GB2528128A - Oligomerisation process - Google Patents
Oligomerisation process Download PDFInfo
- Publication number
- GB2528128A GB2528128A GB1412398.8A GB201412398A GB2528128A GB 2528128 A GB2528128 A GB 2528128A GB 201412398 A GB201412398 A GB 201412398A GB 2528128 A GB2528128 A GB 2528128A
- Authority
- GB
- United Kingdom
- Prior art keywords
- olefins
- alpha
- process according
- ionic liquid
- olefinic feedstock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 67
- 230000008569 process Effects 0.000 title claims abstract description 59
- 239000002608 ionic liquid Substances 0.000 claims abstract description 121
- 239000004711 α-olefin Substances 0.000 claims abstract description 92
- 150000001450 anions Chemical class 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000003446 ligand Substances 0.000 claims abstract description 35
- 150000001768 cations Chemical class 0.000 claims abstract description 32
- 239000000460 chlorine Substances 0.000 claims abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 15
- 239000000539 dimer Substances 0.000 claims abstract description 15
- 239000013638 trimer Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 239000011669 selenium Substances 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 48
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 40
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 39
- 230000002378 acidificating effect Effects 0.000 claims description 30
- -1 tetrafluoroborate Chemical compound 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 229940069096 dodecene Drugs 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 235000013877 carbamide Nutrition 0.000 claims description 6
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 125000002883 imidazolyl group Chemical group 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 4
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 claims description 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002785 azepinyl group Chemical group 0.000 claims description 2
- 125000002393 azetidinyl group Chemical group 0.000 claims description 2
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- VEVMZUUBBOJHFD-UHFFFAOYSA-N ethyl acetate;methylsulfinylmethane Chemical compound CS(C)=O.CCOC(C)=O VEVMZUUBBOJHFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000002632 imidazolidinyl group Chemical group 0.000 claims description 2
- 125000002636 imidazolinyl group Chemical group 0.000 claims description 2
- 125000004628 isothiazolidinyl group Chemical group S1N(CCC1)* 0.000 claims description 2
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 2
- 125000003971 isoxazolinyl group Chemical group 0.000 claims description 2
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000002757 morpholinyl group Chemical group 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000001715 oxadiazolyl group Chemical group 0.000 claims description 2
- 125000000160 oxazolidinyl group Chemical group 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 125000003566 oxetanyl group Chemical group 0.000 claims description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000002755 pyrazolinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 2
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 claims description 2
- 125000001984 thiazolidinyl group Chemical group 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 150000003556 thioamides Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 125000005323 thioketone group Chemical group 0.000 claims description 2
- 125000004568 thiomorpholinyl group Chemical group 0.000 claims description 2
- 150000003585 thioureas Chemical class 0.000 claims description 2
- 125000004306 triazinyl group Chemical group 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- 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 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000002199 base oil Substances 0.000 abstract description 7
- 239000000314 lubricant Substances 0.000 abstract description 7
- 230000001050 lubricating effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 55
- 239000003054 catalyst Substances 0.000 description 42
- RVNZEJNWTUDQSC-JOCHJYFZSA-N (2r)-n-(6-aminohexyl)-1-tridecanoylpyrrolidine-2-carboxamide Chemical compound CCCCCCCCCCCCC(=O)N1CCC[C@@H]1C(=O)NCCCCCCN RVNZEJNWTUDQSC-JOCHJYFZSA-N 0.000 description 21
- 239000003921 oil Substances 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229910052796 boron Inorganic materials 0.000 description 9
- 239000002841 Lewis acid Substances 0.000 description 8
- 235000019647 acidic taste Nutrition 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000007848 Bronsted acid Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011831 acidic ionic liquid Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002500 ions Chemical class 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
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000002904 solvent 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
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZKIBBIKDPHAFLN-UHFFFAOYSA-N boronium Chemical compound [H][B+]([H])([H])[H] ZKIBBIKDPHAFLN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
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- 241000894007 species Species 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 241000776457 FCB group Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 241000083552 Oligomeris Species 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000008186 active pharmaceutical agent Substances 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
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- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
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- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
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Abstract
A process for the preparation of alpha-olefin oligomers, comprising contacting an olefinic feedstock comprising C5 to C20 alpha-olefins with an ionic liquid comprising: (i) at least one borenium cation of the formula [BX2L]+, wherein L is a Lewis basic donor ligand containing a donor atom selected from oxygen, sulphur, selenium, nitrogen, phosphorus, arsenic, and each X is independently selected from fluorine, chlorine and bromine; and (ii) at least one non-coordinating anion. The process may be selective for the preparation of dimers, trimers and tetramers in an oligomerisation reaction of a feed stock comprising C5 to C20 alpha-olefins, preferably with a molecular weight distribution that is suitable for use in lubricant base oils. In another aspect, the use of said ionic liquid as a selective Lewis acid catalyst in Friedel-Crafts alkylation and alkane isomerisation reactions. The oligomerisation process is suitable for forming base oils for lubricating compositions.
Description
I
Oligomerisation Process This invention relates to an oligomerisation process for forming base oils for lubricating compositions. In particular, the present invention provides a process for the selective oligomerisation of 05 to 020 alpha-olefins to produce polyalphaolefin oligomers, preferably with a molecular weight distribution that is suitable for use in lubricant base oils.
Lubricant compositions generally comprise a base oil of lubricating viscosity together with one or more additives to deliver properties such as reduced friction and wear, improved viscosity index, detergency, and resistance to oxidation and corrosion. A lubricant base oil may comprise one or more sources of lubricating oil, referred to as base stocks.
Lubricant base stocks useful in automotive engine lubricants may be obtained as higher boiling fractions from the refining as crude oil or via synthetic routes, and are classified as Group I, II, Ill, IV and V base stocks according to API standard 1509, ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", April 2007 version ISm edition Appendix F. Group IV refers to polyalphaolefin (PAO) base stocks, which are typically synthesised by oligomerisation of 1 -decene. The principal component of these base stocks is decene trimer, although the dimer, tetramer and pentamer are typically also present in the various base stock blends.
A number of catalytic processes are currently in use for the oligomerisation of alpha olefins to produce materials for use as lubricant base stocks.
Ziegler-Natta catalysts are a class of catalysts that comprise titanium compounds in combination with an organoaluminium compound. Typically, Ziegler-Natta catalysts used commercially for the polymerisation of alpha-olefins comprise a titanium complex (such as Ti014) together with an organoaluminium compound (such as triethylaluminium) on a magnesium chloride support.
Metallocene complexes (such as dicyclopentadienylzirconium dichloride, Cp2ZrCI2) have also been used as catalysts for the oligomerisation of alpha-olefins in combination with a methylaluminoxane activator.
It is also known that Lewis acids such as BF3, AICI3 and EtAICI2 can be used as catalysts for cationic polymerisation of alpha-olefins in conjunction with an alkyl halide (for instance tert-butyl chloride), alcohol or Brønsted acid.
US 7,572,944 discloses the use of ionic liquids as catalysts for the cationic polymerisation of alpha-olefins. Ionic liquids are a class of compounds that have been developed over the last few decades. The term "ionic liquid" as used herein refers to a liquid that can be obtained by melting a salt, and which is composed entirely of ions. The term "ionic liquid" by standard definition includes salts melting below 100 °C. Ionic liquids having melting points below around 30 °C are commonly referred to as "room temperature ionic liquids" and are often derived from organic salts having nitrogen-containing heterocyclic cations, such as imidazolium and pyridinium-based cations.
The ionic liquid catalysts disclosed in us 7,572,944 comprise pyridinium or imidazolium cations together with acidic chloroaluminate anions, such as [AI2CI7f. The use of ionic liquids as polymerisation catalysts is known to provide certain advantages over conventional catalysts. In particular, ionic liquids are generally immiscible with hydrocarbons and thus can be separated from polyalphaolefin products by phase separation and recycled. In contrast, conventional Lewis acid catalysts are generally quenched during the isolation of products.
However, a disadvantage of known ionic liquid systems is that the organic cations are spectator ions which play no part in the catalytic reaction, other than to moderate the melting point of the ionic liquid reaction medium. In the case of, for instance, chloroaluminate ionic liquids, the cation also represents an expensive component of the ionic liquid. A further disadvantage of known ionic liquid systems, in common with other Lewis acid catalysts, is that the catalysts can be extremely active, particularly those ionic liquids comprising acidic chloroaluminate anions, such as [AI2CI7f. High catalytic activity tends to result in the formation of undesired highly oligomerised products, thereby wasting resources. While the use of dopants to moderate the Lewis acidity of chloroaluminate ionic liquid systems has been investigated, these provide in general only modest improvements.
Accordingly, there is a need in the art for new processes for the production of polyalphaolefin oligomers which overcome one or more of the disadvantages of the processes that are known in the art.
The present invention is based on the discovery that a certain class of Lewis acidic ionic liquids has been found to give unexpected selectivity when used as a catalyst for the production of polyalphaolefin oligomers. More specifically, the class of ionic liquids comprises a tricoordinate boreniumOll) cation. This cation is a Lewis acidic species, and therefore not merely a spectator cation, as in known Lewis acid ionic liquid systems.
In general, boron(lll) cations may be classified into three distinct structural classes based on the coordination number at boron. The three different classes, borinium (a), borenium (b) and boronium (c), are illustrated below: + L L R"I
L R
(a) borinium(lll) (b) borenium(lll) (c) boronium(lll) Neutral tricoordinate boron group species, such as 3F3, have found use as Lewis acid catalysts in the past. Meanwhile, the corresponding tricoordinate borenium (b) cationic species illustrated above has been postulated to be an even stronger Lewis acid as a result of its increased electron deficiency (Angew. Chem. Int. Ed. 2005, 44, 5016 to 5036). Dicoordinate borinium (a) cations are speculated to be extremely strong Lewis acids, but are so reactive that they only exist transiently. Of the three classes of boron cationic species, tetracoordinate boronium (c) cations have received most attention historically, as they are inherently more stable as a result of a filled octet and a complete coordination sphere, but for the same reasons their Lewis acidity is compromised.
De Vries et at., Chem Rev. 2012 July 11; 112(7): 4246 to 4282, "Cationic Tricoordinate Boron Intermediates: Borenium Chemistry from the Organic Perspective" (hereinafter "De Vries et a!'), provides an overview of the reactivity of cationic, tricoordinated borenium ions, which are strongly Lewis acidic. As mentioned therein, the first observable borenium salt was reported by Ryschkewitsch et at., J. Am. Chem Soc., 92:6, 1790-1791 (1970) and was formed when 2 equivalents of AICI3 were added to an adduct of BOb and picoline in a solution of dichloromethane. In that case, the borenium cation is formed by chloride abstraction, as illustrated below.
+ ci cici CH,C12 -ci rn r'I CI CI tci S S ci ci ci_B ci Notably, absent solvent, a 1:2 mixture of BOI3-picoline adduct and AId3 was found to be a mobile liquid at room temperature, now understood to be an ionic liquid.
The observation by Ryschkewitsch et a! set a precedent for the generation of other borenium species by B-X heterolysis in the presence of halophilic Lewis acids. Other examples of borenium cation containing salts have emerged as result. For instance, De Vries et at reports the formation of a borenium cation formed following chloride abstraction from an adduct of B013 and 2,6-lutidene base, which was subsequently isolated in the form of the tetrachloroaluminate salt (Del Grosso A et at., Chem Commun, 2011, 47, 12459).
The present inventors have prepared ionic liquids comprising a borenium cation together with conventional anions, such as [AIOI4f or [NTf2f, including Lewis acidic chloroaluminates, such as [AI2CI7f, thereby forming a class of ionic liquids comprising two Lewis acidic centres, having overall Lewis acidities far exceeding those of conventional Lewis acidic ionic liquid systems. For instance, the Gutmann Acceptor Number (AN) value for Lewis acidity of the borenium cation alone is over 160, whilst the AN value for the chloroaluniinateOll) anion is approximately 100.
In view of the level of Lewis acidity associated with the borenium ionic liquid systems described herein, it follows that catalytic activity is higher than with conventional Lewis acid ionic liquid catalyst systems, especially when there are two Lewis acidic centres present. However, in spite of such high catalytic activity, normally associated with the formation of undesired highly oligomerised products in oligornerisation reactions, it has been surprisingly found that the specific class of Lewis acidic ionic liquids described herein leads to the formation of dimers, trimers, tetramers and pentamers in high proportion, and with little or no formation of undesired highly oligomerised products.
Thus, in a first aspect, the present invention provides a process for the preparation of alpha-olefin oligomers, comprising contacting an olefinic feedstock comprising Cs to 020 alpha-olefins with an ionic liquid comprising: (i) at least one borenium cation of the formula [BX2L], wherein L is a Lewis basic donor ligand containing a donor atom selected from oxygen, sulphur, selenium, nitrogen, phosphorus, arsenic, and each X is independently selected from fluorine, chlorine and bromine; and (ii) at least one non-coordinating anion.
In preferred embodiments, each X is independently selected from fluorine and chlorine.
In more preferred embodiments, X is either fluorine or chlorine. In even more preferred embodiments, X is chlorine.
The Lewis basic donor ligand is preferably selected from small molecule donor ligands having a molecular weight of 500 or less, preferably a molecular weight of 400 or less, more preferably a molecular weight of 300 or less, still more preferably a molecular weight of 200 or less, and most preferably a molecular weight of 100 or less.
In preferred embodiments, the Lewis basic donor ligand is selected from ligands containing a donor atom selected from oxygen, sulphur, selenium, nitrogen and phosphorus, more preferably from oxygen, nitrogen and phosphorus, still more preferably from nitrogen and phosphorus. Most preferably, the Lewis basic donor ligand is selected from ligands containing a nitrogen donor atom.
In further preferred embodiments, the Lewis basic donor ligand is selected from the group of compounds consisting of ketones, sulfoxides, phosphine-oxides, ureas, esters, amides, ethers, thioketones, thioureas, thioamides, thioethers, amines, nitriles and phosphines. More preferably, the Lewis basic donor ligand is selected from the group of compounds consisting of amines, amides and phosphines. Still more preferably, the Lewis basic donor ligand is selected from the group of compounds consisting of amines and amides. Most preferably, the Lewis basic donor ligand is an amine.
In other preferred embodiments, the Lewis basic donor ligand is selected from a heterocyclic group, which is an aromatic or non-aromatic cyclic, fused bi-or tn-cyclic, substituted or unsubstituted hydrocarbon group comprising one or more of 0, N, NH and S in the ring. Examples of suitable Lewis basic donor ligands comprising a heterocyclic group include ethylene oxide, azetidinyl, pyrrolidinyl, pyrrolyl, pyrazolyl, oxetanyl, pyrazolinyl, imidazolyl, imidazolinyl, imidazolidinyl, oxazolyl, oxazolidinyl, isoxazolinyl, isoxazolyl, thiazolyl, thiadiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, furyl, tetrahydrofuryl, thienyl, oxadiazolyl, piperidinyl, piperazinyl, azepinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, triazolyl, tetrazolyl, tetrahydropyranyl, morpholinyl, thiamorpholinyl.
Preferred heterocyclic groups for use as the Lewis basic donor ligand in accordance with the present invention are selected from imidazolyl, pyridyl and pyrrolyl, more preferably selected from imidazolyl and pyridyl.
Heterocyclic group Lewis basic donor ligands for use in the present invention may be unsubstituted or substituted. Examples of suitable substituents include C to 010, preferably C to C6, straight chain or branched alkyl, C to C alkoxy, 02 to 012 alkoxyalkoxy, 03 to 0 cycloalkyl, 03 to 0 heterocyclic, 06 to 0o aryl, 07 to 010 alkaryl, 07 to 010 aralkyl, -ON, -OH, -SH, -NO2, CO2Rx, -OC(O)R', C(O)Rx, C(S)Rx, -CS 2Rx, SC(S)Rx, -S(O)(C1 to C6)alkyl, -S(O)O(C1 to 05)alkyl,-OS(O)(01 to C5)alkyl, -S(C1 to C6)alkyl, -S-S(01 to C6alkyl), NRXC(O)NRYRZ, -NR'<C(O)OR', OC(O)NRYRZ, NRXC(S) 0R, 0O(S)NRRz, -NRt(S)SR', -SO(S)N RYRZ NRt(S)NRIRz, C(0)NRRz, O(S)NRs' or NRYRz, wherein R", R and Rz are independently selected from hydrogen or C to 06 alkyl. Preferred substituents include C to 010, preferably C to 0, straight chain or branched alkyl, C to 06 alkoxy, 02 to C alkoxyalkoxy, 0 to C cycloalkyl, -OH or NRvRz, wherein R and Rz are independently selected from hydrogen or C to 0 straight chain or branched alkyl group.
Examples of suitable C to alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, trifluoromethyl and pentafluoroethyl. Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. More preferred alkyl groups include methyl, ethyl, propyl, and isopropyl. Most preferably, the alkyl group is methyl.
Examples of particularly preferred heterocyclic compounds for use as Lewis basic donor ligands in accordance with the present invention are selected from picoline, lutidine, pyridine, collidine, dimethylaminopyridine (DMAP), 1-alkylimidazole, for example 1-methylimidazole (mim).
In other preferred embodiments, the Lewis basic donor ligand is selected from compounds having a formula selected from R1-C(O)-R1, R1-S(O)-R1, R2NH-C(O)-NHR2, R2NH-C(S)-NHR2' R1-C(O)-N(R2)2, R1-C(O)-0R1, (R3)3P, (R3)3P(O) and R1-CN wherein: each R1 independently represents a C to 010 straight chain or branched alkyl group, preferably a C to 06 alkyl group, more preferably a C to C alkyl group and most preferably a methyl group; R2 is selected from hydrogen or a C to 010 straight chain or branched alkyl group, more preferably from hydrogen or a C to C alkyl group, still more preferably from hydrogen or a C1 to C alkyl group, and most preferably from hydrogen or a methyl group; and R3 represents a 04 to C10 straight chain or branched alkyl group, wherein any of R1, R2 and R3 may optionally be substituted by one or more fluorine atoms.
Examples of suitable C to alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, trifluoromethyl and pentafluoroethyl. Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. More preferred alkyl groups include methyl, ethyl, propyl, and isopropyl. Most preferably, the alkyl group is methyl.
In other preferred embodiments, the Lewis basic donor ligand is selected from compounds having a formula selected from R1-S(O)-R1, R2NH-0(O)-NHR2, R2NH-C(S)-NHR2, R1-C(O)-NR22, (R3)3P and (R3)3P(O); more preferably, the Lewis basic donor ligand is selected from compounds having a formula selected from R2NH-0(O)-NHR2 and R1-0(O)-N(R2)2; and most preferably the Lewis basic donor ligand is a compound having the formula R2NH-0(O)-NHR2, wherein R1 and R2 are as defined above.
Examples of suitable Lewis basic donor ligands in accordance with the present invention include urea, N,N'-dimethylurea, N,N'-dimethylthiourea, acetamide, dimethylacetamide, acetone, ethyl acetate dimethylsulfoxide, trioctylphosphine oxide, and trioctyiphosphine.
In some embodiments of the invention, the Lewis basic donor ligand may comprise a mixture of two or more Lewis basic donor ligands as described herein.
The term "non-coordinating anion" used herein, which is common in the field of olefin oligomerisation, is intended to mean an anion that does not coordinate with the metal cation, or does so only weakly. Typically, non-coordinating anions have their charge dispersed over several atoms in the molecule which significantly limits their coordinating capacity. Preferred non-coordinating anions are selected from a) halometallate anions of the formula [MX4f or [M2X71, where M is Al or Ga, preferably Al, and X is independently Cl or Br, preferably Cl; b) bis(triflamide) ([NTf2f) or triflate ([01ff); c) bis(perfluoroalkylsulphonyl)imides (preferably methyl, ethyl, butyl and nonyl) d) tetrafluoroborate ([BF4f) or tetrachloroborate ([BCI4fl; e) hexafluorophosphate ([PF6] f) [SnXJ or [Sn2X5f, where X is independently Cl or Br g) dichlorocuprate ([CuCl2fl; h) hexafluoroantimonate ([SbF6fl; i) hexafluoroarsenate ([AsF6fl; j) fluorosulphonate ([F- 502-Of) and perfluoroalkyl sulphonates (preferably methyl); and k) chlorozincate(ll) anions, such as [ZnCI4]2 or [Zn2Cl6]2.
More preferred non-coordinating anions are selected from a) halometallate anions of the formula [MX4I or [M2X7f, where M is Al or Ga, preferably Al, and X is independently Cl or Br, preferably Cl; b) bis(triflamide) ([N1f2]); c) bis(perfluoroalkylsulphonyl)imides (preferably methyl, ethyl, butyl or nonyl); d) tetrafluoroborate ([BF4]); e) hexafluorophosphate ([PF6fl; and f) [SnX3f or [Sn2X5f where and X is independently Cl or Br.
Yet more preferred non-coordinating anions are selected from a) halometallate anions of the formula [MX4r or [M2X7f, where M is Al or Ga and X is independently Cl or Br.
Still more preferred non-coordinating anions are those selected from the preferred non-coordinating anions mentioned above which are also Lewis acidic, for example, [M2X7f, where M is Al or Ga, preferably Al, and X is independently Cl or Br, preferably Cl. Non-coordinating anions which are also Lewis acidic (as opposed to Lewis neutral) are particularly advantageous for use in the present invention, for example [A12C17]-, [Ga20l7], [Sn20151 or [Zn2016]2. Most preferably, the non-coordinating anion is Lewis acidic anion [AI2CI7f.
Particularly preferred ionic liquids for use in the present invention include [BCI2(4pic)][A12017], [B012(4pic)][A1014], [B012(4pic)][Ga2017], [B012(4pic)][Ga014], [B012(mim)][A12C17], [B012(mim)][AICI4], [3C12(mim)][Ga014], [BCI2(mim)][0a2017], [BCI2(P5550)][AICI4], [B012(P5550)][A12C17], [BCI2(P5550)][GaCI4], [B012(P5550)][Ga2017], [BCI2(SUr)][A1014], [BCI2(SUr)][A12017], [BCI2(SUr)][Ga014], [B012(SUr)][Ga2017], [BCI2(DMA)][A12017], [B012(DMA)][A1014], [B012(DMA)][Ga2017], and [B012(DMA)][Ga014].
Most preferred ionic liquids for use in the present invention are those having a Lewis acidic, non-coordinating anion, for example: [B012(4pic)][A12C17], [B012(4pic)][0a2017], [BCI2(mim)][A12017], [B012(mim)][Ga2017], [B012(P5550)][A12C17], [B012(P5550)][Ga2017], [BCI2(SUr)][A12C17], [B012(SUr)][Ga2CI7], [BCI2(DMA)][A12017], and [B012(DMA)][3a2017].
As will be appreciated by the person of skill in the art, where reference is made herein to the borenium ionic liquid comprising (i) at least one borenium cation of the formula [BX2L] and ii) at least one non-coordinating anion, this also covers the option of the ionic liquid consisting of only components (i) and (U). Thus, in accordance with the present invention, the borenium ionic liquid may consist solely of components (i) and (ii) defined hereinbefore. It will also be appreciated by the skilled person that the step of contacting the olefinic feedstock with the ionic liquid includes embodiments where the olefinic feedstock is contacted with the borenium ionic liquid described hereinbefore in the absence of a solvent and/or a carrier material.
The present inventors have surprisingly found that the use of borenium ionic liquids as defined above as catalysts for the oligomerisation of 05 to 020 alpha-olefins provides an oligomerised product with a molecular weight distribution that is particularly suitable for use as a lubricant base stock, i.e. consisting predominantly of dimers, trimers, tetramers and pentamers, and with only low levels of undesired highly oligomerised products, such nonamers and decamers. The ionic liquids are also immiscible with the oligomeric product and thus can readily be separated from the product by phase separation.
Furthermore, the separated ionic liquids can be readily recycled to the oligomerisation reaction. A further advantage of the ionic liquid systems of the present invention is that cheap, widely available Lewis donor ligands such as urea, thiourea, acetamide and dimethylsulfoxide may be used to prepare the borenium ionic liquids. This is in contrast to conventional ionic liquids systems used in oligomerisation, such as chloroaluminates(lll), where the halide salt of the spectator cation has to be typically pre-prepared in an expensive quaternisation step.
Many mechanisms have been suggested for the catalysis of oligomerisation reactions.
One suggested mechanism for oligomerisation of olefins is a carbocationic mechanism.
According to that route, catalysis proceeds following the formation of acidic protons, formed by the presence of protic promoter (e.g. alcohol) or water (residual traces of moisture in the reaction system being sufficient). Thus, in some embodiments of the present invention, the oligomerisation reaction is performed in the presence of trace amounts of moisture (for example, between 50 and 500 ppm, preferably 50 to 150 ppm of water).
In the borenium ionic liquids described herein, protons may be generated as illustrated in Equation I below. The acidity of these protons depends on the strongest base in the system, which in this case will be the anions of the ionic liquids. Consequently, the weaker the basicity of the anion, the weaker will be its association with the proton, hence the stronger will be the acidity of the protons.
[BX2L] + H20 -. [BX2(OH)L] + H Eq la [Al2X7 + H20 [AlX4 + [AIX3(OH)i + Ht Eq lb Generation of the carbocation according to the carbocation mechanism for oligomerisation involves attack of the acidic proton on the olefin. The reaction rate of this step depends on the acidity of the proton. The more acidic the system, the more exothermic the reaction and the more rapid is the generation of the carbocation. The ionic liquids described herein are strongly Lewis acidic and are thus able to generate very potent superacids, even protonating substrates that would normally be difficult to protonate.
In some embodiments of the invention, the ionic liquid catalyst is used in the presence of a Brønsted acid. A Brønsted acid may act as a source of an acidic proton in addition to or in place of residual traces of moisture. The superior Lewis acid strength of the ionic liquids described herein is believed to lead to the formation of superacidic protons upon reaction with a Brønsted acid, which may further enhance the catalytic activity of the ionic liquids described herein. Suitable Brønsted acids include, for example, H2504, HF, HCI, HBr, HI and H3P04. Other protic promotors, such as alcohols, may also be used in place of, or in combination with, Brønsted acids.
After generation of the carbocation, which is rapid in the case of the ionic liquids described herein, charge migration along the chain and/or skeletal isomerisation may occur, eventually leading to attack of another olefin unit to form a dimer. Subsequent reactions involve further chain propagations and isomerisations, which compete with termination processes.
Surprisingly, despite the increased catalytic activity of the ionic liquids described herein in comparison to conventional chloroaluminate Lewis acidic ionic liquids, there is an increased selectivity for the formation of dimers, trimers, tetramers and pentamers, rather than undesired highly oligomerised products associated with the ionic liquids described herein. Without being bound by any particular theory, it is thought that the Lewis acidic borenium cation of the ionic liquids described herein affects ionic interactions with the propagating carbocation formed during the oligomerisation reaction, in a manner different to that of the cation of known chloroaluminate Lewis acid ionic liquid systems. Thus, the ionic liquid described herein, unexpectedly benefits from both high catalytic activity, and high selectivity for lower oligomers, which are particularly suitable for use in the manufacture of lubricating base oils.
Moreover, it has also been found that the presence of the borenium cation as described herein mitigates against the lack of selectivity in oligomerisation reactions which is exhibited in the case of conventional Lewis acidic anions, such as [Al2Cl7. Absent the borenium cation, use of an ionic liquid comprising Lewis acidic [AI2CI7r in combination with a spectator cation results in the formation of a significant proportion of undesirable highly oligomerised products. However, when a borenium cation as described herein is substituted for the spectator cation, catalytic activity is not only increased but also selectivity. Thus, the presence of the borenium cation also blocks any lack of selectivity which results from the presence of the Lewis acidic [Al2Cl7 anion, whilst the benefit of increased catalytic activity resulting from the presence of two Lewis acidic centres is realised.
The borenium ionic liquids used in the present invention may be prepared by methods known to the skilled person, and which are described in Ryschkewitsch et al., J. Am. Chem Soc., 92:6, 1790-1791 (1970). Thus, a suitable method for preparing borenium ionic liquids comprises B-X bond heterolysis, as illustrated below in example reactions (i) to (iv): OH3 OH3 H30% H30.
LJ H3C 000 Me3SiOTf F_BF N F_B,F F.B..F OH3 OH3 OH3 OH3 + 3 00 -Me3SiOTf [OT-
F N F_BF FBF
H3CN..CH3 H3CN..CH3 (Ui) + Me3Si-O-g-CF3 50°C, 16 h -O--CF3 + Me3SiCI (g) I 2equiv. 0 OH3 (iv) + Me3Si-0--OF3 5000, 16 h -0--GF3 + Me3SiCI () 2 equiv. I oi-CI A notable advantage in the preparation of the borenium ionic liquid catalysts used in the process of the present invention is that they may be made by recycling a boron based compound which may have previously been used as a catalyst, such as a Lewis acid catalyst. For example, a boron trihalide, which has wide catalytic applications, may be converted into a borenium ionic liquid as illustrated above and in the Examples hereinbelow. This may make preparation of a borenium ionic liquid even more economical. For instance, existing systems utilising boron trihalides for catalysing oligomerisation reactions can be readily adapted so that the boron trihalide catalyst may be converted into a borenium ionic liquid oligomeristation catalyst as described herein.
Thus, in a preferred embodiment, the borenium ionic liquid used in the process of the invention is prepared from the recycle of a boron trihalide which has previously been used as a catalyst. Furthermore, by selecting a Lewis donor ligand from cheap, widely available donor ligands such as urea, thiourea, acetamide and dimethylsulfoxide, preparation of the borenium ionic liquid catalyst may be prepared at even lower cost.
As used herein, the term "olefinic feedstock comprising 0 to 020 alpha-olefins" preferably refers to a hydrocarbonaceous feedstock that comprises at least one C to alpha-olefin hydrocarbon. Preferably, the olefinic feedstock comprises at least 50 wt% of one or more 05 to 020 alpha-olefins, more preferably at least 60 wt% of one or more Os to 020 alpha-olefins, more preferably at least 70 wt% of one or more 05 to 020 alpha-olefins, more preferably at least 80 wt% of one or more 0 to 020 alpha-olefins, more preferably at least 90 wt% of one or more 0 to 020 alpha-olefins, and most preferably at least 95 wt% of one or more 0 to 020 alpha-olefins. In some embodiments, the olefinic feedstock may comprise at least 98 wt% of one or more 05 to 020 alpha-olefins, or at least 99 wt% of one or more 05 to 020 alpha-olefins. The remainder of the olefinic feedstock may suitably be composed of other olefins, paraffins, or a mixture thereof.
In preferred embodiments, the olefinic feedstock comprises at least 50 wt% C to 015 alpha-olefins, more preferably at least 60 wt% 0 to alpha-olefins, more preferably at least 70 wt% 06 to 018 alpha-olefins, still more preferably at least 80 wt% 06 to 015 alphaolefins, and most preferably at least 90 wt% 05 to 018 alpha-olefins. For example, the olefinic feedstock 5 may comprise at least 95 wt% C to alpha-olefins, at least 98 wt% 06 to alpha-olefins or at least 99 wt% 06 to C alpha-olefins.
In some embodiments, the olefinic feedstock comprises at least 30 wt% 0 to 014 alphaolefins, more preferably at least 50 wt% 08 to 014 alpha-olefins, more preferably at least 70 wt% 0 to 014 alpha-olefins, still more preferably at least 80 wt% C to 014 alpha olefins, and most preferably at least 90 wt% 0 to 014 alpha-olefins. For example, the olefinic feedstock may comprise at least 95 wt% 0 to 014 alpha-olefins, at least 98 wt% C to 014 alpha-olefins or at least 99 wt% C to 014 alpha-olefins.
In some embodiments, the olefinic feedstock comprises at least 30 wt% 010 to 014 alphaolefins, more preferably at least 50 wt% 010 to 014 alpha-olefins, more preferably at least 70 wt% 010 to 014 alpha-olefins, still more preferably at least 80 wt% Og to 014 alpha olefins, and most preferably at least 90 wt% 010 to 014 alpha-olefins. For example, the olefinic feedstock may comprise at least 95 wt% 010 to 014 alpha-olefins, at least 98 wt% 010 to 014 alpha-olefins or at least 99 wt% 010 to 014 alpha-olefins.
In more preferred embodiments, the olefinic feedstock comprises at least 30 wt% Co to 012 alpha-olefins, more preferably at least 50 wt% 010 to 012 alpha-olefins, more preferably at least 70 wt% 010 to 012 alpha-olefins, still more preferably at least 80 wt% to 012 alpha-olefins, and most preferably at least 90 wt% 010 to 012 alpha-olefins.
For example, the olefinic feedstock may comprise at least 95 wt% 010 to 012 alphaolefins, at least 98 wt% 010 to 012 alpha-olefins or at least 99 wt% 010 to 012 alphaolefins.
In some embodiments, the olefinic feedstock preferably comprises at least 30 wt% 1- decene, more preferably at least 50 wt% 1-decene, more preferably at least 70 wt% 1-decene, still more preferably at least 80 wt% 1-decene, and most preferably at least 90 wt% 1-decene. For example, the olefinic teedstock may comprise at least 95 wt% 1-decene, at least 98 wt% I -decene or at least 99 wt% I -decene.
In other embodiments, the olefinic feedstock preferably comprises at least 30 wt% 1-dodecene, more preferably at least 50 wt% 1-dodecene, more preferably at least 70 wt% 1-dodecene, still more preferably at least 80 wt% 1-dodecene and most preferably at least 90 wt% 1-dodecene. For example, the olefinic feedstock may comprise at least 95 wt% 1 -dodecene, at least 98 wt% I -dodecene or at least 99 wt% I -dodecene.
In further embodiments, the olefinic feedstock may comprise at least 30 wt% 016 to alpha-olefins, more preferably at least 50 wt% to alpha-olefins, more preferably at least 70 wt% 016 to 018 alpha-olefins, still more preferably at least 80 wt% 016 to alpha-olefins, and most preferably at least 90 wt% to 0 alpha-olefins. For example, the olefinic feedstock may comprise at least 95 wt% 016 to 015 alpha-olefins, at least 98 wt% to 016 alpha-olefins or at least 99 wt% to 018 alpha-olefins.
In some embodiments, the olefinic feedstock preferably comprises at least 30 wt% 1-hexadecene, more preferably at least 50 wt% 1-hexadecene, more preferably at least 70 wt% 1-hexadecene, still more preferably at least 80 wt% 1-hexadecene, and most preferably at least 90 wt% 1-hexadecene. For example, the olefinic feedstock may comprise at least 95 wt% 1-hexadecene, at least 98 wt% 1-hexadecene or at least 99 wt% 1-hexadecene.
In other embodiments, the olefinic feedstock preferably comprises at least 30 wt% 1-octadecene, more preferably at least 50 wt% 1 -octadecene, more preferably at least 70 wt% 1-octadecene, still more preferably at least 80 wt% 1-octadecene and most preferably at least 90 wt% 1-octadecene. For example, the olefinic feedstock may comprise at least 95 wt% 1-octadecene, at least 98 wt% 1-octadecene or at least 99 wt% 1-octadecene.
In some embodiments of the invention, the olefinic feedstock may also comprise paraffins. In general, the olefinic feedstock comprises a minor amount of paraffins. For instance, the olefinic feedstock may optionally comprise up to 20 wt% paraffins, for instance up to 10 wt% paraffins, or up to 5 wt% paraffins. However, it will be appreciated that olefinic feedstocks comprising larger amounts of paraffins are also suitable as feedstocks for the present invention. For instance, olefinic feedstocks comprising up to wt%, 70 wt%, 80 wt% or 90 wt% paraffins are found to be suitable feedstocks for the process of the present invention. The presence of a minor amount of paraffins in the olefinic feedstock is observed to suppress the formation of undesired heavy oligomers.
Suitable paraffins include 05 to 020 paraffins, such as 010 to 012 paraffins.
The olefinic feedstock may suitably be contacted with the borenium ionic liquid catalyst at a temperature of from 0 °C up to the boiling point of the alpha-olefins at the reaction pressure. Preferably, the olefinic feedstock is contacted with the ionic liquid at a temperature of from 0 to 160 °C, more preferably 40 to 140 °C, more preferably 80 to 00, still more preferably 100 to 140 00, and most preferably about 120 00 The formation of oligomers in accordance with the present invention is exothermic, and thus cooling system may be used so as to maintain the desired reaction temperature.
The olefinic feedstock may suitably be contacted with the borenium ionic liquid catalyst at a pressure of from 10 to 1000 kPa, preferably from 20 to 500 kPa, more preferably from 50 to 200 kPa, for instance from 80 to 120 kPa. Preferably, the olefinic feedstock is contacted with the ionic liquid at ambient pressure, i.e. around 100 kPa.
The olefinic feedstock may suitably be contacted with the borenium ionic liquid catalyst for a 10 period of from 1 minute to 10 hours, for example from 10 minutes to 1 hour.
The reaction is preferably carried out under an inert atmosphere and substantially in the absence of moisture, defined as less than 500 ppm by weight water based on the total weight of ionic liquid and olefinic feedstock.
The process of the present invention may suitably be carried out by contacting the olefinic feedstock with at least 0.01 wt% of the ionic liquid catalyst, more preferably at least 0.05 wt% of the borenium ionic liquid catalyst, still more preferably at least 0.1 wt% of the borenium ionic liquid catalyst, and most preferably at least 0.2 wt% of the borenium ionic liquid catalyst, based on the total weight of the borenium ionic liquid catalyst and olefinic feedstock. For example, the olefinic feedstock may suitably be contacted with from 0.01 to 5 wt% of 20 the borenium ionic liquid catalyst, preferably from 0.05 to 2 wt% of the borenium ionic liquid catalyst, still more preferably from 0.1 to I wt% of the borenium ionic liquid catalyst, and still more preferably from 0.2 to 0.8 wt% of the borenium ionic liquid catalyst, based on the total weight of the borenium ionic liquid catalyst and olefinic feedstock. Most preferably, the olefinic feedstock is contacted with about 0.5 wt% of the borenium ionic liquid catalyst, based on the total weight of the borenium ionic liquid catalyst and olefinic feedstock.
It has been found that the oligomerised product distribution is not dependent on the catalyst loading to any significant degree. However, higher catalyst loadings generally reduce the reaction time and improve conversion of starting materials. Due to the exothermic nature of the reaction, the use of higher catalyst loadings may in some cases necessitate additional measures to maintain the desired reaction temperature.
The oligomer product obtained by the present invention may be separated from the ionic liquid catalyst by any suitable means, for instance by gravity separation and decantation or by centrifugation. In this way, the ionic liquid catalyst may also be recycled.
Alternatively, the reaction may be quenched by the addition of water, optionally containing a mild base, and the organic and aqueous phases may be separated, for instance by gravity separation and decantation or by centrifugation. Quenching the reaction in this way may be preferred where recycling of the ionic liquid catalyst is not practical or economical.
The oligomerised product obtained by the process of the present invention typically contains minor amounts of highly oligomerised products (defined herein as hexamers and higher oligomers) as well as unreacted starting material. In some embodiments, the process of the invention may further comprise distillation of the oligomerised product to separate starting material and/or highly oligomerised products from the desired lower oligomers (defined herein as dimers, trimers, tetramers and pentamers).
The catalytic oligomerisation of alpha-olefins generally provides oligomerised products that contain one remaining double bond. The presence of double bonds generally reduces the oxidative stability of a lubricating oil base stock. Thus, in some embodiments, the process of the present invention further comprises a step in which the remaining olefinic double bonds in the oligomerised product are reduced to carbon-carbon single bonds so as to improve the oxidation stability of the product. Suitably, the reduction of olefinic double bonds may be carried out by hydrogenation in the presence of a suitable hydrogenation catalyst, for instance a Group VIII metal such as platinum, palladium, nickel, rhodium or iridium on a solid support. In other embodiments, the process may further comprise a step in which the remaining olefinic double bonds in the oligomerised product are alkylated.
In preferred embodiments, the process of the present invention is selective for the preparation of dimers, trimers and tetramers. In further preferred embodiments, the process of the present invention is selective for the preparation of dimers and trimers.
As noted above, the formation of higher oligomers may be further suppressed, if required, by the inclusion of paraffins in the olefinic feedstock.
The oligomerised products produced according to the process of the present invention have a range of desirable properties.
In some embodiments, the oligomerised products produced according to the process of the present invention have a Kv40 of from 5 to 60 cSt, preferably from 10 to 40 cSt.
In some embodiments, the oligomerised products produced according to the process of the present invention have a KvlOO of from ito 15 cSt, preferably from 1.5 to 10 cSt, more preferably from 1.5 to 8.5 cst (such as 2, 4, 5, 6, 7 or 8), still more preferably from 3.5 to 8.5 cst (such as 4, 5, 6, 7 or 8), and most preferably from 3.5 to 6.5 cst (such as 4, 5 or 6).
In some embodiments, the oligomerised products produced according to the process of the present invention have a pour point of -40 °C or less, preferably of -60 °C or less (in accordance with ASTM D97-1 1).
In some embodiments, the oligomerised products produced according to the process of the present invention have a viscosity index (VI) of 100 or greater, more preferably from to 160 (according to ASTM D2270).
It is believed that the borenium ionic liquids described hereinbefore will also exhibit selectivity in other reactions comprising a carbocation mechanism, including Friedel-Crafts alkylation and alkane isomerisation reactions. Thus, in another aspect, the present invention provides a use of the borenium ionic liquids described hereinbefore as a selective Lewis acid catalyst in Friedel-Crafts alkylation and alkane isomerisation reactions.
The present invention will now be illustrated by way of the following examples and with reference to the following figures: FIGURE 1 shows the SimDist GO chromatograph for the products of oligomerisation of 1-decene in the presence of [B012(4pic)][A12C17]; FIGURE 2 shows the Simoist analysis of the product distribution obtained by oligomerising 1-decene in the presence of [C2mim][A12C17] (not of the invention) and [B012(4pic)][A12C17] (according to the invention); FIGURE 3 shows the SimDist GO chromatograph for the products of oligomerisation of 1-hexadecene in the presence of [B012(4pic)][A12C17]; and FIGURE 4 shows the SimDist analysis of the product distribution obtained by oligomerising 1-hexadecene in the presence of [BCI2(4pic)][A12C17] and [BCI2(4pic)][A12C17].HCI.
Examples
Unless otherwise mentioned, all chemicals were purchased from Sigma-Aldrich. 1-Hexadecene was purchased from Id. All starting materials used were dried (for at least 24 hours prior to use) over 3 A molecular sieves. All glassware, stirring bars, syringes etc. were oven-dried (Ca. 140 00, for at least 24 hours prior to use).
Preparation of Ionic Liquids All borenium (b) ionic liquids were prepared following a similar method to that described Ryschkewitsch et at., J. Am. Chem Soc., 92:6, 1790-1791 (1970), involving B-X bond heterolysis reactions.
In a typical experiment, a boron halide solution was transferred into a dry Schlenk flask, under argon. The solution was cooled to -78 00 and subsequently a dry base (or its solution in dichloromethane) was added dropwise to the vigorously stirred solution.
Subsequently, the solvent was removed under reduced pressure and the [BX3(base)] complex was purified by recrystallization. Two equivalents of AId3 were added in small portions to dry [BX3(base)] complex, to form [BX2(base)][A12017] ionic liquid in an exothermic reaction. As an example of an alternative, alkyl triflate was added slowly using a dry gas-tight syringe or a dry pressure-equalising dropping funnel to a vigorously stirred solution of the [BX3(base)] complex in dichloromethane under argon, at 0 00.
Alkyl chloride gas was evolved before the removal of solvent under reduced pressure, affording the dry ionic liquid.
Saturation of ionic liquids with HO! In a typical experiment, the apparatus for HCI generation comprised of a dropping funnel containing sulfuric acid, mounted on top of a two-necked round-bottomed flask containing sodium chloride. Drop-wise addition of the acid to the salt resulted in generation of HCI, following the reaction: H2S04 + NaCI -* Na[HSO4] + H0I The second neck of the two-necked flask was connected (via bubbler with H2504) to a dry Schienk flask, containing vigorously stirred borenium ionic liquid (e.g. [BCI2(4pic)][A12C17]). Excess of HCI gas was captured in a bubbler filled with a basic solution, placed after the Schlenk flask with the ionic liquid. The ionic liquid was stirred under flow of HCI gas for 30 mm. The resulting liquid was more viscous that the starting ionic liquid, the mass balance indicated absorption of nearly equimolar amount of HCI.
Experimental procedure for oligom er/sat/on reactions In a typical experiment, olefin (40 cm3) was placed in a dry, glass reactor (AutoMATE H.E.L. Reactor system), equipped with an overhead stirrer (Hastelloy®), a thermocouple, a heating coil, a cooling mantle, argon inlet and a septum inlet. The reactor was purged with argon, and maintained under positive pressure of argon throughout the experiment. The olefin was stirred vigorously (1000 rpm) and equilibrated at the temperature of reaction (120 °C).
Ionic liquid (1.0 wt %) was added drop-wise to the vigorously stirred olefin, via a gas-tight syringe through the septum of the reactor, which resulted in a strong exotherm.
After the addition, the mixture was allowed to react (30 mm, 120 °C). Afterwards, stirring and heating was stopped, and the reaction was quenched with deionised water. A sample from the top (hydrocarbon) layer was dissolved in toluene, dried over magnesium sulfate, and analysed using gas chromatography (Simoist).
Example I
Ol/gomerLsation of 1-decene Oligomerisation of 1-decene was carried out according to the general procedure described above. Catalysis was conducted with conventional chloroaluminate ionic liquids, [C2mimn][A12C17], [C5mim][A12C17] and [P66614][A12C17] (Entries 1, 2 and 3 in Table 1 below), as well as various borenium ionic liquids in accordance with the present invention (Entries 3 to 13 in Table 1 below). Borenium ionic liquids tested either contained one Lewis acidic centre (the borenium cation) (Entries 4 and 11) or two Lewis acidic centres (the second centre associated with the anion) (Entries 5 to 10, 13 and 13).
Results of the oligomerisation reactions are provided in Table I below.
Table I -Product distribution for oligomerisation of 1-decene Product Product Ent' IL Feed Appearance distribution
-
-3.0%
1 [O2mim][A12017] 010 Yellow oil 040 4.0% 8.0% 10.0% _______ __________________ _____ __________________ 070+ 75.0% 20.3% 16.0% 14.0% 2 [O5mim][A12017] 010 Yellow oil 040 13.0% 13.0% _______ __________________ _____ __________________ 060+ 23.7% 9.3% 23.0% 17.0% 3 [P6661 4][A12017] 010 Yellow oil 040 15.0% 15.0% _______ __________________ _____ __________________ 060+ 20.7% 38.3% 37.0% 4 [B012(4pic)][A1014] 010 Yellow oil 030 19.0% 4.00% ______ _______________ _____ _______________ 050 1.7% 13.3% 31.0% 28.0% [B012(4pic)][A12C17] 010 Yellow oil 040 14.0% 7.0% 3.0% _______ __________________ _____ __________________ 070+ 3.7% 27.3% 24.0% 21.0% 10.0% 6 [B012(DMA)][A12017] 010 Yellow oil 050 6.0% 5.0% 3.0% _______ __________________ _____ __________________ 080+ 3.7% 19.3% 35.0% 29.0% 10.0% 7 [B012(mim)][A12017] 010 Pale yellow oil 050 3.0% 1.0% 1.7% ______ _______________ _____ _______________ 080+ 1.7% 8 [B012(SUr)][A12017] 010 Yellow oil 010 14.3% 26.0% 27.0% 15.0% 7.0% 4.0% 3.0% _______ __________________ _____ __________________ 080+ 3.7% 29.3% 32.0% 9 [B012(P855)][A12C17] 010 Yellow oil gg 4.0% ______ _______________ _____ _______________ 060+ 1.7% 25.3% 38.0% [B012(P5550)][A12017] 010 Yellow oil 030 23.0% 9.0% _______ _________________ _____ _________________ 050+ 47% 50.3% 23.0% 11 [B012(P555)][A1014] 010 Yellow oil 030 17.0% 8.0% ______ _______________ _____ _______________ 050+ 1.7% 24.3% 36.0% 12 [B012(mim)][Ga2017] 010 Pale-yellow oil 030 27.0% 9.0% _______ __________________ _____ __________________ 050 3.7% 72.3% 13 [B012(P8580)][Ga2017] 010 Yellow oil gg _______ _________________ _____ _________________ 040+ 2.7% As illustrated in the results of Table 1 above, in the absence of the borenium cation (Entries 1, 2 and 3), the amount of highly oligomerised products (hexamers and higher oligomers) is significant. Hexamers and higher oligomers for Entries 1, 2 and 3 amount to 85%, 23.7% and 20.7% of the oligomerisation products respectively, which far exceeds the amount of (hexamers and higher oligomers) produced as a result of catalysis with ionic liquids comprising a borenium cation.
For example, replacing [O2mim] of [C2mim][A12C17] (Entry 1) with [B012(4pic)] (Entry 5) reduces the level of highly oligomerised products dramatically. Hexamers and higher oligomers for Entry 5 amount to only 6.7% of the oligomerisation products, compared with 85% for Entry 1. A SimDist GO chromatograph for the products of oligomerisation of 1-decene in the presence of [BCI2(4pic)][A12C17] (Entry 5) are shown in Figure 1. A comparison of the product distributions for the oligomerisation of 1-decene in the presence of [3C12(4pic)][A12C17] (Entry 5) and [C2mim][A12C17] (Entry 1) is provided in Figure 2 in the form of overlaid SimDist curves (simulated distillation curves derived from SimDist GC chromatogram).
The results in Table I also demonstrate that ionic liquids comprising a single Lewis acidic centre in the form of the borenium ion (Entries 3 and 10) also result in good selectivity, with little formation of highly oligomerised products (1.7% in each case).
Where two Lewic acidic centres are present (one in the cation and one in the anion), catalytic activity is increased. For example, replacing neutral anion [AICI4] of [BCI2(4pic)][AICI4] (Entry 3) with Lewis acidic anion [A12C17] (Entry 4) reduces the level of ClO starting materials, from 38.3% to 13.3%, indicating increased catalytic activity, without loss of selectivity.
The borenium cation is thus an active Lewis acidic species which confers favourable selectivity in an oligomerisation reaction, whilst also mitigating against a lack of selectivity associated with the Lewis acidic anion, when present. This is especially advantageous since it means that a catalytic system comprising two Lewis acidic centres having particularly high activity can be used whilst retaining favourable selectivity, which has not previously been realised.
Example 2
Oligomerisation of 1-Hexadecene Oligomerisation of 1-hexadecene was carried out according to the general procedure described above. Catalysis was conducted with borenium ionic liquids in accordance with the present invention, [BCI2(4pic)][A12C17] (Entry 14) and [BCI2(4pic)][A12C17]HCI (Entry 15). [8C12(4pic)][A12017]HCI was prepared in accordance with the procedure described above. Results of the oligomerisation reactions are provided in Table 2 below.
Table 2 -Product distribution for oligomerisation of 1-hexadecene E t IL F d Product Product n ry ee Appearance distribution 14 [BCI2(4pic)][A12C17] C16 Pale yellow oil C16 25.3% C32 35.0% C48 23.0% _______ _________________ _____ ____________ C64 16.7% 016 20.2% 032 35 0°/ [B012(4pic)][A12017]HCl 016 Pale orange oil C48 25.0% _______ _________________ _____ ____________ C64 19.7% The results in Table 2 demonstrate the selectivity of borenium ionic liquids for the formation of dimers (032), trimers (048) and tetramers (064) over highly oligomerised products in the oligomerisation of 1-hexadecene. A SimDist GO chromatograph for the products of oligomerisation of 1-hexadecene in the presence of [BCI2(4pic)][A12017] (Entry 14) are shown in Figure 3.
Furthermore, the results in Table 2 demonstrate the effect of the presence of a Brønsted acid (HOl), which increases catalytic activity, as shown by the decrease in 016 starting material from 25.3% for Entry 14 to 20.2% for Entry 15. The effect of the presence of a Brensted acid is illustrated in Figure 4 which provides a comparison of the product distributions for the oligomerisation of 1-hexadecene in the presence of [B012(4pic)][A12C17] (Entry 14) and [B012(4pic)][A12017].HOl (Entry 15) in the form of overlaid Simoist curves (simulated distillation curves derived from SimDist GO chromatogram).
Example 3
Oligomeri.sation of a mixture of 1-Hexadecene and 1-Octadecene Oligomerisation of a 1:1 weight ratio mixture of I -hexadecene/1 -octadecene was carried out according to the general procedure described above. Oatalysis was conducted with borenium ionic liquids in accordance with the present invention, [B012(P5550)][A12017] (Entry 16) and [B012(P888)][A12017] (Entry 17). Results of the oligomerisation reactions are provided in Table 3 below.
Table 3 -Product distribution for oligomerisation of 1-hexadeceneli-octadecene mixture Product Entry IL Feed Product distnbution __________ __________________ ________ Appearance _______________________ C34 34.3% 16 [B012(P8680)][A12017] 018+16 Yellow oil 0102 ________ _______________ _______ __________ 0136 7.7% 034 25.3% 17 [B012(P555)][A12017] 018+16 Yellow oil 0102 28.0% ________ _______________ _______ __________ 0136 10.7% The results in Table 3 demonstrate the selectivity of further borenium ionic liquids for the formation of dimers (068), trimers (0102) and tetramers (0136) over highly oligomerised products in the oligornerisation of a blend of 1-hexadecene and 1-octadecene. No oligomerisation products aside from dimers, trimers and tetramers were observed.
Example 4
OligomerLsation of 1-Octadecene Oligomerisation of 1-octadecene was carried out according to the general procedure described above. Catalysis was conducted with borenium ionic liquids in accordance with the present invention, [3C12(P3350)][A12C17] (Entry 18) and [B012(P333)][A12C17] (Entry 19). Results of the oligomerisation reactions are provided in Table 4 below.
Table 4 -Product distribution for oligomerisation of 1-octadecene Entry IL Feed tnce Product distribution 018 20.3% C36 37.0% 18 [B012(P5550)][A12C17] 018 Yellow oil C54 27.0% C72 12.0% _________ _________________ _____ ___________ 090+ 3.7% 018 22.3% 036 36.0% 19 [BCI2(P555)][A12C17] 018 Yellow oil 054 28.0% 072 11.0% _________ _________________ _____ ___________ 090+ 2.7% The results in Table 4 demonstrate the selectivity of borenium ionic liquids for the formation of dimers (C36), trimers (C54) and tetramers (072) over highly oligomerised products in the oligomerisation of 1-octadecene. Higher oligomerisation products amounted to only 3.7% or 2.7% of the oligomerisation reaction products for Entries 18 and 19 respectively.
Claims (34)
- CLAIMS1. A process for the preparation of alpha-olefin oligomers, comprising contacting an olefinic feedstock comprising C5 to C20 aipha-olefins with an ionic liquid comprising: (i) at least one borenium cation of the formula [BX2L], wherein L is a Lewis basic donor ligand containing a donor atom selected from oxygen, sulphur, selenium, nitrogen, phosphorus, arsenic, and each X is independently selected from fluorine, chlorine and bromine; and (ii) at least one non-coordinating anion.
- 2. A process according to Claim I wherein each X is independently selected from fluorine or chlorine, preferably chlorine.
- 3. A process according to Claim 1 or Claim 2 wherein the Lewis basic donor ligand is selected from ligands containing a donor atom selected from oxygen, sulphur, nitrogen and phosphorus, preferably nitrogen.
- 4. A process according to any of the preceding claims, wherein the Lewis basic donor ligand is selected from the group of compounds consisting of ketones, sulfoxides, phosphine-oxides, ureas, esters, amides, ethers, thioketones, thioureas, thioamides, thioethers, amines, nitriles and phosphines.
- 5. A process according to Claim 4, wherein the Lewis basic donor ligand is selected from amides and amines, preferably amines.
- 6. A process according to Claim 4, wherein the Lewis basic donor ligand is selected from compounds having a formula selected from Ri-C(O)-Ri, R1-S(O)-R1,R2NH-C(O)-NHR2, R2NH-C(S)-NHR2. R1-C(O)-NR2, Ri-C(O)-ORi, (Ra)aP, (Rs)sP(O) and Ri-CN; wherein: each Ri independently represents a Ci to Cio alkyl group, preferably a Ci to C6 alkyl group, more preferably a Ci to Cs alkyl group and most preferably a methyl group; R2is selected from hydrogen ora Cito Cioalkyl group, more preferably from hydrogen or a Ci to C6 alkyl group, still more preferably from hydrogen or a Ci to Cs alkyl group, and most preferably from hydrogen or a methyl group; and Ra represents a 04 to Ow alkyl group; wherein any of Ri, R2 and Rs may optionally be substituted by one or more fluorine atoms.
- 7. A process according to Claim 6, wherein the at least one Lewis basic donor ligand is selected from urea, N,N'-dimethylurea, N,N'-dimethylthiourea, acetamide, dimethylacetamide, acetone, ethyl acetate dimethylsulfoxide, trioctylphosphine and trioctylphosphine oxide.
- 8. A process according to any of Claims I to 4, wherein the Lewis basic donor ligand is selected from a heterocyclic group comprising one or more of 0, N, NH and S in the ring.
- 9. A process according to Claim 8, wherein the heterocyclic group is selected from ethylene oxide, azetidinyl, pyrrolidinyl, pyrrolyl, pyrazolyl, oxetanyl, pyrazolinyl, imidazolyl, imidazolinyl, imidazolidinyl, oxazolyl, oxazolidinyl, isoxazolinyl, isoxazolyl, thiazolyl, thiadiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, furyl, tetrahydrofuryl, thienyl, oxadiazolyl, piperidinyl, piperazinyl, azepinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, triazolyl, tetrazolyl, tetrahydropyranyl, morpholinyl, thiamorpholinyl, preferably selected from imidazolyl, pyridyl and pyrrolyl.
- 10. A process according to Claim 9, wherein the heterocyclic group is selected from picoline, lutidine, pyridine, collidine, dimethylaminopyridine (DMAP), 1-alkyl-imidazole, preferably 1 -methyl-imadazole (mim).
- 11. A process according to any of the preceding claims wherein the at least one non-coordinating anion is selected from a) halometallate anions of the formula [MX4f or [M2X7f, where M is Al or Ga, preferably Al, and X is independently Cl or Br, preferably Cl; b) bis(triflamide) ([NTf2f) or triflate ([01ff); c) bis(perfluoroalkylsulphonyl)imides (preferably methyl, ethyl, butyl and nonyl) d) tetrafluoroborate ([BF4f) or tetrachloroborate ([BCI4fl; e) hexafluorophosphate ([PF5f); f) [SnX3f or [Sn2X5], where X is independently Cl or Br; g) dichlorocuprate ([CuCI2]); h) hexafluoroantimonate ([SbF5fl; i) hexafluoroarsenate ([AsF6fl; j) fluorosulphonate ([F-S02-0]) and pertluoroalkyl suiphonates (preferably methyl); and k) chlorozincate(ll) anions, preferably [ZnCI4]2 or [Zn2CI6]2.
- 12. A process according to Claim 11 wherein the at least one non-coordinating anion is selected from a) halometallate anions of the formula [MX4r or [M2X7f, where M is Al or Ga, preferably Al, and X is independently Cl or Br, preferably Cl; b) bis(triflamide) ([N1f2])); c) bis(perfluoroalkylsulphonyl)imides (preferably methyl, ethyl, butyl or nony; d) tetrafluoroborate ([BF4]); e) hexafluorophosphate ([PF8fl; and f) [SnX3f or [Sn2X5r where and X is independently Cl or Br.
- 13. A process according to Claim 12 wherein the at least one non-coordinating anion is selected from halometallate anions of the formula [MX4f or [M2X7f, where M is Al or Ga and X is independently Cl or Br.
- 14.A process according to Claim 13 wherein the at least one non-coordinating anion is selected from halometallate anions of the formula [M2X7f, where M is Al or Ga, preferably Al, and X is independently Cl or Br, preferably Cl.
- 15. A process according to Claim 11, wherein the at least one non-coordinating anion is Lewis acidic and selected from the group consisting of [A12C17]-, [Ga2Cl7, [Sn2Cl5f and [Zn2CI6]2.
- 16.A process according to any one of the preceding claims, wherein the olefinic feedstock comprises at least 50 wt% of one or more C5 to C20 alpha-olefins, more preferably at least 60 wt% of one or more 05 to 020 alpha-olefins, more preferably at least 70 wt% of one or more C5 to C20 alpha-olefins, more preferably at least 80 wt% of one or more 05 to C20 alpha-olefins, more preferably at least 90 wt% of one or more C5 to C20 alpha-olefins, and most preferably at least 95 wt% of one or more C5to C2oalphaolefins.
- 17.A process according to Claim 16, wherein the olefinic feedstock comprises at least 50 wt% Cs to Gm alpha-olefins, more preferably at least 60 wt% Cs to Cia alphaolefins, more preferably at least 70 wt% 06 to Cia alpha-olefins, still more preferably at least 80 wt% Cs to Cia alpha-olefins, and most preferably at least 90 wt% C6to Cia alpha-olefins.
- 18.A process according to any one of the preceding claims, wherein the olefinic feedstock comprises at least 30 wt% Cs to 014 alpha-olefins, preferably at least 50 wt% Cs to 014 alpha-olefins, more preferably at least 70 wt% Cs to C14 alpha-olefins, still more preferably at least 80 wt% Cs to C14 alpha-olefins, and most preferably at least 90 wt% 10 Cs to C14 alpha-olefins.
- 19.A process according to Claim 18, wherein the olefinic feedstock comprises at least 30 wt% C10 to C14 alphaolefins, more preferably at least 50 wt% 010 to C14 alpha-olefins, more preferably at least 70 wt% C10 to C14 alpha-olefins, still more preferably at least 80 wt% C5 to C14 alpha olefins, and most preferably at least 90 wt% C10 to C14 alpha-olefins.
- 20.A process according to Claim 18 or Claim 19, wherein the olefinic feedstock comprises at least 30 wt% Cioto Cl2alpha-olefins, preferably at least 50 wt% Cm to Cl2alpha-olefins, more preferably at least 70 wt% Cioto Cl2alpha-olefins, still more preferably at least 80 wt% Cm to C12 alpha-olefins, and most preferably at least 90 wt% Ci o to C12 alphaolefins.
- 21. A process according to Claim 20, wherein the olefinic feedstock comprises at least 30 wt% 1-decene, preferably at least 50 wt% 1-decene, more preferably at least 70 wt% 1-decene, still more preferably at least 80 wt% 1-decene, and most preferably at least 90 wt% 1-decene.
- 22. A process according to Claim 20, wherein the olefinic feedstock comprises at least 30 wt% 1 -dodecene, preferably at least 50 wt% 1 -dodecene, more preferably at least 70 wt% 1-dodecene, still more preferably at least 80 wt% 1-dodecene and most preferably at least 90 wt% 1-dodecene.
- 23.A process according to any one of Claims Ito 17, wherein the olefinicfeedstock comprises at least 30 wt% Cm to Cm alpha-olefins, more preferably at least 50 wt% C16 to Cia alpha-olefins, more preferably at least 70 wt% Cm to Cia alpha-olefins, still more preferably at least 80 wt% 016 to Cia alpha-olefins, and most preferably at least 90 wt% 016 to Cia aipha-olefins.
- 24. A process according to Claim 23, wherein the olefinic feedstock comprises at least 30 wt% 1-hexadecene, more preferably at least 50 wt% 1-hexadecene, more preferably at least 70 wt% 1-hexadecene, still more preferably at least 80 wt% 1-hexadecene, and most preferably at least 90 wt% 1-hexadecene.
- 25. A process according to Claim 23, wherein the olefinic feedstock comprises at least 30 wt% 1-octadecene, more preferably at least 50 wt% 1-octadecene, more preferably at least 70 wt% 1-octadecene, still more preferably at least 80 wt% 1-octadecene and most preferably at least 90 wt% 1-octadecene.
- 26. A process according to any one of the preceding claims, wherein the olefinic feedstock comprises a minor amount of paraffins.
- 27. A process according to any one of the preceding claims, wherein the olefinic feedstock is contacted with the ionic liquid at a temperature of from 0 to 160 00, more preferably 40 to 140 °C, more preferably 80 to 140 °C, still more preferably to 140 °C, and most preferably about 120 °C.
- 28. A process according to any one of the preceding claims, wherein the olefinic feedstock is contacted with the ionic liquid at a pressure of from 10 to 1000 kPa, preferably from 20 to 500 kPa, more preferably from 50 to 200 kPa, still more preferably from 80 to 120 kPa, and most preferably about 100 kPa.
- 29. A process according to any one of the preceding claims, wherein the olefinic feedstock is contacted with at least 0.01 wt% of the ionic liquid, more preferably at least 0.05 wt% of the ionic liquid, still more preferably at least 0.1 wt% of the ionic liquid, and most preferably at least 0.2 wt% of the ionic liquid, based on the total weight of the ionic liquid and olefinic feedstock.
- 30. A process according to Claim 29, wherein the olefinic feedstock is contacted with from 0.01 to 5 wt% of the ionic liquid, preferably from 0.05 to 2 wt% of the ionic liquid, still more preferably from 0.1 to 1 wt% of the ionic liquid and still more preferably from 0.2 to 0.8 wt% of the ionic liquid, based on the total weight of the ionic liquid and olefinic feedstock.
- 31. A process according to Claim 30, wherein the olefinic feedstock is contacted with about 0.5 wt% of the ionic liquid, based on the total weight of the ionic liquid and olefinic feedstock.
- 32. A process according to any one of the preceding claims which is selective for the preparation of dimers, trimers and tetramers.
- 33. Use of an ionic liquid as defined in any of Claims I to 15 as a selective Lewis acid catalyst for selectively forming dimers, trimers and tetramers in an oligomerisation reaction of a feed stock comprising 05 to 020 alpha-olefins.
- 34. Use of an ionic liquid as defined in any of Claims I to 15 as a selective Lewis acid catalyst in Friedel-Crafts alkylation and alkane isomerisation reactions.
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| GB1412398.8A GB2528128A (en) | 2014-07-11 | 2014-07-11 | Oligomerisation process |
| PCT/GB2015/052007 WO2016005769A1 (en) | 2014-07-11 | 2015-07-10 | Oligomerisation process |
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| GB2538758A (en) | 2015-05-27 | 2016-11-30 | Green Lizard Tech Ltd | Process for removing chloropropanols and/or glycidol |
| EP3098292A1 (en) | 2015-05-27 | 2016-11-30 | Evonik Degussa GmbH | A process for refining glyceride oil comprising a basic quaternary ammonium salt treatment |
| DE102015212749A1 (en) | 2015-07-08 | 2017-01-12 | Evonik Degussa Gmbh | Method for dehumidifying moist gas mixtures |
| ES2670473T3 (en) | 2015-12-04 | 2018-05-30 | Evonik Degussa Gmbh | Improved procedure for the extraction of flavoring substances from fatty and / or aqueous liquid phases |
| DE102016210484A1 (en) | 2016-06-14 | 2017-12-14 | Evonik Degussa Gmbh | Method for dehumidifying moist gas mixtures |
| DE102016210478A1 (en) | 2016-06-14 | 2017-12-14 | Evonik Degussa Gmbh | Method for dehumidifying moist gas mixtures |
| EP3257568B1 (en) | 2016-06-14 | 2019-09-18 | Evonik Degussa GmbH | Method for the removal of moisture from moist gas mixtures by use of ionic liquids |
| EP3483237A1 (en) | 2017-11-10 | 2019-05-15 | Evonik Degussa GmbH | Method of extracting fatty acids from triglyceride oils |
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|---|---|---|---|---|
| US3769363A (en) * | 1972-03-13 | 1973-10-30 | Mobil Oil Corp | Oligomerization of olefins with boron trifluoride |
| EP0364889A2 (en) * | 1988-10-17 | 1990-04-25 | Idemitsu Petrochemical Co. Ltd. | Process for manufacturing an olefin oligomer and process for recovering catalysts therefrom |
| EP0594065A1 (en) * | 1992-10-19 | 1994-04-27 | Idemitsu Petrochemical Co., Ltd. | Process for recovering boron trifluoride |
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| GB9603754D0 (en) * | 1996-02-22 | 1996-04-24 | Bp Chem Int Ltd | Lubricating oils |
| JP2000202299A (en) * | 1999-01-20 | 2000-07-25 | Tosoh Corp | Catalyst for trimerizing ethylene and method for trimerizing ethylene using the same |
| US6395948B1 (en) * | 2000-05-31 | 2002-05-28 | Chevron Chemical Company Llc | High viscosity polyalphaolefins prepared with ionic liquid catalyst |
| US7572944B2 (en) * | 2005-12-20 | 2009-08-11 | Chevron U.S.A. Inc. | Process for making and composition of superior lubricant or lubricant blendstock |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769363A (en) * | 1972-03-13 | 1973-10-30 | Mobil Oil Corp | Oligomerization of olefins with boron trifluoride |
| EP0364889A2 (en) * | 1988-10-17 | 1990-04-25 | Idemitsu Petrochemical Co. Ltd. | Process for manufacturing an olefin oligomer and process for recovering catalysts therefrom |
| EP0594065A1 (en) * | 1992-10-19 | 1994-04-27 | Idemitsu Petrochemical Co., Ltd. | Process for recovering boron trifluoride |
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