EP3463653A1 - Catalytic composition comprising chromium and a phosphine-based ligand, and use thereof in an octene production method - Google Patents
Catalytic composition comprising chromium and a phosphine-based ligand, and use thereof in an octene production methodInfo
- Publication number
- EP3463653A1 EP3463653A1 EP17723148.7A EP17723148A EP3463653A1 EP 3463653 A1 EP3463653 A1 EP 3463653A1 EP 17723148 A EP17723148 A EP 17723148A EP 3463653 A1 EP3463653 A1 EP 3463653A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- groups
- chromium
- chosen
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000011651 chromium Substances 0.000 title claims abstract description 45
- 239000003446 ligand Substances 0.000 title claims abstract description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 title description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 title description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 239000012190 activator Substances 0.000 claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 aluminum halides Chemical class 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 239000005977 Ethylene Substances 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000005609 naphthenate group Chemical group 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000003606 oligomerizing effect Effects 0.000 claims 1
- 125000001072 heteroaryl group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000006384 oligomerization reaction Methods 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 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 5
- 150000004820 halides Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 3
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 3
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 3
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 3
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 3
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 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 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HFKJQIJFRMRSKM-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 HFKJQIJFRMRSKM-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- SUTWPJHCRAITLU-UHFFFAOYSA-N 6-aminohexan-1-ol Chemical compound NCCCCCCO SUTWPJHCRAITLU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- LCKHOIUMRVRUKY-UHFFFAOYSA-N [Cr+] Chemical compound [Cr+] LCKHOIUMRVRUKY-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- UZEDIBTVIIJELN-UHFFFAOYSA-N chromium(2+) Chemical compound [Cr+2] UZEDIBTVIIJELN-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-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
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical class CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- SRSUADNYIFOSLP-UHFFFAOYSA-N tris(2,3,4,5,6,7,8-heptafluoronaphthalen-1-yl)borane Chemical compound FC1=C(F)C(F)=C2C(B(C=3C4=C(F)C(F)=C(F)C(F)=C4C(F)=C(F)C=3F)C=3C4=C(F)C(F)=C(C(=C4C(F)=C(F)C=3F)F)F)=C(F)C(F)=C(F)C2=C1F SRSUADNYIFOSLP-UHFFFAOYSA-N 0.000 description 1
- VGEPZRRRDGHRMI-UHFFFAOYSA-N tris(2,3,4,6-tetrafluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC(F)=C1B(C=1C(=C(F)C(F)=CC=1F)F)C1=C(F)C=C(F)C(F)=C1F VGEPZRRRDGHRMI-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- BPKXQSLAVGBZEM-UHFFFAOYSA-N tris[3,5-bis(trifluoromethyl)phenyl]borane Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(B(C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)=C1 BPKXQSLAVGBZEM-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
- B01J31/188—Amide derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—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
- B01J31/143—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 of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
-
- 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
- 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
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- 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
- C07C2531/24—Phosphines
Definitions
- the present invention describes a catalyst composition based on chromium and a particular ligand.
- the invention also relates to the process for preparing said composition and its use in a process for producing octene from ethylene.
- Chromium-based catalyst systems or compositions and diphosphine ligands are known to catalyze the selective conversion of ethylene to octene-1.
- the effectiveness of such systems is a function of the reaction conditions and the choice of the ligand structure. In particular, the nature and position of all the substituents of the ligand used have a decisive influence on the performance of the catalytic system.
- One of the defects of these catalytic compositions is the obligation of their implementation at low temperature, that is to say at a temperature of between 45 and 60 ° under penalty of significant deactivation of the catalytic system and the loss of selectivity. in octene-1.
- the operation at high temperature is advantageous in that it makes it possible in particular to increase the viscosity and thus the management of the heavy by-products formed.
- None of the ligands described comprises the molecule fragment corresponding to the structure N (R 6 ) with R 6 corresponding to the formula -XOP-, with X being a divalent bridging group advantageously chosen from alkylidenes.
- the described catalytic compositions have shown a high-temperature degraded octene-1 selectivity.
- the Applicant in his research has developed a novel catalyst composition
- a novel catalyst composition comprising at least one chromium precursor, at least one heteroatomic ligand described by the general formula (I) (R 1 ) 2 P-O- (CH 2 ) nN [P (R 2 ) 2] 2, and at least one activator.
- the composition according to the invention has shown particularly advantageous catalytic properties, especially in the olefin tetramerization reaction and more particularly in the tetramerization reaction of ethylene in octene-1. Surprisingly, it has been observed that the compositions according to the invention have a very good productivity in octene-1 notwithstanding the implementation of the tetramerisation process at temperatures going beyond 60 ⁇ , or even beyond 80 ⁇ .
- compositions according to the invention can be implemented in a tetramerization reaction under higher temperature conditions than the conventional compositions of the prior art, without impairing the productivity of octene-1 of the catalytic system, nor its selectivity towards the production of octene-1.
- alkyl means a linear or branched hydrocarbon chain having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.
- Preferred alkyl groups are preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl. These alkyl groups may be substituted with heteroelements or groups containing heteroelements such as a halide, an alkoxy.
- alkoxy substituent means an alkyl-O- group in which the term alkyl has the meaning given above. Preferred examples of alkoxy substituents are methoxy or ethoxy.
- cyclic alkyl is meant a monocyclic hydrocarbon group having a number of carbons greater than 3, preferably between 4 and 24, more preferably between 5 and 18, preferably a cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl, or polycyclic (bicyclic or tricyclic) group having a carbon number greater than 3, preferably between 5 and 18, such as, for example, adamantyl or norbornyl groups; .
- These groups may be substituted by heteroelements or groups containing heteroelements such as a halide, an alkoxy.
- aromatic is meant a mono- or polycyclic aromatic group substituted or not, preferably mono- or bicyclic substituted or unsubstituted, having a number of carbon atoms between 5 and 20.
- the group is polycyclic, it is that is, it comprises more than one ring aromatic ring, the ring rings can advantageously be condensed two by two or attached in pairs by bonds ⁇ .
- the aromatic group according to the invention may contain a heteroelement such as nitrogen, oxygen or sulfur. These groups may be substituted by heteroelements or groups containing heteroelements such as a halide, an alkoxy.
- the present invention relates to a composition
- a composition comprising:
- groups R 1 and R 2 which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
- the integer n of the fragment - (CH 2) n - of the ligand is between 1 and 15.
- the molar ratio between the ligand and the chromium precursor is between 0.01 and 100.
- the molar ratio between the activator and the chromium precursor is between 1 and 10,000.
- the chromium precursor is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
- the groups R 1 and R 2 of the ligand which are identical or different from each other, whether or not they are linked together, are chosen from a cyclic or non-cyclic alkyl group, aromatic or otherwise, having from 1 to 15 carbon atoms.
- the groups R 1 and R 2 which are identical to or different from each other, linked or not to each other, are chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl groups, and -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, adamantyl, substituted or unsubstituted, whether or not containing heteroelements; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 2-ch
- the activating agent is chosen from tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminum compounds, aluminum halides, aluminoxanes, organoboron compounds, organic compounds capable of giving a proton, taken alone. or in mixture.
- the invention also relates to the process for preparing the composition according to the invention, comprising contacting
- groups R 1 and R 2 which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
- compositions according to the invention as a catalyst.
- the invention relates to a process for the tetramination of ethylene to octene-1.
- compositions according to the invention are provided.
- the present invention relates to a composition
- a composition comprising:
- groups R 1 and R 2 which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
- the chromium precursor according to the invention may be chosen from chromium compounds used in olefin oligomerization processes.
- the chromium precursor present in the composition according to the invention may comprise one or more identical or different anions chosen from the group formed by halides, carboxylates, acetylacetonates, alkoxy and aryloxy anions.
- the chromium compound may be a chromium (II) or chromium (III) salt, but also a salt of different oxidation state that may comprise one or more identical or different anions such as, for example, halides, carboxylates, acetylacetonates, alkoxy or aryloxy anions.
- the chromium precursors preferably used in the invention are the chromium (III) compounds because they are more accessible, but a chromium (I) or chromium (II) compound may also be suitable.
- the chromium precursor is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
- the heteroatomic liqand is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
- the integer number n of the - (CH 2 ) n - fragment of the ligand according to the invention is preferably between 1 and 15, more preferably between 2 and 15, even more preferably between 2 and 10, and even more preferably between 3 and 6.
- the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another, are chosen from a cyclic or non-cyclic alkyl group having from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms, or an aromatic group having a number of carbons greater than 3, preferably between 4 and 24, more preferably between 5 and 18.
- the groups R 1 and R 2 identical or different.
- the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another are chosen from methyl, ethyl, i-propyl, n-butyl, i-butyl and t-butyl groups. , cyclopentyl, cyclohexyl.
- the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another are chosen from phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl and 2-methoxyphenyl groups.
- the activating agent is the activating agent
- the composition according to the invention may include an activating agent.
- the activating agent may be chosen from compounds known to those skilled in the art. Mixtures of activating agents may also be used.
- the activating agents according to the invention are chosen from tris (hydrocarbyl) aluminum compounds, chlorinated or brominated compounds of hydrocarbylaluminium, aluminum halides, aluminoxanes, organoboron compounds, organic compounds capable of giving a proton , taken alone or mixed.
- alkylaluminium halides such as dimethylaluminum chloride, diethylaluminum chloride, ethylaluminium dichloride, methylaluminum sesquichloride, ethylaluminium sesquichloride, methylaluminum dichloride, dichloride, and the like. isobutylaluminum, aluminum trichloride; and aluminoxanes, used alone or as a mixture.
- Aluminoxanes are well known to those skilled in the art as oligomeric compounds that can be prepared by the controlled addition of water to an aluminum alkyl, for example trimethylaluminum. Such compounds can be linear, cyclic or mixtures of these compounds. They are generally represented by the formula [RAIO] a wherein R is a hydrocarbon group and a is a number from 2 to 50.
- the aluminoxane is chosen from methylaluminoxane (MAO) and / or ethylaluminoxane (EAO) and or among modified aluminoxanes such as modified methylaluminoxane (MMAO).
- said activating agent is preferably chosen from Lewis acids of tris (aryl) borane type such as tris (perfluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, tris (2,3,4,6-tetrafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluobiphenyl) borane and their derivatives and (aryl) borates associated with a triphenylcarbenium cation or to a trisubstituted ammonium cation such as triphenylcarbenium tetrakis (perfluorophenyl) borate, ⁇ , ⁇ -dimethylanilinium tetrakis (perfluorophenyl) borate, ⁇ , ⁇ -diethylanilinium tetrakis (3,5-bis
- said activating agent is chosen from organic compounds capable of giving a proton
- said activating agent is preferably chosen from the acids of formula HY in which Y represents an anion, such as HBF 4 or F 3 CS0 3 H.
- compositions according to the invention are preferably prepared by placing in contact with each other.
- groups R 1 and R 2 which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
- the molar ratio between the ligand and the chromium precursor is between 0.01 and 100, and preferably between 0.5 and 5, in particular 0.8 and 3.
- the molar ratio between the activator and the chromium precursor is between 1 and 10,000, preferably between 100 and 5000, even more preferably between 200 and 3500.
- compositions according to the invention may be prepared in situ in the presence or in the absence of the filler, in particular ethylene.
- the compositions according to the invention may be in the presence or absence of a solvent.
- a solvent advantageously chosen from solvents capable of dissolving the reagents.
- organic solvents There may be mentioned saturated or unsaturated aliphatic hydrocarbon solvents such as pentane, hexane, cyclohexane, methylcyclohexane, or heptane, cyclohexene, cyclooctene or cyclooctadiene.
- Aromatic solvents such as benzene, toluene or xylenes may be mentioned. There may be mentioned oxygenated solvents such as diethyl ether or tetrahydrofuran, chlorinated solvents such as dichloromethane or chlorobenzene. These solvents can be used alone or as a mixture.
- the temperature at which the components of the composition according to the invention are mixed is advantageously between -40 and + 150 °, preferably between 0 and + 80 °, for example at a temperature close to room temperature (15 to 30 ° C.). The mixing can be carried out under an atmosphere of ethylene or inert gas.
- Another object of the invention relates to the use of the compositions according to the invention as a catalyst.
- compositions according to the invention can be used as a catalyst in a chemical transformation reaction, in particular in an oligomerization process comprising contacting said feedstock comprising olefins having a number of carbon atoms of between 2 and 10 with the composition according to the invention, said method is advantageously operated at a total pressure of between atmospheric pressure and 20 MPa and at a temperature between -40 and 250 ⁇ C.
- composition according to the invention is advantageously used in an olefin tetramerization process, in particular in an ethylene tetramerisation process in octene-1.
- the solvent of the oligomerization process may be chosen from organic solvents and preferably from ethers, alcohols, chlorinated solvents and saturated or unsaturated hydrocarbons, aromatic or otherwise, cyclic or otherwise.
- said solvent is chosen from hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, monoolefins or diolefins preferably comprising 4 to 20 carbon atoms, benzene, toluene, toluene or toluene.
- reaction solvent is an ionic liquid
- it is advantageously chosen from the ionic liquids described in US Pat. Nos. 6,951,831 B2 and FR 2,895,406 B1.
- Oligomerization is defined as the conversion of a monomer unit into a compound or mixture of compounds of the general formula C p H 2p with 4 ⁇ p ⁇ 80, preferably with 4 ⁇ p ⁇ 50, most preferably with 4 ⁇ p ⁇ 26 and more preferably with 4 ⁇ p ⁇ 14.
- the olefins used in the oligomerization process are olefins having from 2 to 10 carbon atoms.
- said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted.
- said olefins are diluted, said olefins are diluted with one or more alkane (s), as found in "cuts" from petroleum refining processes, such as catalytic cracking or cracking at the same time. steam.
- the olefin used in the oligomerization process and in particular in the tetramerization process according to the invention is ethylene.
- Said olefins can come from non-fossil resources such as biomass.
- the olefins used in the oligomerization process according to the invention and in particular in the tetramerization process according to the invention can be produced from alcohols, and in particular by dehydration of alcohols.
- the oligomerization process in particular the tetramerization process according to the invention, advantageously operates at a total pressure of between atmospheric pressure and 20 MPa, preferably between 0.1 and 8 MPa, and at a temperature of between -40 and + 250 °, preferably between 0 and 150 °, preferably between 20 and 135 °, preferably between 45 and 100 °, preferably between 75 and 100 °, preferably between 80 and 100 °.
- the heat generated by the reaction can be removed by any means known to those skilled in the art.
- the oligomerization process in particular the tetramerization process according to the invention, can be carried out in a closed system, in a semi-open system or continuously, with one or more reaction stages. Vigorous agitation is advantageously used to ensure good contact between the reagent (s) and the catalytic system.
- the products of the present process can be used, for example, as components in plastics and more particularly polyethylene, motor fuels, as fillers in a hydroformylation process for the synthesis of aldehydes and alcohols, as components for chemical, pharmaceutical or perfume industry and / or as fillers in a metathesis process for the synthesis of propylene for example.
- the molar ratio between the ligand and the chromium is 2.
- methylaluminoxane (MAO) is used in a MAO molar ratio on the Cr (acac) 3 precursor of 600.
- the reaction is carried out under 4.5 MPa. ethylene.
- the ligands are evaluated at three different temperatures or 45 ⁇ C, 80 ⁇ and 100 ⁇ C.
- the Ref ligand below is used as a comparative and evaluated under the same conditions and L3.
- a 100 ml reactor is pressurized with ethylene.
- the reaction solvent is introduced into the reactor as well as the MAO (10% by weight in toluene).
- the reactor is then placed under 0.5 MPa of ethylene and stirred for 5 minutes.
- the solution formed by the chromium precursor Cr (acac) 3 and the ligand is then introduced into the reactor.
- the reactor is then placed under 2 MPa of ethylene pressure and heated to the test temperature. The pressure is completed at 4.5 MPa and agitation at 1000 rpm is started.
- the system is under pressure control.
- the ethylene feed is cut off and the reactor cooled.
- the liquid phase and the optionally formed polymer are recovered and weighed.
- the polymer is weighed after drying at 100 ° for one night.
- the liquid phase is then neutralized with a sulfuric acid solution at 10% by weight.
- the analysis of the liquid phase is carried out by gas phase chromatography with an HP 685 GC equipped with a PONA brand column.
- the results of the experiments are shown in the table below.
- the ethylene consumption described in the table corresponds to the amount (in grams) of ethylene converted during the catalytic test into reaction products.
- the activity described in g / (g Cr. H) in the table corresponds to the amount of ethylene (in grams) converted by one gram of chromium from the catalytic composition reported over one hour of reaction.
- Figure 1 shows the evolution of the C8 productivity as a function of the reaction temperature.
- the productivity C8 described in FIG. 1 corresponds to the amount of octenes (in gram) transformed by one gram of chromium resulting from the catalytic composition reported over one hour of reaction. It is calculated by multiplying the activity by the percentage of C8 which is the weight percentage of C8 compared to the products formed.
- a % percentage weight compared to the products formed.
- b % 1 -C 6 percentage of hexene-1 in the C 6 section .
- c % 1 -C 8 percentage of octene-1 in the C 8 section .
- compositions according to the invention make it possible to significantly increase the proportion of C8 (% C8) relative to the other products formed when the temperature is brought from 45 ⁇ to 80 ⁇ .
- productivity 08 observed with the compositions (with L1, L2 and L3) according to the invention is thus much greater than that observed with the composition used as a comparative example (Ref).
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Abstract
The invention relates to a composition comprising at least one chromium precursor, at least one heteroaromatic ligand and, optionally, at least one activator. The invention also relates to the method for producing the composition according to the invention, and to the use of said composition in an olefin oligomerisation method.
Description
COMPOSITION CATALYTIQUE A BASE DE CHROME ET D'UN LIGAND CATALYTIC COMPOSITION BASED ON CHROME AND A LIGAND
A BASE DE PHOSPHINE ET SON UTILISATION DANS UN PROCEDE DE PROCUCTION DOCTENES PHOSPHINE BASED AND USE THEREOF IN A PROCESS FOR PROCESSING
La présente invention décrit une composition catalytique à base de chrome et d'un ligand particulier. L'invention concerne également le procédé de préparation de ladite composition ainsi que son utilisation dans un procédé de production d'octène à partir d'éthylène. The present invention describes a catalyst composition based on chromium and a particular ligand. The invention also relates to the process for preparing said composition and its use in a process for producing octene from ethylene.
Art antérieur Prior art
Les systèmes ou compositions catalytiques à base de chrome et des ligands de type diphosphine sont connus pour catalyser la conversion sélective de l'éthylène en octène-1 . L'efficacité de tels systèmes est fonction des conditions de réaction et du choix de la structure du ligand. En particulier, la nature et la position de tous les substituants du ligand utilisé ont une influence déterminante sur les performances du système catalytique. Chromium-based catalyst systems or compositions and diphosphine ligands are known to catalyze the selective conversion of ethylene to octene-1. The effectiveness of such systems is a function of the reaction conditions and the choice of the ligand structure. In particular, the nature and position of all the substituents of the ligand used have a decisive influence on the performance of the catalytic system.
Parmi les compositions catalytiques connues, on peut citer les exemples de compositions à base de chrome et de ligand bis(phosphino)amine de type «PNP». L'article J. Am. Chem. Soc. 2004, 126, 14712-14713 de Bollmann et al. et les demandes de la famille WO2004/056479 A1 rapportent l'utilisation de ligands décrits par la formule (R)nA-B-C(R)n, avec A et C étant sélectionnés parmi les atomes de phosphore, d'arsenic, d'antimoine, d'oxygène, de bismuth, de sulfure, de sélénium ou d'azote, oxydés ou non. Ces ligands sont utilisés pour la réaction de tétramérisation de l'éthylène en octène-1 dans des conditions de température de 45^. Parmi la longue liste de ligan ds cités, aucun n'est décrit comme répondant à la formule (PR)2N-X-0-PR2, avec X étant un groupement pontant divalent. Among the known catalyst compositions, examples of chromium-based compositions and bis (phosphino) amine ligand of "PNP" type can be cited. J. Am. Chem. Soc. 2004, 126, 14712-14713 of Bollmann et al. and the applications of the WO2004 / 056479 A1 family report the use of ligands described by the formula (R) nA-BC (R) n, with A and C being selected from phosphorus, arsenic and antimony atoms. Oxygen, bismuth, sulphide, selenium or nitrogen, oxidized or not. These ligands are used for the tetramination reaction of ethylene to octene-1 under temperature conditions of 45%. Of the long list of ligan of cities, none are described as having the formula (PR) 2 NX-O-PR 2 , where X is a divalent bridging group.
Un des défauts de ces compositions catalytiques est l'obligation de leur mise en œuvre à basse température, c'est-à-dire à une température comprise entre 45 et 60^ sous peine de désactivation notable du système catalytique ainsi que la perte de sélectivité en octène-1 . Mais, le fonctionnement à haute température a ceci d'avantageux, qu'il permet notamment d'augmenter la viscosité et donc la gestion des sous-produits lourds formés. One of the defects of these catalytic compositions is the obligation of their implementation at low temperature, that is to say at a temperature of between 45 and 60 ° under penalty of significant deactivation of the catalytic system and the loss of selectivity. in octene-1. However, the operation at high temperature is advantageous in that it makes it possible in particular to increase the viscosity and thus the management of the heavy by-products formed.
Pour tenter de résoudre ce problème, les demandes de brevet WO2013/168102 A1 et WO2013/168106 A1 ont récemment décrit la tétramérisation des oléfines à des températures élevées, notamment supérieures à 80^, réalisés ave c des systèmes catalytiques à base de ligands R1 R2P-X-PR3R4, avec des groupements R1 , R2, R3 et R4 fluorés ou non, et X pouvant
être un groupement N(R6) dans lequel R6 est choisi parmi entre autres les groupements alkyle, cycloalkyle, aryle, aryloxy, alcoxy, les aminocarbonyl, les groupes silyl et leurs dérivés. Aucun des ligands décrits ne comprend le fragment de molécule répondant à la structure N(R6) avec R6 répondant à la formule -X-O-P-, avec X étant un groupement pontant divalent avantageusement choisi parmi les alkylidènes. D'autre part, les compositions catalytiques décrites ont montré une sélectivité en octène-1 dégradée à haute température. In an attempt to solve this problem, patent applications WO2013 / 168102 A1 and WO2013 / 168106 A1 have recently described the tetramerisation of olefins at high temperatures, in particular greater than 80%, carried out with catalytic systems based on R 1 ligands. R 2 PX-PR 3 R 4 , with groups R 1 , R 2 , R 3 and R 4 fluorinated or not, and X being able to to be a group N (R 6 ) in which R 6 is chosen from, among others, alkyl, cycloalkyl, aryl, aryloxy, alkoxy groups, aminocarbonyl groups, silyl groups and their derivatives. None of the ligands described comprises the molecule fragment corresponding to the structure N (R 6 ) with R 6 corresponding to the formula -XOP-, with X being a divalent bridging group advantageously chosen from alkylidenes. On the other hand, the described catalytic compositions have shown a high-temperature degraded octene-1 selectivity.
La demanderesse dans ses recherches a mis au point une nouvelle composition catalytique comprenant au moins un précurseur de chrome, au moins un ligand hétéroatomique décrit par la formule générale (I) (R1)2P-0-(CH2)n-N[P(R2)2]2, et au moins un activateur. La composition selon l'invention a montré des propriétés catalytiques particulièrement intéressantes, notamment dans la réaction de tétramérisation des oléfines et plus particulièrement dans la réaction de tétramérisation de l'éthylène en octène-1 . De manière surprenante, il a été observé que les compositions selon l'invention présentent une très bonne productivité en octène-1 nonobstant la mise en œuvre du procédé de tétramérisation à des températures allant au-delà de 60Ό, voire au -delà de 80Ό. The Applicant in his research has developed a novel catalyst composition comprising at least one chromium precursor, at least one heteroatomic ligand described by the general formula (I) (R 1 ) 2 P-O- (CH 2 ) nN [P (R 2 ) 2] 2, and at least one activator. The composition according to the invention has shown particularly advantageous catalytic properties, especially in the olefin tetramerization reaction and more particularly in the tetramerization reaction of ethylene in octene-1. Surprisingly, it has been observed that the compositions according to the invention have a very good productivity in octene-1 notwithstanding the implementation of the tetramerisation process at temperatures going beyond 60Ό, or even beyond 80Ό.
Un avantage des compositions selon l'invention réside en ce qu'elles peuvent être mises en œuvre dans une réaction de tétramérisation dans des conditions de température plus élevée que les compositions classiques de l'art antérieur, sans nuire à la productivité en octène-1 du système catalytique, ni à sa sélectivité envers la production d'octène-1 . Définitions An advantage of the compositions according to the invention is that they can be implemented in a tetramerization reaction under higher temperature conditions than the conventional compositions of the prior art, without impairing the productivity of octene-1 of the catalytic system, nor its selectivity towards the production of octene-1. Definitions
Au sens de la présente invention, on entend par « alkyle » une chaîne hydrocarbonée linéaire ou ramifiée ayant de 1 à 15 atomes de carbone, de préférence de 1 à 10 atomes de carbone. Des groupes alkyles préférés sont avantageusement choisis parmi les groupes méthyle, éthyle, propyle, isopropyle, butyle, isobutyle, tertio-butyle, pentyle et hexyle. Ces groupements alkyles peuvent être substitués par des hétéroéléments ou des groupes contenant des hétéroéléments tels qu'un halogénure, un alcoxy. On entend par un substituant « alcoxy », un groupe alkyl-O- dans lequel le terme alkyle a la signification donnée ci-dessus. Des exemples préférés de substituants alcoxy sont les groupes méthoxy ou éthoxy. Par « alkyle cyclique », on entend on entend un groupe hydrocarboné monocyclique ayant un nombre de carbones supérieur à 3, de préférence entre 4 et 24, de manière plus préférée
entre 5 et 18, de préférence un groupe cyclopentyle, cyclohexyle, cyclooctyle ou cyclododécyle, ou polycyclique (bi- ou tricyclique) ayant un nombre de carbones supérieur à 3, de préférence entre 5 et 18, tels que par exemple les groupes adamantyle ou norbornyle. Ces groupements peuvent être substitués par des hétéroéléments ou des groupes contenant des hétéroéléments tels qu'un halogénure, un alcoxy. For the purposes of the present invention, the term "alkyl" means a linear or branched hydrocarbon chain having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. Preferred alkyl groups are preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl. These alkyl groups may be substituted with heteroelements or groups containing heteroelements such as a halide, an alkoxy. The term "alkoxy" substituent means an alkyl-O- group in which the term alkyl has the meaning given above. Preferred examples of alkoxy substituents are methoxy or ethoxy. By "cyclic alkyl" is meant a monocyclic hydrocarbon group having a number of carbons greater than 3, preferably between 4 and 24, more preferably between 5 and 18, preferably a cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl, or polycyclic (bicyclic or tricyclic) group having a carbon number greater than 3, preferably between 5 and 18, such as, for example, adamantyl or norbornyl groups; . These groups may be substituted by heteroelements or groups containing heteroelements such as a halide, an alkoxy.
Par « aromatique », on entend un groupe mono- ou polycyclique aromatique substitué ou non, de préférence mono- ou bicyclique substitué ou non, ayant un nombre d'atomes de carbone entre 5 et 20. Lorsque le groupe est polycyclique, c'est-à-dire qu'il comprend plus d'un noyau aromatique cyclique, les noyaux cycliques peuvent avantageusement être condensés deux à deux ou rattachés deux à deux par des liaisons σ. Le groupe aromatique selon l'invention peut contenir un hétéroélément tel l'azote, l'oxygène ou le soufre. Ces groupements peuvent être substitués par des hétéroéléments ou des groupes contenant des hétéroéléments tels qu'un halogénure, un alcoxy. By "aromatic" is meant a mono- or polycyclic aromatic group substituted or not, preferably mono- or bicyclic substituted or unsubstituted, having a number of carbon atoms between 5 and 20. When the group is polycyclic, it is that is, it comprises more than one ring aromatic ring, the ring rings can advantageously be condensed two by two or attached in pairs by bonds σ. The aromatic group according to the invention may contain a heteroelement such as nitrogen, oxygen or sulfur. These groups may be substituted by heteroelements or groups containing heteroelements such as a halide, an alkoxy.
Description sommaire de l'invention La présente invention porte sur une composition comprenant : Brief Description of the Invention The present invention relates to a composition comprising:
- au moins un précurseur de chrome, at least one chromium precursor,
- au moins un ligand hétéroatomique décrit par la formule générale (I) at least one heteroatomic ligand described by the general formula (I)
(R1)2P-0-(CH2)n-N[P(R2)2]2 (R 1 ) 2 P-O- (CH 2 ) n -N [P (R 2 ) 2 ] 2
dans lequel les groupements R1 et R2, identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements alkyles cycliques ou non et les groupements aromatiques, et n est un entier supérieur ou égal à 1 , in which the groups R 1 and R 2 , which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
- et optionnellement, au moins un activateur. and optionally, at least one activator.
Avantageusement selon l'invention, le nombre entier n du fragment -(CH2)n- du ligand est compris entre 1 et 15. Avantageusement, le rapport molaire entre le ligand et le précurseur de chrome est compris entre 0,01 et 100. Advantageously according to the invention, the integer n of the fragment - (CH 2) n - of the ligand is between 1 and 15. Advantageously, the molar ratio between the ligand and the chromium precursor is between 0.01 and 100.
Avantageusement, le rapport molaire entre l'activateur et le précurseur de chrome est compris entre 1 et 10000.
De préférence, le précurseur de chrome est choisi parmi CrCI3, CrCI3(tétrahydrofurane)3,Cr(acétylacétonate)3, Cr(naphténate)3, Cr(2-éthylhexanoate)3, Cr(acétate)3. Advantageously, the molar ratio between the activator and the chromium precursor is between 1 and 10,000. Preferably, the chromium precursor is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
Avantageusement, les groupements R1 et R2 du ligand, identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi un groupement alkyle cyclique ou non, aromatique ou non, ayant de 1 à 15 atomes de carbone. Advantageously, the groups R 1 and R 2 of the ligand, which are identical or different from each other, whether or not they are linked together, are chosen from a cyclic or non-cyclic alkyl group, aromatic or otherwise, having from 1 to 15 carbon atoms.
De préférence, les groupements R1 et R2 identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements méthyle, trifluorométhyle, éthyle, n-propyle, i- propyle, n-butyle, i-butyle, t-butyle, pentyle, cyclopentyle, hexyle, cyclohexyle, adamantyle, substitués ou non, contenant ou non des hétéroéléments; les groupements phényle, o-tolyle, m-tolyle, p-tolyle, mésityle, 3,5-diméthylphényle, 4-n-butylephényle, 2-méthoxyphényle, 3- méthoxyphényle, 4-méthoxyphényle, 2-isopropoxyphényle, 4-méthoxy-3,5-diméthylphényle, 3,5-ditert-butyl-4-méthoxyphényle, 2-chlorophényle, 3-chlorophényle, 4-chlorophenyle, 2- fluorophényle, 3-fluorophényle, 4-fluorophényle, 4-trifluorométhylphényle, 3,5- di(trifluorométhyl)phényle, benzyle, naphthyle, bisnaphthyle, pyridyle, bisphényle, furanyle, thiophényle, substitués ou non, contenant ou non des hétéroéléments. Preferably, the groups R 1 and R 2 which are identical to or different from each other, linked or not to each other, are chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl groups, and -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, adamantyl, substituted or unsubstituted, whether or not containing heteroelements; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, 3,5-dimethylphenyl di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or unsubstituted, whether or not containing heteroelements.
Avantageusement, l'agent activateur est choisi parmi les composés tris(hydrocarbyl)aluminium, les composés chlorés ou bromés d'hydrocarbylaluminium, les halogénures d'aluminium, les aluminoxanes, les composés organoborés, les composés organiques susceptibles de donner un proton, pris seuls ou en mélange. Advantageously, the activating agent is chosen from tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminum compounds, aluminum halides, aluminoxanes, organoboron compounds, organic compounds capable of giving a proton, taken alone. or in mixture.
L'invention porte également sur le procédé de préparation de la composition selon l'invention comprenant la mise en contact The invention also relates to the process for preparing the composition according to the invention, comprising contacting
- d'au moins un précurseur de chrome, at least one chromium precursor,
- avec au moins un ligand hétéroatomique décrit par la formule générale (I) with at least one heteroatomic ligand described by the general formula (I)
(R1)2P-0-(CH2)n-N[P(R2)2]2 (R 1 ) 2 P-O- (CH 2 ) n -N [P (R 2 ) 2 ] 2
dans lequel les groupements R1 et R2, identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements alkyles cycliques ou non et les groupements aromatiques, et n est un entier supérieur ou égal à 1 , in which the groups R 1 and R 2 , which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
- et optionnellement, avec au moins un activateur.
Un autre aspect de l'invention concerne l'utilisation des compositions selon l'invention en tant que catalyseur. - and optionally, with at least one activator. Another aspect of the invention relates to the use of the compositions according to the invention as a catalyst.
De manière avantageuse, l'invention porte sur un procédé de tétramérisation de l'éthylène en octène-1 . Advantageously, the invention relates to a process for the tetramination of ethylene to octene-1.
Description détaillée de l'invention Detailed description of the invention
Compositions selon l'invention Compositions according to the invention
La présente invention porte sur une composition comprenant : The present invention relates to a composition comprising:
- au moins un précurseur de chrome, at least one chromium precursor,
- au moins un ligand hétéroatomique décrit par la formule générale (I) at least one heteroatomic ligand described by the general formula (I)
(R1)2P-0-(CH2)n-N[P(R2)2]2 (R 1 ) 2 P-O- (CH 2 ) n -N [P (R 2 ) 2 ] 2
dans lequel les groupements R1 et R2, identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements alkyles cycliques ou non et les groupements aromatiques, et n est un entier supérieur ou égal à 1 , in which the groups R 1 and R 2 , which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
- et optionnellement, au moins un activateur. Le précurseur de chrome and optionally, at least one activator. The precursor of chromium
Le précurseur de chrome selon l'invention peut être choisi parmi les composés de chrome utilisés dans les procédés d'oligomérisation des oléfines. The chromium precursor according to the invention may be chosen from chromium compounds used in olefin oligomerization processes.
Le précurseur de chrome présent dans la composition selon l'invention peut comporter un ou plusieurs anions identiques ou différents choisis dans le groupe formé par les halogénures, les carboxylates, les acétylacétonates, les anions alcoxy et aryloxy. Le composé du chrome peut être un sel de chrome(ll) ou de chrome(lll), mais aussi un sel de degré d'oxydation différent pouvant comporter un ou plusieurs anions identiques ou différents tels que par exemple des halogénures, des carboxylates, des acétylacétonates, des anions alcoxy ou aryloxy. Les précurseurs du chrome utilisés de préférence dans l'invention sont les composés du chrome(lll) car ils sont plus accessibles, mais un composé du chrome(l) ou du chrome(ll) peut aussi convenir. The chromium precursor present in the composition according to the invention may comprise one or more identical or different anions chosen from the group formed by halides, carboxylates, acetylacetonates, alkoxy and aryloxy anions. The chromium compound may be a chromium (II) or chromium (III) salt, but also a salt of different oxidation state that may comprise one or more identical or different anions such as, for example, halides, carboxylates, acetylacetonates, alkoxy or aryloxy anions. The chromium precursors preferably used in the invention are the chromium (III) compounds because they are more accessible, but a chromium (I) or chromium (II) compound may also be suitable.
De préférence selon l'invention, le précurseur de chrome est choisi parmi CrCI3, CrCI3(tétrahydrofurane)3,Cr(acétylacétonate)3, Cr(naphténate)3, Cr(2-éthylhexanoate)3, Cr(acétate)3.
Le liqand hétéroatomigue Preferably according to the invention, the chromium precursor is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 . The heteroatomic liqand
Le ligand de la composition catalytique selon l'invention est décrit par la formule générale (I) The ligand of the catalytic composition according to the invention is described by the general formula (I)
(R1)2P-0-(CH2)n-N[P(R2)2]2 dans lequel les groupements R1 et R2, identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements alkyles cycliques ou non et les groupements aromatiques, et n est un entier supérieur ou égal à 1 . (R 1 ) 2 P-O- (CH 2 ) n -N [P (R 2 ) 2 ] 2 in which the groups R 1 and R 2 , which are identical to or different from one another, linked or not to each other, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1.
Le nombre entier n du fragment -(CH2)n- du ligand selon l'invention est de préférence compris entre 1 et 15, de manière plus préférée entre 2 et 15, de manière encore plus préférée entre 2 et 10, et encore plus préférentiellement entre 3 et 6. Selon l'invention, les groupements R1 et R2 identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi un groupement alkyle cyclique ou non ayant de 1 à 15 atomes de carbone, de préférence de 1 à 10 atomes de carbone, ou un groupement aromatique ayant un nombre de carbones supérieur à 3, de préférence entre 4 et 24, de manière plus préférée entre 5 et 18. De préférence, les groupements R1 et R2 identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements méthyle, trifluorométhyle, éthyle, n-propyle, i- propyle, n-butyle, i-butyle, t-butyle, pentyle, cyclopentyle, hexyle, cyclohexyle, adamantyle, substitués ou non, contenant ou non des hétéroéléments; les groupements phényle, o-tolyle, m-tolyle, p-tolyle, mésityle, 3,5-diméthylphényle, 4-n-butylephényle, 2-méthoxyphényle, 3- méthoxyphényle, 4-méthoxyphényle, 2-isopropoxyphényle, 4-méthoxy-3,5-diméthylphényle, 3,5-ditert-butyl-4-méthoxyphényle, 2-chlorophényle, 3-chlorophényle, 4-chlorophenyle, 2- fluorophényle, 3-fluorophényle, 4-fluorophényle, 4-trifluorométhylphényle, 3,5- di(trifluorométhyl)phényle, benzyle, naphthyle, bisnaphthyle, pyridyle, bisphényle, furanyle, thiophényle, substitués ou non, contenant ou non des hétéroéléments. Dans une mise en œuvre particulière, les groupements R1 et R2 identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements méthyle, éthyle, i- propyle, n-butyle, i-butyle, t-butyle, cyclopentyle, cyclohexyle.
Dans une mise en œuvre particulière, les groupements R1 et R2 identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements phényle, o-tolyle, m- tolyle, p-tolyle, mésityle, 2-méthoxyphényle, 3-méthoxyphényle, 4-méthoxyphényle, 2- chlorophényle, 3-chlorophényle, 4-chlorophenyle, 2-fluorophényle, 3-fluorophényle, 4- fluorophényle. The integer number n of the - (CH 2 ) n - fragment of the ligand according to the invention is preferably between 1 and 15, more preferably between 2 and 15, even more preferably between 2 and 10, and even more preferably between 3 and 6. According to the invention, the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another, are chosen from a cyclic or non-cyclic alkyl group having from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms, or an aromatic group having a number of carbons greater than 3, preferably between 4 and 24, more preferably between 5 and 18. Preferably, the groups R 1 and R 2 identical or different. between them, linked or not with each other, are chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, adamantyl, substituted or unsubstituted, whether or not containing heteroelements; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, 3,5-dimethylphenyl di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl, substituted or unsubstituted, whether or not containing heteroelements. In a particular embodiment, the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another, are chosen from methyl, ethyl, i-propyl, n-butyl, i-butyl and t-butyl groups. , cyclopentyl, cyclohexyl. In a particular embodiment, the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another, are chosen from phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl and 2-methoxyphenyl groups. , 3-methoxyphenyl, 4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl.
L'agent activateur The activating agent
La composition selon l'invention peut inclure un agent activateur. L'agent activateur peut être choisi parmi les composés connus de l'homme du métier. Des mélanges d'agents activateurs peuvent également être utilisés. Avantageusement, les agents activateurs selon l'invention sont choisis parmi les composés tris(hydrocarbyl)aluminium, les composés chlorés ou bromés d'hydrocarbylaluminium, les halogénures d'aluminium, les aluminoxanes, les composés organoborés, les composés organiques susceptibles de donner un proton, pris seuls ou en mélange. The composition according to the invention may include an activating agent. The activating agent may be chosen from compounds known to those skilled in the art. Mixtures of activating agents may also be used. Advantageously, the activating agents according to the invention are chosen from tris (hydrocarbyl) aluminum compounds, chlorinated or brominated compounds of hydrocarbylaluminium, aluminum halides, aluminoxanes, organoboron compounds, organic compounds capable of giving a proton , taken alone or mixed.
Parmi les dérivés d'aluminium on peut citer les halogénures d'alkylaluminiums tels que le chlorure de diméthylaluminium, le chlorure de diéthylaluminium, le dichlorure d'éthylaluminium, le sesquichlorure de méthylaluminium, le sesquichlorure d'éthylaluminium, le dichlorure de méthylaluminium, le dichlorure d'isobutylaluminium, le trichlorure d'aluminium ; et les aluminoxanes, utilisés seuls ou en mélange. Among the aluminum derivatives mention may be made of alkylaluminium halides such as dimethylaluminum chloride, diethylaluminum chloride, ethylaluminium dichloride, methylaluminum sesquichloride, ethylaluminium sesquichloride, methylaluminum dichloride, dichloride, and the like. isobutylaluminum, aluminum trichloride; and aluminoxanes, used alone or as a mixture.
Les aluminoxanes sont bien connus par l'homme de l'art comme des composés oligomériques pouvant être préparés par l'addition contrôlée d'eau sur un alkylaluminium, par exemple le triméthylaluminium. De tels composés peuvent être linéaires, cycliques ou des mélanges de ces composés. Ils sont généralement représentés par la formule [RAIO]a où R est un groupement hydrocarboné et a est un nombre de 2 à 50. Préférentiellement, l'aluminoxane est choisi parmi le méthylaluminoxane (MAO) et/ou l'éthylaluminoxane (EAO) et/ou parmi les aluminoxanes modifiés tels que le méthylaluminoxane modifié (MMAO). Aluminoxanes are well known to those skilled in the art as oligomeric compounds that can be prepared by the controlled addition of water to an aluminum alkyl, for example trimethylaluminum. Such compounds can be linear, cyclic or mixtures of these compounds. They are generally represented by the formula [RAIO] a wherein R is a hydrocarbon group and a is a number from 2 to 50. Preferably, the aluminoxane is chosen from methylaluminoxane (MAO) and / or ethylaluminoxane (EAO) and or among modified aluminoxanes such as modified methylaluminoxane (MMAO).
Dans le cas où ledit agent activateur est choisi parmi les composés organoborés, ledit agent activateur est de préférence choisi parmi les acides de Lewis de type tris(aryl)borane tels que le tris(perfluorophényl)borane, le tris(3,5-bis(trifluorométhyl)phényl)borane, le tris(2,3,4,6-tétrafluorophényl)borane, le tris(perfluoronaphtyl)borane, le tris(perfluobiphényl)borane et leurs dérivés et les (aryl)borates associés à un cation triphénylcarbénium ou à un cation ammonium trisubstitué tels que le triphénylcarbenium
tétrakis(perfluorophényl)borate, le Ν,Ν-diméthylanilinium tétrakis(perfluorophényl)borate, le Ν,Ν-diéthylanilinium tétrakis(3,5-bis(trifluorométhyl)phényl)borate, le triphénylcarbenium tétrakis(3,5-bis(trifluorométhyl)phényl)borate. In the case where said activating agent is chosen from organoboron compounds, said activating agent is preferably chosen from Lewis acids of tris (aryl) borane type such as tris (perfluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, tris (2,3,4,6-tetrafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluobiphenyl) borane and their derivatives and (aryl) borates associated with a triphenylcarbenium cation or to a trisubstituted ammonium cation such as triphenylcarbenium tetrakis (perfluorophenyl) borate, Ν, Ν-dimethylanilinium tetrakis (perfluorophenyl) borate, Ν, Ν-diethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate.
Dans le cas où ledit agent activateur est choisi parmi les composés organiques susceptibles de donner un proton, ledit agent activateur est de préférence choisi parmi les acides de formule HY dans lequel Y représente un anion, tels que HBF4 ou F3CS03H. In the case where said activating agent is chosen from organic compounds capable of giving a proton, said activating agent is preferably chosen from the acids of formula HY in which Y represents an anion, such as HBF 4 or F 3 CS0 3 H.
Préparation des compositions selon l'invention Preparation of the compositions according to the invention
Un autre objet de l'invention porte sur le procédé de préparation des compositions selon l'invention. Les compositions selon l'invention sont de préférence préparées par la mise en contact Another subject of the invention relates to the process for preparing the compositions according to the invention. The compositions according to the invention are preferably prepared by placing in contact with each other.
- d'au moins un précurseur de chrome, at least one chromium precursor,
- avec au moins un ligand hétéroatomique décrit par la formule générale (I) with at least one heteroatomic ligand described by the general formula (I)
(R1)2P-0-(CH2)n-N[P(R2)2]2 (R 1 ) 2 P-O- (CH 2 ) n -N [P (R 2 ) 2 ] 2
dans lequel les groupements R1 et R2, identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements alkyles cycliques ou non et les groupements aromatiques, et n est un entier supérieur ou égal à 1 , in which the groups R 1 and R 2 , which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
- et optionnellement, avec au moins un activateur. - and optionally, with at least one activator.
Dans une mise en œuvre particulière, le rapport molaire entre le ligand et le précurseur de chrome est compris entre 0,01 et 100, et de préférence entre 0,5 et 5, en particulier de 0,8 et 3. In a particular embodiment, the molar ratio between the ligand and the chromium precursor is between 0.01 and 100, and preferably between 0.5 and 5, in particular 0.8 and 3.
Lorsque l'activateur est présent dans la composition, le rapport molaire entre l'activateur et le précurseur de chrome est compris entre 1 et 10000, de préférence entre 100 et 5000, de manière encore plus préférée entre 200 et 3500. When the activator is present in the composition, the molar ratio between the activator and the chromium precursor is between 1 and 10,000, preferably between 100 and 5000, even more preferably between 200 and 3500.
Lors du procédé de préparation, les composants de la composition peuvent être ajoutés simultanément ou séquentiellement, dans n'importe quel ordre. La composition selon l'invention peut être préparée in-situ en présence ou en l'absence de la charge, notamment de l'éthylène.
Les compositions selon l'invention peuvent être en présence ou non de solvant. On peut utiliser un solvant avantageusement choisi parmi les solvants capables de dissoudre les réactifs. On préfère pour ce faire utiliser des solvants organiques. On peut citer les solvants hydrocarbures aliphatiques saturés ou non tels que le pentane, l'hexane, le cyclohexane, le méthylecyclohexane, ou l'heptane, le cyclohexène, le cyclooctène ou le cyclooctadiène. On peut citer les solvants aromatiques tels que le benzène, le toluène ou les xylènes. On peut citer les solvants oxygénés tels que le diéthyléther ou le tétrahydrofurane, les solvants chlorés tels que le dichlorométhane ou le chlorobenzène. Ces solvants peuvent être utilisés seuls ou en mélange. La température à laquelle les composants de la composition selon l'invention sont mélangés est avantageusement comprise entre -40 et +150Ό, d e préférence entre 0 et +80Ό, par exemple à une température voisine de l'ambiante (15 à 30 Ό). Le mélange peut être effectué sous une atmosphère d'éthylène ou de gaz inerte. During the preparation process, the components of the composition may be added simultaneously or sequentially, in any order. The composition according to the invention may be prepared in situ in the presence or in the absence of the filler, in particular ethylene. The compositions according to the invention may be in the presence or absence of a solvent. It is possible to use a solvent advantageously chosen from solvents capable of dissolving the reagents. For this purpose it is preferred to use organic solvents. There may be mentioned saturated or unsaturated aliphatic hydrocarbon solvents such as pentane, hexane, cyclohexane, methylcyclohexane, or heptane, cyclohexene, cyclooctene or cyclooctadiene. Aromatic solvents such as benzene, toluene or xylenes may be mentioned. There may be mentioned oxygenated solvents such as diethyl ether or tetrahydrofuran, chlorinated solvents such as dichloromethane or chlorobenzene. These solvents can be used alone or as a mixture. The temperature at which the components of the composition according to the invention are mixed is advantageously between -40 and + 150 °, preferably between 0 and + 80 °, for example at a temperature close to room temperature (15 to 30 ° C.). The mixing can be carried out under an atmosphere of ethylene or inert gas.
Utilisation des compositions selon l'invention Un autre objet de l'invention concerne l'utilisation des compositions selon l'invention comme catalyseur. Another object of the invention relates to the use of the compositions according to the invention as a catalyst.
Les compositions selon l'invention peuvent être utilisées comme catalyseur dans une réaction de transformation chimique, en particulier, dans un procédé d'oligomerisation comprenant la mise en contact de ladite charge comprenant des oléfines ayant un nombre d'atomes de carbone compris entre 2 et 10 avec la composition selon l'invention, ledit procédé étant avantageusement opéré à une pression totale comprise entre la pression atmosphérique et 20 MPa et à une température comprise entre -40 et +250<C. The compositions according to the invention can be used as a catalyst in a chemical transformation reaction, in particular in an oligomerization process comprising contacting said feedstock comprising olefins having a number of carbon atoms of between 2 and 10 with the composition according to the invention, said method is advantageously operated at a total pressure of between atmospheric pressure and 20 MPa and at a temperature between -40 and 250 <C.
La composition selon l'invention est avantageusement mise en œuvre dans un procédé de tétramérisation d'oléfines, en particulier dans un procédé de tétramérisation d'éthylène en octène-1 . The composition according to the invention is advantageously used in an olefin tetramerization process, in particular in an ethylene tetramerisation process in octene-1.
Le solvant du procédé d'oligomérisation peut être choisi parmi les solvants organiques et de préférence parmi les éthers, les alcools, les solvants chlorés et les hydrocarbures saturés, insaturés, aromatiques ou non, cycliques ou non. En particulier, ledit solvant est choisi parmi l'hexane, le cyclohexane, le méthylecyclohexane, l'heptane, le butane ou l'isobutane, les monooléfines ou dioléfines comportant de préférence 4 à 20 atomes de carbone, le benzène, le toluène, l'ortho-xylène, le mésitylène, l'éthylbenzène, le dichlorométhane, le
chlorobenzène, le méthanol, l'ethanol, purs ou en mélange, et les liquides ioniques. Dans le cas où ledit solvant de réaction est un liquide ionique, il est avantageusement choisi parmi les liquides ioniques décrits dans les brevets US 6, 951 ,831 B2 et FR 2895406 B1 . The solvent of the oligomerization process may be chosen from organic solvents and preferably from ethers, alcohols, chlorinated solvents and saturated or unsaturated hydrocarbons, aromatic or otherwise, cyclic or otherwise. In particular, said solvent is chosen from hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, monoolefins or diolefins preferably comprising 4 to 20 carbon atoms, benzene, toluene, toluene or toluene. ortho-xylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, methanol, ethanol, pure or in mixture, and ionic liquids. In the case where said reaction solvent is an ionic liquid, it is advantageously chosen from the ionic liquids described in US Pat. Nos. 6,951,831 B2 and FR 2,895,406 B1.
L'oligomérisation est définie comme la transformation d'une unité monomère en un composé ou mélange de composés de formule générale CpH2p avec 4 < p < 80, de préférence avec 4 < p < 50, de manière préférée avec 4 < p < 26 et de manière plus préférée avec 4 < p < 14. Oligomerization is defined as the conversion of a monomer unit into a compound or mixture of compounds of the general formula C p H 2p with 4 <p <80, preferably with 4 <p <50, most preferably with 4 <p <26 and more preferably with 4 <p <14.
Les oléfines utilisées dans le procédé d'oligomérisation sont des oléfines comportant de 2 à 10 atomes de carbone. De préférence, lesdites oléfines sont choisies parmi l'éthylène, le propylène, les n-butènes et les n-pentènes, seules ou en mélange, pures ou diluées. Dans le cas où lesdites oléfines sont diluées, lesdites oléfines sont diluées par un ou plusieurs alcane(s), tels qu'on les trouve dans des « coupes » issues des procédés de raffinage du pétrole, comme le craquage catalytique ou le craquage à la vapeur. The olefins used in the oligomerization process are olefins having from 2 to 10 carbon atoms. Preferably, said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted. In the case where said olefins are diluted, said olefins are diluted with one or more alkane (s), as found in "cuts" from petroleum refining processes, such as catalytic cracking or cracking at the same time. steam.
De manière préférée, l'oléfine utilisée dans le procédé d'oligomérisation et en particulier dans le procédé de tétramérisation selon l'invention est l'éthylène. Lesdites oléfines peuvent venir de ressources non fossiles telles que la biomasse. Par exemple, les oléfines utilisées dans le procédé d'oligomérisation selon l'invention et en particulier dans le procédé de tétramérisation selon l'invention peuvent être produites à partir d'alcools, et en particulier par déshydratation des alcools. Preferably, the olefin used in the oligomerization process and in particular in the tetramerization process according to the invention is ethylene. Said olefins can come from non-fossil resources such as biomass. For example, the olefins used in the oligomerization process according to the invention and in particular in the tetramerization process according to the invention can be produced from alcohols, and in particular by dehydration of alcohols.
Le procédé d'oligomérisation, en particulier le procédé de tétramérisation selon l'invention opère avantageusement à une pression totale comprise entre la pression atmosphérique et 20 MPa, de préférence entre 0,1 et 8 MPa, et à une température comprise entre -40 et +250Ό, de préférence entre 0 et 150Ό, de préfé rence entre 20 et 135Ό, de préférence entre 45 et 100Ό, de préférence entre 75 et 100Ό, de préférence entre 80 et 100Ό. The oligomerization process, in particular the tetramerization process according to the invention, advantageously operates at a total pressure of between atmospheric pressure and 20 MPa, preferably between 0.1 and 8 MPa, and at a temperature of between -40 and + 250 °, preferably between 0 and 150 °, preferably between 20 and 135 °, preferably between 45 and 100 °, preferably between 75 and 100 °, preferably between 80 and 100 °.
La chaleur engendrée par la réaction peut être éliminée par tous les moyens connus de l'homme du métier. The heat generated by the reaction can be removed by any means known to those skilled in the art.
Le procédé d'oligomérisation, en particulier le procédé de tétramérisation selon l'invention, peut être conduit en système fermé, en système semi-ouvert ou en continu, avec un ou plusieurs étages de réaction. Une vigoureuse agitation est avantageusement mise en œuvre pour assurer un bon contact entre le ou les réactifs et le système catalytique.
Les produits du présent procédé peuvent trouver une application par exemple comme composants dans les plastiques et plus particulièrement le polyéthylène, de carburants pour automobiles, comme charges dans un procédé d'hydroformylation pour la synthèse d'aldéhydes et d'alcools, comme composants pour l'industrie chimique, pharmaceutique ou la parfumerie et/ou comme charges dans un procédé de métathèse pour la synthèse de propylène par exemple. The oligomerization process, in particular the tetramerization process according to the invention, can be carried out in a closed system, in a semi-open system or continuously, with one or more reaction stages. Vigorous agitation is advantageously used to ensure good contact between the reagent (s) and the catalytic system. The products of the present process can be used, for example, as components in plastics and more particularly polyethylene, motor fuels, as fillers in a hydroformylation process for the synthesis of aldehydes and alcohols, as components for chemical, pharmaceutical or perfume industry and / or as fillers in a metathesis process for the synthesis of propylene for example.
Les exemples suivants illustrent l'invention sans en limiter la portée. Exemples The following examples illustrate the invention without limiting its scope. Examples
Synthèse des liqands Lists synthesis
Liqand L1 Liqand L1
L1 L1
Dans un Schlenk de 100 mL, on introduit 30 mL de dichlorométhane (CH2CI2), 6 mL de triéthylamine (44,4 mmol) et 2,71 g (12,3 mmol) de Ph2PCI. A 0<C, on additionne 0,256 g (3,4 mmol) de 3-aminopropanol. On laisse agiter 2 h à température ambiante. On évapore le solvant. On extrait le produit au pentane, puis on évapore le pentane sous vide. On purifie le produit sur une colonne d'alumine avec un mélange de Dichlorométhane/Pentane dans un rapport 30/70 (volume/volume). On obtient 0,4g d'une huile blanchâtre très visqueuse, soit un rendement d'environ 19%. In a Schlenk of 100 ml, are introduced 30 ml of dichloromethane (CH 2 Cl 2 ), 6 ml of triethylamine (44.4 mmol) and 2.71 g (12.3 mmol) of Ph 2 PCI. A 0 <C, is added 0.256 g (3.4 mmol) of 3-aminopropanol. The mixture is stirred for 2 hours at room temperature. The solvent is evaporated. The product is extracted with pentane and then the pentane is evaporated under vacuum. The product is purified on a column of alumina with a mixture of dichloromethane / pentane in a ratio of 30/70 (volume / volume). 0.4 g of a highly viscous whitish oil is obtained, ie a yield of about 19%.
RMN 1 H (300,1 MHz, CD2CI2); 5(ppm): 7,55-7,12 (m, 30H); 3,48 (m, 2H); 3,41 (m, 2H); 1 ,55- 1 ,40 (m, 2H); RMN 31 P (121 ,5 MHz, CD2CI2); 5(ppm): 1 1 1 ,4; 63,4; RMN 13C (75,5MHz, CD2CI2); 5(ppm): 142,6; 140,0; 133,1 ; 130,4; 129,6; 129,2; 128,6; 128,5; 68,2; 50,7; 33,6. Liqand L2
1 H NMR (300.1 MHz, CD 2 Cl 2 ); (Ppm): 7.55-7.12 (m, 30H); 3.48 (m, 2H); 3.41 (m, 2H); 1.55-1.40 (m, 2H); 31 P NMR (121.5 MHz, CD 2 Cl 2 ); (Ppm): 1 1 1, 4; 63.4; 13 C NMR (75.5 MHz, CD 2 Cl 2 ); Δ (ppm): 142.6; 140.0; 133.1; 130.4; 129.6; 129.2; 128.6; 128.5; 68.2; 50.7; 33.6. Liqand L2
L2
Dans un Schlenk de 100 ml_, on introduit 60 ml_ de CH2CI2, 3,0 g (29,6 mmol) de triéthylamine et 4,37 g (19,8 mmol) Ph2PCI. A 0<C, on ajoute 0,54 g (6,0 mmol) de 4- aminobutanol. On laisse agiter une nuit à température ambiante. On filtre puis on évapore le solvant. On élimine la triéthylamine par co-évaporation avec du toluène. On purifie par recristallisation dans l'éthanol. On obtient environ 1 g d'huile très visqueuse, soit un rendement d'environ 26%. L2 In a 100 ml Schlenk, 60 ml of CH 2 Cl 2 , 3.0 g (29.6 mmol) of triethylamine and 4.37 g (19.8 mmol) Ph 2 ILC were added. A 0 <C was added 0.54 g (6.0 mmol) of 4-aminobutanol. It is left to stir overnight at room temperature. It is filtered and the solvent is evaporated. Triethylamine is removed by coevaporation with toluene. It is purified by recrystallization from ethanol. About 1 g of highly viscous oil is obtained, a yield of about 26%.
RMN 1 H (300,1 MHz, CD2CI2); 5(ppm): 7,55-7,27 (m, 30H); 3,54 (m, 2H); 3,31 (dt, 2H); 1 ,44- 1 ,27 (m, 2H); 1 ,27-1 ,13 (m, 2H); RMN 13C (75,5MHz, CD2CI2); 5(ppm): 142,8; 140,1 ; 133,1 ; 130,4; 129,5; 129,1 ; 128,6; 128,5; 70,0; 53,1 ; 29,1 ; 28,5; RMN 31 P (121 ,5 MHz, CD2CI2); 5(ppm): 1 10,4; 62,6. 1 H NMR (300.1 MHz, CD 2 Cl 2 ); (Ppm): 7.55-7.27 (m, 30H); 3.54 (m, 2H); 3.31 (dt, 2H); 1.44-1.27 (m, 2H); 1, 27-1, 13 (m, 2H); 13 C NMR (75.5 MHz, CD 2 Cl 2 ); Δ (ppm): 142.8; 140.1; 133.1; 130.4; 129.5; 129.1; 128.6; 128.5; 70.0; 53.1; 29.1; 28.5; 31 P NMR (121.5 MHz, CD 2 Cl 2 ); (Ppm): 1-10.4; 62.6.
Liqand L3 Liqand L3
L3 L3
Dans un Schlenk, on pèse 0,436 g (3,72 mmol) de 6-aminohexanol. On ajoute 6 ml_ de triéthylamine (44,45 mmol) et 30 ml_ de dichlorométhane (CH2CI2). A ΟΌ, on additionner goutte à goutte 1 ,81 g (8,20 mmol) de Ph2PCI. On laisse agiter 2 h à température ambiante. On filtre puis on évapore les produits volatiles. On extrait avec 6 fois 7 ml_ de pentane. On élimine le solvant sous vide. On obtient 1 ,2 g d'une huile jaunâtre très visqueuse, soit un rendement d'environ 66%. In a Schlenk, 0.436 g (3.72 mmol) of 6-aminohexanol is weighed. 6 ml of triethylamine (44.45 mmol) and 30 ml of dichloromethane (CH 2 Cl 2 ) are added. A ΟΌ, 1. 81 g (8.20 mmol) of Ph 2 PCI are added dropwise. The mixture is stirred for 2 hours at room temperature. The mixture is filtered and the volatile products are evaporated. Extracted with 6 times 7 ml of pentane. The solvent is removed under vacuum. 1.2 g of a very viscous yellowish oil are obtained, ie a yield of approximately 66%.
RMN 1 H (300,1 MHz, CD2CI2); 5(ppm): 7,53-7,22 (m, 30H); 3,71 (m, 2H); 3,23 (m, 2H); 1 ,44 (m, 2H); 1 ,06 (m, 4H); 0,91 (m, 2H). RMN 31 P (121 ,5 MHz, CD2CI2); 5(ppm): 1 10,6; 62,5; RMN 13C (75,5MHz, CD2CI2); 5(ppm): 143,0; 140,2; 133,1 ; 130,4; 129,5; 129,1 ; 128,7; 128,4; 70,4; 53,4; 31 ,7; 31 ,6; 26,7; 25,7. 1 H NMR (300.1 MHz, CD 2 Cl 2 ); (Ppm): 7.53-7.22 (m, 30H); 3.71 (m, 2H); 3.23 (m, 2H); 1.44 (m, 2H); 1, 06 (m, 4H); 0.91 (m, 2H). 31 P NMR (121.5 MHz, CD 2 Cl 2 ); (Ppm): 1, 10.6; 62.5; 13 C NMR (75.5 MHz, CD 2 Cl 2 ); (Ppm) 143.0; 140.2; 133.1; 130.4; 129.5; 129.1; 128.7; 128.4; 70.4; 53.4; 31, 7; 31, 6; 26.7; 25.7.
Tests catalvtiques Catalytic tests
Les ligands L1 , L2 et L3 sont évalués en présence de Cr(acac)3 (acac=acétylacétonate) pour la réaction de tétramérisation de l'éthylène. Le rapport molaire entre le ligand et le chrome est de 2. On utilise comme agent activateur le méthylaluminoxane (MAO) dans un rapport molaire MAO sur le précurseur Cr(acac)3 de 600. La réaction est opérée sous 4,5 MPa d'éthylène. Les ligands sont évaluées à trois températures différentes soit 45<C, 80Ό et 100<C.
Le ligand Ref ci-dessous est utilisé comme comparatif et évalué dans les mêmes conditions et L3. The L1, L2 and L3 ligands are evaluated in the presence of Cr (acac) 3 (acac = acetylacetonate) for the tetramerization reaction of ethylene. The molar ratio between the ligand and the chromium is 2. As an activating agent, methylaluminoxane (MAO) is used in a MAO molar ratio on the Cr (acac) 3 precursor of 600. The reaction is carried out under 4.5 MPa. ethylene. The ligands are evaluated at three different temperatures or 45 <C, 80Ό and 100 <C. The Ref ligand below is used as a comparative and evaluated under the same conditions and L3.
Conditions opératoires : un réacteur de 100 ml_ est mis sous pression d'éthylène. Le solvant de réaction est introduit dans le réacteur ainsi que le MAO (10% poids dans le toluène). Le réacteur est alors placé sous 0,5 MPa d'éthylène et agité pendant 5 minutes. Après dépressurisation, la solution formée par le précurseur de chrome Cr(acac)3 et le ligand est alors introduite dans le réacteur. Le réacteur est ensuite mis sous 2 MPa de pression d'éthylène et chauffé à la température de test. La pression est complétée à 4,5 MPa et l'agitation à 1000 tours/minute est démarrée. Le système est alors sous contrôle de pression.Operating conditions: a 100 ml reactor is pressurized with ethylene. The reaction solvent is introduced into the reactor as well as the MAO (10% by weight in toluene). The reactor is then placed under 0.5 MPa of ethylene and stirred for 5 minutes. After depressurization, the solution formed by the chromium precursor Cr (acac) 3 and the ligand is then introduced into the reactor. The reactor is then placed under 2 MPa of ethylene pressure and heated to the test temperature. The pressure is completed at 4.5 MPa and agitation at 1000 rpm is started. The system is under pressure control.
A la fin du test, l'alimentation en éthylène est coupée et le réacteur refroidi. Une fois le réacteur dégazé, la phase liquide et le polymère éventuellement formé sont récupérés et pesés. Le polymère est pesé après séchage à 100Ό p endant une nuit. La phase liquide est alors neutralisée par une solution d'acide sulfurique à 10% poids. L'analyse de la phase liquide est réalisée par chromatographie phase gaz avec un GC HP 685 équipé d'une colonne de marque PONA. At the end of the test, the ethylene feed is cut off and the reactor cooled. Once the reactor has degassed, the liquid phase and the optionally formed polymer are recovered and weighed. The polymer is weighed after drying at 100 ° for one night. The liquid phase is then neutralized with a sulfuric acid solution at 10% by weight. The analysis of the liquid phase is carried out by gas phase chromatography with an HP 685 GC equipped with a PONA brand column.
Les résultats des expériences sont indiqués dans le tableau ci-dessous. La consommation en éthylène décrite dans le tableau correspond à la quantité (en gramme) d'éthylène transformé au cours du test catalytique en produits de réaction. L'activité décrite en g/(gCr.h) dans le tableau correspond à la quantité d'éthylène (en gramme) transformée par un gramme de chrome issu de la composition catalytique rapportée sur une heure de réaction.The results of the experiments are shown in the table below. The ethylene consumption described in the table corresponds to the amount (in grams) of ethylene converted during the catalytic test into reaction products. The activity described in g / (g Cr. H) in the table corresponds to the amount of ethylene (in grams) converted by one gram of chromium from the catalytic composition reported over one hour of reaction.
La figure 1 représente l'évolution de la productivité en C8 en fonction de la température de réaction. La productivité C8 décrite dans la figure 1 correspond à la quantité d'octènes (en gramme) transformée par un gramme de chrome issu de la composition catalytique rapportée sur une heure de réaction. Elle est calculée en multipliant l'activité par le pourcentage de C8 qui est le pourcentage poids de C8 par rapport aux produits formés.
Temp. Tps Consommation Activité Figure 1 shows the evolution of the C8 productivity as a function of the reaction temperature. The productivity C8 described in FIG. 1 corresponds to the amount of octenes (in gram) transformed by one gram of chromium resulting from the catalytic composition reported over one hour of reaction. It is calculated by multiplying the activity by the percentage of C8 which is the weight percentage of C8 compared to the products formed. Temp. Tps Consumption Activity
Ligand (<C) (min) en C 2H4 (g) (g/(9cr- ) %C6 a %1 -C6 b %C8 a %1 -C8 C %a (mg)Ligand ( < C) (min) at C 2 H 4 (g) (g / (9cr-)% C 6 a % 1 -C 6 b % C 8 a % 1 -C 8 C % a (mg)
Ref* 45 8 21 ,5 621 21 ,2 76,0 62,6 98,8 1 ,0 210 Ref * 45 8 21, 5 621 21, 2 76.0 62.6 98.8 1, 0 210
Ref* 80 30 18,1 140 33,2 88,6 55,8 99,1 1 ,6 283 Ref * 80 30 18.1 140 33.2 88.6 55.8 99.1 1, 6 283
Ref* 100 30 16,2 125 46,1 93,9 39,6 98,9 3,7 569 Ref * 100 30 16.2 125 46.1 93.9 39.6 98.9 3.7 569
L1 45 8 17,3 494 14,7 31 ,5 42,3 93,7 14,0 2259 L1 45 8 17.3 494 14.7 31, 5 42.3 93.7 14.0 2259
L1 80 15 18,2 278 27,9 66,3 57,4 97,4 1 ,3 228 L1 80 15 18.2 278 27.9 66.3 57.4 97.4 1, 3 228
L1 100 30 16,6 127 38,6 84,3 44,3 97,9 4,0 628 L1 100 30 16.6 127 38.6 84.3 44.3 97.9 4.0 628
L2 45 15 21 ,1 321 16,7 35,6 50,0 94,4 8,3 1615 L2 45 15 21, 1,321 16.7 35.6 50.0 94.4 8.3 1615
L2 80 10 16,7 380 27,4 66,6 58,4 97,5 2,2 334 L2 80 10 16.7 380 27.4 66.6 58.4 97.5 2.2 334
L2 100 15 19,5 296 38,3 82,8 45,7 97,8 3,0 562 L2 100 15 19.5 296 38.3 82.8 45.7 97.8 3.0 562
L3 45 8 10,0 288 14,7 32,9 53,1 95,2 5,2 497 L3 45 8 10.0 288 14.7 32.9 53.1 95.2 5.2 497
L3 80 15 7,8 274 27,3 68,4 60,1 97,8 1 ,5 260 L3 80 15 7.8 274 27.3 68.4 60.1 97.8 1, 5 260
L3 100 30 19,9 153 36,0 83,5 43,8 97,9 7,8 1437L3 100 30 19.9 153 36.0 83.5 43.8 97.9 7.8 1437
Conditions de réaction: Cr(acac)3, nCr=5 μηιοΙ; Ligand/Cr=2, (MAO/Cr=600); Solvant =Cyclohexane (50 ml_), Pression = 4,5 MPa de C2H4.* = exemple comparatif. a % = pourcentage poids par rapport aux produits formés. b %1 -C6 : pourcentage d'hexène-1 dans la coupe C6. c %1 -C8 : pourcentage d'octène-1 dans la coupe C8. PE= Polyéthylène, Temp.= température, Tps = temps.
Reaction conditions: Cr (acac) 3 , n Cr = 5 μηιοΙ; Ligand / Cr = 2, (MAO / Cr = 600); Solvent = cyclohexane (50 ml), pressure = 4.5 MPa C 2 H 4 . * = comparative example. a % = percentage weight compared to the products formed. b % 1 -C 6 : percentage of hexene-1 in the C 6 section . c % 1 -C 8 : percentage of octene-1 in the C 8 section . PE = Polyethylene, Temp = temperature, Tps = time.
On observe que les compositions selon l'invention permettent d'augmenter de manière significative la proportion de C8 (%C8) par rapport aux autres produits formés lorsque la température est amenée de 45Ό à 80Ό. En particuli er à 80Ό, on peut noter que la productivité 08 observée avec les compositions (avec L1 , L2 et L3) selon l'invention est ainsi largement supérieure à celle observée avec la composition utilisée comme exemple comparatif (Ref).
It is observed that the compositions according to the invention make it possible to significantly increase the proportion of C8 (% C8) relative to the other products formed when the temperature is brought from 45Ό to 80Ό. In particular at 80 °, it can be noted that the productivity 08 observed with the compositions (with L1, L2 and L3) according to the invention is thus much greater than that observed with the composition used as a comparative example (Ref).
Claims
REVENDICATIONS
Composition comprenant : Composition comprising:
- au moins un précurseur de chrome, at least one chromium precursor,
- au moins un ligand hétéroatomique décrit par la formule générale (I) at least one heteroatomic ligand described by the general formula (I)
(R1)2P-0-(CH2)n-N[P(R2)2]2 dans lequel les groupements R1 et R2, identiques ou différents entre eux, liés ou non entre eux, sont choisis parmi les groupements alkyles cycliques ou non et les groupements aromatiques, et n est un entier supérieur ou égal à 1 . (R 1 ) 2 P-O- (CH 2 ) n -N [P (R 2 ) 2 ] 2 in which the groups R 1 and R 2 , which are identical to or different from one another, linked or not to each other, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1.
- et optionnellement, au moins un activateur. and optionally, at least one activator.
Composition selon la revendication 1 dans laquelle le nombre entier n du fragment -(CH2)n- du ligand est compris entre 1 et 15. The composition of claim 1 wherein the integer number n of the - (CH 2 ) n - ligand moiety is from 1 to 15.
Composition selon la revendication 1 ou 2 dans laquelle le rapport molaire entre le ligand et le précurseur de chrome est compris entre 0,01 et 100. The composition of claim 1 or 2 wherein the molar ratio of ligand to chromium precursor is from 0.01 to 100.
Composition selon l'une des revendications précédentes dans laquelle le rapport molaire entre l'activateur et le précurseur de chrome est compris entre 1 et 10000. Composition according to one of the preceding claims wherein the molar ratio between the activator and the chromium precursor is between 1 and 10,000.
Composition selon l'une des revendications précédentes dans laquelle le précurseur de chrome est choisi parmi CrCI3, CrCI3(tétrahydrofurane)3,Cr(acétylacétonate)3, Cr(naphténate)3, Cr(2-éthylhexanoate)3, Cr(acétate)3. Composition according to one of the preceding claims wherein the chromium precursor is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate ) 3 .
Composition selon l'une des revendications précédentes dans laquelle, l'agent activateur est choisi parmi les composés tris(hydrocarbyl)aluminium, les composés chlorés ou bromés d'hydrocarbylaluminium, les halogénures d'aluminium, les aluminoxanes, les composés organoborés, les composés organiques susceptibles de donner un proton, pris seuls ou en mélange.
Composition according to one of the preceding claims wherein the activating agent is chosen from tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminium compounds, aluminum halides, aluminoxanes, organoboron compounds, compounds organic substances capable of giving a proton, alone or as a mixture.
7. Procédé de préparation de la composition selon l'une des revendications précédentes comprenant la mise en contact 7. Process for preparing the composition according to one of the preceding claims comprising contacting
- d'au moins un précurseur de chrome, at least one chromium precursor,
- avec au moins un ligand hétéroatomique décrit par la formule générale (I) with at least one heteroatomic ligand described by the general formula (I)
(R1)2P-0-(CH2)n-N[P(R2)2]2 (R 1 ) 2 P-O- (CH 2 ) n -N [P (R 2 ) 2 ] 2
dans lequel les groupements R1 , R2 et n répondent à la définition selon l'une des revendications précédentes, in which the groups R 1 , R 2 and n satisfy the definition according to one of the preceding claims,
- et optionnellement, avec au moins un activateur répondant à la définition selon l'une des revendications précédentes. 8. Procédé de préparation selon la revendication 7 dans laquelle les composants de la composition sont mélangés à une température comprise entre -40 et +150<C. and optionally, with at least one activator corresponding to the definition according to one of the preceding claims. 8. Preparation process according to claim 7 wherein the components of the composition are mixed at a temperature between -40 and +150 < C.
9. Utilisation des compositions selon l'une des revendications 1 à 6 ou préparées selon la revendication 7 ou 8 en tant que catalyseur. 9. Use of the compositions according to one of claims 1 to 6 or prepared according to claim 7 or 8 as a catalyst.
10. Procédé d'oligomérisation d'une charge d'oléfines comprenant la mise en contact de ladite charge comprenant des oléfines ayant un nombre d'atomes de carbone compris entre 2 et 10 avec une composition selon l'une des revendications 1 à 6 ou préparée selon la revendication 7 ou 8, ledit procédé étant opéré à une pression totale comprise entre la pression atmosphérique et 20 MPa et à une température comprise entre -40 et +250<C. 1 1 . Procédé selon la revendication 10 dans lequel le procédé est un procédé de tétramérisation de l'éthylène en octène-1 .
A process for oligomerizing an olefin feedstock comprising contacting said feedstock comprising olefins having a carbon number of from 2 to 10 with a composition according to one of claims 1 to 6 or prepared according to claim 7 or 8, said process being operated at a total pressure between atmospheric pressure and 20 MPa and at a temperature between -40 and +250 < C. 1 1. The process of claim 10 wherein the process is a process for tetramilating ethylene to octene-1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1654932A FR3051683B1 (en) | 2016-05-31 | 2016-05-31 | CATALYTIC COMPOSITION BASED ON CHROME AND A LIGAND BASED ON PHOSPHINE AND ITS USE IN A PROCESS FOR PROCESSING OCTENS |
| PCT/EP2017/061884 WO2017207280A1 (en) | 2016-05-31 | 2017-05-17 | Catalytic composition comprising chromium and a phosphine-based ligand, and use thereof in an octene production method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3463653A1 true EP3463653A1 (en) | 2019-04-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17723148.7A Withdrawn EP3463653A1 (en) | 2016-05-31 | 2017-05-17 | Catalytic composition comprising chromium and a phosphine-based ligand, and use thereof in an octene production method |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US10646858B2 (en) |
| EP (1) | EP3463653A1 (en) |
| CN (1) | CN109195703B (en) |
| FR (1) | FR3051683B1 (en) |
| WO (1) | WO2017207280A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10303931B4 (en) | 2002-02-04 | 2013-04-18 | Institut Français du Pétrole | Catalytic composition for dimerization, co-dimerization, oligomerization and polymerization of olefins |
| BRPI0317510B1 (en) * | 2002-12-20 | 2020-01-07 | Sasol Technology ( Pty) Ltd | Olefin tetramerization process and catalyst system |
| FR2895406B1 (en) | 2005-12-22 | 2010-08-13 | Inst Francais Du Petrole | PROCESS FOR THE PRODUCTION OF 2,3-DIMETHYLBUT-1-ENE |
| CN100443178C (en) * | 2006-03-10 | 2008-12-17 | 中国石油天然气股份有限公司 | Catalyst composition for ethylene oligomerization and application thereof |
| KR101074202B1 (en) * | 2007-01-18 | 2011-10-14 | 에스케이종합화학 주식회사 | Ethylene tetramerization catalyst systems and method for preparing 1-octene using the same |
| CN103044181A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Method for preparing octene-1 by ethylene tetramerization reaction |
| US9499456B2 (en) | 2012-05-09 | 2016-11-22 | Sasol Technology (Proprietary) Limited | Tetramerisation of ethylene |
| SG11201407142WA (en) * | 2012-05-09 | 2014-11-27 | Sasol Tech Pty Ltd | Tetramerisation of ethylene |
| CN104511311B (en) * | 2013-09-30 | 2017-07-07 | 华东理工大学 | A kind of ethylene trimer of high selectivity, four poly- catalyst systems and its application method |
-
2016
- 2016-05-31 FR FR1654932A patent/FR3051683B1/en not_active Expired - Fee Related
-
2017
- 2017-05-17 WO PCT/EP2017/061884 patent/WO2017207280A1/en unknown
- 2017-05-17 EP EP17723148.7A patent/EP3463653A1/en not_active Withdrawn
- 2017-05-17 US US16/306,037 patent/US10646858B2/en not_active Expired - Fee Related
- 2017-05-17 CN CN201780033929.6A patent/CN109195703B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017207280A1 (en) | 2017-12-07 |
| CN109195703B (en) | 2022-06-24 |
| FR3051683B1 (en) | 2020-10-09 |
| US20190168202A1 (en) | 2019-06-06 |
| US10646858B2 (en) | 2020-05-12 |
| CN109195703A (en) | 2019-01-11 |
| FR3051683A1 (en) | 2017-12-01 |
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