CN102245302A - 一种具有高Al/N 摩尔比的离子液体催化剂 - Google Patents
一种具有高Al/N 摩尔比的离子液体催化剂 Download PDFInfo
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- CN102245302A CN102245302A CN2009801502252A CN200980150225A CN102245302A CN 102245302 A CN102245302 A CN 102245302A CN 2009801502252 A CN2009801502252 A CN 2009801502252A CN 200980150225 A CN200980150225 A CN 200980150225A CN 102245302 A CN102245302 A CN 102245302A
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- ionic
- liquid catalyst
- aluminate
- catalyst
- alkyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 154
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 120
- 229910052782 aluminium Inorganic materials 0.000 title description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title 2
- 229910052757 nitrogen Inorganic materials 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 230000029936 alkylation Effects 0.000 claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- -1 halogen ions Chemical class 0.000 claims description 37
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 230000021736 acetylation Effects 0.000 claims description 3
- 238000006640 acetylation reaction Methods 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000005695 dehalogenation reaction Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000006471 dimerization reaction Methods 0.000 claims description 3
- 238000007037 hydroformylation reaction Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- 150000001348 alkyl chlorides Chemical class 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 2
- 229910016467 AlCl 4 Inorganic materials 0.000 description 2
- 240000004160 Capsicum annuum Species 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 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 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CZHLPWNZCJEPJB-UHFFFAOYSA-N 1-chloro-3-methylbutane Chemical compound CC(C)CCCl CZHLPWNZCJEPJB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical group CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- CDNBBXKOCUDMCC-UHFFFAOYSA-N but-1-ene;2-methylpropane Chemical compound CCC=C.CC(C)C CDNBBXKOCUDMCC-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical group CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007871 hydride transfer reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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- C07C2/58—Catalytic processes
- C07C2/60—Catalytic processes with halides
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- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G2300/1081—Alkanes
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
提供了一种离子液体催化剂，其包含铵氯铝酸盐，并当所述离子液体催化剂在≤25℃的温度下保存至少2小时时，具有大于2.0的Al/N摩尔比。还提供了包含烷基-吡啶卤铝酸盐和杂质的离子液体催化剂，其中当所述离子液体催化剂在≤25℃的温度下保存至少2小时时，所述离子液体催化剂具有大于2.0的Al/N摩尔比。在第三实施方案中，提供了用于异链烷烃/烯烃烷基化的离子液体体系，包含：季铵氯铝酸盐、混合聚合物和氯化氢。所述离子液体体系具有2.1至8.0的Al/N摩尔比。当所述离子液体体系在25℃或更低温度下保存3小时或更长时间时，小于0.1wt％的AlCl3从所述离子液体体系中沉淀出来。
Description
本申请涉及共同提交的题目为“一种具有高Al/N摩尔比的液体催化剂的制备方法”和“一种酸催化剂的组成、其制备方法和使用其进行烃转化的方法”的专利申请，通过引用将它们的全文并入本文。
发明领域
本发明涉及离子液体催化剂和具有大于2.0的Al/N摩尔比的离子液体催化剂体系。
发明详述
提供了一种包含铵氯铝酸盐的离子液体催化剂。当所述离子液体催化剂在≤25℃的温度下保存至少2小时时，所述离子液体催化剂具有大于2.0的Al/N摩尔比。
还提供了包含烷基-吡啶
卤铝酸盐和杂质的离子液体催化剂，其中当所述离子液体催化剂在≤25℃的温度下保存至少2小时时，所述离子液体催化剂具有大于2.0的Al/N摩尔比。
在第三实施方案中，提供了用于异链烷烃/烯烃烷基化的离子液体体系，包含：季铵氯铝酸盐、混合聚合物(conjunct polymer)和氯化氢。所述离子液体体系具有从2.1至8.0的Al/N摩尔比。当所述离子液体体系在≤25℃下保存3小时或更长时间时，小于0.1wt％的AlCl3从所述离子液体体系中沉淀出来。
定义：
术语“包含”是指包括在该术语之后指明的元素或步骤，但任何这样的元素或步骤不是穷举性的，且实施方案可包括其它元素或步骤。
“离子液体”是其组成由作为阳离子和阴离子的结合的离子组成的液体。最常见的离子液体是由有机基的阳离子和无机或有机阴离子制备的那些。离子液体催化剂用于多种反应，包括Friedel-Crafts反应。
“烷基”是指1-9个碳原子的直链饱和烃或3-12个碳原子的支链饱和烃。在一个实施方案中，所述烷基是甲基。烷基的实例包括但不限于：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基，等等。
离子液体催化剂：
离子液体催化剂由形成络合物的至少两种组分组成。为了在烷基化反应中有效，离子液体催化剂是酸性的。该离子液体催化剂包含第一组分和第二组分。该催化剂的第一组分一般包含路易斯酸化合物。用于烷基化反应的路易斯酸包括但不限于卤化铝、卤化镓、卤化铟、卤化铁、卤化锡和卤化钛。在一个实施方案中，所述第一组分是卤化铝或卤化镓。例如，三氯化铝(AlCl3)可用作制备所述离子液体催化剂的第一组分。
构成所述离子液体催化剂的第二组分是有机盐或盐的混合物。这些盐可用通式Q+A-来表示，其中Q+是铵、鏻或锍阳离子，和A-是负电荷离子例如Cl-、Br-、ClO4 -、NO3 -、BF4 -、BCl4 -、PF6W、SbF6 -、AlCl4 -、Al2Cl7 -、Al3Cl10 -、AlF6 -、TaF6 -、CuCl2 -、FeCl3 -、SO3CF3 -和3-硫三氧苯基。在一个实施方案中，所述第二组分选自具有含有一个或多个具有约1-约9个碳原子的烷基结构部分的季铵卤化物的那些，例如三甲基胺盐酸盐，甲基三丁基铵卤化物、1-丁基吡啶
卤化物或烃基取代的咪唑卤化物例如1-乙基-3-甲基-咪唑
氯化物。
在一个实施方案中，Al处于AlCl3的形式和N处于R4N+X-或R3NH+X-的形式，其中R是烷基和X是卤离子。合适的卤离子的实例是氯离子、溴离子和碘离子。
在一个实施方案中，所述离子液体催化剂是通式为RR’R”N H+Al2Cl7 -的季铵氯铝酸盐离子液体，其中RR’和R”为含有1-12个碳的烷基。
季铵氯铝酸盐离子液体的实例是N-烷基-吡啶
氯铝酸盐、N-烷基-烷基吡啶
氯铝酸盐、吡啶
氢氯铝酸盐(pyridinium hydrogenchloroaluminate)、烷基吡啶氢氯铝酸盐、二-烷基-咪唑
氯铝酸盐、四-烷基-铵氯铝酸盐、三-烷基-铵氢氯铝酸盐、或它们的混合物。
第一组分的存在应该为离子液体提供了路易斯酸特性或富兰克林酸特性。一般来说，第一组分与第二组分的摩尔比越大，离子液体混合物的酸度就越大。
例如，制备Al/N摩尔比为2.0的正丁基吡啶
氯铝酸盐离子液体盐的典型的混合物如下所示：
对于以上反应的情况，和对于典型的季铵氯铝酸盐的情况，在室温下Al/N摩尔比不能长时间地超过2.0。这是因为有一些额外的AlCl3沉淀出来且不会停留在该离子液体中。
已经发现，本发明的离子液体催化剂中的Al/N摩尔比能够高于Al/N摩尔比最大值为2.0的新鲜制备的季铵氯铝酸盐或烷基吡啶
卤铝酸盐离子液体中可能的Al/N摩尔比。在一些实施方案中，Al/N摩尔比大于2.1，大于2.5，或甚至大于2.8。在一些实施方案中，Al/N摩尔比小于9，小于8，小于5，或小于4。在一个实施方案中，Al/N摩尔比为2.1至8；例如，2.5至5.1或2.5至约4。
一方面，所述离子液体催化剂在该催化剂中包含杂质，该杂质增加了催化剂在催化剂相中吸收(uptake)更多AlCl3的能力。在一个实施方案中，所述催化剂包含混合聚合物作为杂质，该杂质增加了催化剂吸收AlCl3的能力。在该实施方案中，混合聚合物的含量以仍然能够使所述离子液体催化剂或催化剂体系发挥其期望的催化功能的量存在。
与其它包含杂质的离子液体催化剂相比，所述杂质的存在是有利的，因为该实施方案中的该杂质不会使所述催化剂显著失活。所述离子液体催化剂保持有效地发挥其期望的催化功能。所述离子液体催化剂能够用于烃转化反应而不必长时间地停止该反应并再生该催化剂。
在一个实施方案中，具有大于2.0的Al/N摩尔比的所述离子液体催化剂的优势在于：其连续发挥有效地转化烃的功能，而不变得被混合聚合物显著失活。在该实施方案中，可以连续地使用酸催化剂而不必长时间地从反应器中将其移出，或能够减少催化剂的排放。在该实施方案中，所述酸催化剂可以部分再生，以使得每次仅一部分酸催化剂被再生，且烃转化过程不需要被中断。例如，所述离子液体催化剂流出物的滑流(slip stream)能被再生并循环到烃转化反应器中。在一个实施方案中，通过在连续烃转化过程中部分再生，所述混合聚合物的含量被维持在期望的范围内。
杂质(例如混合聚合物)的含量一般小于或等于30wt％，但杂质在所述离子液体催化剂或催化剂体系中的其它期望范围的实例为1-24wt％、1-20wt％、0.5-15wt％或0.5-12wt％。
术语混合聚合物首先由Pines和Ipatieff用来把这些聚合的分子与普通的聚合物区分开。与一般的聚合物(一般的聚合物是由较小分子的重复单元通过受控的或半受控的聚合反应形成的化合物)不同，“混合聚合物”是通过并发的酸催化的转变(包括聚合反应、烷基化反应、环化反应、加成反应、消去反应和氢负离子转移反应)由两个或更多个反应单元非对称地形成的“拟聚合的”化合物。因此，所产生的“拟聚合的”物质可包括很多具有不同结构和取代模式的的化合物。因此，“混合聚合物”的骨架结构从非常简单的线性分子变化到非常复杂的多特征分子。
Miron等人(Journal of Chemical and Engineering Data，1963)和Pines(Chem.Tech，1982)报道了混合聚合物中可能的聚合物种的一些实例。混合聚合物因其微红色-琥珀色的颜色又被炼油工业中的技术人员通常称为“红油”或因为它们在催化相中高吸收而被称为“酸溶性的油”，而具有低的烯属性(olefinicity)和低官能团的链烷属产物和烃通常是不混溶于该催化剂相中的。在本申请中，术语“混合聚合物”也包括ASO(酸溶性的油)和红油。
酸催化剂中的混合聚合物的含量通过已知重量的该催化剂的水解来测定。合适的测试方法的实例描述于共同受让的美国专利公布号US20070142213A1的实施例3中。通过水解从酸催化剂中回收混合聚合物。该水解回收方法采用的程序导致混合聚合物完全回收且通常用于分析和表征的目的，因为它导致催化剂的破坏。例如通过将废催化剂在过量水的存在下搅拌来进行酸催化剂的水解，然后用低沸点烃溶剂例如戊烷或己烷萃取。在该水解过程中，催化剂盐和在水解过程中形成的其它盐进入水层中而混合聚合物进入有机溶剂中。在旋转蒸发器上在真空和中等温度下将含所述混合聚合物的低沸点溶剂浓缩，以除去萃取剂，剩下高沸点的残留油(混合聚合物)，对其进行收集和分析。也可通过蒸馏方法将低沸点萃取剂除去。
在一个实施方案中，所述离子液体催化剂或催化剂体系中的混合聚合物的含量越高，Al/N摩尔比就越高。这是因为催化剂吸收AlCl3的能力在催化剂相中有较高浓度的混合聚合物时增加。
在一个实施方案中，所述离子液体催化剂或催化剂体系中Al/N摩尔比高于2.0时所增加的AlCl3的溶解度在50℃或更低温度下为3wt％或更高。在其它实施方案中，所述离子液体催化剂或催化剂体系中Al/N摩尔比高于2.0时所增加的AlCl3的溶解度在50℃或更低温度下为3wt％-20wt％，或4wt％-15wt％。
在一个实施方案中，所述离子液体催化剂或催化剂体系中Al/N摩尔比高于2.0时所增加的AlCl3的溶解度在100℃下比在50℃下显著更高。例如，所述离子液体催化剂或催化剂体系中Al/N摩尔比高于2.0时所增加的AlCl3的溶解度在100℃下能大于10wt％，例如在100℃下为12-50wt％，12-40wt％，或15-35wt％。在一个实施方案中，所述离子液体催化剂或催化剂体系中Al/N摩尔比高于2.0时所增加的AlCl3的溶解度在100℃下比在50℃下高出至少10wt％。
在一个实施方案中，在所述离子液体催化剂或催化剂体系中可溶且稳定的AlCl3在所述离子液体催化剂或催化剂体系中保持可溶。其实例是，当所述离子液体催化剂或催化剂体系在25℃或更低温度下保存至少3小时时，小于0.1wt％、小于0.05wt％、小于0.01wt％或0wt％的AlCl3从所述离子液体催化剂或催化剂体系中沉淀出来。
在一个实施方案中，所述混合聚合物是可提取的。在催化剂再生过程中，可例如通过用金属铝或用金属铝和氯化氢来处理所述催化剂来提取该混合聚合物。再生离子液体催化剂的方法的实例教导于美国专利公布US20070142215A1、US20070142213A1、US20070142676A1、US20070142214A1、US20070142216A1、US20070142211A1、US20070142217A1、US20070142218A1、US20070249485A1和2007年12月19日提交的美国专利申请11/960319、2007年12月28日提交的12/003577、2007年12月28日提交的12/003578、2008年4月8日提交的12/099486和2008年11月26日提交的61/118215中。
在一些实施方案中，所述离子液体催化剂用于催化烃转化反应。烃转化反应的一个实例是Friedel-Crafts反应。其它实例是烷基化、异构化、加氢裂化、聚合、二聚、低聚、酰化、乙酰化、复分解、共聚、加氢甲酰化、脱卤、脱水、烯烃加氢以及它们的组合。例如，一些所述离子液体催化剂用于异链烷烃/烯烃烷基化反应。离子液体催化剂以及它们用于异链烷烃/烯烃烷基化反应的实例教导于例如美国专利号7,432,408和7,432,409、7,285,698和2008年7月31日提交的美国专利申请号12/184069中。可由这些方法制得高品质的汽油调和组分和中间蒸馏物。在一些实施方案中，来自异链烷烃/烯烃烷基化反应的烷基化物的研究法辛烷值(RON)为86或更高，或甚至92或更高。使用ASTMD 2699-07a测定该RON。此外，RON可由气相色谱沸程分布数据来计算[RON (GC)]。
所述催化剂在≤25℃的温度下保存的时间能够相当长。通常，该时间为至少2小时、3小时或更长，直至2周、多于50天、数月或甚至一年。
所述烷基-吡啶
卤铝酸盐可包含选自由氯铝酸盐、氟铝酸盐、溴铝酸盐、碘铝酸盐和它们的混合物组成的组中的卤铝酸盐。在一个实施方案中，所述烷基为甲基、乙基、丙基、丁基、戊基或己基。
在一个实施方案中，由烷基氯至少部分地产生氯化氢。在一个实施方案中，该氯化氢增加了酸度，且因此增加了离子液体催化剂的活性。在一个实施方案中，氯化氢，与铝组合，有助于非活性的阴离子AlCl4 -的转化以形成用于烷基化反应的更具酸性且更有效的氯铝酸盐物种，例如AlCl3、Al2Cl7 -或甚至Al3Cl10 -。在一些实施方案中，所述烷基氯衍生自在给定反应中使用的异链烷烃或烯烃。例如，对于在氯铝酸盐离子液体中异丁烯与丁烷的烷基化反应来说，烷基氯可以是1-丁基氯、2-丁基氯、叔丁基氯或它们的混合物。可使用的烷基氯的其它实例是乙基氯、异戊基氯、己基氯或庚基氯。在一个实施方案中，烷基氯的量应该保持在低浓度，且不超过该催化剂的路易斯酸部分即AlCl3的摩尔浓度。在一个实施方案中，所使用的烷基氯的量可为离子液体催化剂的路易斯酸部分即AlCl3的0.05mol％-100mol％。可调整烷基氯的量以保持所述离子液体催化剂或离子液体催化剂体系的酸度在期望的发挥作用的能力上。在另一实施方案中，烷基氯的量与烯烃的量成比例，且不超过异链烷烃/烯烃烷基化反应中的烯烃的摩尔浓度。
在本申请提交时，任何未被定义的术语、缩写或速记被理解为具有本领域技术人员所使用的普通含义。单数形式“一个”、“一种”和“该”包括复数被指物，除非明确且明白地限制于一个的情形。
通过引用将本申请中所引用的所有出版物、专利和专利申请全文并入本文中，并入程度仿佛各个出版物、专利申请或专利的公开内容被专门地且单独地指出，以通过引用将它们的全部内容并入本文。
该书面描述使用实施例来公开本发明，包括最佳方式，且也使本领域技术人员能够实施和使用本发明。本领域技术人员将容易对以上公开的本发明的示例性实施方案做出许多改变。因此，本发明将被理解为包括落入所附权利要求范围的所有结构和方法。
实施例
实施例1：
用丁基吡啶氯铝酸盐离子液体催化且用叔丁基氯助催化的异丁烷-丁烯烷基化反应在连续液相反应器中进行。在所述烷基化过程中，通过将离子液体催化剂在每次通过该烷基化反应器之后与金属铝在100℃下混合来连续再生该离子液体催化剂。金属铝再生处理通过除去大部分的作为烷基化反应的副产物积聚于催化剂相中的混合聚合物并通过制备-再制备AlCl3来对催化剂进行再次活化。该再生导致过量AlCl3的形成，取决于有多少氯离子从用作助催化剂的烷基氯中进入到催化剂相中。
在烷基化过程中，所述离子液体催化剂中混合聚合物的含量维持在2-23wt％。离子液体的元素分析表明，Al/N摩尔比在烷基化过程中随时间而增加，在连续生成循环过程中，没有形成过量AlCl3的沉淀。没有混合聚合物的新鲜制备的离子液体的Al/N摩尔比为2.0。在烷基化过程中，当在五十多天期间内取样时，液体催化剂中的Al/N摩尔比增加到2.1，然后增加到2.5且然后增加到4.0。即便具有较高的Al/N摩尔比，所述离子液体催化剂仍对于烷基化反应保持有效，且产生RON大于92的烷基化物产物。催化剂中较高的Al/N摩尔比以及混合聚合物延长了所述离子液体催化剂在其需要彻底再生之前的寿命。
实施例2：
在四个不同的温度下，测试了具有不同含量的混合聚合物杂质的正丁基吡啶
氯铝酸盐离子液体催化剂的不同样品中Al/N摩尔比高于2.0时所增加的AlCl3的溶解度。下表1中总结了溶解度研究的结果。
表1
在离子液体催化剂中，所有包含混合聚合物的催化剂样品在100℃下的增加的AlCl3的溶解度比在50℃下高出至少10wt％。将具有不同量的溶解的增加的AlCl3的样品移至室温下且随时间观察AlCl3沉淀。室温为约25℃或更低。
最初可溶于新鲜催化剂中的所有增加的AlCl3在室温(例如≤25℃)下放置2小时内沉淀出来。原本可溶于具有约2wt％混合聚合物的再生催化剂中的增加的AlCl3的约75％在室温下放置72小时内沉淀出来。
当将具有11wt％混合聚合物的再生催化剂放置在室温下整夜时，微量的增加的AlCl3从该再生催化剂中沉淀出来。经在室温下放置2周时间，基本上没有额外量沉淀出来。
在室温下保存超过2周的废催化剂样品中，没有观察到沉淀。
权利要求书(按照条约第19条的修改)
1.一种离子液体催化剂，其包含铵氯铝酸盐和1-24wt％的混合聚合物，其中当所述离子液体催化剂在≤25℃的温度下保存至少2小时时，所述离子液体催化剂具有大于2.0的Al/N摩尔比；其中在50℃或更低温度下，所述离子液体催化剂中Al/N摩尔比高于2.0时增加的AlCl3的溶解度为3wt％或更高；且其中所述离子液体催化剂对于发挥催化功能来说是有效的。
2.权利要求1的离子液体催化剂，其中Al处于AlCl3的形式和N处于R4N+X-或R3NH+X-的形式，其中R是烷基和X是卤离子。
3.权利要求1的离子液体催化剂，其中所述Al/N摩尔比大于2.1。
4.权利要求1的离子液体催化剂，其中所述混合聚合物以2-23wt％的含量存在于所述催化剂中。
5.权利要求1的离子液体催化剂，其中在50℃或更低温度下，所述离子液体催化剂中Al/N摩尔比高于2.0时增加的AlCl3的溶解度为4-15wt％。
6.权利要求1的离子液体催化剂，其中所述离子液体催化剂中Al/N摩尔比高于2.0时增加的AlCl3的溶解度在100℃下比在50℃下高出至少10wt％。
7.权利要求1的离子液体催化剂，其中当所述离子液体催化剂在25℃下保存3小时或更长时间时，小于0.1wt％的AlCl3从所述离子液体催化剂中沉淀出来。
8.权利要求1的离子液体催化剂，其中所述催化功能是选自下组的烃转化反应：烷基化、异构化、加氢裂化、聚合、二聚、低聚、酰化、乙酰化、复分解、共聚、加氢甲酰化、脱卤、脱水、烯烃加氢以及它们的组合。
9.权利要求1的离子液体催化剂，其中铵氯铝酸盐是N-烷基-吡啶
氯铝酸盐、N-烷基-烷基吡啶
氯铝酸盐、吡啶
氢氯铝酸盐、烷基吡啶
氢氯铝酸盐、二-烷基-咪唑
氯铝酸盐、四-烷基-铵氯铝酸盐、三-烷基-铵氢氯铝酸盐、或它们的混合物。
10.一种离子液体催化剂，包含烷基-吡啶
卤铝酸盐和杂质，其中当所述离子液体催化剂在≤25℃的温度下保存至少2小时时，所述离子液体催化剂具有大于2.0的Al/N摩尔比；其中所述离子液体催化剂对于发挥催化功能来说是有效的；且其中所述杂质以1-24wt％的含量存在于所述离子液体催化剂中。
11.权利要求10的离子液体催化剂，其中所述烷基-吡啶
卤铝酸盐包含选自由氯铝酸盐、氟铝酸盐、溴铝酸盐、碘铝酸盐和它们的混合物组成的组的卤铝酸盐。
12.权利要求1或权利要求10的离子液体催化剂，其中Al/N摩尔比为2.1至8.0。
13.权利要求10的离子液体催化剂，其中所述离子液体催化剂中Al/N摩尔比高于2.0时，在100℃或更低温度下增加的AlCl3的溶解度为3-100wt％。
14.权利要求10的离子液体催化剂，其中所述杂质以2-23wt％的含量存在于所述催化剂中。
15.用于异链烷烃/烯烃烷基化的离子液体体系，包含：季铵氯铝酸盐、混合聚合物和氯化氢；其中所述离子液体体系具有2.1至8.0的Al/N摩尔比，其中所述离子液体体系对于实施异链烷烃/烯烃烷基化是有效的；且其中当所述离子液体体系在≤25℃的温度下保存3小时或更长时间时，小于0.1wt％的AlCl3从所述离子液体体系中沉淀出来。
16.包含权利要求1或权利要求10的离子液体催化剂的烷基化反应器。
17.权利要求15的离子液体体系，其中所述混合聚合物以1-24wt％的含量存在于所述离子液体体系中。
Claims (16)
1.一种离子液体催化剂，其包含铵氯铝酸盐，并且当所述离子液体催化剂在≤25℃的温度下保存至少2小时时，具有大于2.0的Al/N摩尔比。
2.权利要求1的离子液体催化剂，其中Al处于AlCl3的形式和N处于R4N+X-或R3NH+X-的形式，其中R是烷基和X是卤离子。
3.权利要求1的离子液体催化剂，其中所述Al/N摩尔比大于2.1。
4.权利要求1的离子液体催化剂，还包含混合聚合物，其中所述混合聚合物以1-24wt％的含量存在于所述催化剂中。
5.权利要求1的离子液体催化剂，其中在50℃或更低温度下，所述离子液体催化剂中Al/N摩尔比高于2.0时增加的AlCl3的溶解度为3wt％或更高。
6.权利要求1的离子液体催化剂，其中所述离子液体催化剂中Al/N摩尔比高于2.0时增加的AlCl3的溶解度在100℃下比在50℃下高出至少10wt％。
7.权利要求1的离子液体催化剂，其中当所述离子液体催化剂在25℃下保存3小时或更长时间时，小于0.1wt％的AlCl3从所述离子液体催化剂中沉淀出来。
8.权利要求1的离子液体催化剂，其中所述离子液体催化剂用于选自下组的烃转化反应：烷基化、异构化、加氢裂化、聚合、二聚、低聚、酰化、乙酰化、复分解、共聚、加氢甲酰化、脱卤、脱水、烯烃加氢以及它们的组合。
9.权利要求1的离子液体催化剂，其中铵氯铝酸盐是N-烷基-吡啶
氯铝酸盐、N-烷基-烷基吡啶
氯铝酸盐、吡啶
氢氯铝酸盐、烷基吡啶
氢氯铝酸盐、二-烷基-咪唑
氯铝酸盐、四-烷基-铵氯铝酸盐、三-烷基-铵氢氯铝酸盐、或它们的混合物。
10.一种离子液体催化剂，包含烷基-吡啶
卤铝酸盐和杂质，其中当所述离子液体催化剂在≤25℃的温度下保存至少2小时时，所述离子液体催化剂具有大于2.0的Al/N摩尔比。
11.权利要求10的离子液体催化剂，其中所述烷基-吡啶
卤铝酸盐包含选自由氯铝酸盐、氟铝酸盐、溴铝酸盐、碘铝酸盐和它们的混合物组成的组的卤铝酸盐。
12.权利要求1或权利要求10的离子液体催化剂，其中Al/N摩尔比为2.1至8.0。
13.权利要求10的离子液体催化剂，其中所述离子液体催化剂中Al/N摩尔比高于2.0时，在100℃或更低温度下增加的AlCl3的溶解度为3-100wt％。
14.权利要求10的离子液体催化剂，其中所述杂质以1-24wt％的含量存在于所述催化剂中。
15.用于异链烷烃/烯烃烷基化的离子液体体系，包含：季铵氯铝酸盐、混合聚合物和氯化氢；其中所述离子液体体系具有2.1至8.0的Al/N摩尔比，且当所述离子液体体系在≤25℃的温度下保存3小时或更长时间时，小于0.1wt％的AlCl3从所述离子液体体系中沉淀出来。
16.包含权利要求1或权利要求10的离子液体催化剂的烷基化反应器。
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| PCT/US2009/064596 WO2010074835A2 (en) | 2008-12-15 | 2009-11-16 | An ionic liquid catalyst having a high molar ratio of aluminum to nitrogen |
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| US20100158762A1 (en) | 2010-06-24 |
| GB201109410D0 (en) | 2011-07-20 |
| AU2009330564B2 (en) | 2014-06-12 |
| SG172186A1 (en) | 2011-07-28 |
| WO2010074835A3 (en) | 2010-08-19 |
| WO2010074835A4 (en) | 2010-10-07 |
| DE112009004600T5 (de) | 2012-11-22 |
| WO2010074835A2 (en) | 2010-07-01 |
| KR20110097952A (ko) | 2011-08-31 |
| US20100167916A1 (en) | 2010-07-01 |
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