functional groups.
- Inert means that the functional groups do not interfere to any substantial degree with the oligomerization process. Examples of these inert groups include fluoride, chloride, iodide, stannanes, ethers, hydroxides, alkoxides and amines with adequate steric shielding.
- the optionally substituted hydrocarbyl group may include primary, secondary and tertiary carbon atoms groups.
- Primary carbon atom groups are a -CH 2 -R group wherein R may be hydrogen, an optionally substituted hydrocarbyl or an inert functional group.
- Examples of primary carbon atom groups include -CH 3 , -C 2 H 5 , -CH 2 Cl, -CH 2 OCH 3 , -CH 2 N (C 2 H 5 ) 2 , and -CH 2 Ph.
- Secondary carbon atom groups are a -CH-R 2 or -CH (R)(R') group wherein R and R' may be optionally substituted hydrocarbyl or an inert functional group.
- Examples of secondary carbon atom groups include - CH(CH 3 ) 2 , -CHCl 2 , -CHPh 2 , -CH(CH 3 )(OCH 3 ), -CH-CH 2 , and cyclohexyl.
- Tertiary carbon atom groups are a -C-(R)(R')(R") group wherein R, R', and R" may be optionally substituted hydrocarbyl or an inert functional group.
- Examples of tertiary carbon atom groups include -C(CH 3 ) 3 , -CCl 3 , - C ⁇ CPh, 1-Adamantyl, and -C(CH 3 ) 2 (OCH 3 )
- An inert functional group is a group other than optionally substituted hydrocarbyl that is inert under the oligomerization conditions. Inert has the same meaning as provided above. Examples of inert functional groups include halide, ethers, and amines, in particular tertiary amines.
- R 1 -R 5 , R 8 -R 12 and R 13 -R 17 may be selected to enhance other properties of the ligand, for example, solubility in non-polar solvents.
- R 8 -R 12 and R 13 -R 17 may be selected to enhance other properties of the ligand, for example, solubility in non-polar solvents.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 11 and R 14 -R 16 are hydrogen; and R 8 , R 12 , R 13 and R 17 are fluorine.
- a ligand of Formula III wherein R 1 -R 5 , R 8 , R 10 , R 12 , R 14 and R 16 ate hydrogen; R 13 , R 15 and R 17 are methyl and R 9 and R 11 are tert-butyl.
- a ligand of Formula III wherein R 1 -R 5 , R 8 , R 12 , R 14 and R 16 are hydrogen; R 13 , R 15 and R 17 are methyl; R 9 and R 11 are phenyl and R 10 is an alkoxy.
- a ligand of Formula III wherein R 1 -R 5 , R 8 , R 10 , R 11 and R 14 -R 16 are hydrogen; R 9 and R 12 are methyl; and R 13 and R 17 are fluorine.
- a ligand of Formula III wherein R 1 -R 3 , R 9 -R 11 and R 14 -R 16 are hydrogen; R 4 and R 5 are phenyl and R 8 , R 12 , R 13 and R 17 are fluorine.
- a ligand of Formula III wherein R 1 -R 5 , R 8 - R 9 , R 11 -R 12 , R 13 - R 14 and R 16 - R 17 are hydrogen; and R 10 and R 15 are fluorine.
- a ligand of Formula III wherein R 1 -R 5 , R 8 , R 10 , R 12 , R 13 , R 15 and R 17 are hydrogen; and R 9 , R 11 , R 14 and R 16 are fluorine.
- a ligand of Formula III wherein R 1 -R 5 , R 9 ,R 11 - R 12 , R 14 andR 16 - R 17 are hydrogen; and R 8 , R 10 , R 13 and R 15 are fluorine.
- a ligand of Formula III wherein R 1 -R 5 , R 8 -R 9 ,R 11 -R 12 , R 14 and R 16 are hydrogen; R 10 is tert-butyl; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III is provided wherein R 1 -R 5 , R 9 -R 12 , R 14 and R 16 , are hydrogen; R 8 is fluorine; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 12 , R 13 , R 15 and R 17 are hydrogen; R 8 is tert-butyl; and R 14 and R 16 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 12 , R 13 -R 14 andR 16 -R 17 are hydrogen; and R 8 and R 15 are tert-butyl.
- a ligand of Formula III wherein R 1 -R 5 , R 8 -R 10 , R 13 -R 14 and R 16 -R 17 are hydrogen; R 15 is tert-butyl; and R 11 and R 12 are taken together to form an aryl group.
- a ligand of Formula III is provided wherein R 1 -R 5 , R 9 -R 12 , R 14 -R 17 are hydrogen; and R 8 and R 13 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 8 -R 9 , R 11 - R 12 , R 14 and R 16 are hydrogen; R 10 is fluorine; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 8 , R 10 , R 12 , R 14 and R 16 are hydrogen; R 9 and R 11 are fluorine; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 8 -R 9 , R 11 -R 12 , R 14 and R 16 are hydrogen; R 10 is an alkoxy; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 8 -R 9 , R 11 -R 12 , R 14 and R 16 are hydrogen; R 10 is a silyl ether; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 8 , R 10 , R 12 , R 14 -R 16 are hydrogen; R 9 and R 11 are methyl; and R 13 and R 17 are ethyl.
- a ligand of Formula III is provided wherein R 1 -R 5 , R 9 -R 12 , and R 14 -R 17 are hydrogen; and R 8 and R 13 are ethyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 11 and R 14 -R 16 are hydrogen; and R 8 , R 12 , R 13 and R 17 are chlorine.
- a ligand of Formula III wherein R 1 -R 5 , R 9 , R 11 , R 14 and R 16 are hydrogen; and R 8 , R 10 , R 12 , R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III is provided wherein R 1 -R 5 , R 9 - R 10 , R 12 , R 14 -R 15 and R 17 are hydrogen; and R 8 , R 11 , R 13 and R 16 are methyl.
- a ligand of Formula III is provided wherein R 1 -R 17 are hydrogen.
- a ligand of Formula III is provided wherein R 1 -R 5 , R 8 , R 10 , R 12 , R 13 , R 15 and R 17 are hydrogen; and R 9 , R 11 , R 14 and R 16 are tert-butyl. In one embodiment, a ligand of Formula III is provided wherein R 1 -R 5 , R 8 -R 12 , R 14 and R 16 are hydrogen; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 , R 11 -R 12 , R 14 and R 16 are hydrogen; R 8 and R 10 are fluorine; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III is provided wherein R 1 -R 5 , R 9 , R 11 -R 12 , R 14 and R 16 -R 17 are hydrogen; and R 8 , R 10 , R 13 and R 15 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 11 and R 14 -R 16 are hydrogen; R 8 and R 12 are chlorine; and R 13 and R 17 are fluorine.
- a ligand of Formula III wherein R 1 -R 5 , R 8 , R 10 , R 12 , R 14 and R 16 are hydrogen; and R 9 , R 11 , R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 11 and R 13 -R 14 and R 16 -R 17 are hydrogen; R 8 and R 12 are chlorine; and R 15 is tert-butyl.
- a ligand of Formula III is provided wherein R 1 -R 5 , R 9 -R 11 and R 13 -R 17 are hydrogen; and R 8 and R 12 are chlorine.
- a ligand of Formula III is provided wherein R 1 -R 5 , R 9 -R 12 , and R 14 -R 17 are hydrogen; and R 8 and R 13 are chlorine.
- a ligand of Formula III wherein R 1 -R 5 , R 9 ,R 11 -R 12 , R 14 and R 16 - R 17 are hydrogen; and R 8 , R 10 , R 13 and R 15 are chlorine.
- a ligand of Formula III wherein R 1 -R 5 , R 9 , R 11 -R 12 , and R 14 , and R 16 -R 17 are hydrogen; R 10 and R 15 are methyl; and R 8 and R 13 are chlorine.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 11 and R 13 -R 14 and R 16 -R 17 are hydrogen; R 15 is fluorine; and R 8 and R 12 are chlorine.
- a ligand of Formula III wherein R 1 -R 5 , R 8 -R 9 , R 11 -R 12 , R 14 - R 15 and R 17 are hydrogen; R 10 is tert-butyl; and R 13 and R 16 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 11 , R 14 and R 16 are hydrogen; R 8 and R 12 are fluorine; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 10 , R 12 , R 14 -R 15 and R 17 are hydrogen; R 8 and R 13 are methyl; and R 11 and R 16 are isopropyl.
- a ligand of Formula III wherein R 1 -R 5 , R 9 -R 12 and R 14 -R 16 are hydrogen; R 8 is ethyl; and R 13 and R 17 are fluorine.
- a ligand of Formula III is provided wherein R 2 -R 5 , R 9 -R 10 , R 12 , R 14 -R 15 and R 17 are hydrogen; R 1 is methoxy; and R 8 , R 11 , R 13 and R 16 are methyl.
- a ligand of Formula III is provided wherein R 2 -R 5 , R 8 - R 12 , R 14 and R 16 , are hydrogen; R 1 is methoxy; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 2 -R 5 , R 9 -R 12 , and R 14 -R 17 are hydrogen; R 1 is methoxy; and R 8 and R 13 are ethyl.
- a ligand of Formula III wherein R 2 -R 5 , R 9 , R 11 -R 12 , R 14 and R 16 - R 17 are hydrogen; R 1 is tert-butyl; and R 8 , R 10 , R 13 and R 15 are methyl.
- a ligand of Formula III wherein R 2 -R 5 , R 8 -R 12 , R 14 and Rie are hydrogen; R 1 is tert-butyl; and R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 2 -R 5 , R 9 , R 11 , R 14 and R 17 , are hydrogen; R 1 is methoxy; and R 8 , R 10 , R 12 , R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 2 -R 5 , R 9 , R 11 , R 14 and R 16 , are hydrogen; R 1 is alkoxy; and R 8 , R 10 , R 12 , R 13 , R 15 and R 17 are methyl.
- a ligand of Formula III wherein R 2 -R 5 , R 9 , R 11 , R 14 and Rio are hydrogen; R 1 is tert-butyl; and R 8 , R 10 , R 12 , R 13 , R 15 and R 17 are methyl.
- the ligand may be a compound having the structure of Formula I, wherein one of R 6 and R 7 is aryl as shown in Formula II and one of R 6 and R 7 is pyridyl as shown in Formula IV.
- R 6 and R 7 may be pyrrolyl.
- R 1 , R 2 and R3 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- R 4 and R 5 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- R 8 -R 12 and R 18 -R 21 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano, an inert functional group, fluorine, or chlorine. Any two of R 1 -R 3 , and R 9 -R 11 vicinal to one another taken together may form a ring.
- R 12 may be taken together with R 11 , R 4 or R 5 to form a ring.
- R 2 and R 4 or R 3 and R 5 may be taken together to form a ring.
- a ligand of Formula V is provided wherein R 1 -R 5 , R 9 , R 11 and R18-R 21 are hydrogen; and R 8 , R 10 , and R 12 are methyl.
- a ligand of Formula V is provided wherein R 1 -R 5 , R 9 -R 11 and R 18 -R 21 are hydrogen; and R 8 and R 12 are ethyl.
- the ligand may be a compound having the structure of Formula I, wherein one of R 6 and R 7 is aryl as shown in Formula II and one of R 6 and R 7 is cyclohexyl as shown in Formula VI. In another embodiment, R 6 and R 7 may be cyclohexyl.
- R 1 , R 2 and R 3 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- R 4 and R 5 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- R 8 -R 12 and R 22 -R 26 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano, an inert functional group, fluorine, or chlorine. Any two of R 1 -R 3 , and R 9 -R 11 vicinal to one another taken together may form a ring.
- R 12 may be taken together with R 11 , R 4 or R 5 to form a ring.
- R 2 and R 4 or R 3 and R 5 may be taken together to form a ring.
- a ligand of Formula VII is provided wherein R 1 -R 5 , R 9 , R 11 and R 22 -R 26 are hydrogen; and R 8 , R 10 , and R 12 are methyl.
- R 6 and R 7 may be adamantyl or another cycloalkane.
- the ligand may be a compound having the structure of Formula I, wherein one of R 6 and R 7 is aryl as shown in Formula II and one of R 6 and R 7 is ferrocenyl as shown in Formula VIII. In another embodiment, R 6 and R 7 may be ferrocenyl.
- R 1 , R 2 and R 3 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- R 4 and R 5 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
- R 8 -R 12 and R 27 -R 35 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano, an inert functional group, fluorine, or chlorine. Any two of R 1 -R 3 , and R 9 -R 11 vicinal to one another taken together may form a ring.
- R 12 may be taken together with R 11 , R 4 or R 5 to form a ring.
- R 2 and R 4 or R 3 and R 5 may be taken together to form a ring.
- a ligand of Formula IX is provided wherein R 1 -R 5 , R 9 , R 11 and R 2 7 -R 35 are hydrogen; and R 8 , R 10 , and R 12 are methyl.
- a ligand of Formula IX is provided wherein R 1 -R 5 , R 9 -R 11 , and R 2 7 -R 35 are hydrogen; and R « and R 12 are ethyl.
- the ligand may be a bis(alkylamino)pyridine.
- the alkyl group may have from 1 to 50 carbon atoms.
- the alkyl group may be a primary, secondary, or tertiary alkyl group.
- the alkyl group may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, and tert-butyl.
- the alkyl group may be selected from any n-alkyl or structural isomer of an n-alkyl having 5 or more carbon atoms, e.g., n-pentyl; 2-methyl-butyl; and 2,2-dimethylpropyl.
- the ligand may be an alkyl-alkyl iminopyridine, where the two alkyl groups are different. Any of the alkyl groups described above as being suitable for a bis(alkylamino)pyridine are also suitable for this alkyl-alkyl iminopyridine.
- the ligand may be an aryl alkyl iminopyridine.
- the aryl group may be of a similar nature to any of the aryl groups described with respect to the bis(arylimino)pyridine compound and the alkyl group may be of a similar nature to any of the alkyl groups described with respect to the bis(alkylamino)pyridine compound.
- any structure that combines features of any two or more of these ligands can be a suitable ligand for this process.
- the oligomerization catalyst system may comprise a combination of one or more of any of the described oligomerizations catalysts.
- the ligand feedstock may contain between 0 and 10 wt.% bisimine pyridine impurity, preferably 0-1 wt.% bisimine pyridine impurity, most preferably 0-0.1 wt.% bisimine pyridine impurity. This impurity is believed to cause the formation of polymers in the reactor, so it is preferable to limit the amount of this impurity that is present in the catalyst system.
- the bisimine pyridine impurity is a ligand of Formula II in which three of R 8 , R 12 , R 13 , and R 17 are each independently optionally substituted hydrocarbyl.
- the bisimine pyridine impurity is a ligand of Formula II in which all four of R 8 , R 12 , R 13 , and R 17 are each independently optionally substituted hydrocarbyl.
- the metal may be a transition metal, and the metal is preferably present as a compound having the formula MX n , where M is the metal, X is a monoanion and n represents the number of monoanions (and the oxidation state of the metal).
- the metal can comprise any Group 4-10 transition metal.
- the metal can be selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, platinum, ruthenium and rhodium.
- the metal is cobalt or iron.
- the metal is iron.
- the metal of the metal compound can have any positive formal oxidation state of from 2 to 6 and is preferably 2 or 3.
- the monoanion may comprise a halide, a carboxylate, a [ ⁇ -diketonate, a hydrocarboxide, an optionally substituted hydrocarbyl, an amide or a hydride.
- the hydrocarboxide may be an alkoxide, an aryloxide or an aralkoxide.
- the halide may be fluorine, chlorine, bromine or iodine.
- the carboxylate may be any C 1 to C 20 carboxylate.
- the carboxylate may be acetate, a propionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, an undecanoate, or a dodecanoate.
- the carboxylate may be 2-ethylhexanoate or trifluoroacetate.
- the ⁇ -diketonate may be any C 1 to C 20 [ ⁇ -diketonate.
- the [3-diketonate may be acetylacetonate, hexafluoroacetylacetonate, or benzoylacetonate.
- the hydrocarboxide may be any C 1 to C 20 hydrocarboxide.
- the hydrocarboxide may be a C 1 to C 20 alkoxide, or a C 6 to C 20 aryloxide.
- the alkoxide may be methoxide, ethoxide, a propoxide (e.g., iso-propoxide) or a butoxide (e.g., tert-butoxide).
- the aryloxide may be phenoxide
- the number of monoanions equals the formal oxidation state of the metal atom.
- metal compounds include iron acetylacetonate, iron chloride, and iron bis(2-ethylhexanoate).
- a co-catalyst is used in the ohgomerization reaction.
- the co-catalyst may be a compound that is capable of transferring an optionally substituted hydrocarbyl or hydride group to the metal atom of the catalyst and is also capable of abstracting an X' group from the metal atom M.
- the co-catalyst may also be capable of serving as an electron transfer reagent or providing sterically hindered counterions for an active catalyst.
- the co-catalyst may comprise two compounds, for example one compound that is capable of transferring an optionally substituted hydrocarbyl or hydride group to metal atom M and another compound that is capable of abstracting an X group from metal atom M.
- Suitable compounds for transferring an optionally substituted hydrocarbyl or hydride group to metal atom M include organoaluminum compounds, alkyl lithium compounds, Grignards, alkyl tin and alkyl zinc compounds.
- Suitable compounds for abstracting an X group from metal atom M include strong neutral Lewis acids such as SbF 5 , BF 3 and Ar 3 B wherein Ar is a strong electron-withdrawing aryl group such as
- a neutral Lewis acid donor molecule is a compound which may suitably act as a Lewis base, such as ethers, amines, sulfides and organic nitrites.
- the co-catalyst is preferably an organoaluminum compound which may comprise an alkylaluminum compound, an aluminoxane or a combination thereof.
- the alkylaluminum compound may be trialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide or a combination thereof.
- the alkyl group of the alkylaluminum compound may be any C 1 to C 20 alkyl group.
- the alkyl group may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
- the alkyl group may be an iso-alkyl group.
- the trialkylaluminum compound may comprise trimethylaluminum (TMA), triethylaluminum (TEA), triptopylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, triheptylaluminum, trioctylaluminum or mixtures thereof.
- the trialkylaluminum compound may comprise tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), tri-iso- butylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum (TNOA).
- the halide group of the alkylaluminum halide may be chloride, bromide or iodide.
- the alkylaluminum halide may be diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride or mixtures thereof.
- the alkoxide group of the alkylaluminum alkoxide may be any C 1 to C 20 alkoxy group.
- the alkoxy group may be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy.
- the alkylaluminum alkoxide may be diethylaluminum ethoxide.
- the aluminoxane compound may be methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, iso-propyl-aluminoxane, n- butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butylaluminoxane, 1-pentyl- aluminoxane, 2-pentyl-aluminoxane, 3-pentyl-aluminoxane, iso-pentyl-aluminoxane, neopentylaluminoxane, or mixtures thereof.
- MAO methylaluminoxane
- MMAO modified methylaluminoxane
- n-propylaluminoxane iso-propyl-aluminoxane
- the preferred co-catalyst is modified methylaluminoxane.
- the synthesis of modified methylaluminoxane may be carried out in the presence of other trialkylaluminum compounds in addition to trimethylaluminum.
- the products incorporate both methyl and alkyl groups from the added trialkylaluminum and are referred to as modified methyl aluminoxanes, MMAO.
- the MMAO may be more soluble in nonpolar reaction media, more stable to storage, have enhanced performance as a cocatalyst, or any combination of these.
- the performance of the resulting MMAO may be superior to either of the trialkylaluminum starting materials or to simple mixtures of the two starting materials.
- the added trialkylaluminum may be triethylaluminum, triisobutylaluminum or triisooctylaluminum.
- the co-catalyst is MMAO, wherein preferably about 25% of the methyl groups are replaced with iso-butyl groups.
- the co-catalyst may be formed in situ in the reactor by providing the appropriate precursors into the reactor.
- One or more solvents may be used in the reaction.
- the solvent(s) may be used to dissolve or suspend the catalyst or the co-catalyst and/ or keep the ethylene dissolved.
- the solvent may be any solvent that can modify the solubility of any of these components or of reaction products. Suitable solvents include hydrocarbons, for example, alkanes, alkenes, cycloalkanes, and aromatics. Different solvents may be used in the process, for example, one solvent can be used for the catalyst and another for the co-catalyst. It is preferred for the solvent to have a boiling point that is not substantially similar to the boiling point of any of the alpha olefin products as this will make the product separation step more difficult. Aromatics
- Aromatic solvents can be any solvent that contains an aromatic hydrocarbon, preferably having a carbon number of 6 to 20. These solvents may include pure aromatics, or mixtures of pure aromatics, isomers as well as heavier solvents, for example C 9 and C 10 solvents. Suitable aromatic solvents include benzene, toluene, xylene (including ortho-xylene, meta-xylene, para-xylene and mixtures thereof) and ethylbenzene.
- Alkane solvents may be any solvent that contains an alkyl hydrocarbon. These solvents may include straight chain alkanes and branched or iso-alkanes having from 3 to 20 carbon atoms and mixtures of these alkanes. The alkanes may be cycloalkanes.
- Suitable solvents include propane, isobutane, n-butane, butane (n-butane or a mixture of linear and branched C 4 acyclic alkanes), pentane (n-pentane or a mixture of linear and branched acyclic alkanes), hexane (n-hexane or a mixture of linear and branched C 6 acychc alkanes), heptane (n-heptane or a mixture of linear and branched C 7 acyclic alkanes), octane (n-octane or a mixture of linear and branched C 8 acychc alkanes) and isooctane.
- Suitable solvents also include cyclohexane and methylcyclohexane.
- the solvent comprises C 6 , C 7 and C 8 alkanes, that may include linear, branched and iso-alkanes.
- the choice of solvent may affect the reaction, including the production of by-products, for example, dienes.
- dienes for example, dienes.
- heptane as a solvent has been found to produce a lower number of dienes, especially, 3-methyl-l, 4, -pentadiene and 1,4-hexadiene.
- the catalyst system may be formed by mixing together the ligand, the metal, the co-catalyst and optional additional compounds in a solvent.
- the feed may be present in this step.
- the catalyst system may be prepared by contacting the metal or metal compound with the ligand to form a catalyst precursor mixture and then contacting the catalyst precursor mixture with the co-catalyst in the reactor to form the catalyst system.
- the catalyst system may be prepared outside of the reactor vessel and fed into the reactor vessel. In other embodiments, the catalyst system may be formed in the reactor vessel by passing each of the components of the catalyst system separately into the reactor. In other embodiments, one or more catalyst precursors may be formed by combining at least two components outside of the reactor and then passing the one or more catalyst precursors into the reactor to form the catalyst system. Reaction Conditions
- the oligomerization reaction is a reaction that converts the olefin feed in the presence of an oligomerization catalyst and a co-catalyst into a higher oligomer product stream.
- the oligomerization reaction may be conducted over a range of temperatures of from -100 °C to 300 °C, preferably in the range of from 0 °C to 200 °C, and more preferably in the range of from 50 °C to 150 °C.
- the oligomerization reaction may be conducted at a pressure of from 0.01 to 15 MPa and more preferably from 1 to 10 MPa.
- the optimum conditions of temperature and pressure used for a specific catalyst system, to maximize the yield of oligomer, and to minimize the impact of competing reactions, for example dimerization and polymerization can be determined by one of ordinary skill in the art.
- the temperature and pressure are selected to yield a product slate with a K-factor in the range of from 0.40 to 0.90, preferably in the range of from 0.45 to 0.80, more preferably in the range of from 0.5 to 0.7.
- Residence times in the reactor of from 3 to 60 min have been found to be suitable, depending on the activity of the catalyst.
- the reaction is carried out in the absence of air and moisture.
- the oligomerization reaction can be carried out in the Equid phase or mixed gas-liquid phase, depending on the volatility of the feed and product olefins at the reaction conditions.
- the oligomerization reaction may be carried out in a conventional fashion. It may be carried out in a stirred tank reactor, wherein solvent, olefin and catalyst or catalyst precursors are added continuously to a stirred tank and solvent, product, catalyst, and unused reactant are removed from the stirred tank with the product separated and the unused reactant recycled back to the stirred tank.
- the oligomerization reaction may be carried out in a batch reactor, wherein the catalyst precursors and reactant olefin are charged to an autoclave or other vessel and after being reacted for an appropriate time, product is separated from the reaction mixture by conventional means, for example, distillation.
- the oligomerization reaction may be carried out in a gas Eft reactor.
- This type of reactor has two vertical sections (a riser section and a downcomer section) and a gas separator at the top.
- the gas feed (ethylene) is injected at the bottom of the riser section to drive circulation around the loop (up the riser section and down the downcomer section).
- the oEgomerization reaction may be carried out in a pump loop reactor.
- This type of reactor has two vertical sections, and it uses a pump to drive circulation around the loop.
- a pump loop reactor can be operated at a higher circulation rate than a gas Eft reactor.
- the oEgomerization reaction may be carried out in a once-through reactor.
- This type of reactor feeds the catalyst, co-catalyst, solvent and ethylene to the inlet of the reactor and/ or along the reactor length and the product is coUected at the reactor outlet.
- This type of reactor is a plug flow reactor.
- the higher oligomers produced in the oEgomerization reaction contains catalyst from the reaction step. To stop further reactions that can produce byproducts and other undesired components, it is important to deactivate the catalyst downstream from the reactor.
- the catalyst is deactivated by addition of an acidic species having a pKA(aq) of less than 25.
- the deactivated catalyst can then be removed by water washing in a liquid/Equid extractor.
- the resulting alpha-olefins have a chain length of from 4 to 100 carbon atoms, preferably 4 to 30 carbon atoms and most preferably 4 to 20 carbon atoms.
- the alpha-olefins are even- numbered alpha-olefins.
- the product olefins can be recovered by distillation or other separation techniques depending on the intended use of the products.
- the solvents) used in the reaction preferably have a boiling point that is different from the boiling point of any of the alpha-olefin products to make the separation easier.
- the distillation steps comprise columns for separating ethylene and the main linear alpha olefin products, for example, butene, hexene, and octene.
- the products produced by the process may be used in a number of applications.
- the olefins produced by this process may have improved qualities as compared to olefins produced by other processes.
- the butene, hexene and/ or octene produced may be used as a comonomer in making polyethylene.
- the octene produced may be used to produce plasticizer alcohols.
- the decene produced may be used to produce polyalphaolefins.
- the dodecene and/ or tetradecene produced may be used to produce alkylbenzene and/ or detergent alcohols.
- the hexadecene and/ or octadecene produced may be used to produce alkenyl succinates and/or oilfield chemicals.
- the C20+ products may be used to produce lubricant additives and/ or waxes.
- olefins When the olefins will be used as a comonomer, it is beneficial to produce olefins which have a lower content of dienes as the dienes can act as a catalyst poison in the polymerization reaction.
- a portion of any unreacted ethylene that is removed from the reactor with the products may be recycled to the reactor.
- This ethylene may be recovered in the distillation steps used to separate the products.
- the ethylene may be combined with the fresh ethylene feed or it may be fed separately to the reactor.
- a portion of any solvent used in the reaction may be recycled to the reactor.
- the solvent may be recovered in the distillation steps used to separate the products.
- the amount of dienes produced in an oligomerization process as described herein is affected by the oligomerization catalyst used. As it is beneficial to reduce the amount of dienes produced, catalysts that produce a reduced amount of dienes are preferable.
- the catalyst comprises a ligand of either formula III or formula V.
- the ligand preferably has methyl groups located at positions R 4 , R 5 , R 8 and R 12 .
- the ligand also has methyl groups at R 10 . It is believed that the steric nature of these ligands provides for a reduced level of dienes being produced. Examples
- ethylene was oEgomerized in the presence of various different catalysts, each a complex of iron with a different Egand, to form alpha-olefins in an autoclave reactor.
- Table 1 shows the amount of dienes, specificaUy 1,4-hexadiene and 3-methyl 1,4-pentadiene that were formed during each experiment.
- R 4 , R 5 , R 8 , R 10 and R 12 are methyl; R 14 and R 16 are tert-butyl; and R 1 -R 3 , R 9 , R 11 , R 13 , R 15 , and R 17 are hydrogen.
- Egand B R 4 , R 5 , R 8 , R 10 and R 12 are methyl; R 14 and R 16 , are phenyl; R 15 is C 20 H 41 O; and R 1 -R 3 , R 9 , R 11 , R 13 , and R 17 are hydrogen.
- R 4 , R 5 , R 8 , R 10 and R 12 are methyl; R 15 is tert-butyl; and R 1 -R 3 , R 9 , R 11 , R 13 -R 14 and R 16 -R 17 are hydrogen.
- Egand D R 4 , R 5 , R 8 , R 10 and R 12 are methyl; R 15 is fluoride; and R 1 -R 3 , R 9 , R 11 , R 13 R 14 and R 16 -R 17 are hydrogen.
- R 4 , R 5 , R 8 , R 10 and R 12 are methyl; and R 1 -R 3 , R 9 , R 11 , R 13 --R 17 are hydrogen.
- R 4 , R 5 , R 8 , R 10 , R 12 , R 14 and R 16 are methyl; and R 1 -R 3 , R 9 , R 11 , R 13 , R 15 , and R 17 are hydrogen.
- R 4 , R 5 are methyl; and R 1 -R 3 , R 9 , R 11 , R 13 , R 15 , and R 17 are hydrogen.
- the comparative Egands had the foUowing substituents.
- Egand H aE R groups were hydrogen.
- Egand I R 13 and R 16 were methyl; R 10 was tert-butyl and the remaining R groups were hydrogen.
- Egand J R 8 , R 11 , R 13 and R 16 were methyl; and the remaining R groups were hydrogen.
- R 4 , R 5 , R 8 , R 10 and R 12 are methyl; and R 1 -R 3 , R 9 , R 11 and R 18 -R 21 are hydrogen.
- Table 1
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention provides a process for producing alpha-olefins comprising contacting an ethylene feed with an oligomerization catalyst system in an oligomerization reaction zone under oligomerization conditions to produce a product stream comprising alpha-olefins wherein the oligomerization catalyst system comprises an iron-ligand complex wherein the ligand comprises a bis-aryliminepyridine compound of formula (III) wherein R4, R5, R8 and R12 are methyl; R13 and R17 are hydrogen; and R1-R3, R9-R11, R14-R16 are selected from hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. The invention further provides a process for producing alpha-olefins comprising contacting an ethylene feed with an oligomerization catalyst system in an oligomerization reaction zone under oligomerization conditions wherein the oligomerization catalyst system comprises an iron-ligand complex wherein the ligand comprises a compound of formula (V) wherein R8 and R12 are methyl; R18 and R21 are hydrogen; and R1-R5, R9-R11, R19-R20 are selected from hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
Description
A PROCESS FORPRODUCING ALPHA-OLEFINS
Field of the Invention
The invention relates to a process for producing alpha-olefins from an ethylene feed using specific iron-ligand complex catalyst systems.
Background
The oligomerization of olefins, such as ethylene, produces butene, hexene, octene, and other valuable linear alpha olefins. Linear alpha olefins are a valuable comonomer for linear low-density polyethylene and high-density polyethylene. Such olefins are also valuable as a chemical intermediate in the production of plasticizer alcohols, fatty acids, detergent alcohols, polyalphaolefins, oil field drilling fluids, lubricant oil additives, linear alkylbenzenes, alkenylsuccinic anhydrides, alkyldimethylamines, dialkylmethylamines, alpha-olefin sulfonates, internal olefin sulfonates, chlorinated olefins, linear mercaptans, aluminum alkyls, alkyldiphenylether disulfonates, and other chemicals.
US 6,683,187 describes a bis(arylimino)pyridine ligand, catalyst precursors and catalyst systems derived from this ligand for ethylene oligomerization to form linear alpha olefins. The patent teaches the production of linear alpha olefins with a Schulz-Flory oligomerization product distribution. In such a process, a wide range of oligomers are produced, and the fraction of each olefin can be determined by calculation on the basis of the K-factor. The K-factor is the molar ratio of (Cn+2)/Cn, where n is the number of carbons in the linear alpha olefin product.
As described above, alpha olefins are commonly used as comonomers in the production of polyethylene. The catalysts used for manufacturing polyethylene can be poisoned by impurities in the feed, including by dienes present in the comonomer. In addition, there is a specification requirement for the level of dienes present in certain alpha-olefin streams. It would be advantageous to develop an improved process that would provide an oligomerization product having reduced levels of dienes.
Summary of the Invention
The invention provides a process for producing alpha-olefins comprising contacting an ethylene feed with an oligomerization catalyst system in an oligomerization reaction zone under ohgomerization conditions to produce a product stream comprising alpha-olefins wherein the
oligomerization catalyst system comprises an iron-ligand complex wherein the ligand comprises a bis-aryliminepyridine compound of formula (III):
wherein R4, R5, R8 and R12 are methyl; R13 and R17 are hydrogen; and R1-R3, R9-R11, R14-R16 are selected from hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
The invention further provides a process for producing alpha-olefins comprising contacting an ethylene feed with an oligomerization catalyst system in an oligomerization reaction zone under oligomerization conditions wherein the oligomerization catalyst system comprises an iron-ligand complex wherein the ligand comprises a compound of formula (V):
wherein R8 and R12 are methyl; R18 and R21 are hydrogen; and R1- R5, R9-R11, R19-R20 are selected from hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
Detailed Description The process comprises converting an olefin feed into a higher oligomer product stream by contacting the feed with an oligomerization catalyst system and a co-catalyst in an oligomerization reaction zone under oligomerization conditions. In one embodiment, an ethylene feed may be contacted with an iron-ligand complex and modified methyl aluminoxane under oligomerization conditions to produce a product slate of alpha olefins having a specific k-factor. Olefin Feed
The olefin feed to the process comprises ethylene. The feed may also comprise olefins having from 3 to 8 carbon atoms. The ethylene may be pretreated to remove impurities, especially impurities that impact the reaction, product quality or damage the catalyst. In one embodiment, the ethylene may be dried to remove water. In another embodiment, the ethylene may be treated to reduce the oxygen content of the ethylene. Any pretreatment method known to one of ordinary skill in the art can be used to pretreat the feed.
Oligomerization Catalyst
The oligomerization catalyst system may comprise one or more oligomerization catalysts as described further herein. The oligomerization catalyst is a metal-ligand complex that is effective for
catalyzing an oligomerization process. The ligand may comprise a bis(arylimino)pyridine compound, a bis(alkylimino)pyridine compound or a mixed aryl-alkyl iminopyridine compound.
Ligand
In one embodiment, the ligand comprises a pyridine bis(imine) group. The ligand may be a bis(aryltmino)pyridine compound having the structure of Formula I.
R1, R2 and R3 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. R4 and R5 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. R6 and R7 are each independently an aryl group as shown in Formula II. The two aryl groups ( R6 and R7) on one ligand may be the same or different.
R8, R9, R10, R11, R12 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano, an inert functional group, fluorine, or chlorine. Any two of R1-R3, and R9-R11 vicinal
to one another taken together may form a ring. R12 may be taken together with R11, R4 or R5 to form a ring. R2 and R4 or R3 and R5 may be taken together to form a ring.
A hydrocarbyl group is a group containing only carbon and hydrogen. The number of carbon atoms in this group is preferably in the range of from 1 to 30.
An optionally substituted hydrocarbyl is a hydrocarbyl group that optionally contains one or more “inert” heteroatom-containing functional groups. Inert means that the functional groups do not interfere to any substantial degree with the oligomerization process. Examples of these inert groups include fluoride, chloride, iodide, stannanes, ethers, hydroxides, alkoxides and amines with adequate steric shielding. The optionally substituted hydrocarbyl group may include primary, secondary and tertiary carbon atoms groups.
Primary carbon atom groups are a -CH2-R group wherein R may be hydrogen, an optionally substituted hydrocarbyl or an inert functional group. Examples of primary carbon atom groups include -CH3, -C2H5, -CH2Cl, -CH2OCH3, -CH2N (C2H5)2, and -CH2Ph. Secondary carbon atom groups are a -CH-R2 or -CH (R)(R') group wherein R and R' may be optionally substituted hydrocarbyl or an inert functional group. Examples of secondary carbon atom groups include - CH(CH3)2, -CHCl2, -CHPh2, -CH(CH3)(OCH3), -CH-CH2, and cyclohexyl. Tertiary carbon atom groups are a -C-(R)(R')(R") group wherein R, R', and R" may be optionally substituted hydrocarbyl or an inert functional group. Examples of tertiary carbon atom groups include -C(CH3)3, -CCl3, - C≡CPh, 1-Adamantyl, and -C(CH3)2(OCH3)
An inert functional group is a group other than optionally substituted hydrocarbyl that is inert under the oligomerization conditions. Inert has the same meaning as provided above. Examples of inert functional groups include halide, ethers, and amines, in particular tertiary amines.
Substituent variations of R1-R5, R8-R12 and R13-R17 may be selected to enhance other properties of the ligand, for example, solubility in non-polar solvents. Several embodiments of possible oligomerization catalysts are further described below having the structure shown in Formula 3.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R11 and R14-R16 are hydrogen; and R8, R12, R13 and R17 are fluorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8, R10, R12, R14 and R16 ate hydrogen; R13, R15 and R17 are methyl and R9 and R11 are tert-butyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8, R12, R14 and R16 are hydrogen; R13, R15 and R17 are methyl; R9 and R11 are phenyl and R10 is an alkoxy.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8, R10, R11 and R14-R16 are hydrogen; R9 and R12 are methyl; and R13 and R17 are fluorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R3, R9-R11 and R14-R16 are hydrogen; R4 and R5 are phenyl and R8, R12, R13 and R17 are fluorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8- R9, R11-R12, R13- R14 and R16- R17 are hydrogen; and R10 and R15 are fluorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8, R10, R12, R13, R15 and R17 are hydrogen; and R9, R11, R14 and R16 are fluorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9,R11- R12, R14 andR16- R17 are hydrogen; and R8, R10, R13 and R15 are fluorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8-R9,R11-R12, R14 and R16 are hydrogen; R10 is tert-butyl; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R12, R14 and R16, are hydrogen; R8 is fluorine; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R12, R13, R15 and R17 are hydrogen; R8 is tert-butyl; and R14 and R16 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R12, R13-R14 andR16-R17 are hydrogen; and R8 and R15 are tert-butyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8-R10, R13-R14 and R16-R17 are hydrogen; R15 is tert-butyl; and R11 and R12 are taken together to form an aryl group.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R12, R14-R17 are hydrogen; and R8 and R13 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8-R9, R11- R12, R14 and R16 are hydrogen; R10 is fluorine; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8, R10, R12, R14 and R16 are hydrogen; R9 and R11 are fluorine; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8-R9, R11-R12, R14 and R16 are hydrogen; R10 is an alkoxy; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8-R9, R11-R12, R14 and R16 are hydrogen; R10 is a silyl ether; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8, R10, R12, R14-R16 are hydrogen; R9 and R11 are methyl; and R13 and R17 are ethyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R12, and R14-R17 are hydrogen; and R8 and R13 are ethyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R11 and R14-R16 are hydrogen; and R8, R12, R13 and R17 are chlorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9, R11, R14 and R16 are hydrogen; and R8, R10, R12, R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9- R10, R12, R14-R15 and R17 are hydrogen; and R8, R11, R13 and R16 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R17 are hydrogen.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8, R10, R12, R13, R15 and R17 are hydrogen; and R9, R11, R14 and R16 are tert-butyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8-R12, R14 and R16 are hydrogen; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9, R11-R12, R14 and R16 are hydrogen; R8 and R10 are fluorine; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9, R11-R12, R14 and R16-R17 are hydrogen; and R8, R10, R13 and R15 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R11 and R14-R16 are hydrogen; R8 and R12 are chlorine; and R13 and R17 are fluorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8, R10, R12, R14 and R16 are hydrogen; and R9, R11, R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R11 and R13-R14 and R16-R17 are hydrogen; R8 and R12 are chlorine; and R15 is tert-butyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R11 and R13-R17 are hydrogen; and R8 and R12 are chlorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R12, and R14-R17 are hydrogen; and R8 and R13 are chlorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9,R11-R12, R14 and R16- R17 are hydrogen; and R8, R10, R13 and R15 are chlorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9, R11-R12, and R14, and R16-R17 are hydrogen; R10 and R15 are methyl; and R8 and R13 are chlorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R11 and R13-R14 and R16-R17 are hydrogen; R15 is fluorine; and R8 and R12 are chlorine.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R8-R9, R11-R12, R14- R15 and R17 are hydrogen; R10 is tert-butyl; and R13 and R16 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R11, R14 and R16 are hydrogen; R8 and R12 are fluorine; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R10, R12, R14-R15 and R17 are hydrogen; R8 and R13 are methyl; and R11 and R16 are isopropyl.
In one embodiment, a ligand of Formula III is provided wherein R1-R5, R9-R12 and R14-R16 are hydrogen; R8 is ethyl; and R13 and R17 are fluorine.
In one embodiment, a ligand of Formula III is provided wherein R2-R5, R9-R10, R12, R14-R15 and R17 are hydrogen; R1 is methoxy; and R8, R11, R13 and R16 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R2-R5, R8- R12, R14 and R16, are hydrogen; R1 is methoxy; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R2-R5, R9-R12, and R14-R17 are hydrogen; R1 is methoxy; and R8 and R13 are ethyl.
In one embodiment, a ligand of Formula III is provided wherein R2-R5, R9, R11-R12, R14 and R16- R17 are hydrogen; R1 is tert-butyl; and R8, R10, R13 and R15 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R2-R5, R8-R12, R14 and Rie are hydrogen; R1 is tert-butyl; and R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R2-R5, R9, R11, R14 and R17, are hydrogen; R1 is methoxy; and R8, R10, R12, R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R2-R5, R9, R11, R14 and R16, are hydrogen; R1 is alkoxy; and R8, R10, R12, R13, R15 and R17 are methyl.
In one embodiment, a ligand of Formula III is provided wherein R2-R5, R9, R11, R14 and Rio are hydrogen; R1 is tert-butyl; and R8, R10, R12, R13, R15 and R17 are methyl.
In another embodiment, the ligand may be a compound having the structure of Formula I, wherein one of R6 and R7 is aryl as shown in Formula II and one of R6 and R7 is pyridyl as shown in Formula IV. In another embodiment, R6 and R7 may be pyrrolyl.
R1, R2 and R3 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. R4 and R5 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. R8-R12 and R18-R21 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano, an inert functional
group, fluorine, or chlorine. Any two of R1-R3, and R9-R11 vicinal to one another taken together may form a ring. R12 may be taken together with R11, R4 or R5 to form a ring. R2 and R4 or R3 and R5 may be taken together to form a ring.
In one embodiment, a ligand of Formula V is provided wherein R1-R5, R9, R11 and R18-R21 are hydrogen; and R8, R10, and R12 are methyl.
In one embodiment, a ligand of Formula V is provided wherein R1-R5, R9-R11 and R18-R21 are hydrogen; and R8 and R12 are ethyl.
In another embodiment, the ligand may be a compound having the structure of Formula I, wherein one of R6 and R7 is aryl as shown in Formula II and one of R6 and R7 is cyclohexyl as shown in Formula VI. In another embodiment, R6 and R7 may be cyclohexyl.
R1, R2 and R3 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. R4 and R5 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. R8-R12 and R22-R26 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano, an inert functional group, fluorine, or chlorine. Any two of R1-R3, and R9-R11 vicinal to one another taken together may form a ring. R12 may be taken together with R11, R4 or R5 to form a ring. R2 and R4 or R3 and R5 may be taken together to form a ring.
In one embodiment, a ligand of Formula VII is provided wherein R1-R5, R9, R11 and R22-R26 are hydrogen; and R8, R10, and R12 are methyl.
In another embodiment, R6 and R7 may be adamantyl or another cycloalkane.
In another embodiment, the ligand may be a compound having the structure of Formula I, wherein one of R6 and R7 is aryl as shown in Formula II and one of R6 and R7 is ferrocenyl as shown in Formula VIII. In another embodiment, R6 and R7 may be ferrocenyl.
(VIII)
R1, R2 and R3 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. R4 and R5 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group. R8-R12 and R27 -R35 are each independently hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano, an inert functional group, fluorine, or chlorine. Any two of R1-R3, and R9-R11 vicinal to one another taken together may form a ring. R12 may be taken together with R11, R4 or R5 to form a ring. R2 and R4 or R3 and R5 may be taken together to form a ring.
In one embodiment, a ligand of Formula IX is provided wherein R1-R5, R9, R11 and R27 -R35 are hydrogen; and R8, R10, and R12 are methyl.
In one embodiment, a ligand of Formula IX is provided wherein R1-R5, R9-R11, and R27 -R35 are hydrogen; and R« and R12 are ethyl.
In another embodiment, the ligand may be a bis(alkylamino)pyridine. The alkyl group may have from 1 to 50 carbon atoms. The alkyl group may be a primary, secondary, or tertiary alkyl group. The alkyl group may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, and tert-butyl. The alkyl group may be selected from any n-alkyl or structural isomer of an n-alkyl having 5 or more carbon atoms, e.g., n-pentyl; 2-methyl-butyl; and 2,2-dimethylpropyl.
In another embodiment, the ligand may be an alkyl-alkyl iminopyridine, where the two alkyl groups are different. Any of the alkyl groups described above as being suitable for a bis(alkylamino)pyridine are also suitable for this alkyl-alkyl iminopyridine.
In another embodiment, the ligand may be an aryl alkyl iminopyridine. The aryl group may be of a similar nature to any of the aryl groups described with respect to the bis(arylimino)pyridine compound and the alkyl group may be of a similar nature to any of the alkyl groups described with respect to the bis(alkylamino)pyridine compound.
In addition to the ligand structures described hereinabove, any structure that combines features of any two or more of these ligands can be a suitable ligand for this process. Further, the oligomerization catalyst system may comprise a combination of one or more of any of the described oligomerizations catalysts.
The ligand feedstock may contain between 0 and 10 wt.% bisimine pyridine impurity, preferably 0-1 wt.% bisimine pyridine impurity, most preferably 0-0.1 wt.% bisimine pyridine impurity. This impurity is believed to cause the formation of polymers in the reactor, so it is preferable to limit the amount of this impurity that is present in the catalyst system.
In one embodiment, the bisimine pyridine impurity is a ligand of Formula II in which three of R8, R12, R13, and R17 are each independently optionally substituted hydrocarbyl.
In one embodiment, the bisimine pyridine impurity is a ligand of Formula II in which all four of R8, R12, R13, and R17 are each independently optionally substituted hydrocarbyl.
Metal
The metal may be a transition metal, and the metal is preferably present as a compound having the formula MXn, where M is the metal, X is a monoanion and n represents the number of monoanions (and the oxidation state of the metal).
The metal can comprise any Group 4-10 transition metal. The metal can be selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, platinum, ruthenium and rhodium. In one embodiment, the metal is cobalt or iron. In a preferred embodiment, the metal is iron. The metal of the metal compound can have any positive formal oxidation state of from 2 to 6 and is preferably 2 or 3.
The monoanion may comprise a halide, a carboxylate, a [β-diketonate, a hydrocarboxide, an optionally substituted hydrocarbyl, an amide or a hydride. The hydrocarboxide may be an alkoxide, an aryloxide or an aralkoxide. The halide may be fluorine, chlorine, bromine or iodine.
The carboxylate may be any C1 to C20 carboxylate. The carboxylate may be acetate, a propionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, an undecanoate, or a dodecanoate. In addition, the carboxylate may be 2-ethylhexanoate or trifluoroacetate.
The β-diketonate may be any C1 to C20 [β-diketonate. The [3-diketonate may be acetylacetonate, hexafluoroacetylacetonate, or benzoylacetonate.
The hydrocarboxide may be any C1 to C20 hydrocarboxide. The hydrocarboxide may be a C1 to C20 alkoxide, or a C6 to C20 aryloxide. The alkoxide may be methoxide, ethoxide, a propoxide (e.g., iso-propoxide) or a butoxide (e.g., tert-butoxide). The aryloxide may be phenoxide
Generally, the number of monoanions equals the formal oxidation state of the metal atom.
Preferred embodiments of metal compounds include iron acetylacetonate, iron chloride, and iron bis(2-ethylhexanoate). In addition to the oligomerization catalyst, a co-catalyst is used in the ohgomerization reaction.
Co-catalyst
The co-catalyst may be a compound that is capable of transferring an optionally substituted hydrocarbyl or hydride group to the metal atom of the catalyst and is also capable of abstracting an X' group from the metal atom M. The co-catalyst may also be capable of serving as an electron transfer reagent or providing sterically hindered counterions for an active catalyst.
The co-catalyst may comprise two compounds, for example one compound that is capable of transferring an optionally substituted hydrocarbyl or hydride group to metal atom M and another compound that is capable of abstracting an X group from metal atom M. Suitable compounds for transferring an optionally substituted hydrocarbyl or hydride group to metal atom M include organoaluminum compounds, alkyl lithium compounds, Grignards, alkyl tin and alkyl zinc compounds. Suitable compounds for abstracting an X group from metal atom M include strong neutral Lewis acids such as SbF5, BF3 and Ar3B wherein Ar is a strong electron-withdrawing aryl group such as
A neutral Lewis acid donor molecule is a compound which may suitably act as a Lewis base, such as ethers, amines, sulfides and organic nitrites.
The co-catalyst is preferably an organoaluminum compound which may comprise an alkylaluminum compound, an aluminoxane or a combination thereof.
The alkylaluminum compound may be trialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide or a combination thereof. The alkyl group of the alkylaluminum compound may be any C1 to C20 alkyl group. The alkyl group may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. The alkyl group may be an iso-alkyl group.
The trialkylaluminum compound may comprise trimethylaluminum (TMA), triethylaluminum (TEA), triptopylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, triheptylaluminum, trioctylaluminum or mixtures thereof. The trialkylaluminum compound may comprise tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), tri-iso- butylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum (TNOA).
The halide group of the alkylaluminum halide may be chloride, bromide or iodide. The alkylaluminum halide may be diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride or mixtures thereof.
The alkoxide group of the alkylaluminum alkoxide may be any C1 to C20 alkoxy group. The alkoxy group may be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy. The alkylaluminum alkoxide may be diethylaluminum ethoxide.
The aluminoxane compound may be methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, iso-propyl-aluminoxane, n- butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butylaluminoxane, 1-pentyl- aluminoxane, 2-pentyl-aluminoxane, 3-pentyl-aluminoxane, iso-pentyl-aluminoxane, neopentylaluminoxane, or mixtures thereof.
The preferred co-catalyst is modified methylaluminoxane. The synthesis of modified methylaluminoxane may be carried out in the presence of other trialkylaluminum compounds in addition to trimethylaluminum. The products incorporate both methyl and alkyl groups from the added trialkylaluminum and are referred to as modified methyl aluminoxanes, MMAO. The MMAO may be more soluble in nonpolar reaction media, more stable to storage, have enhanced performance as a cocatalyst, or any combination of these. The performance of the resulting MMAO may be superior to either of the trialkylaluminum starting materials or to simple mixtures of the two starting materials. The added trialkylaluminum may be triethylaluminum, triisobutylaluminum or triisooctylaluminum. In one embodiment, the co-catalyst is MMAO, wherein preferably about 25% of the methyl groups are replaced with iso-butyl groups.
In one embodiment, the co-catalyst may be formed in situ in the reactor by providing the appropriate precursors into the reactor.
Solvent
One or more solvents may be used in the reaction. The solvent(s) may be used to dissolve or suspend the catalyst or the co-catalyst and/ or keep the ethylene dissolved. The solvent may be any solvent that can modify the solubility of any of these components or of reaction products. Suitable solvents include hydrocarbons, for example, alkanes, alkenes, cycloalkanes, and aromatics. Different solvents may be used in the process, for example, one solvent can be used for the catalyst and another for the co-catalyst. It is preferred for the solvent to have a boiling point that is not substantially similar to the boiling point of any of the alpha olefin products as this will make the product separation step more difficult.
Aromatics
Aromatic solvents can be any solvent that contains an aromatic hydrocarbon, preferably having a carbon number of 6 to 20. These solvents may include pure aromatics, or mixtures of pure aromatics, isomers as well as heavier solvents, for example C9 and C10 solvents. Suitable aromatic solvents include benzene, toluene, xylene (including ortho-xylene, meta-xylene, para-xylene and mixtures thereof) and ethylbenzene.
Alkanes
Alkane solvents may be any solvent that contains an alkyl hydrocarbon. These solvents may include straight chain alkanes and branched or iso-alkanes having from 3 to 20 carbon atoms and mixtures of these alkanes. The alkanes may be cycloalkanes. Suitable solvents include propane, isobutane, n-butane, butane (n-butane or a mixture of linear and branched C4 acyclic alkanes), pentane (n-pentane or a mixture of linear and branched acyclic alkanes), hexane (n-hexane or a mixture of linear and branched C6 acychc alkanes), heptane (n-heptane or a mixture of linear and branched C7 acyclic alkanes), octane (n-octane or a mixture of linear and branched C8 acychc alkanes) and isooctane. Suitable solvents also include cyclohexane and methylcyclohexane. In one embodiment, the solvent comprises C6, C7 and C8 alkanes, that may include linear, branched and iso-alkanes.
The choice of solvent may affect the reaction, including the production of by-products, for example, dienes. In some embodiment, the use of heptane as a solvent has been found to produce a lower number of dienes, especially, 3-methyl-l, 4, -pentadiene and 1,4-hexadiene.
Catalyst System
The catalyst system may be formed by mixing together the ligand, the metal, the co-catalyst and optional additional compounds in a solvent. The feed may be present in this step.
In one embodiment, the catalyst system may be prepared by contacting the metal or metal compound with the ligand to form a catalyst precursor mixture and then contacting the catalyst precursor mixture with the co-catalyst in the reactor to form the catalyst system.
In some embodiments, the catalyst system may be prepared outside of the reactor vessel and fed into the reactor vessel. In other embodiments, the catalyst system may be formed in the reactor vessel by passing each of the components of the catalyst system separately into the reactor. In other embodiments, one or more catalyst precursors may be formed by combining at least two components outside of the reactor and then passing the one or more catalyst precursors into the reactor to form the catalyst system.
Reaction Conditions
The oligomerization reaction is a reaction that converts the olefin feed in the presence of an oligomerization catalyst and a co-catalyst into a higher oligomer product stream.
Temperature
The oligomerization reaction may be conducted over a range of temperatures of from -100 °C to 300 °C, preferably in the range of from 0 °C to 200 °C, and more preferably in the range of from 50 °C to 150 °C.
Pressure
The oligomerization reaction may be conducted at a pressure of from 0.01 to 15 MPa and more preferably from 1 to 10 MPa.
The optimum conditions of temperature and pressure used for a specific catalyst system, to maximize the yield of oligomer, and to minimize the impact of competing reactions, for example dimerization and polymerization can be determined by one of ordinary skill in the art. The temperature and pressure are selected to yield a product slate with a K-factor in the range of from 0.40 to 0.90, preferably in the range of from 0.45 to 0.80, more preferably in the range of from 0.5 to 0.7.
Residence Time
Residence times in the reactor of from 3 to 60 min have been found to be suitable, depending on the activity of the catalyst. In one embodiment, the reaction is carried out in the absence of air and moisture.
Gas Phase, Liquid Phase or Mixed Gas-Liquid Phase
The oligomerization reaction can be carried out in the Equid phase or mixed gas-liquid phase, depending on the volatility of the feed and product olefins at the reaction conditions.
Reactor type
The oligomerization reaction may be carried out in a conventional fashion. It may be carried out in a stirred tank reactor, wherein solvent, olefin and catalyst or catalyst precursors are added continuously to a stirred tank and solvent, product, catalyst, and unused reactant are removed from the stirred tank with the product separated and the unused reactant recycled back to the stirred tank.
In another embodiment, the oligomerization reaction may be carried out in a batch reactor, wherein the catalyst precursors and reactant olefin are charged to an autoclave or other vessel and after being reacted for an appropriate time, product is separated from the reaction mixture by conventional means, for example, distillation.
In another embodiment, the oligomerization reaction may be carried out in a gas Eft reactor. This type of reactor has two vertical sections (a riser section and a downcomer section) and a gas separator at the top. The gas feed (ethylene) is injected at the bottom of the riser section to drive circulation around the loop (up the riser section and down the downcomer section).
In another embodiment, the oEgomerization reaction may be carried out in a pump loop reactor. This type of reactor has two vertical sections, and it uses a pump to drive circulation around the loop. A pump loop reactor can be operated at a higher circulation rate than a gas Eft reactor.
In another embodiment, the oEgomerization reaction may be carried out in a once-through reactor. This type of reactor feeds the catalyst, co-catalyst, solvent and ethylene to the inlet of the reactor and/ or along the reactor length and the product is coUected at the reactor outlet. One example of this type of reactor is a plug flow reactor.
Catalyst Deactivation
The higher oligomers produced in the oEgomerization reaction contains catalyst from the reaction step. To stop further reactions that can produce byproducts and other undesired components, it is important to deactivate the catalyst downstream from the reactor.
In one embodiment, the catalyst is deactivated by addition of an acidic species having a pKA(aq) of less than 25. The deactivated catalyst can then be removed by water washing in a liquid/Equid extractor.
Product Separation
The resulting alpha-olefins have a chain length of from 4 to 100 carbon atoms, preferably 4 to 30 carbon atoms and most preferably 4 to 20 carbon atoms. The alpha-olefins are even- numbered alpha-olefins.
The product olefins can be recovered by distillation or other separation techniques depending on the intended use of the products. The solvents) used in the reaction preferably have a boiling point that is different from the boiling point of any of the alpha-olefin products to make the separation easier.
In one embodiment, the distillation steps comprise columns for separating ethylene and the main linear alpha olefin products, for example, butene, hexene, and octene.
Product qualities and characteristics
The products produced by the process may be used in a number of applications. The olefins produced by this process may have improved qualities as compared to olefins produced by other processes. In one embodiment, the butene, hexene and/ or octene produced may be used as a comonomer in making polyethylene. In one embodiment, the octene produced may be used to produce plasticizer alcohols. In one embodiment, the decene produced may be used to produce polyalphaolefins. In one embodiment, the dodecene and/ or tetradecene produced may be used to produce alkylbenzene and/ or detergent alcohols. In one embodiment, the hexadecene and/ or octadecene produced may be used to produce alkenyl succinates and/or oilfield chemicals. In one embodiment, the C20+ products may be used to produce lubricant additives and/ or waxes.
When the olefins will be used as a comonomer, it is beneficial to produce olefins which have a lower content of dienes as the dienes can act as a catalyst poison in the polymerization reaction.
Recycle
A portion of any unreacted ethylene that is removed from the reactor with the products may be recycled to the reactor. This ethylene may be recovered in the distillation steps used to separate the products. The ethylene may be combined with the fresh ethylene feed or it may be fed separately to the reactor.
A portion of any solvent used in the reaction may be recycled to the reactor. The solvent may be recovered in the distillation steps used to separate the products.
Dienes
The amount of dienes produced in an oligomerization process as described herein is affected by the oligomerization catalyst used. As it is beneficial to reduce the amount of dienes produced, catalysts that produce a reduced amount of dienes are preferable.
The catalyst, according to this invention, comprises a ligand of either formula III or formula V. The ligand preferably has methyl groups located at positions R4, R5, R8 and R12. In certain embodiments, the ligand also has methyl groups at R10. It is believed that the steric nature of these ligands provides for a reduced level of dienes being produced.
Examples
In the foUowing examples, ethylene was oEgomerized in the presence of various different catalysts, each a complex of iron with a different Egand, to form alpha-olefins in an autoclave reactor. Table 1 shows the amount of dienes, specificaUy 1,4-hexadiene and 3-methyl 1,4-pentadiene that were formed during each experiment.
In Egand A: R4, R5, R8, R10 and R12 are methyl; R14 and R16 are tert-butyl; and R1-R3, R9, R11, R13, R15, and R17 are hydrogen. In Egand B: R4, R5, R8, R10 and R12 are methyl; R14 and R16, are phenyl; R15 is C20H41O; and R1-R3, R9, R11, R13, and R17 are hydrogen. In Egand C: R4, R5, R8, R10 and R12 are methyl; R15 is tert-butyl; and R1-R3, R9, R11, R13-R14 and R16-R17 are hydrogen. In Egand D: R4, R5, R8, R10 and R12 are methyl; R15 is fluoride; and R1-R3, R9, R11, R13 R14 and R16-R17 are hydrogen. In Egand E: R4, R5, R8, R10 and R12 are methyl; and R1-R3, R9, R11, R13 --R17 are hydrogen. In Egand F: R4, R5, R8, R10, R12, R14 and R16, are methyl; and R1-R3, R9, R11, R13, R15, and R17 are hydrogen. In Egand H; R4, R5 are methyl; and R1-R3, R9, R11, R13, R15, and R17 are hydrogen.
The comparative Egands had the foUowing substituents. In Egand H: aE R groups were hydrogen. In Egand I: R13 and R16 were methyl; R10 was tert-butyl and the remaining R groups were hydrogen. In Egand J: R8, R11, R13 and R16 were methyl; and the remaining R groups were hydrogen.
One Egand, G, was of the formula (V):
In ligand G: R4, R5, R8, R10 and R12 are methyl; and R1-R3, R9, R11 and R18-R21 are hydrogen. Table 1
The Examples show that catalysts having a ligand which has methyl groups at the R4, R5, R8, R10 and R12 positions produce fewer C6 dienes than those which do not have methyl groups at these locations.
Claims
1. A process for producing alpha-olefins comprising contacting an ethylene feed with an oligomerization catalyst system in an oligomerization reaction zone under oligomerization conditions to produce a product stream comprising alpha-olefins wherein the oligomerization catalyst system comprises an iron-ligand complex wherein the ligand comprises a bis-aryliminepyridine compound of formula (III):
wherein R4, R5, R8 and R12 are methyl; R13 and R17 are hydrogen; and R1-R3, R9-R11, R14-R16 are selected from hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group .
2. The process of claim 1 wherein R10 is methyl. (L32)
3. The process of any of claims 1-2 wherein R14 and R16 are tert-butyl. (L2)
4. The process of any of claims 1-2 wherein R15 is tert-butyl. (L10)
5. The process of any of claims 1-2 wherein R14 and R16 are fluorine. (L18)
6. The process of any of claims 1-2 wherein R15 is fluorine. (L17)
7. The process of any of claims 1-2 wherein R14 and R16, are phenyl and R15 is an alkoxy group. (L3)
8. The process of any of claims 1-2 wherein R15 is methoxy. (L19)
9. The process of any of claims 1-2 wherein R15 is silica-methoxy. (L20)
10. A process for producing alpha-olefins comprising contacting an ethylene feed with an oligomerization catalyst system in an oligomerization reaction zone under oligomerization conditions wherein the oligomerization catalyst system comprises an iron-ligand complex wherein the ligand comprises a compound of formula (V):
wherein R8 and R12 are methyl; R18 and R21 are hydrogen; and R1-R5, R9-R11, R19-R20 are selected from hydrogen, optionally substituted hydrocarbyl, hydroxo, cyano or an inert functional group.
11. The process of claim 5 wherein R10 is methyl.
12. The process of any of claims 1-11 wherein the process produces a mixture comprising linear alpha olefins and dienes.
13. The process of claim 12 wherein the mixture comprises less than 300 ppm of total C6 dienes, relative to the C6 fraction.
14. The process of claim 12 wherein the mixture comprises less than 200 ppm of total C6 dienes, relative to the C6 fraction.
15. The process of any of claims 12-14 wherein the total C6 dienes comprises 1,4 hexadiene; 3- methyl- 1 ,4-pentadiene
16. The process of any of claims 1-15 wherein the oligomerization conditions comprise a temperature in the range of from 0 to 200 °C and a pressure in the range of from 1 to 5 MPa.
17. The process of any of claims 1-16 further comprising a co-catalyst in the reaction zone.
18. The process of claim 17 wherein the co-catalyst comprises an alkylaluminum compound, an aluminoxane or a combination thereof.
19. The process of any of claims 1-18 further comprising a solvent in the reaction zone.
20. The process of claim 19 wherein the solvent comprises xylene.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US202063125675P | 2020-12-15 | 2020-12-15 | |
US63/125,675 | 2020-12-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022132866A1 true WO2022132866A1 (en) | 2022-06-23 |
Family
ID=80112076
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2021/063457 WO2022132866A1 (en) | 2020-12-15 | 2021-12-15 | A process for producing alpha-olefins |
Country Status (2)
Country | Link |
---|---|
AR (1) | AR124325A1 (en) |
WO (1) | WO2022132866A1 (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001058874A1 (en) * | 2000-02-09 | 2001-08-16 | Shell Internationale Research Maatschappij B.V. | Non-symmetrical ligands and catalyst systems thereof for ehtylene oligomerisation to linear alpha olefins |
WO2003011876A1 (en) * | 2001-08-01 | 2003-02-13 | Shell Internationale Research Maatschappij B.V. | Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins |
US6683187B2 (en) | 2000-06-30 | 2004-01-27 | Shell Oil Company | Ligands and catalyst systems thereof for ethylene oligomerization to linear alpha olefins |
WO2004037415A2 (en) * | 2002-09-25 | 2004-05-06 | Shell Internationale Research Maatschappij B.V. | Catalyst systems for ethylene oligomerisation to linear alpha olefins |
WO2005005354A1 (en) * | 2003-07-07 | 2005-01-20 | Shell Internationale Research Maatschappij B.V. | Process for producing linear alpha olefins |
WO2005090371A1 (en) * | 2004-03-24 | 2005-09-29 | Shell Internationale Research Maatschappij B.V. | Transition metal complexes |
WO2018125826A1 (en) * | 2016-12-29 | 2018-07-05 | Chevron Phillips Chemical Company Lp | Ethylene oligomerization processes |
-
2021
- 2021-12-13 AR ARP210103458A patent/AR124325A1/en unknown
- 2021-12-15 WO PCT/US2021/063457 patent/WO2022132866A1/en active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001058874A1 (en) * | 2000-02-09 | 2001-08-16 | Shell Internationale Research Maatschappij B.V. | Non-symmetrical ligands and catalyst systems thereof for ehtylene oligomerisation to linear alpha olefins |
US6683187B2 (en) | 2000-06-30 | 2004-01-27 | Shell Oil Company | Ligands and catalyst systems thereof for ethylene oligomerization to linear alpha olefins |
WO2003011876A1 (en) * | 2001-08-01 | 2003-02-13 | Shell Internationale Research Maatschappij B.V. | Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins |
WO2004037415A2 (en) * | 2002-09-25 | 2004-05-06 | Shell Internationale Research Maatschappij B.V. | Catalyst systems for ethylene oligomerisation to linear alpha olefins |
WO2005005354A1 (en) * | 2003-07-07 | 2005-01-20 | Shell Internationale Research Maatschappij B.V. | Process for producing linear alpha olefins |
WO2005090371A1 (en) * | 2004-03-24 | 2005-09-29 | Shell Internationale Research Maatschappij B.V. | Transition metal complexes |
WO2018125826A1 (en) * | 2016-12-29 | 2018-07-05 | Chevron Phillips Chemical Company Lp | Ethylene oligomerization processes |
Non-Patent Citations (3)
Title |
---|
IONKIN A S ET AL: "nitro-substituted iron (II) tridentate bis(imino)pyridine complexes as high temperature catalysts for the production of alpha olefins", JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY, JOHN WILEY & SONS, INC, US, vol. 44, no. 8, 1 January 2006 (2006-01-01), pages 2615 - 2635, XP002417531, ISSN: 0887-624X, DOI: 10.1002/POLA.21360 * |
IONKIN ALEX S ET AL: "High-temperature catalysts for the production of .alpha.-olefins based on iron(II) and iron(III) tridentate bis(imino)pyridine complexes modified by nitrilo group", JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY, JOHN WILEY & SONS, INC, US, vol. 46, no. 2, 1 January 2007 (2007-01-01), pages 585 - 611, XP002606503, ISSN: 0887-624X, DOI: 10.1002/POLA.22408 * |
IONKIN ALEX S ET AL: "High-Temperature Catalysts for the Production of .alpha.-Olefins Based on Iron(II) and Iron(III) Tridentate Bis(imino)pyridine Complexes with Double Pattern of Substitution: Ortho-Methyl plus meta-Aryl", ORGANOMETALLICS, AMERICAN CHEMICAL SOCIETY, vol. 25, no. 12, 1 January 2006 (2006-01-01), pages 2978 - 2992, XP002426869, ISSN: 0276-7333, DOI: 10.1021/OM051069O * |
Also Published As
Publication number | Publication date |
---|---|
AR124325A1 (en) | 2023-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4857269B2 (en) | Process for the preparation of linear alpha olefins | |
JP6621472B2 (en) | Deactivator and method for reducing by-products of olefin oligomerization using the same | |
EP0257696B1 (en) | Process for dimerizing alpha-olefins | |
US20240002316A1 (en) | A process for producing alpha-olefins | |
US20230406787A1 (en) | A process for producing alpha-olefins | |
WO2022132866A1 (en) | A process for producing alpha-olefins | |
CN109701642B (en) | Catalyst composition and application thereof | |
US20230416171A1 (en) | A process for producing alpha-olefins | |
WO2022132711A1 (en) | A process for producing alpha-olefins | |
WO2022132865A1 (en) | A process for producing alpha-olefins | |
WO2022132707A1 (en) | An oligomerization catalyst, method of preparation and process for using the catalyst | |
US20240018069A1 (en) | A process for producing alpha olefins | |
WO2022132749A1 (en) | A process for producing alpha-olefins | |
US20230416170A1 (en) | A process for producing alpha olefins | |
CN111328326A (en) | Neo-acids and process for their preparation | |
WO2022132860A1 (en) | A process for producing alpha olefins | |
WO2022132743A2 (en) | A process for producing alpha-olefins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21841119 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21841119 Country of ref document: EP Kind code of ref document: A1 |