CN101622214A - 使用卤代烷促进的离子液体催化剂的烷基化方法 - Google Patents
使用卤代烷促进的离子液体催化剂的烷基化方法 Download PDFInfo
- Publication number
- CN101622214A CN101622214A CN200780045924A CN200780045924A CN101622214A CN 101622214 A CN101622214 A CN 101622214A CN 200780045924 A CN200780045924 A CN 200780045924A CN 200780045924 A CN200780045924 A CN 200780045924A CN 101622214 A CN101622214 A CN 101622214A
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- China
- Prior art keywords
- haloalkane
- butyl
- alkylation
- halo
- alkene
- 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.)
- Granted
Links
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 51
- 150000001350 alkyl halides Chemical class 0.000 title claims abstract description 39
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 230000029936 alkylation Effects 0.000 claims abstract description 47
- 150000001336 alkenes Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000000460 chlorine Substances 0.000 claims description 36
- 229910052801 chlorine Inorganic materials 0.000 claims description 34
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 33
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 32
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 26
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- -1 imidazolium halides Chemical class 0.000 claims description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 14
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 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 description 6
- 238000005647 hydrohalogenation reaction Methods 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 3
- CDXLWOUTFCMPDM-UHFFFAOYSA-N 1-butyl-4-methyl-2h-pyridine Chemical compound CCCCN1CC=C(C)C=C1 CDXLWOUTFCMPDM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 12
- 239000001273 butane Substances 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011831 acidic ionic liquid Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical group CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 14
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 10
- 229940063656 aluminum chloride Drugs 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000002152 alkylating effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003442 catalytic alkylation reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FRCCEHPWNOQAEU-UHFFFAOYSA-N heptachlor Chemical compound ClC1=C(Cl)C2(Cl)C3C=CC(Cl)C3C1(Cl)C2(Cl)Cl FRCCEHPWNOQAEU-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000001291 vacuum drying Methods 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 class CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical class CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 description 1
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical group 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229940055858 aluminum chloride anhydrous Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000007871 hydride transfer reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CRNIHJHMEQZAAS-UHFFFAOYSA-N tert-amyl chloride Chemical compound CCC(C)(C)Cl CRNIHJHMEQZAAS-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—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
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—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
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/8995—Catalyst and recycle considerations
- Y10S585/906—Catalyst preservation or manufacture, e.g. activation before use
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
公开了一种来自炼油炼油工艺料流的高质量汽油调和组分的生产方法,其通过使用离子液体催化剂用烯烃对轻质异链烷烃进行烷基化而得到。该烷基化方法包括在烷基化条件下将包括至少一种具有2到6个碳原子的烯烃的烃混合物与至少一种具有3到6个碳原子的异链烷烃接触,所述的催化剂包括至少一种酸性离子液体和至少一种卤代烷的混合物。卤代烷由至少一部分烯烃和卤化氢反应得到。
Description
技术领域
本发明涉及一种使用包括离子液体和卤代烷的催化剂来将轻质异链烷烃用烯烃进行烷基化的方法。
发明背景
通常,将轻质链烷烃和轻质烯烃转化成更有价值的馏分对于炼油油工业来说是非常有利的。这已经通过用烯烃对链烷烃的烷基化,以及通过烯烃聚合实现了。该领域中最广泛使用的工艺之一是使用硫酸和氢氟酸来对异丁烷用C3-C5的烯烃进行烷基化来制备具有高辛烷值的汽油馏分。该工艺已经从1940年代开始为炼油工业所使用。这种工艺由人们对高质量和清洁燃烧的高辛烷值汽油的需求的增加而推动。
烷基化汽油是一种高质量和高效率燃烧的汽油,其占汽油总量的大约14%。烷基化汽油通常通过用低级烯烃(主要是丁烯)对炼厂异丁烷的烷基化而制备得到的。目前,烷基化物使用HF和H2SO4作为催化剂而制得。虽然这些催化剂已经成功地用来经济地生产优质烷基化物,但是对于更安全和环境友好的催化体系的需要已经变成了相关工业的新课题。
对于能代替目前环境不友好的催化剂的替代催化体系的探索已经是学术和工业机构中科研小组的课题。不幸的是,到目前为止,还没有可行的替待技术运用到工业炼厂的实践中。
离子液体是一种完全由离子组成的液体。所谓的“低温”离子液体通常是熔点在100℃以下、通常甚至比室温更低的有机盐。离子液体适合在例如烷基化和聚合反应以及在二聚反应、低聚乙酰化、复分解和共聚反应中用作催化剂和溶剂。
一类离子液体是熔融盐组合物,其在低温下熔化并用作催化剂、溶剂和电解质。这样的组合物是在低于单个组分熔点温度下是液体的组分混合物。
离子液体可被定义为那些完全由包括阳离子和阴离子的离子组成的液体。最常用的离子液体是那些由有机阳离子和无机的或有机阴离子制备得到的液体。最常用的有机阳离子是铵阳离子,但是鏻和锍阳离子也经常被使用。吡啶和咪唑的离子液体也许是最常用的阳离子。阴离子包括但不限于BF4 -,PF6 -,卤铝酸根例如Al2Cl7 -和Al2Br7 -,[(CF3SO2)2N]-,烷基硫酸根(RSO3 -),羧酸根(RCO2 -)以及更多其它的离子。最令人感兴趣的用于酸催化的催化离子液体是那些衍生自铵卤化物和路易斯酸(例如AlCl3,TiCl4,SnCl4,FeCl3...等等)的离子液体。氯铝酸盐离子液体也许是在酸催化反应中最常使用的离子液体催化体系。
这种低温离子液体或熔融盐的例子是氯铝酸盐。烷基咪唑盐或氯化吡啶例如可以与三氯化铝(AlCl3)混合形成熔融的氯铝酸盐。作为电解质使用的1-烷基吡啶氯化物和三氯化铝的熔融盐已经在美国专利4,122,245中公开。其它讨论了三氯化铝和烷基咪唑卤化物熔融盐作为电解质的用途的专利是美国专利4,463,071和4,463,072。
美国专利5,104,840描述了包含至少一个烷基铝二卤化物和至少一个季铵卤化物和/或至少一个季铵卤化鏻的离子液体,以及它们作为溶剂在催化反应中的用途。
美国专利6,096,680描述了液体包合物组合物在Friedel-Crafts反应中用作可再生铝催化剂。在一个实施方案中,这种液体包合物组合物由下列成分形成:(i)至少一种三卤化铝,(ii)至少一种盐,其选自碱金属卤化物、碱土金属卤化物、碱金属拟卤化物、季铵盐、季鏻盐或叔锍盐,或上述盐的任何两种或多种的混合物,和(iii)至少一种芳烃化合物。
离子液体及其制备方法的其它例子还公开在美国专利5,731,101和6,797,853和美国专利申请公开2004/0077914和2004/0133056中。
在最近十年左右,氯铝酸盐离子液体的出现激发了人们在离子液体中的AlCl3-催化烷基化作为可能的替代方面的兴趣。例如,在离子液体中用丁烯和乙烯对异丁烷的烷基化已经在美国专利5,750,455;6,028,024和6,235,959和公开文献(Journal of Molecular Catalysis,92(1994),155-165;″IonicLiquids in Synthesis″,P.Wasserscheid and T.Welton(eds.),Wiley-VCH Verlag,2003,pp 275)中公开。
在离子液体中进行的氯化铝催化的烷基化和聚合反应被证明是在炼油工业中制备各种各样的产品的经济适用的工艺。这些产品包括从异丁烷和异戊烷用轻质烯烃烷基化而制备得到的烷基化汽油,到通过烷基化和聚合反应制备得到的柴油和润滑油。
发明内容
本发明涉及一种烷基化方法,其包括在烷基化条件下,将包括至少一种具有2到6个碳原子的烯烃的第一烃物料和包括至少一种具有3到6个碳原子的异链烷烃的第二烃物料与催化剂接触,所述的催化剂包括至少一种酸性离子液体和至少一种卤代烷的混合物,其中卤代烷通过将至少一部分第一烃物料与卤化氢在氢卤化条件下反应来将包含在第一烃物料中的至少一部分烯烃转化为卤代烷来制备。
具体实施方式
本发明涉及一种烷基化方法,其包括在烷基化条件下,将包括至少一种具有2到6个碳原子的烯烃和至少一种具有3到6个碳原子的异链烷烃的烃混合物与催化剂接触,所述的催化剂包括至少一种酸性离子液体和至少一种卤代烷的混合物。
本发明方法进料的一个组分是至少一种具有2到6个碳原子的烯烃。该组分例如可以是任何含有烯烃的炼厂烃物流。
本发明方法进料的另一个组分是至少一种具有3到6个碳原子的异链烷烃。该组分例如可以是任何含有异链烷烃的炼厂烃物流。
根据本发明的方法不局限于任何具体的进料并且通常适用于用来自任何来源以及任何组合的C2-C6烯烃对C3-C6异链烷烃进行烷基化。
根据本发明,将上述烃混合物在烷基化条件下与催化剂接触。根据本发明的催化剂包括至少一种酸性离子液体和至少一种卤代烷。已经通过参照某些具体的离子液体催化剂对本发明方法进行了描述和例举,但是这些描述并不是为了限制本发明的范围。所述的方法可以由本领域普通技术人员使用任何酸性离子液体催化剂基于本文中所包括的教导、说明和例子来进行实施。
本文中使用的具体的实施例涉及使用离子液体体系的烷基化方法,该离子液体体系是与氯化铝混合的基于胺的阳离子物质。在这种体系中,为了获得适合于烷基化化学的适当酸性,离子液体催化剂通常是通过将一摩尔份的合适的氯化铵与二摩尔份的氯化铝进行混合来制备全酸性强度。烷基化方法中的例举的催化剂为氯铝酸1-烷基-吡啶,例如七氯铝酸1-丁基吡啶。
七氯铝酸1-丁基吡啶
如上所指,酸性离子液体可以是任何酸性离子液体。在一个实施方案里,酸性离子液体是氯铝盐离子液体,其通过将三氯化铝(AlCl3)和通式分别为A,B,C和D的烃基取代的吡啶卤化物、烃基取代的咪唑卤化物、三烷基铵氢卤化物或四烷基铵卤化物进行混合来制备得到。
其中R=H,甲基乙基,丙基,丁基,戊基或己基,X是卤根且优选氯根,R1和R2=H,甲基,乙基,丙基,丁基,戊基或己基且R1和R2可以相同也可以不同,R3,R4,R5和R6=甲基,乙基,丙基,丁基,戊基或己基且R3,R4,R5和R6可以相同也可以不同。
酸性离子液体优选选自氯铝酸1-丁基-4-甲基吡啶、氯铝酸1-丁基吡啶、氯铝酸1-丁基-3甲基咪唑和氯铝酸1-H-吡啶。
根据本发明的方法中,卤代烷作为促进剂。
根据本发明,卤代烷是通过使至少一部分烯烃物料与卤化氢在氢卤化反应条件下反应从而将至少一部分烯烃转化成卤代烷来制备。这根据本发明通过将至少一部分烯烃物料流与氢卤化物在氢卤化反应条件下进行反应并将得到的卤代烷加入到烷基化反应区中来实现。换言之,卤代烷是由烯烃原料产生的。例如,可以使用含有烯烃的炼厂进料的支流(slip-stream)并将其与HCl在能将该支流中的烯烃转化成卤代烷例如仲丁基氯和叔丁基氯的条件下反应。含有卤代烷的该料流可以被加到加入烷基化反应器中的催化剂料流中。
烯烃的氢卤化反应是众所周知的。美国专利5,831,137描述了一种制备叔丁基氯的方法,该方法使气相的无水HCl和异丁烯(1.2摩尔比率)在大气压下的混合物通过保持在60℃的浓盐酸。产品叔丁基氯从反应器的蒸气相流出物中浓缩出来。其它的专利(例如FR2,300,751)描述了在大气压力和-25到+50℃条件下,使用叔丁基氯作为溶剂,在路易氏酸催化剂例如ZnCl2存在下,用无水HCl和丁烯的反应来制备叔丁基氯。美国专利2,434,094描述了在惰性载体上的路易氏酸催化剂存在下,在惰性稀释剂存在下,将气相丁烯和无水HCl反应制备叔丁基氯。为了避免氯代烷分解,工作温度是在300°F以下。美国专利2,418,093具有该方面的通用化学的不错的描述。在少量丁烯的存在下,很明显异丁烯选择性地反应得到叔丁基氯。然而,上述一些专利描述了在过量线性丁烯存在下叔丁基氯的选择性合成。
卤代烷通过在类似Friedel-Crafts反应的情况下与氯化铝起反应形成必要的阳离子来促进烷基化。可以使用的卤代烷包括溴代烷、氯代烷和碘代烷。优选异戊基卤化物、异丁基卤化物、丁基卤化物、丙基卤化物和乙基卤化物。当氯铝酸盐离子液体用作催化剂体系时,卤代烷中氯代烷是优选的。其它具有1到8个碳原子的氯代烷或卤代烷也可以使用。卤代烷可以单独或结合使用。
对于氯铝酸盐离子液体,卤代烷优选氯代烷例如乙基氯,叔丁基氯,异戊基氯或丁基氯。氯代烷是选自那些衍生自在给定的烷基化反应里所使用的异链烷烃和烯烃的氯代烷。例如对于在氯铝酸盐离子液体里用丁烯烷基化异丁烷来说,优选的卤代烷是1-丁基氯、2-丁基氯或叔丁基氯或这些氯化物的组合。最优选,氯代烷是烯烃物流的衍生物从而理论上引起氢负离子转移和异链烷烃的参与。这里的卤代烷以催化量使用。理想地,卤代烷的量应当保持在低浓度并且不超过催化剂AlCl3的摩尔浓度。使用的卤代烷的量可以在路易斯酸AlCl3的0.001mol%-100mol%范围内。为了在需要的操作容量下保持催化剂的酸性,优选卤代烷的浓度在AlCl3的0.001mol%-10mol%范围内。并且,卤代烷的量应该与烯烃的量成比例并且不超过烯烃的摩尔浓度。
不受任何理论的约束,当氯乙烷例如加入到酸性氯铝酸盐离子液体中时,氯乙烷与AlCl3反应形成四氯铝酸盐(AlCl4 -)和乙基阳离子。氢负离子从异链烷烃(异戊烷或异丁烷)到产生的乙基阳离子的转移产生叔阳离子,其使反应中的异链烷烃得到增殖并因此使烷基化路径得到增殖。
可以使用金属卤化物来改变催化剂活性和选择性。在氯化铝催化的烯烃-异链烷烃的烷基化中最常用作抑制剂/改性剂的金属卤化物包括NaCl,LiCl,KCl,BeCl2,CaCl2,BaCl2,SrCl2,MgCl2 PbCl2,CuCl,ZrCl4和AgCl,正如Roebuck和Evering(Ind.Eng.Chem.Prod.Res.Develop.,Vol.9,77,1970)中所描述的。优选的金属卤化物是CuCl,AgCl,PbCl2,LiCl和ZrCl4。
HCl或任何Broensted酸可以用作共催化剂通过激发(boasting)基于离子液体的催化剂的总酸性来提高这些催化剂的活性。在本发明的实施中有用的这种共催化剂和离子液体催化剂的使用在美国公布的专利申请2003/0060359和2004/0077914中公开。其它可用于提高活性的共聚催化剂包括IVB族金属化合物,优选IVB族金属卤化物例如ZrCl4,ZrBr4,TiCl4,TiCl3,TiBr4,TiBr3,HfCl4,HfBr4,如Hirschauer等人在美国专利6,028,024中所描述。
由于烃类在离子液体中的低溶解度,烯烃-异链烷烃的烷基化,正如在离子液体里的大多数反应一样,其通常是两相的而且在液相的界面发生。催化烷基化反应通常在间歇体系、半间歇体系或连续体系中在液态烃相中来使用一个反应级进行,就像通常脂肪烃烷基化那样。异链烷烃和烯烃可以是分别地引入也可以是作为混合物引入。异链烷烃和烯烃摩尔比在1到100范围内,有利地在2到50范围内,优选在2到20范围内。在半间歇体系中,首先引入异链烷烃,然后是烯烃或者异链烷烃和烯烃的混合物。反应器中催化剂量是在2vol%到70vol%之间,优选在5vol%到50vol%范围内。需要强烈搅拌来确保反应物和催化剂之间的良好接触。反应温度可以是-40℃到+150℃,优选-20℃到+100℃。压力可以在常压到8000kPa范围内,优选是足以保持反应物是液相的压力。反应物在容器中的停留时间是从数秒到几小时,优选0.5min到60min。反应产生的热可以使用本领域技术人员熟知的手段去除。在反应器出口,烃相通过滗析来与离子相分离,然后烃通过蒸馏分离出来并且没有转化的异链烷烃原料再循环到反应器中。典型的烷基化条件可以包括在反应器中催化剂量在1vol%到50vol%,温度从-10℃到+100℃,压力从300kPa到2500kPa,异戊烷和烯烃的摩尔比率从2到8,停留时间为5分钟到1小时。
在一个本发明方法的实施方案中,低挥发性的高质量汽油调和组分从烷基化区中进行回收。然后这些调和组分优选再混入汽油中。
以下实施例用来说明本发明,但并不是以任何包含在如下权利要求之外的方式对本发明进行限制。
实施例
实施例1新鲜的氯铝酸1-丁基吡啶离子液体催化剂A的制备(Fresh ILA)
氯铝酸1-丁基吡啶是一种室温离子液体,其通过在惰性气氛下将纯的氯化1-丁基吡啶(固体)与纯的固态三氯化铝相混合来制备得到。氯化丁基吡啶以及相应的氯铝酸1-丁基吡啶的合成描述如下。
在一个2L聚四氟乙烯内衬的加压釜中,将400克(5.05mol)无水吡啶(99.9%纯,购自Aldrich)与650克(7mol)1-氯丁烷(99.5%纯,购自Aldrich)进行混合。将加压釜进行密封并将上述纯的混合物在自生压力下在125℃下进行搅拌过夜。将加压釜冷却并排空后,将反应混合物进行稀释并将其溶解在氯仿中,并转移至一个三升的圆底烧瓶中。将反应混合物在旋转蒸发仪上进行减压浓缩(在热水浴中)来除去过量的氯化物、未反应的吡啶和氯仿溶剂,产生褐色固态产物。产品的纯化是通过将得到的固体溶解在热丙酮中并通过冷却和加入乙醚来沉淀出纯产物来进行的。过滤和真空干燥和在旋转蒸发仪上的加热得到750克(88%产率)所需产品,其为一种灰白色有光泽的固体。1H-NMR和13C-NMR与氯化1-丁基吡啶一致且没有发现杂质。
氯铝酸1-丁基吡啶是根据下述步骤将干燥的氯化1-丁基吡啶与无水氯化铝(AlCl3)进行混合来制备得到的。将氯化1-丁基吡啶(其制备如上描述)在80℃下真空干燥48小时以除去残余水(氯化1-丁基吡啶具有吸湿性并与空气接触容易吸收水)。在手套箱中,在氮气氛下将500克(2.91mol)干燥的氯化1-丁基吡啶转入一个2升的烧杯中。然后,将777.4克(5.83mol)无水AlCl3粉末(99.99%,购自Aldrich)分小份(在搅拌下)加入,以控制高度放热反应的温度。当将所有的AlCl3全部加入后,将产生的琥珀色液体在手套箱中温和搅拌过夜。然后将该液体过滤去掉任何未溶解的AlCl3。得到的酸性氯铝酸1-丁基吡啶作为异戊烷用乙烯进行烷基化的催化剂。
实施例2在无促进剂存在下用乙烯对异戊烷进行烷基化
在一个300毫升加压釜中装入40克离子液体催化剂、100克无水异戊烷和10克乙烯。反应然后在自生压力下在~1200rpm搅拌并且加热到50℃。起始压力是288psi。反应一直进行至压力下降成个位数范围(在本例中反应28分钟后为5psi)。在慢速反应情况下,反应进行1个小时,反应结束时,将反应器排空并且将气体样品试样用GC来进行检测乙烯浓度。使液相反应混合物分成2相。将有机相滗析出并通过GC分析来分析产品分布。反应结果显示在表1中。
实施例3在作为共催化剂的HCl的存在下用乙烯对异戊烷进行烷基化
下表1显示了在氯乙烷和氯异戊烷存在下,乙烯与异戊烷的烷基化结果。乙烯对异戊烷的烷基化是按照以下步骤进行的。
一个300毫升加压釜中装入40克离子液体催化剂、100克无水异戊烷、10克乙烯和0.35克的无水HCl。反应然后在自生压力下在~1200rpm搅拌并且被加热到50℃。起始压力是320psi。反应一直进行至压力下降成个位数范围(在本例中4分钟反应时间后为9psi)。在慢速反应情况下,反应进行1个小时。反应结束时,将反应器排空并且将气体样品试样用GC检测乙烯浓度。使液相反应混合物分成2相。将有机相滗析出并通过GC分析来分析产品分布。反应结果显示在表1中。
实施例4在作为促进剂的氯乙烷的存在下用乙烯对异戊烷进行烷基化
将实施例3中描述的反应进行重复但用氯乙烷(CH3CH2Cl)代替盐酸(HCl)。反应在40克氯铝酸1-丁基吡啶离子液体催化剂中的100克异戊烷、10克乙烯和0.9克氯乙烷来进行。在反应中使用氯乙烷与使用HCl一样有效。表1总结了本反应结果和条件。
实施例5在作为促进剂的2-氯-2-甲基丁烷(氯异戊烷)的存在下用乙烯对异戊烷进行烷基化
将实施例4描述的反应进行重复但用氯异戊烷代替氯乙烷。反应在40克氯铝酸1-丁基吡啶离子液体催化剂中的100克异戊烷、10克乙烯和1.2克的氯异戊烷来进行。氯异戊基比氯乙烷和HCl在乙烯对异戊烷的烷基化作用中更有效。本反应大量放热并且不需要增加反应温度到50℃(反应温度)。压力瞬时从337psi的起始压力降到个位数。表1总结了本反应结果和条件。
如表1所示,当氯乙烷或氯异戊烷加入,反应时间显著地缩短。在氯异戊烷存在下的烷基化作用更快(几乎是瞬间)。反应大量放热且不需要加热。实验结果清楚地显示出,氯代烷在离子液体中的烷基化过程中的加入具有非常显著的效果。
表1
无HCl或R-Cl | W/HCl | W/乙基-Cl | W/异戊基-Cl | |
起始压力 | 288psig | 240psig | 331psig | 337psig |
终止压力 | 5psig | 11psig | 9psig | 7 |
反应时间 | 28min | 4min | 6min | 2min |
%选择性 | ||||
C3- | 0.04 | 0 | 0.01 | 0 |
C4 | 0.86 | 1.88 | 1.93 | 4.97 |
C5 | 67.78 | 67.7 | 62.79 | 65.53 |
C6 | 1.14 | 2.6 | 2.44 | 5.19 |
C7 | 22.33 | 19.32 | 22.53 | 14.78 |
C8 | 2.94 | 3.25 | 3.68 | 3.27 |
C9 | 2.41 | 2.12 | 2.93 | 2.65 |
C10 | 1.5 | 1.59 | 1.78 | 1.64 |
C11 | 0.5 | 0.8 | 0.93 | 0.95 |
C12+ | 0.5 | 0.75 | 0.98 | 1.02 |
总计 | 100 | 100 | 100 | 100 |
前面实施例中的烷基化作用是通过使用纯异戊烷原料来完成的。
表2显示了在使用HCl、水或氯乙烷作为促进剂,用乙烯对炼厂戊烷的烷基化中,不同催化剂方案之间的比较。
炼厂戊烷的分析显示原料中含有86.4%异戊烷,8%正戊烷,0.9%正丁烷,3.4%C6s-C9s和0.2%烯烃(C4和C5烯烃)。炼厂戊烷料流也包含88ppm硫(如硫醇)和0.4ppm氮。这些反应按实施例6,7,8和9中所述进行。
实施例6在氯铝酸1-丁基吡啶中用乙烯对炼厂戊烷进行烷基化-无促进剂
将先前描述的规格的炼厂异戊烷通过分子筛进行干燥以去掉残余水。然后,101克干燥原料与10克纯乙烯在42克离子液体催化剂中按照实施例1描述的步骤进行反应。表2总结了该反应和结果。
实施例7在氯铝酸1-丁基吡啶中用乙烯对炼厂戊烷进行烷基化-HCl作为促进剂
使用实施例3描述的步骤,先前描述的规格的干燥炼厂异戊烷101克,在0.6克HCl存在下用10克纯乙烯在42克离子液体催化剂中进行烷基化。图2总结了本反应和结果。
实施例8在氯铝酸1-丁基吡啶中用乙烯对炼厂戊烷进行烷基化-H2O作为促进剂
使用实施例3描述的步骤,先前描述的规格的干燥炼油异戊烷101克,在0.1克H2O存在下用10克纯乙烯在42克离子液体催化剂中进行烷基化。图2总结了本反应和结果。
实施例9在氯铝酸1-丁基吡啶中用乙烯对炼油戊烷进行烷基化-氯乙烷作为促进剂
使用实施例3描述的步骤,先前描述的规格的干燥炼厂异戊烷101克,在1克氯乙烷存在下用10克纯乙烯在42克离子液体催化剂中进行烷基化。表2总结了本反应和结果。
表2总结了实施例6,7,8和9中用纯乙烯对炼厂异戊烷原料的烷基化结果。
表2(在氯化丁基吡啶-2AlCl3/EtCl中炼厂原料的烷基化)
炼厂原料无HCl或R-Cl | 炼厂原料W/HCl | 炼厂原料W/乙基-Cl | 炼厂原料W/H2O | |
起始压力 | 226psi | 249psi | 295psig | 313psi |
终止压力 | 104psi | 10psi | 13psig | 15psi |
反应时间 | 64min | 19min | 24min | 28min |
%选择性 | ||||
C3- | 0.21 | 0.07 | 0.05 | 0.19 |
C4 | 0.77 | 1.19 | 1.39 | 1.27 |
C5 | 81.34 | 69.35 | 62.69 | 68.93 |
C6 | 2.82 | 3.06 | 3.87 | 2.97 |
C7 | 8.74 | 18.36 | 21.03 | 18.18 |
C8 | 3 | 3.8 | 5.05 | 3.93 |
C9 | 1.41 | 2.02 | 2.55 | 2.14 |
C10 | 0.82 | 1.26 | 1.70 | 1.24 |
C11 | 0.37 | 0.42 | 0.83 | 0.53 |
C12+ | 0.53 | 0.48 | 0.84 | 0.61 |
总计 | 100 | 100 | 100 | 100 |
根据本文教导和所述的可支持实施例,本发明可以有多种变化。因此应理解为在下述权利要求的范围内,本发明可以在上述具体描述或实施例之外实施。
Claims (16)
1.一种烷基化方法,其包括在烷基化条件下,将包括至少一种具有2到6个碳原子的烯烃的第一烃物料和包括至少一种具有3到6个碳原子的异链烷烃的第二烃物料与催化剂接触,所述催化剂包括至少一种酸性离子液体和至少一种卤代烷的混合物,其中所述卤代烷通过将至少一部分第一烃物料与卤化氢在氢卤化条件下反应来将包含在第一烃物料中的至少一部分烯烃转化为卤代烷来制备。
2.如权利要求1的方法,其中所述酸性离子液体是氯铝酸盐离子液体,其通过将三氯化铝(AlCl3)和通式分别为A,B,C和D的烃基取代的吡啶卤化物、烃基取代的咪唑卤化物、三烷基铵氢卤化物或四烷基铵卤化物进行混合来制备,
其中R=H,甲基,乙基,丙基,丁基,戊基或己基,X是卤根且优选氯根,R1和R2=H,甲基,乙基,丙基,丁基,戊基或己基且R1和R2可以相同也可以不同,且R3,R4,R5和R6=甲基,乙基,丙基,丁基,戊基或己基且其中R3,R4,R5和R6可以相同也可以不同。
3.如权利要求2的方法,其中所述酸性离子液体选自氯铝酸1-丁基-4-甲基吡啶(BMP)、氯铝酸1-丁基吡啶(BP)、氯铝酸1-丁基-3-甲基咪唑(BMIM)和氯铝酸1-H-吡啶(HP)。
4.如权利要求1的方法,其中所述异链烷烃选自异丁烷,异戊烷及其混合物。
5.如权利要求1的方法,其中所述烯烃选自乙烯,丙烯,丁烯,戊烯及其混合物。
6.如权利要求1的方法,其中所述烷基化条件包括在反应器中催化剂量在1vol%到50vol%,温度从-10℃到+100℃,压力从300kPa到2500kPa,异戊烷与烯烃的摩尔比率从2到8,停留时间为1分钟到1小时。
7.如权利要求1的方法,进一步包括回收低挥发性高质量汽油调和组分。
8.如权利要求1的方法,其中包含在第一烃物料中的烯烃至少有50%转化成卤代烷。
9.如权利要求1的方法,其中卤代烷有1至8个碳原子。
10.如权利要求9的方法,其中卤代烷选自卤代甲烷,卤代乙烷,卤代丙烷,卤代1-丁烷,卤代2-丁烷,卤代叔丁烷,卤代戊烷,卤代异戊烷,卤代己烷,卤代异己烷,卤代庚烷,卤代异庚烷,卤代辛烷和卤代异辛烷。
11.如权利要求8的方法,其中卤代烷选自溴代烷,碘代烷和氯代烷。
12.一种烷基化方法,其中在烷基化条件下,将至少一种具有2到6个碳原子的烯烃和至少一种具有3到6个碳原子的异链烷烃与包括酸性离子液体和卤代烷的催化剂在烷基化区中进行接触,改进之处包括使一部分所述的至少一种烯烃与氢卤化物在氢卤化反应条件下反应,以将多于50%的其中所含烯烃转化成卤代烷,并将得到的富含卤代烷的料流加入到烷基化区中。
13.如权利要求12的方法,其中所述酸性离子液体选自氯铝酸1-丁基-4-甲基吡啶(BMP)、氯铝酸1-丁基吡啶(BP)、氯铝酸1-丁基-3-甲基咪唑(BMIM)和氯铝酸1-H-吡啶(HP)。
14.如权利要求12的方法,其中所述氢卤化物是无水HCl。
15.如权利要求12的方法,其中所述烯烃选自乙烯,丙烯,丁烯,戊烯及其混合物。
16.如权利要求12的方法,其中所述异链烷烃选自异丁烷,异戊烷及其混合物。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103781746A (zh) * | 2011-09-12 | 2014-05-07 | 雪佛龙美国公司 | 改造hf烷基化单元用于离子液体催化烷基化方法 |
CN103781746B (zh) * | 2011-09-12 | 2016-05-18 | 雪佛龙美国公司 | 改造hf烷基化单元用于离子液体催化烷基化方法 |
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GB2458069B (en) | 2011-05-18 |
US20080142413A1 (en) | 2008-06-19 |
GB0912043D0 (en) | 2009-08-19 |
KR101472150B1 (ko) | 2014-12-12 |
MY146478A (en) | 2012-08-15 |
CN101622214B (zh) | 2013-09-18 |
AU2007334057A1 (en) | 2008-06-26 |
WO2008076722A1 (en) | 2008-06-26 |
AU2007334057B2 (en) | 2011-06-23 |
US7531707B2 (en) | 2009-05-12 |
KR20090087489A (ko) | 2009-08-17 |
BRPI0720041A2 (pt) | 2013-12-17 |
DE112007003012T5 (de) | 2009-11-05 |
GB2458069A (en) | 2009-09-09 |
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