EP4076720A1 - Reacteur gaz/liquide d'oligomerisation comprenant des internes transversaux - Google Patents
Reacteur gaz/liquide d'oligomerisation comprenant des internes transversauxInfo
- Publication number
- EP4076720A1 EP4076720A1 EP20817034.0A EP20817034A EP4076720A1 EP 4076720 A1 EP4076720 A1 EP 4076720A1 EP 20817034 A EP20817034 A EP 20817034A EP 4076720 A1 EP4076720 A1 EP 4076720A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction chamber
- reactor
- gas
- liquid
- ethylene
- 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.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 87
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000005977 Ethylene Substances 0.000 claims abstract description 134
- 238000006243 chemical reaction Methods 0.000 claims abstract description 113
- 239000007791 liquid phase Substances 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 43
- 230000003197 catalytic effect Effects 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000004064 recycling Methods 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 18
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 90
- -1 nickel (II) carboxylates Chemical class 0.000 description 42
- 239000002904 solvent Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 12
- 239000011651 chromium Substances 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2,5-dimethylpyridine Chemical compound CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 4
- HJKGBRPNSJADMB-UHFFFAOYSA-N 3-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CN=C1 HJKGBRPNSJADMB-UHFFFAOYSA-N 0.000 description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 125000002496 methyl group Chemical group [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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 2
- IRYKBVQRUQDDKJ-UHFFFAOYSA-N 1-butylpyrrole 1-methylimidazole Chemical compound Cn1ccnc1.CCCCn1cccc1 IRYKBVQRUQDDKJ-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 description 2
- PJUOHDQXFNPPRF-UHFFFAOYSA-N 2,6-diphenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=N1 PJUOHDQXFNPPRF-UHFFFAOYSA-N 0.000 description 2
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical compound C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 description 2
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 2
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 description 2
- KLYTUKWIWXAUFO-UHFFFAOYSA-N 2-n,3-n-diphenylbutane-2,3-diimine Chemical compound C=1C=CC=CC=1N=C(C)C(C)=NC1=CC=CC=C1 KLYTUKWIWXAUFO-UHFFFAOYSA-N 0.000 description 2
- OAQWHMYUSBYPOV-UHFFFAOYSA-N 2-n,3-n-ditert-butylbutane-2,3-diimine Chemical compound CC(C)(C)N=C(C)C(C)=NC(C)(C)C OAQWHMYUSBYPOV-UHFFFAOYSA-N 0.000 description 2
- CELKOWQJPVJKIL-UHFFFAOYSA-N 3-fluoropyridine Chemical compound FC1=CC=CN=C1 CELKOWQJPVJKIL-UHFFFAOYSA-N 0.000 description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 2
- XQABVLBGNWBWIV-UHFFFAOYSA-N 4-methoxypyridine Chemical compound COC1=CC=NC=C1 XQABVLBGNWBWIV-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
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 125000004429 atom Chemical group 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
- 239000001273 butane Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- YRHYXWGIOLWSEI-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diimine Chemical compound CN=CC=NC YRHYXWGIOLWSEI-UHFFFAOYSA-N 0.000 description 2
- QAHVEIHCWHKZET-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diimine Chemical compound C=1C=CC=CC=1N=CC=NC1=CC=CC=C1 QAHVEIHCWHKZET-UHFFFAOYSA-N 0.000 description 2
- HACCVLBYBQLWMC-UHFFFAOYSA-N n,n'-ditert-butylethane-1,2-diimine Chemical compound CC(C)(C)N=CC=NC(C)(C)C HACCVLBYBQLWMC-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 238000005829 trimerization reaction Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- UAXNXOMKCGKNCI-UHFFFAOYSA-N 1-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 UAXNXOMKCGKNCI-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- OKAMTPRCXVGTND-UHFFFAOYSA-N 2-methoxyoxolane Chemical compound COC1CCCO1 OKAMTPRCXVGTND-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- UZEDIBTVIIJELN-UHFFFAOYSA-N chromium(2+) Chemical class [Cr+2] UZEDIBTVIIJELN-UHFFFAOYSA-N 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 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
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 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
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- ZJXKJXNVHCQBTO-UHFFFAOYSA-N n,n'-bis(2,6-dimethylphenyl)ethane-1,2-diimine Chemical compound CC1=CC=CC(C)=C1N=CC=NC1=C(C)C=CC=C1C ZJXKJXNVHCQBTO-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- VBLNFWKVZVKXPH-UHFFFAOYSA-L nickel(2+);2,2,2-trifluoroacetate Chemical compound [Ni+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F VBLNFWKVZVKXPH-UHFFFAOYSA-L 0.000 description 1
- KVRSDIJOUNNFMZ-UHFFFAOYSA-L nickel(2+);trifluoromethanesulfonate Chemical compound [Ni+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F KVRSDIJOUNNFMZ-UHFFFAOYSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 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
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
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- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/32—Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
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- 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
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- 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
- C07C2/10—Catalytic processes with metal oxides
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- 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
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- C07C2/24—Catalytic processes with metals
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- 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
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
- B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00761—Details of the reactor
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- B01J2219/00765—Baffles attached to the reactor wall
- B01J2219/00777—Baffles attached to the reactor wall horizontal
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/185—Details relating to the spatial orientation of the reactor vertical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/2402—Monolithic-type reactors
- B01J2219/2422—Mixing means, e.g. fins or baffles attached to the monolith or placed in the channel
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/2491—Other constructional details
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2491—Other constructional details
- B01J2219/2498—Additional structures inserted in the channels, e.g. plates, catalyst holding meshes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/322—Basic shape of the elements
- B01J2219/32203—Sheets
- B01J2219/32237—Sheets comprising apertures or perforations
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
Definitions
- the present invention relates to the field of gas / liquid reactors allowing the oligomerization of ethylene to linear olefins by homogeneous catalysis with a reaction chamber comprising transverse internals capable of slowing the rise of gaseous ethylene in said reactor.
- the invention also relates to the use of said gas / liquid reactor in a process for the oligomerization of ethylene into linear alpha-olefins, such as but-1-ene, hex-1-ene, or oct-. 1-ene or a mixture of linear alpha-olefins.
- linear alpha-olefins such as but-1-ene, hex-1-ene, or oct-. 1-ene or a mixture of linear alpha-olefins.
- the invention relates to the field of gas / liquid reactors also called bubble column, as well as their use in an ethylene oligomerization process.
- One drawback encountered when using such reactors in ethylene oligomerization processes is the management of the gas overhead, corresponding to the upper part of the reactor in the gaseous state.
- Said gas sky comprises gaseous compounds which are sparingly soluble in the liquid phase, compounds which are partially soluble in the liquid but inert, as well as gaseous ethylene not dissolved in said liquid.
- the passage of the gaseous ethylene from the lower liquid part of the reaction chamber to the gas overhead is a phenomenon called piercing.
- the gaseous sky is purged in order to remove said gaseous compounds.
- the Applicant has observed that in a reactor operating at a constant flow of injected gaseous ethylene, the quantity of dissolved ethylene and therefore the piercing rate depends on the dimensions of the reactors implementing the process and in particular the height of the liquid phase. In fact, the lower the height, the lower the time during which the gaseous ethylene travels through the liquid phase to dissolve and the higher the piercing rate.
- the Applicant has discovered that it is possible to improve the conversion of olefin (s), while retaining a high selectivity for the desired linear olefin (s), and in particular for alpha-olefin (s). , by limiting the drilling phenomena by means of a gas / liquid reactor making it possible to increase the residence time of the gaseous ethylene in the liquid phase by means of internals capable of slowing the rise of the gaseous ethylene.
- a reactor according to the present invention makes it possible to slow the rise of the gaseous ethylene, which has the effect of improving the dissolution of the gaseous ethylene and therefore of limiting the phenomenon of piercing for a given volume of liquid phase. .
- the invention also relates to a process for the oligomerization of olefins and in particular of ethylene using the reactor according to the invention comprising at least two transverse internals.
- the Applicant has developed a gas / liquid gaseous ethylene oligomerization reactor that can contain a liquid phase and a gaseous sky, said reactor comprising:
- said enclosure 1 comprises at least two transverse internals 11 arranged on at least part of a section of the enclosure (1) of said reactor so as to increase the residence time of gaseous ethylene in the liquid phase,
- each of said internal having at least one opening 12 of hydraulic diameter between 21 and 500 mm, and
- the transverse internals are arranged to increase the residence time of ethylene gas, by disrupting the rise of ethylene gas within the liquid phase.
- the transverse internals have at least one opening 12 with a hydraulic diameter of between 25 and 450 mm, preferably between 30 and 400 mm.
- the transverse internals have a plurality of openings with a hydraulic diameter of between 21 and 500 mm, preferably between 25 and 450 mm, preferably between 30 and 400 mm.
- said one opening or the sum of the openings occupies (s) between 25 and 75% of the total area of a cross section of the enclosure on which said internal is located, preferably between 40 and 70 %, preferably between 40 and 60% and more preferably between 45 and 55%.
- the transverse internals extend radially over the entire section of enclosure 1 of said reactor, so as to be able to slow the rise of gaseous ethylene in the liquid phase.
- the transverse internals are chosen from a perforated plate, a slotted plate such as a grid, valve plate, discs and crowns. In a preferred embodiment, the transverse internals extend radially over part of the section of the enclosure 1 of said reactor, so as to be able to slow the rise of the gaseous ethylene in the liquid phase.
- the transverse internals are chosen from flat, curved or pyramidal side plates, or any other internal capable of playing the role of baffle.
- said reactor comprises at least two transverse internals extending partially over part of the section of said enclosure, said internals being positioned alternately on the walls of enclosure 1.
- the enclosure comprises a number of transverse internals between 2 and 30, preferably between 2 and 20, preferably between 2 and 15.
- said reactor further comprises means for withdrawing a gaseous fraction at the level of the gas overhead of the reaction chamber and means for introducing said gaseous fraction withdrawn into the liquid phase in the lower part. of the reaction chamber.
- said reactor further comprises a recirculation loop comprising a withdrawal means on the lower part of the reaction chamber, preferably at the bottom, so as to withdraw a liquid fraction to one or more exchanger (s). ) thermal (s) capable of cooling said liquid fraction, and means for introducing said cooled fraction into the upper part of the reaction chamber.
- a recirculation loop comprising a withdrawal means on the lower part of the reaction chamber, preferably at the bottom, so as to withdraw a liquid fraction to one or more exchanger (s). ) thermal (s) capable of cooling said liquid fraction, and means for introducing said cooled fraction into the upper part of the reaction chamber.
- Another object of the present invention relates to a process for oligomerization of gaseous ethylene using the reactor according to any one of the preceding embodiments.
- the oligomerization process is carried out at a pressure between 0.1 and 10.0 MPa, at a temperature between 30 and 200 ° C comprising the following steps:
- oligomerization denotes any reaction of addition of a first olefin to a second olefin, identical or different from the first and includes dimerization, trimerization and tetramerization.
- the olefin thus obtained is of type C n H 2n where n is equal to or greater than 4.
- olefin denotes both an olefin and a mixture of olefins.
- alpha-olefin denotes an olefin, on which the double bond is located at the terminal position of the alkyl chain.
- heteroatom is an atom other than carbon and hydrogen.
- a heteroatom can be selected from oxygen, sulfur, nitrogen, phosphorus, silicon and halides such as fluorine, chlorine, bromine or iodine.
- hydrocarbon is an organic compound consisting exclusively of carbon (C) and hydrogen (H) atoms of the crude formula C m H p , with m and p natural integers.
- catalytic system denotes a mixture of at least one metal precursor, at least one activating agent, optionally at least one additive and optionally at least one solvent.
- alkyl is a hydrocarbon chain comprising between 1 and 20 carbon atoms, preferably from 2 to 15 carbon atoms and even more preferably from 2 to 8 carbon atoms, denoted CC 20 alkyl, saturated or not, linear or branched, non-cyclic, cyclic or polycyclic.
- CC 6 alkyl is meant an alkyl chosen from methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl and cyclohexyl groups.
- aryl is an aromatic group, mono or polycyclic, fused or not, comprising between 6 and 30 carbon atoms, denoted C 6 -C 3 o aryl.
- alkoxy is a monovalent radical consisting of an alkyl group bonded to an oxygen atom such as the C 4 H 9 0 group .
- aryloxy is a monovalent radical consisting of an aryl group bonded to an oxygen atom such as the C 6 H 5 O- group.
- lower part of the gas / liquid reactor enclosure refers to the lower half of the reactor and the reaction zone.
- upper part of the reaction chamber of the gas / liquid reactor refers to the upper half of the reactor or the reaction zone.
- withdrawal flow rate designates the mass of liquid withdrawn from the reactor per unit of time, it is expressed in tonnes per hour (t / h).
- non-condensable gas designates a species in the physical form of a gas which dissolves only partially in the liquid at the temperature and pressure conditions of the reaction chamber, and which can, under certain conditions, accumulate in the air. of the reactor (example here: ethane).
- liquid phase is understood to mean the mixture of all the compounds which are in a liquid physical state under the temperature and pressure conditions of the reaction chamber, said phase possibly comprising gaseous compounds such as gaseous ethylene under bubble shape.
- gaseous sky is understood to mean the upper part of the enclosure in the gaseous state located at the top of the reaction enclosure, that is to say directly above the liquid phase and consisting of a mixture of compounds which are found in the physical gas state when operating a reactor in an oligomerization process.
- lower lateral part of the reaction chamber is meant a part of the casing of the reaction chamber of the reactor located at the bottom and on the side.
- reactor or device denote all of the means allowing the implementation of the oligomerization process according to the invention, such as in particular the reaction chamber and the recirculation loop.
- bottom of the reaction chamber is understood to mean the lower quarter of the reaction chamber.
- the top of the reaction chamber is understood to mean the upper quarter of the reaction chamber.
- transverse we mean the surface, the interior or the section perpendicular to the vertical axis of the enclosure.
- solvent designates a liquid which has the property of dissolving, diluting or extracting other substances without chemically modifying them and without modifying itself.
- the expression "between ... and " should be understood as including the limits mentioned.
- chamber or "reaction chamber” denote the wall of the reactor in which the oligomerization reaction takes place.
- saturation rate is understood to mean the percentage of ethylene dissolved in the liquid phase relative to the maximum quantity of ethylene which could be dissolved in said liquid phase, defined by the thermodynamic equilibrium between the partial pressure of gaseous ethylene and said liquid phase. The degree of saturation can be measured by gas chromatography.
- updraft is meant the direction of the gaseous ethylene flowing through the liquid phase within the reactor.
- FIG. 1 illustrates a gas / liquid reactor according to the prior art.
- This device consists of a reaction chamber 1 comprising a lower part comprising a liquid phase, an upper part comprising a gas overhead, and a means for introducing gaseous ethylene 2 via a gas distributor 3 in the liquid phase.
- the upper part comprises a purge means 4.
- In the bottom of the reaction chamber 1 There is a pipe for drawing off a liquid fraction 5. Said fraction 5 is divided into two streams, a first main stream 7 sent to a heat exchanger 8 then introduced via a pipe 9 into the liquid phase and a second stream 6 corresponding to the effluent sent to a subsequent stage.
- Line 10 at the bottom of the reaction chamber allows the introduction of the catalytic system.
- Figure 2 illustrates a gas / liquid reactor, of bubble column type, according to a first embodiment of the invention, which differs from Figure 1 in that the reaction chamber comprises two transverse internals of the perforated tray type so to slow the rise of bubbles of ethylene gas.
- FIG. 3 shows a top view of a transverse internal 11 of the reactor according to FIG. 2, said internal is a plate of which each perforation 12 has a hydraulic diameter D2, and of which the diameter D1 corresponds to the internal diameter of the reaction chamber .
- FIG. 4 illustrates a gas / liquid reactor, of the bubble column type, according to a second embodiment of the invention, which differs from FIG. 1 in that the enclosure comprises four transverse internals of the baffle type arranged so as to slow the rise of ethylene gas bubbles.
- FIG. 5 illustrates a gas / liquid reactor, of the bubble column type, according to a third embodiment of the invention, which differs from that of FIG. 4 in that the transverse internals of the baffle type have different geometric shapes.
- Figure 6 shows a top view of a transverse internal which can act as a baffle, the diameter D1 of which corresponds to the internal diameter of the reactor enclosure and the diameter D2 corresponds to that of the opening.
- the invention relates to a gas / liquid reactor for gaseous ethylene oligomerization, preferably with an ascending current, which may contain a liquid phase and a gaseous sky, said reactor comprising:
- Said enclosure 1 comprises at least two transverse internals 11 arranged on at least part of a section of the enclosure (1) of said reactor so as to increase the residence time of gaseous ethylene in the liquid phase;
- Each of said internal having at least one opening 12 of hydraulic diameter between 21 and 500 mm;
- Said reactor may also include a means for introducing gaseous ethylene 2, 3, located in the lower part of the enclosure, more particularly in the bottom of the enclosure, implementing a means for injecting the gas. olefin within said liquid phase of the reaction chamber.
- Said reactor may also include a means for introducing the catalytic system 4, located in the lower part, more particularly in the bottom of the reaction chamber.
- the enclosure 1 has a height to width ratio (denoted H / L) of between 1 and 8, preferably between 2 and 7.
- the reaction enclosure is cylindrical in shape.
- the gas / liquid reactor comprises a means 4 for purging the gas overhead located at the top of the reactor.
- the gas / liquid reactor comprises a means for withdrawing a reaction effluent from the bottom of the enclosure, preferably the withdrawing means is located under the means for introducing gaseous ethylene.
- the gas / liquid reactor also comprises a pressure sensor, making it possible to maintain the pressure constant, within the reaction chamber.
- said pressure is kept constant by introducing additional olefin into the enclosure.
- the gas / liquid reactor also comprises a liquid level sensor, said level being able to be kept constant by modulating the flow rate of the effluent withdrawn in step c) described below, of the process implementing the reactor according to invention.
- the level sensor is located at the interphase between the liquid phase and the gaseous sky.
- the gas / liquid reactor comprises at least two transverse internals positioned on at least part of a section of the enclosure 1 of said reactor.
- Said transverse internals advantageously make it possible to increase the residence time of the gaseous ethylene, by disturbing the rise of the gaseous ethylene within the liquid phase, which has the effect of improving the dissolution of the gaseous ethylene and therefore to limit the phenomenon of drilling.
- the transverse internals have at least one opening 12 with a hydraulic diameter of between 21 and 500 mm, preferably between 25 and 450 mm, preferably between 30 and 400 mm.
- the transverse internals 11 have a plurality of openings with a hydraulic diameter of between 21 and 500 mm, preferably between 25 and 450 mm, preferably between 30 and 400 mm.
- said one opening 12 or the sum of the openings 12 occupies (s) between 20 and 80% of the total area of a cross section of the reaction chamber on which said interior is located, preferably between 25 and 75%, preferably between 40 and 70%, preferably between 40 and 60% and more preferably between 45 and 55%.
- said transverse internals 11 extend radially over the entire section of enclosure 1 of said reactor, so as to be able to slow the rise of gaseous ethylene in the liquid phase when said reactor is put into operation. artwork.
- said transverse internals 11 are preferably chosen from a perforated plate, a slotted plate such as a grid, valve plate, discs and rings.
- said opening 12 corresponds to the perforations, holes, slots or any other void made in said internal so as to allow the liquid phase and gaseous ethylene to pass.
- the transverse internals 11 extend radially over part of the section of the enclosure 1 of said reactor, so as to be able to slow the rise of gaseous ethylene in the liquid phase when said reactor is implemented.
- the transverse internals are positioned on the side walls of the reactor enclosure 1.
- the transverse internals 11 are chosen from flat, curved or pyramidal side plates, or any other internal capable of playing the role of baffle.
- said opening 12 with a hydraulic diameter of between 21 and 500 mm, corresponds to the space between one end of the transverse interior and the wall opposite the wall to which the interior is fixed.
- a connection is implemented by fixing the transverse internals, for example by welding, gluing, screwing, bolting, or any means similar.
- the fixing is implemented by welding.
- the enclosure comprises internal transverse 11 according to the first and the second embodiment.
- the enclosure comprises several, preferably at least two, transverse internals according to the second embodiment extending partially over a part of the section of said enclosure, said internals are positioned alternately on a wall of the enclosure. then on the other, as shown schematically in Figures 4 and 5.
- the enclosure comprises a number of transverse internals between 2 and 30, preferably between 2 and 20, more preferably between 2 and 15 and even more preferably the number of retarders is equal to 2, 3, 4, 5 , 6, 7, 8, 9, or 10.
- transverse internals are able to pass the reaction medium comprising the liquid phase containing gaseous ethylene and to slow the rise of said gaseous ethylene within the liquid phase contained in the reaction chamber.
- the transverse internals act as a retarder and increase the residence time of gaseous ethylene in the liquid phase and thus increase the dissolution of ethylene in said liquid phase.
- the transverse internals therefore make it possible to increase the saturation rate by limiting the phenomenon of drilling.
- the transverse internals are arranged at an equal distance from each other within the reaction chamber.
- the reaction chamber comprises a means for introducing gaseous ethylene 2 located in the lower part of said chamber, more particularly in the lower lateral part.
- the means for introducing ethylene is chosen from a pipe, a network of pipes, a multi-tube distributor, a perforated plate or any other means known to those skilled in the art.
- the means for introducing the ethylene is located in the recirculation loop.
- a gas distributor 3 which is a device for dispersing gaseous ethylene uniformly over the entire liquid section, is positioned at the end of the introduction means within the reaction chamber.
- Said device comprises a network of perforated pipes, the diameter of the orifices of which is between 1.0 and 12.0 mm, preferably between 3.0 and 10.0 mm, to form bubbles of ethylene in the liquid of size millimeter.
- the enclosure comprises a means for introducing the catalytic system 10.
- the introduction means is located on the lower part of the enclosure, and preferably at the bottom of said enclosure.
- the introduction of the catalytic system is carried out in the recirculation loop.
- the means for introducing the catalytic system is chosen from any means known to those skilled in the art and preferably is a pipe.
- said solvent is introduced by an introduction means located in the lower part of the enclosure, preferably in bottom of the enclosure or in the recirculation loop.
- the homogeneity of the liquid phase, as well as the regulation of the temperature within the enclosure of the reactor according to the invention can be achieved by the use of a recirculation loop comprising means on the lower part of the reactor. the enclosure, preferably at the bottom, to carry out the withdrawal of a liquid fraction to one or more heat exchanger (s) allowing the cooling of said liquid, and means for introducing said cooled liquid into the liquid phase in the upper part of the enclosure.
- a recirculation loop comprising means on the lower part of the reactor. the enclosure, preferably at the bottom, to carry out the withdrawal of a liquid fraction to one or more heat exchanger (s) allowing the cooling of said liquid, and means for introducing said cooled liquid into the liquid phase in the upper part of the enclosure.
- the recirculation loop allows good homogenization of the concentrations as well as temperature control in the liquid phase within the enclosure.
- the implementation of a recirculation loop makes it possible to induce a direction of circulation of the liquid phase in the chamber from the upper part to the lower part of said chamber, which makes it possible to increase the residence time of the chamber.
- ethylene gas by slowing its rise in said liquid phase and therefore further limiting the phenomenon of piercing.
- the recirculation loop can advantageously be implemented by any means necessary and known to those skilled in the art, such as a pump for withdrawing the liquid fraction, a means capable of regulating the flow rate of the withdrawn liquid fraction, or again a line for purging at least part of the liquid fraction.
- the means for withdrawing the liquid fraction from the enclosure is a pipe.
- the heat exchanger (s) capable of cooling the liquid fraction is (are) chosen from any means known to those skilled in the art.
- the gas / liquid oligomerization reactor according to the invention further comprises a loop for recycling the gas overhead in the lower part of the liquid phase.
- Said loop comprising means for withdrawing a gaseous fraction at the level of the gas overhead located in the upper part of the enclosure and means for introducing said gaseous fraction withdrawn into the liquid phase in the lower part of said enclosure.
- the recycle loop advantageously makes it possible to compensate for the phenomenon of piercing and to limit the loss of productivity of the reactor, by maintaining the saturation of ethylene dissolved in the liquid phase close to the desired value.
- the recycle loop further comprises a compressor.
- the introduction of the withdrawn gaseous fraction is carried out through the means of introducing gaseous ethylene.
- the introduction of the gas fraction withdrawn is carried out via a gas distributor which is a device allowing the gas fraction to be dispersed uniformly over the entire liquid section, and is positioned at the center. end of the means of introduction into the enclosure.
- Said device comprises a network of perforated pipes, the diameter of the orifices of which is between 1.0 and 12.0 mm, preferably between 3.0 and 10.0 mm, to form bubbles of ethylene in the liquid of size millimeter.
- the means for introducing the gaseous fraction withdrawn is chosen from a pipe, a network of pipes, a multitubular distributor, a perforated plate or any other means known to those skilled in the art.
- Another object of the present invention covers an oligomerization process implementing the gas / liquid reactor according to the invention as described above.
- the flow of gaseous ethylene introduced in step b), as described below is controlled by the pressure in the reaction chamber.
- the flow rate of gaseous ethylene introduced in step b), as described above decreases which leads to a decrease in the quantity of ethylene dissolved in the liquid phase, and therefore of the ethylene saturation. Said reduction is detrimental for the conversion of ethylene and is accompanied by a reduction in the productivity of the reactor, and possibly in its selectivity.
- the implementation of the reactor according to the invention in an oligomerization process, preferably by homogeneous catalysis, makes it possible to have a degree of saturation of ethylene dissolved in the liquid phase greater than 70.0%, preferably between 70%. , 0 and 100%, preferably between 80.0 and 100%, preferably between 80.0 and 99.0%, preferably between 85.0 and 99.0% and even more preferably between 89, 0 and 98.0%.
- the degree of saturation in dissolved ethylene can be measured by any method known to those skilled in the art and for example by gas chromatographic analysis (commonly called GC) of a fraction of the liquid phase withdrawn from the reaction chamber. .
- GC gas chromatographic analysis
- the process implementing the gas / liquid reactor according to the invention makes it possible to obtain linear olefins and particularly linear alpha-olefins by contacting olefin (s), in particular ethylene and a catalytic system, optionally in the presence of an additive and / or a solvent, and by the implementation of said gas / liquid reactor according to the invention.
- olefin s
- ethylene in particular ethylene
- a catalytic system optionally in the presence of an additive and / or a solvent
- the catalytic systems comprise, preferably consist of:
- a metal precursor preferably based on nickel, titanium or chromium
- the metal precursor used in the catalytic system is chosen from compounds based on nickel, titanium or chromium.
- the metal precursor is based on nickel and preferably comprises nickel of oxidation degree (+11).
- the nickel precursor is chosen from nickel (II) carboxylates such as, for example, nickel 2-ethylhexanoate, nickel (II) phenates, nickel (II) naphthenates, nickel acetate ( ll), nickel trifluoroacetate (ll), nickel triflate (ll), nickel acetylacetonate (ll), nickel hexafluoroacetylacetonate (ll), TT-allylnickel (ll) chloride, TT-allylnickel (ll), methallylnickel (ll) chloride dimer, h 3 - allylnickel (ll) hexafluorophosphate, r
- the metal precursor is based on titanium and preferably comprises an aryloxy or alkoxy compound of titanium.
- the titanium alkoxy compound advantageously corresponds to the general formula [Ti (OR) 4 ] in which R is a linear or branched alkyl radical.
- R is a linear or branched alkyl radical.
- preferred alkoxy radicals mention may be made, by way of nonlimiting example, of: tetraethoxy, tetraisopropoxy, tetra-n-butoxy and tetra-2-ethyl-hexyloxy.
- the titanium aryloxy compound advantageously corresponds to the general formula [Ti (OR ′) 4] in which R ′ is an aryl radical which may or may not be substituted by alkyl or aryl groups.
- R ′ radical may contain substituents based on a heteroatom.
- the preferred aryloxy radicals are chosen from phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy,
- the metal precursor is based on chromium and preferably comprises a chromium (II) salt, a chromium (III) salt, or a salt of different oxidation degree which may contain one or more identical anions. or different, such as for example halides, carboxylates, acetylacetonates, anions alkoxy or aryloxy.
- the chromium-based precursor is chosen from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
- the concentration of nickel, titanium or chromium is between 0.01 and 300.0 ppm by mass of atomic metal relative to the reaction mass, preferably between 0.02 and 100.0 ppm, preferably between 0, 03 and 50.0 ppm, more preferably between 0.5 and 20.0 ppm and even more preferably between 2.0 and 50.0 ppm by mass of atomic metal relative to the reaction mass.
- the catalytic system further comprises one or more activating agents chosen from aluminum-based compounds such as methylaluminum dichloride (MeAICI 2 ), dichloroethylaluminum (EtAICI 2 ), sesquichloride of ethylaluminum (Et 3 AI 2 CI 3 ), chlorodiethylaluminum (Et 2 AICI), chlorodiisobutylaluminum (i-Bu 2 AICI), triethylaluminum (AIEt 3 ), tripropylaluminum (Al (n- Pr) 3 ), triisobutylaluminum ( Al (i-Bu) 3 ), diethyl-ethoxyaluminum (Et 2 AIOEt), methylaluminoxane (MAO), ethylaluminoxane and modified methylaluminoxanes (MMAO).
- aluminum-based compounds such as methylaluminum dichloride (MeAICI 2 ), dichloroe
- the catalytic system comprises one or more additives.
- the additive is chosen from,
- - compounds of the nitrogen type such as trimethylamine, triethylamine, pyrrole, 2,5-dimethylpyridine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3 -methoxypyridine, 4-methoxypyridine,
- a and A ’ are independently oxygen or a single bond between the phosphorus atom and a carbon atom
- R 1a and R 1b groups are independently chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl groups, substituted or not, containing or not containing heteroelements; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylephenyl, 2-methylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4- methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl,
- the R 2 group is independently chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl, adamantyl, substituted or unsubstituted, containing heteroelements or not ; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylephenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis (trifluoromethyl) phenyl, benzyl, naphthy
- the additive is chosen from diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, dimethoxy- 2,2 propane, di (2-ethylhexyloxy) - 2,2 propane, 2,5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, dimethoxyethane, di (2-methoxyethyl) ether, benzofuran, glyme and diglyme taken alone or as a mixture.
- the additive is chosen from,
- - compounds of the nitrogen type such as trimethylamine, triethylamine, pyrrole, 2,5-dimethylpyridine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3 -methoxypyridine, 4-methoxypyridine,
- M is chosen from magnesium, calcium, strontium and barium, preferably magnesium,
- R 3 is an aryl radical containing from 6 to 30 carbon atoms
- X is a halogen or an alkyl radical containing from 1 to 20 carbon atoms
- n is an integer which can take the values of 0 or 1
- y is an integer between 1 and 10, preferably y is equal to 1, 2, 3 or 4.
- the aryloxy radical R s O is chosen from 4-phenylphenoxy, 2-phenylphenoxy, 2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 2, 3,5,6-tetraphenylphenoxy, 2-tert-butyl-6-phenylphenoxy, 2,4-ditertbutyl-6-phenylphenoxy, 2,6-diisopropylphenoxy, 2,6-dimethylphenoxy, 2,6-ditert-butylphenoxy, 4-methyl-2 , 6-ditert-butylphenoxy, 2,6-dichloro-4-tert-butylphenoxy and 2,6-dibromo-4-tert-butylphenoxy.
- the two aryloxy radicals can be carried by the same molecule, such as for example the biphenoxy radical, binaphthoxy or 1, 8-naphthalene-dioxy,
- the aryloxy radical R s O is 2,6-diphenylphenoxy, 2 -tert-butyl-6-phenylphenoxy or 2,4-ditert-butyl-6-phenylphenoxy.
- the catalytic system optionally comprises one or more solvents.
- the solvent is chosen from the group formed by aliphatic and cycloaliphatic hydrocarbons such as hexane, cyclohexane, heptane, butane or isobutane.
- the solvent used is cyclohexane.
- a solvent or a mixture of solvents can be used during the oligomerization reaction.
- Said solvent is advantageously chosen independently from the group formed by aliphatic and cycloaliphatic hydrocarbons such as hexane, cyclohexane, heptane, butane or isobutane.
- the linear alpha olefins obtained comprise from 4 to 20 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 4 to 10 carbon atoms, and preferably from 4 to 8 carbon atoms.
- the olefins are linear alpha-olefins, selected from but-1-ene, hex-1-ene or oct-1-ene.
- the oligomerization process is carried out at a pressure of between 0.1 and 10.0 MPa, preferably between 0.2 and 9.0 MPa and preferably between 0.3 and 8.0 MPa, at a temperature between 30 and 200 ° C, preferably between 35 and 150 ° C and preferably between 45 and 140 ° C.
- the catalyst concentration is between 0.01 and 500.0 ppm by mass of atomic metal relative to the reaction mass, preferably between 0.05 and 100.0 ppm, preferably between 0.1 and 50 0 ppm and preferably between 0.2 and 30.0 ppm by weight of atomic metal relative to the reaction weight.
- the oligomerization process is carried out continuously.
- the catalytic system formed as described above, is injected at the same time as the ethylene into a reactor stirred by conventional mechanical means known to those skilled in the art or by external recirculation, and maintained at the desired temperature.
- the components of the catalytic system can also be injected separately into the reaction medium.
- the gaseous ethylene is introduced through a pressure-controlled inlet valve, which maintains the latter constant in the reactor.
- the reaction mixture is withdrawn by means of a valve controlled by the liquid level so as to keep the latter constant.
- the catalyst is destroyed continuously by any usual means known to those skilled in the art, then the products resulting from the reaction as well as the solvent are separated, for example. by distillation. Ethylene which has not been converted can be recycled to the reactor.
- the catalyst residues included in a heavy fraction can be incinerated.
- the method implementing the gas / liquid reactor according to the invention comprises a step a) of introducing a catalytic system comprising a metal catalyst and an activating agent, and optionally a solvent or a mixture of solvents, in a reaction chamber comprising a liquid phase in a lower part and a gaseous sky in an upper part.
- the introduction of the catalytic system is carried out in the liquid phase in the lower part of the reaction chamber and preferably in the bottom of the reaction chamber.
- the pressure of introduction into the reaction chamber is between 0.1 and 10.0 MPa, preferably between 0.2 and 9.0 MPa and preferably between 0.3 and 8.0 MPa.
- the temperature of introduction into the reaction chamber is between 30 and 200 ° C, preferably between 35 and 150 ° C and more preferably between 45 and 140 ° C.
- Step b) contacting with gaseous ethylene
- the method implementing the gas / liquid reactor according to the invention comprises a step b) of bringing the catalytic system introduced in step a) into contact with gaseous ethylene.
- Said gaseous ethylene is introduced into the liquid phase at the lower part of the reaction chamber, preferably on the lower lateral part of the reaction chamber.
- the introduced gaseous ethylene comprises fresh gaseous ethylene, and preferably said fresh gaseous ethylene is combined with recycled gaseous ethylene in a separation step subsequent to the oligomerization process.
- the liquid phase comprises undissolved gaseous ethylene, thus depending on the zones of the reaction chamber, the liquid phase liquid phase corresponds to a gas-liquid mixture between in particular the liquid phase and gaseous ethylene.
- the area in the bottom of the reaction chamber below the level of introduction of the gaseous ethylene comprises, preferably consists of the liquid phase without gaseous ethylene.
- the gaseous ethylene is distributed by dispersion during its introduction into the lower liquid phase of the reaction chamber by means suitable for producing said uniformly dispersed over the entire section of the reactor.
- the dispersion means is chosen from a distribution network with a homogeneous distribution of the ethylene injection points over the entire section of the reactor.
- the speed of the gaseous ethylene leaving the orifices is between 1.0 and 30.0 m / s. Its surface speed (volume speed of gas divided by the section of the reaction chamber) is between 0.5 and 10.0 cm / s and preferably between 1.0 and 8.0 cm / s.
- the gaseous ethylene is introduced at a flow rate of between 1 and 250 t / h, preferably between 3 and 200 t / h, preferably between 5 and 150 t / h and preferably between 10 and 100 t / h .
- the flow of gaseous ethylene introduced in step b) is controlled by the pressure in the reaction chamber.
- a flow of gaseous hydrogen can also be introduced into the reaction chamber, with a flow rate representing 0.2 to 1.0% by mass of the incoming ethylene flow rate.
- the flow of gaseous hydrogen is introduced through the pipe used for the introduction of the gaseous ethylene.
- the method implementing the gas / liquid reactor according to the invention comprises a step c) of withdrawing a fraction of the liquid phase, preferably in the lower part of the reaction chamber.
- the withdrawal carried out in step c) is preferably carried out in the lower part of the reaction chamber, preferably below the level of the injection of gaseous ethylene, and preferably in the bottom of the. pregnant.
- the withdrawal is implemented by any means suitable for carrying out the withdrawal and preferably by a pump.
- the withdrawal rate is between 500 and 10,000 t / h, and preferably between 800 and 7,000 t / h.
- a second stream is withdrawn from the liquid phase.
- Said second stream corresponds to the effluent obtained at the end of the oligomerization process and can be sent to a separation section located downstream of the device used in the process according to the invention.
- the liquid fraction withdrawn from the liquid phase is divided into two streams. The first so-called main stream is sent to cooling step d), and the second stream corresponds to the effluent and is sent to the downstream separation section.
- the flow rate of said second stream is regulated to maintain a constant liquid level in the reactor.
- the flow rate of said second stream is 5 to 200 times lower than the liquid flow rate sent to the cooling step.
- the flow rate of said effluent is 5 to 150 times lower, preferably 10 to 120 times lower and preferably 20 to 100 times lower.
- the method implementing the gas / liquid reactor according to the invention comprises a step d) of cooling the liquid fraction withdrawn in step c).
- the cooling step is carried out by circulating the main liquid stream withdrawn in step c), through one or more heat exchangers located inside or outside the reaction chamber and preferably outdoors.
- the heat exchanger makes it possible to decrease the temperature of the liquid fraction from 1.0 to 30.0 ° C, preferably between 2.0 and 20 ° C, preferably between 2.0 and 15.0 ° C, preferably between 2.5 and 10.0 ° C, preferably 3.0 to 9.0 ° C, preferably 4.0 to 8.0 ° C.
- the cooling of the liquid fraction makes it possible to maintain the temperature of the reaction medium within the desired temperature ranges.
- the implementation of the liquid cooling step, via the recirculation loop also makes it possible to perform the stirring of the reaction medium, and thus to homogenize the concentrations of the reactive species throughout the volume. liquid from the reaction chamber.
- the method implementing the gas / liquid reactor according to the invention comprises a step e) of introducing the cooled liquid fraction in step d).
- the introduction of the cooled liquid fraction resulting from step d) is carried out in the liquid phase of the reaction chamber, preferably in the upper part of said chamber, by any means known to those skilled in the art.
- a direction of circulation of said liquid phase is induced from the top to the bottom of said chamber, which slows the rise of ethylene. gas in the liquid phase and therefore improves dissolution of ethylene in the liquid phase.
- the rate of introduction of the cooled liquid fraction is between 500 and 10,000 t / h, and preferably between 800 and 7,000 t / h.
- Steps c) to e) constitute a recirculation loop.
- the recirculation loop makes it possible to stir the reaction medium, and thus to homogenize the concentrations of the reactive species throughout the liquid volume of the reaction chamber.
- the method implementing the gas / liquid reactor according to the invention comprises a step f) of recycling a gas fraction withdrawn from the gas overhead of the reaction chamber and introduced at the lower part of the reaction chamber. in the liquid phase, preferably on the lower lateral part of the reaction chamber, preferably at the bottom of the reaction chamber.
- the optional step f) for recycling the gas fraction is also called the recycling loop.
- the withdrawal of the gas fraction implemented in step f) is carried out by any means suitable for carrying out the withdrawal and preferably by a compressor.
- An advantage of the optional recycling step f) is to make it possible to compensate in a simple and economical manner the phenomenon of piercing of gaseous ethylene in the gas overhead in an oligomerization process whatever the dimensions of the reactor according to the invention.
- the piercing phenomenon corresponds to the gaseous ethylene which passes through the liquid phase without dissolving and which passes into the gas sky.
- the piercing then causes an increase in pressure in the reaction chamber.
- the rate of introduction of ethylene in step b) is controlled by the pressure in the reaction chamber.
- the decrease in saturation is detrimental for the conversion of ethylene and is accompanied by a decrease in the productivity of the reactor.
- the optional step of recycling a gaseous fraction advantageously makes it possible to optimize the saturation of the dissolved ethylene and therefore to improve the volume productivity of the process.
- the gas fraction withdrawn in step f) can be introduced into the reaction chamber alone or as a mixture with the gaseous ethylene introduced in step b).
- the gaseous fraction is introduced as a mixture with the gaseous ethylene introduced in step b).
- the gaseous fraction withdrawn in step f) is introduced into the reaction chamber by dispersion in the lower liquid phase of the reaction chamber by means capable of producing said dispersion uniformly over the whole of the reaction chamber.
- the dispersion means is chosen from a distribution network with a homogeneous distribution of the injection points of the gas fraction withdrawn in step f) over the entire section of the reactor.
- the speed of the gas fraction withdrawn at the outlet of the orifices is between 1.0 and 30.0 m / s. Its surface speed (volume speed of gas divided by the section of the reaction chamber) is between 0.5 and 10.0 cm / s and preferably between 1.0 and 8.0 cm / s.
- the fraction withdrawing flow rate is between 0.1 and 100% of the flow rate of gaseous ethylene introduced in step b), preferably 0.5 and 90.0%, preferably 1.0 and 80.0%, preferably between 2.0 and 70.0%, preferably between 4.0 and 60.0%, preferably between 5.0 and 50.0%, preferably between 10.0 and 40, 0% and preferably between 15.0 and 30.0%.
- the flow rate for withdrawing the gaseous fraction in step f) is controlled by the pressure within the reaction chamber, which makes it possible to maintain the pressure at a desired value or range and therefore to compensate for the phenomenon of piercing ethylene gas in the air.
- the gas fraction withdrawn in step f) is divided into two streams, a first so-called main gas stream is recycled directly into the reaction chamber, and a second gas stream.
- said second gas flow corresponds to a purge of the gas overhead, which makes it possible to eliminate part of the non-condensable gases.
- the flow rate of the second gas stream is between 0.005 and 1.00% of the ethylene flow rate introduced in step b), preferably between 0.01 and 0.50%.
- Example 1 illustrates the reference case corresponding to Figure 1, in which the oligomerization process uses a gas-liquid reactor, according to the prior art.
- a gas / liquid oligomerization reactor according to the prior art comprising a reaction chamber of cylindrical shape having a diameter of 1.8 m and a liquid height of 6 m, is implemented at a pressure of 7.0 MPa. and at a temperature of 120 ° C.
- the catalytic system introduced into the reaction chamber is a chromium-based catalytic system, as described in patent FR3019064, in the presence of cyclohexane as solvent.
- Said catalytic system is contacted with ethylene by introducing said gaseous ethylene into the lower part of said enclosure.
- the effluent is then recovered at the bottom of the reactor.
- the volume productivity of this reactor is 17 kg of alpha-olefin produced per hour and per m 3 of reaction volume.
- This reactor makes it possible to convert 77.4% of the ethylene injected, for a saturation rate of dissolved in the liquid phase of 61.0% and to achieve a selectivity of 83.1% for hexene-1, for a mass content of solvent of 1.6.
- Said solvent level is calculated as the mass ratio of the flow rate of solvent injected over the flow rate of gaseous ethylene injected.
- a reactor according to the invention having two perforated trays as transverse internal ones is implemented under the same conditions as Example 1.
- Each of the perforated trays having the following characteristics - plurality of openings 11 of hydraulic diameter 0.44 meters,
- the volume productivity of this reactor is 38.3 kg of alpha-olefin produced per hour and per m 3 of reaction volume.
- This reactor makes it possible to convert 57.8% of the ethylene injected, for a saturation rate of ethylene dissolved in the liquid phase of 89.0% and to achieve a selectivity of 87.5% in alpha. desired olefin, for a solvent mass content of 1.6.
- Said solvent level is calculated as the mass ratio of the flow rate of solvent injected over the flow rate of gaseous ethylene injected.
- the reactor according to the invention makes it possible to increase the saturation of ethylene by 28%, to increase the selectivity for alpha-olefin by 4.3% and to multiply the productivity by 2.25, relative to in the case according to the prior art of Example 1.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1914760A FR3105018B1 (fr) | 2019-12-18 | 2019-12-18 | Reacteur gaz/liquide d’oligomerisation comprenant des internes transversaux |
PCT/EP2020/085018 WO2021122139A1 (fr) | 2019-12-18 | 2020-12-08 | Reacteur gaz/liquide d'oligomerisation comprenant des internes transversaux |
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EP4076720A1 true EP4076720A1 (fr) | 2022-10-26 |
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EP20817034.0A Pending EP4076720A1 (fr) | 2019-12-18 | 2020-12-08 | Reacteur gaz/liquide d'oligomerisation comprenant des internes transversaux |
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Country | Link |
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US (1) | US20230042372A1 (fr) |
EP (1) | EP4076720A1 (fr) |
KR (1) | KR20220110766A (fr) |
CN (1) | CN114761114A (fr) |
CA (1) | CA3158098A1 (fr) |
FR (1) | FR3105018B1 (fr) |
WO (1) | WO2021122139A1 (fr) |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4242531A (en) * | 1978-08-14 | 1980-12-30 | Phillips Petroleum Company | Olefin dimerization |
US4456504A (en) * | 1980-04-30 | 1984-06-26 | Chevron Research Company | Reactor vessel and process for thermally treating a granular solid |
FR2552079B1 (fr) | 1983-09-20 | 1986-10-03 | Inst Francais Du Petrole | Procede ameliore de synthese du butene-1 par dimerisation de l'ethylene |
DE4338414C1 (de) * | 1993-11-10 | 1995-03-16 | Linde Ag | Verfahren zur Herstellung linearer Olefine |
US6029956A (en) * | 1998-02-06 | 2000-02-29 | Foster Wheeler Usa Corporation | Predominantly liquid filled vapor-liquid chemical reactor |
DE602005019239D1 (de) * | 2005-10-20 | 2010-03-25 | Linde Ag | Verfahren zur Oligomerisierung von Ethylen und Reaktorsystem dafür mit Kühlvorrichtung |
FR2984311B1 (fr) | 2011-12-20 | 2015-01-30 | IFP Energies Nouvelles | Procede de production d'octenes mettant en oeuvre la dimerisation de l'ethylene en butenes et la dimerisation des butenes en octenes |
SG11201407233RA (en) * | 2012-05-11 | 2014-12-30 | Saudi Arabian Oil Co | Ethylene oligomerization process |
US9340802B2 (en) * | 2013-06-20 | 2016-05-17 | Lanzatech New Zealand Limited | Fermentation of gaseous substrates |
FR3019064B1 (fr) | 2014-03-25 | 2020-02-28 | IFP Energies Nouvelles | Nouvelle composition catalytique et procede pour l'oligomerisation de l'ethylene en hexene-1 |
FR3023183A1 (fr) | 2014-07-04 | 2016-01-08 | IFP Energies Nouvelles | Composition catalytique et procede de dimerisation selective de l'ethylene en butene-1 |
DE102014112792A1 (de) * | 2014-09-05 | 2016-03-10 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Verfahren und Anlage zur Herstellung von Olefinen aus Oxygenaten |
US10513473B2 (en) * | 2015-09-18 | 2019-12-24 | Chevron Phillips Chemical Company Lp | Ethylene oligomerization/trimerization/tetramerization reactor |
FR3042989A1 (fr) | 2015-10-30 | 2017-05-05 | Ifp Energies Now | Nouvelle composition catalytique a base de nickel en presence d'un activateur specifique et son utilisation dans un procede d'oligomerisation des olefines |
FR3045414B1 (fr) | 2015-12-18 | 2019-12-27 | IFP Energies Nouvelles | Nouvelle composition catalytique a base de nickel et de ligand de type phosphine et d'une base de lewis et son utilisation dans un procede d'oligomerisation des olefines |
EP3562584B1 (fr) * | 2016-12-30 | 2021-04-07 | SABIC Global Technologies B.V. | Procédé de préparation d'une solution de catalyseur pour la production sélective de 1-hexène |
FR3068620B1 (fr) * | 2017-07-10 | 2020-06-26 | IFP Energies Nouvelles | Procede d’oligomerisation mettant en oeuvre un dispositf reactionnel comprenant un moyen de dispersion |
FR3068621B1 (fr) | 2017-07-10 | 2020-06-26 | IFP Energies Nouvelles | Procede d’oligomerisation mettant en oeuvre un vortex |
US10486131B2 (en) * | 2017-10-26 | 2019-11-26 | Chevron U.S.A. Inc. | Integrated reactor system for ionic liquid-catalyzed hydrocarbon conversion |
CN209237914U (zh) * | 2018-10-31 | 2019-08-13 | 西北民族大学 | 一种用于生物质热解催化加氢制备烯烃的反应器 |
CN109821495B (zh) * | 2019-03-01 | 2021-02-09 | 清华大学 | 烃制乙烯和/或乙炔的多级反应装置及制备方法 |
-
2019
- 2019-12-18 FR FR1914760A patent/FR3105018B1/fr active Active
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2020
- 2020-12-08 CA CA3158098A patent/CA3158098A1/fr active Pending
- 2020-12-08 WO PCT/EP2020/085018 patent/WO2021122139A1/fr unknown
- 2020-12-08 EP EP20817034.0A patent/EP4076720A1/fr active Pending
- 2020-12-08 CN CN202080087679.6A patent/CN114761114A/zh active Pending
- 2020-12-08 KR KR1020227020619A patent/KR20220110766A/ko active Search and Examination
- 2020-12-08 US US17/785,525 patent/US20230042372A1/en active Pending
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Publication number | Publication date |
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FR3105018A1 (fr) | 2021-06-25 |
CN114761114A (zh) | 2022-07-15 |
FR3105018B1 (fr) | 2021-12-10 |
CA3158098A1 (fr) | 2021-06-24 |
KR20220110766A (ko) | 2022-08-09 |
WO2021122139A1 (fr) | 2021-06-24 |
US20230042372A1 (en) | 2023-02-09 |
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