JP7502289B2 - クロム補助エチレンオリゴマー化プロセスにおける1-ヘキセンの生成のための配位子 - Google Patents
クロム補助エチレンオリゴマー化プロセスにおける1-ヘキセンの生成のための配位子 Download PDFInfo
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- JP7502289B2 JP7502289B2 JP2021525666A JP2021525666A JP7502289B2 JP 7502289 B2 JP7502289 B2 JP 7502289B2 JP 2021525666 A JP2021525666 A JP 2021525666A JP 2021525666 A JP2021525666 A JP 2021525666A JP 7502289 B2 JP7502289 B2 JP 7502289B2
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- chromium
- catalyst composition
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- hexene
- activator
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims description 84
- 238000000034 method Methods 0.000 title claims description 45
- 230000008569 process Effects 0.000 title claims description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 34
- 239000005977 Ethylene Substances 0.000 title claims description 34
- 239000003446 ligand Substances 0.000 title claims description 34
- 238000006384 oligomerization reaction Methods 0.000 title claims description 20
- 239000011651 chromium Substances 0.000 title claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title description 6
- 229910052804 chromium Inorganic materials 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims description 77
- 239000000203 mixture Substances 0.000 claims description 65
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 30
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 26
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 239000012190 activator Substances 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 15
- -1 methylaluminoxane compound Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical compound [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 claims description 3
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 claims description 3
- 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 claims description 3
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 239000002198 insoluble material Substances 0.000 description 8
- 125000002015 acyclic group Chemical group 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000001845 chromium compounds Chemical class 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 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 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001343 alkyl silanes Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- SKJQSKHPVGVDMY-UHFFFAOYSA-N bis(chlorophosphino)amine Chemical compound ClPNPCl SKJQSKHPVGVDMY-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000004438 haloalkoxy group Chemical group 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003568 thioethers Chemical group 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- ZIHQUWYJSTVYAT-UHFFFAOYSA-N [NH-][N+]([O-])=O Chemical compound [NH-][N+]([O-])=O ZIHQUWYJSTVYAT-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 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
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LOFJKBAHPJENQS-UHFFFAOYSA-N tris(oxomethylidene)chromium Chemical compound O=C=[Cr](=C=O)=C=O LOFJKBAHPJENQS-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0264—Phosphorus acid amides
- B01J31/0265—Phosphazenes, oligomers thereof or the corresponding phosphazenium salts
-
- 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
-
- 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
- C07C2/34—Metal-hydrocarbon complexes
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- 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
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of chromium, molybdenum or tungsten
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
1)所望の生成物(例えば、1-ヘキセン)に対する低い選択率、
2)C6留分内のLAO異性体に対する低い選択率(例えば、異性化、分岐オレフィン形成など)、
3)ワックス形成(例えば、重くて長鎖の(炭素数の多い)生成物の形成)、
4)LAO製品の収率を大幅に低下させ、装置を汚染する(fouling)可能性のあるポリマーの形成(分岐状および/または架橋PEを含むポリエチレン)、
5)1kgの生成物当りのコストを増大させる、不良な回転率/触媒活性、
6)高い触媒または配位子コスト、
7)不良な触媒提供可能性および高い触媒コストをもたらす、複雑なマルチステップの配位子合成、
8)活性と選択性の両方の観点から、触媒性能が微量の不純物に影響を受けやすいこと(例えば、触媒のロスや被毒の発生につながる)、
9)技術的/商業的環境での触媒成分の取り扱いの難しさ(例えば、触媒複合体の合成、前混合、不活性化、触媒回収、または配位子回収の間)、
10)特殊な設備(投資、メンテナンス、エネルギーコストの増加)を必要とする過酷な反応条件(例えば、高温、高圧)、
11)高い助触媒/活性化剤コストまたは消費、および/または
12)大量の比較的不明確な化合物が活性化剤(例えば、特定のメチルアルミノキサン(MAO)品種)として使用される場合によくある、助触媒の品質の変動に影響を受けやすいこと。
いくつかの実施形態では、R1およびR2は、それぞれ独立に、シクロヘキシル基またはアルキル置換シクロヘキシル基であり、好ましくは両方ともシクロヘキシル基である。一例では、nは0であり、前記触媒は、(CH3)(n-C4H9)NP(C6H11)N(CH3)NP(C6H11)N(CH3)(n-C4H9)であり、次の構造で表される。
前記触媒組成物は、本発明の配位子、クロム(III)種、および活性化剤または助触媒を含み得る。本発明の配位子は、本明細書全体および実施例に記載されているように調製され得る。前記触媒組成物は、脂肪族炭化水素溶媒または芳香族炭化水素溶媒中の溶液として提供され得る。脂肪族炭化水素溶媒としては、ヘキサン、メチルシクロヘキサン、シクロヘキサン、n-ヘプタンなどを挙げることができる。
前記C5~C7脂肪族基とは、置換または非置換シクロアルキル基であり得、シクロペンチル、シクロヘキシル、シクロヘプチル、置換シクロペンチル、置換シクロヘキシル、および置換シクロへプチルを含む。前記C3~C4非環状脂肪族基は、イソプロピルおよびtert-ブチルであり得る。前記配位子は、(CH3)(n-C4H9)NP(R1)N(CH3)NP(R2)N(CH3)(n-C4H9)および(CH3CH2)(n-C5H11)NP(R1)N(CH3)NP(R2)N(CH2CH3)(n-C5H11)、(CH3)(n-C4H9)NP(C6H11)N(CH3)NP(C6H11)N(CH3)(n-C4H9)および(CH3CH2)(n-C5H11)NP(C6H11)N(CH3)NP(C6H11)N(CH2CH3)(n-C5H11)であり得る。前記配位子の構造は、以下で表すことができる:
本発明の触媒組成物は、エチレンを1-ヘキセンにオリゴマー化するためのプロセスにおいて使用され得る。一実施形態では、このプロセスは、1-ヘキセンを生成するのに効果的なエチレンのオリゴマー化条件下で、エチレンを前記触媒組成物と接触させるステップを含む。当業者は、1-ヘキセンを生成するためのエチレンのオリゴマー化は、エチレンの三量体化によって行うことができることを理解するであろう。
ルートA、一般的な手順(スキーム1を参照)。すべての操作を、不活性雰囲気下で行った。ビス(クロロホスフィノ)アミンC6H11P(Cl)N(CH3)P(Cl)C6H11(4.60g、14mmol)を20mLの無水トルエンに溶解した。適切な第2級アミン(29.4mmol)とNEt3(35mmol)を30mLの無水トルエンと混合し、-10℃まで冷却した。ビス(クロロホスフィノ)アミンのトルエン溶液を、不活性雰囲気下で激しく撹拌しながら反応混合物に滴下した。前記試薬を加えると、白いゲル状の物質が析出した。撹拌を続けながら、溶液を3時間かけて25℃まで昇温させた後、75℃まで昇温し、さらに12時間、その温度で撹拌した。真空下ですべての揮発性化合物を蒸発させた後、残渣を無水高温のn-ヘプタンに取り込み、不溶性物質をろ過によって分離した。溶媒を蒸発させると、淡黄色のオイルが得られた。生成物の純度は、1H、13C、および31P NMRを用いて確認した。必要に応じて、前記生成物をn-ヘキサン、シクロヘキサン、n-ヘプタン、またはn-ペンタンから再結晶して前記純度を高めることができる。
ディップチューブ、サーモウェル、メカニカルパドルスターラー、冷却コイル、温度・圧力・スターラー速度用制御ユニット(すべてデータ収集システムに接続)を備えた反応器を、4時間、真空下で130℃まで加熱することにより触媒試験(catalytic run)用に準備し、乾燥窒素気流で30℃まで排気して冷却した。データ収集システムに接続されたガス注入制御ユニットにより、等圧エチレンの供給が維持された。エチレンの消費量は、コンピュータ化されたデータ収集システムを用いて、供給シリンダー内の圧力損失によって経時的にモニターされた。
S12触媒は、上記の構造(2)として示されている(2つのメチルおよび2つのn-ブチル置換基を有する)配位子を含む。
Claims (19)
- 1-ヘキセンへのエチレンのオリゴマー化のための触媒組成物であって、
クロム(III)種と、
以下の式を有する配位子と、を含む、触媒組成物。
- R1およびR2が、それぞれシクロヘキシル基、またはアルキル置換シクロヘキシル基である、請求項1に記載の触媒組成物。
- nが、0であり、以下の構造を有する、請求項2に記載の触媒組成物。
- nが、1であり、以下の構造を有する、請求項2に記載の触媒組成物。
- 活性化剤をさらに含む、請求項1から4のいずれか1項に記載の触媒組成物。
- 前記活性化剤が、メチルアルミノキサン化合物である、請求項5に記載の触媒組成物。
- 前記活性化剤が、メチルイソブチルアルミニウムオキシド化合物である、請求項5に記載の触媒組成物。
- 前記クロム(III)種が、クロム(III)アセチルアセトナート、Cr(2,2,6,6,-テトラメチル-3,5-ヘプタジオナート)3、クロム(III)2-エチルヘキサノエート、塩化クロム(III)テトラヒドロフラン錯体(1:3)、クロム(III)オクタノエート、およびナフテン酸クロム(III)である、請求項1に記載の触媒組成物。
- エチレンから1-ヘキセンを生成するプロセスであって、1-ヘキセンを含む生成物ストリームを生成するために、オレフィン源を含む反応物ストリームを、請求項1から8のいずれか1項に記載の触媒組成物を含む溶液と接触させるステップを含む、プロセス。
- 前記溶液が、溶媒を含む、請求項9に記載のプロセス。
- 前記溶媒が、飽和炭化水素である、請求項10に記載のプロセス。
- 前記溶媒が、n-ヘキサン、メチルシクロヘキサン、またはそれらの混合物である、請求項11に記載のプロセス。
- 前記生成物ストリームが、1-オクテンをさらに含み、1-ヘキセン選択率が、99%超であり、1-ヘキセンに対する1-オクテンの重量比が、0.15未満である、請求項9から12のいずれか1項に記載のプロセス。
- 前記触媒組成物が、前記クロム(III)種、活性化剤、および
- 前記触媒組成物が、前記クロム(III)種、活性化剤、および
- 前記接触させるステップが、15℃~100℃の温度を含む、請求項9から11のいずれか1項に記載のプロセス。
- 前記接触させるステップが、少なくとも2MPaまたは2~20MPaの圧力を含む、請求項9から11のいずれか1項に記載のプロセス。
- 前記接触させるステップが、40℃~70℃の温度を含む、請求項16に記載のプロセス。
- 前記接触させるステップが、2~7MPaの圧力を含む、請求項17に記載のプロセス。
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