CN101365666A - 内烯烃方法 - Google Patents
内烯烃方法 Download PDFInfo
- Publication number
- CN101365666A CN101365666A CNA2006800452286A CN200680045228A CN101365666A CN 101365666 A CN101365666 A CN 101365666A CN A2006800452286 A CNA2006800452286 A CN A2006800452286A CN 200680045228 A CN200680045228 A CN 200680045228A CN 101365666 A CN101365666 A CN 101365666A
- Authority
- CN
- China
- Prior art keywords
- olefin
- dimerization
- reaction
- isomerization
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 52
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 150000001336 alkenes Chemical class 0.000 claims abstract description 53
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 47
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 44
- 239000004711 α-olefin Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005804 alkylation reaction Methods 0.000 claims description 7
- 238000007037 hydroformylation reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000019635 sulfation Effects 0.000 claims description 6
- 238000005670 sulfation reaction Methods 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical group N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 6
- 238000013459 approach Methods 0.000 claims 1
- -1 aluminum alkyl halide Chemical class 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 239000000539 dimer Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 229910052708 sodium Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical class N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KHWHMNYXCVMFGS-UHFFFAOYSA-N Cl.C1(C=CC=C1)[Zr] Chemical compound Cl.C1(C=CC=C1)[Zr] KHWHMNYXCVMFGS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 229910001657 ferrierite group Inorganic materials 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium peroxide Inorganic materials [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052801 chlorine Chemical group 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
- C07C2/34—Metal-hydrocarbon complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
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Abstract
本发明提供制备内烯烃的方法,该方法包括:在异构化催化剂存在下,异构化含一种或多种内烯烃的原料产生α-烯烃,和在二聚催化剂存在下,使所述α-烯烃反应产生内烯烃。
Description
技术领域
本发明涉及将较低碳数的内烯烃转化成较高碳数的内烯烃的方法。
背景技术
已经通过直链烯烃的结构或骨架异构化成它们相应的甲基支链异烯烃来制备支链内烯烃。美国专利5510306公开了一种这样的方法。通过用各种二聚催化剂二聚直链α-烯烃来制备内烯烃。
在许多商业操作中生产较低碳数的内烯烃。有利的是具有将这些具有低的价值的较低碳数的内烯烃转化成较高碳数的内烯烃,优选转化成具有支链的较高碳数的内烯烃(它们具有高的价值且可转化成可用于制备洗涤剂产品的醇类)的方法。本发明提供这样一种方法。
美国专利6291733描述了二聚α-烯烃生产主要为直链内烯烃的方法。据说这一反应具有高的选择性。内烯烃不会通过这种二聚工艺反应。
发明内容
本发明提供制备内烯烃的方法,该方法包括:在异构化催化剂存在下,异构化含一种或多种内烯烃的原料产生α-烯烃,和在二聚催化剂存在下,使所述α-烯烃反应产生具有比原料内烯烃更高碳数的内烯烃。
具体实施方式
产物内烯烃可具有比原料内烯烃更高的碳数,和可以是C6-40、C8-20或C12-18直链和/或烷基支链的内烯烃。原料内烯烃可具有比产物内烯烃更低的碳数,且可以是C4-24、C4-20、C4-14、C4-12、C4-10或C4-8的内烯烃。原料内烯烃物流可任选含有一种或多种α-烯烃。
可以按与通常进行异构化不同的方式进行这一方法中的异构化。众所周知内烯烃可以在异构化条件下与异构化催化剂反应产生α-烯烃(双键异构化)。
另外众所周知的是难以只通过异构化反应由内烯烃高转化率制备α-烯烃。反应是有利于内烯烃存在的平衡反应。在本发明中,该反应由内烯烃的起始原料产生α-烯烃。α-烯烃通过二聚成内烯烃从反应混合物中除去和通过异构化反应的平衡来补充。可在其中所产生的α-烯烃量可尽可能高、优选为异构化反应混合物中α-烯烃的平衡量或者尽可能接近可平衡量的条件下进行本发明的方法。
使α-烯烃与二聚催化剂接触允许进行α-烯烃的二聚反应,由异构化反应过程中产生的α-烯烃产生更长链的内烯烃(与原料内烯烃相比)。优选二聚和异构化催化剂彼此相容,以便不会反应降低活性。优选地,这两种催化剂应当为碱性或者酸性。例如,碱性催化剂的均相溶液应当一般不与可溶酸催化剂混合。存在能使用固体酸和固体碱的工程溶液,只要它们彼此不接触即可。
可从多种催化剂和异构化工艺中选择此处所使用的异构化条件。这些工艺中的一些包括在美国专利3786112、4749819、4727203、5107047、5177281和5510306中描述的那些,这些专利的公开内容在此全文通过参考引入。在异构化反应与涉及二聚催化剂的反应相分离的情况下,所述条件可包括在0-500℃的温度、1-10000kPa的压力和在连续工艺中重时空速为0.1-100下操作。一般地,小于或等于200℃的温度可能足够,和可使用大气压到5000kPa的压力。当温度在0-500℃的范围内增加时,在相同碳数的烯烃混合物内α-烯烃的热力学平衡浓度增加。温度可以尽可能高,以最大化所产生的α-烯烃量。然而,温度不应当高到足以使二聚催化剂和/或异构化催化剂分解。
可使用几乎任何异构化催化剂,但优选它与所选的二聚催化剂相容。可使用的异构化催化剂有美国专利3786112、4749819、4727203、5107047、5177281和5510306中公开的催化剂,这些专利在此通过参考引入。
在本发明中使用的合适的异构化催化剂包括含如下物质的催化剂:第VIII族贵金属即钯、铂或钌;铌或钒的氧化物;第I族、第II族或第III族金属氧化物,其中包括氧化钠、氧化钾、氧化镁、氧化钙、氧化锌、γ-氧化铝、铝土矿、η-氧化铝、氧化钡、氧化锶及它们的混合物;和在氧化铝上的第I组金属的碳酸盐。
可使用的其它异构化催化剂包括硅铝酸盐催化剂。优选的硅铝酸盐催化剂是定义为具有8和10元环通道的镁碱沸石硅铝酸盐催化剂。其它优选的硅铝酸盐是镁碱沸石催化剂,其例子如在美国专利No.4016245(其公开内容在此通过参考全文引入)中公开的ZSM-35硅铝酸盐,或者在美国专利No.4251499(其公开内容在此通过参考全文引入)中公开的哌啶衍生的镁碱沸石。其它有用的沸石包括θ-1、ZSM-12、ZSM-22、ZSM-23和ZSM-48。这些硅铝酸盐可与催化金属结合,所述催化金属优选选自周期表第VIII族或第VIB族。这些金属的例子如钯、铂、钌、镍、钴、钼、锇,和可以彼此组合存在。这些催化金属可以以总的催化剂组合物的0.1wt%-25wt%的量存在。
ZSM-22催化剂更具体地描述于美国专利No.4556477中,其全部内容在此通过参考引入。ZSM-23催化剂更具体地描述于美国专利Nα.4076842中,其全部内容在此通过参考引入。
在美国专利5107047中描述的MCM-22催化剂也可用作本发明中的异构化催化剂。沸石MCM-22可具有涉及下述摩尔关系的组成:
X2O3:(n)YO2
其中X是三价元素,例如铝、硼、铁和/或镓,优选铝,Y是四价元素,例如硅和/或锗,优选硅,和n至少为10,通常为10-150,更通常为10-60,和甚至更通常为20-40。在合成形式中,以无水基准并以每n摩尔YO2氧化物X2O3氧化物的摩尔数计,沸石MCM-22可具有如下所述的通式:
(0.005-0.1)Na2O:(1-4)R:X2O3:nYO2
其中R是有机组分。由于在结晶过程中存在,Na2O和R组分与沸石结合,且容易通过后结晶方法除去。这种沸石,特别是处于其金属、氢和铵型时,可有利地通过热处理转化成其它型式。
在另一实施方案中,如美国专利No.4749819中所讨论的,使用碱金属催化剂,优选钠/钾(NaK)催化剂,该专利在此通过参考全文引入。优选的NaK催化剂是置于氧化铝或二氧化硅载体上的钠和钾的低共熔混合物。可根据美国专利3405196的教导,通过使用钠和钾的混合物作为碱金属组分,制备NaK催化剂,该专利在此通过参考全文引入。
如上所述,内烯烃原料可任选含有一些α-烯烃。在本发明的一些实施方案中,可能优选在原料内存在α-烯烃。在一个这样的实施方案中,α-烯烃可以是乙烯、丙烯或它们的混合物。存在这些α-烯烃将允许生产具有6或7个碳原子的内烯烃。
在其中异构化反应与涉及二聚催化剂的反应分开的情况下,涉及二聚催化剂的反应可在最多200℃、优选-10到100℃和更优选10-50℃的温度下操作。压力范围可以是1-10,000kPa,优选大气压到5000kPa。
有多种二聚催化剂可用于本发明。这些催化剂包括在美国专利4252987、4859646、6222077、6291733和6518473中描述的那些,所有这些专利在此通过参考引入。一种这样的催化剂可包含二环戊二烯基卤代钛化合物、烷基铝卤化物和氮路易斯相。其它这样的催化剂可包含:1)钯化合物,2)螯合配体,所述螯合配体包括通过含两个或更多个碳原子的链相连的至少2个氮原子的化合物,3)质子酸,和4)铜、铁、锌、锡、锰、钒、铝或第VIB族金属的盐。在另一实施方案中,催化剂可以是其中金属、优选镍键合到至少一个烃基上的催化剂或者是由通过混合至少一种镍化合物与至少一种烷基铝化合物和任选的配体形成的络合物组成的催化剂。该催化剂也可以是含羧酸镍或镍螯合物与烷基铝卤化物或烷基铝烷醇盐的组合的催化剂。此外,用于二聚的催化剂实际上可以是任何酸性物质,其中包括沸石、粘土、树脂、BF3络合物、HF、H2SO4、AlCl3、离子液体、过酸等;和优选在无机氧化物载体例如沸石载体上的第VIII族金属。
在本发明中使用的优选的二聚催化剂是在美国专利6291733中所述的过渡金属催化剂/活化助催化剂,该专利在此通过参考全文引入。在这一专利中所述的工艺条件和所使用的催化剂对α-烯烃二聚为主要直链的内烯烃二聚体具有高度选择性。该专利陈述了任何过渡金属络合物与助催化剂均可在所述方法中用作催化剂。优选的实施方案描述为使用活化助催化剂,所述活化助催化剂是铝氧烷或为路易斯酸和烷基化试剂的组合。优选的助催化剂是摩尔过量使用的改性甲基铝氧烷(MMAO)。据说优选的过渡金属络合物是配位到铁中心上的三齿双亚胺配体或者铁中心与取代或未取代的芳环的组合。最优选的催化剂是在该专利的第3栏所示的催化剂1-5。
美国专利6291733中优选的催化剂的有效量相对低。采用少于总的α-烯烃混合物1%质量的催化剂和助催化剂,二聚反应在数分钟内发生。优选的催化剂浓度为0.01-0.1mg催化剂/ml α-烯烃单体。更优选的催化剂浓度为0.02-0.08mg/ml α-烯烃单体,和甚至更优选催化剂浓度为0.05-0.06mg/ml α-烯烃单体。
在美国专利No.4658078中描述了此处所使用的另一优选的二聚催化剂,该专利在此通过参考全文引入。该催化剂可包括锆或铪的茂金属和铝氧烷,其中催化剂内铝与锆和/或铪的总量的原子比范围为1-100。所使用的茂金属可具有通式(环戊二烯基)2MY2,其中M是锆或铪,和每一Y独立地选自氢、C1-C5烷基、C6-C20芳基和卤素。优选Y是氢、甲基或氯。应理解Y可以相同或不同。包括在上述环戊二烯基部分定义内的是低级烷基(C1-C5)-取代、优选甲基取代的环戊二烯基部分。茂金属的具体实例是二环戊二烯基二甲基锆和双(环戊二烯基)锆氯化氢。
异构化反应和涉及二聚催化剂的反应可在间歇或连续工艺中进行。可在分开的反应容器内或者同一反应容器内进行这些反应。若在同一反应容器内发生反应,则它们可按序或同时发生。
在本发明的一个实施方案中,在进行异构化反应产生α-烯烃的间歇反应中,由α-烯烃产生长链内烯烃(具有比原料内烯烃更高的碳数)的同时反应可继续长的时间段。当所有原始的原料内烯烃消耗完时,反应可能减慢,这是因为二聚反应将产生很多种二聚体,其中包括许多不会进一步反应的二聚体。
在其中异构化反应和涉及二聚催化剂的反应在同一反应容器内发生的情况下,在相同的反应区或在不同的反应区内和按序或者同时,可以选择反应条件实现所需的异构化以及还实现所需的涉及二聚催化剂的反应。在这一情况下,温度范围可以是0-200℃,优选10-150℃,更优选50-120℃。反应压力范围可以是1-10,000kPa,优选大气压到5000kPa,最优选100-1000kPa。通常通过在室温下启动反应和允许反应放热加热溶液而获得这些温度。
在本发明的优选实施方案中,异构化反应和二聚反应可以在同一反应容器内发生。所使用的催化剂可以不相容,但优选相容,这是因为这样可在反应容器的同一区内进行反应而不需要保持催化剂彼此分开。通常可在同一反应容器内使不相容的催化剂相容,这通过在不同的区内分开保持它们来实现,例如通过允许烯烃迁移但不允许催化剂彼此接触的膜来实现。单一的反应容器可以是固定床反应容器、高压釜、化学搅拌釜反应器或催化蒸馏塔反应器。可使用一个以上反应器。堆积床反应体系是一种可能性。在这一体系中,顶部床可具有一种催化剂和底部床可具有另一催化剂。这一反应也可在串联的反应器内进行。
衍生于长链烯烃的醇可在多种应用中具有相当大的商业重要性,其中所述应用包括洗涤剂、肥皂、表面活性剂、冻点抑制剂和润滑油、软化剂、农用化学品和药物化学品。这些醇通过许多商业方法中的任何一种生产,其中包括长链烯烃Oxo法和加氢甲酰化。
可通过在美国专利5849960中所述的方法,将本方法的内烯烃转化成醇,该专利在此通过参考全文引入。烯烃与异构化催化剂接触得到异构化烯烃。这一产物优选通过加氢甲酰化转化成醇。除了在这一专利中所述的催化剂以外,也可使用许多其它已知的加氢甲酰化催化剂将本发明的内烯烃转化成醇。
由通过本发明方法制得的产物内烯烃制备的醇适合于制备阴离子、非离子和阳离子表面活性剂。醇可用作制备阴离子硫酸盐和非离子氧烷基化醇的前体,其中阴离子硫酸盐包括醇硫酸盐和氧烷基化醇硫酸盐。
可使用这些醇制备洗涤剂组合物。早就已知由直链醇制备的洗涤剂组合物显示出优良的可生物降解性。近年来,越来越需要找到既可生物降解又能在冷的洗涤温度下显示出良好洗涤性的醇中间体。含有一些支链的醇已经变得重要。可由支链烯烃、特别是根据本发明制备的支链内烯烃来制备这种醇。
此处可使用硫酸化醇的任何技术。醇可直接硫酸化,或者首先氧烷基化之后硫酸化。在美国专利no.5849960中描述了硫酸化和氧烷基化方法,其全文在此通过参考引入。
硫酸化醇可在多种应用中用作表面活性剂,其中包括粒状和液体洗衣用洗涤剂、器皿洗涤用洗涤剂、清洁剂、液体皂、香波和液体擦洗剂。它们通常由硫酸化醇以外的多种组分组成。这些组分可以是其它表面活性剂、助洗剂、辅助的助洗剂、漂白剂及它们的活化剂、泡沫控制剂、酶、抗发灰试剂、荧光增白剂和稳定剂。洗涤剂和清洁领域中公知这些组分中哪些优选用于任何特定的应用。
本发明方法的内烯烃产品可在油田钻探应用中用作油包水钻井流体内的基油。可以制备的内烯烃衍生物包括烷基苯、烷基二甲苯、洗涤剂醇、增塑剂醇、链烯基琥珀酸酯、醚仲醇和通过使用过氧化氢催化二羟化内烯烃生产的二醇和多元醇。
在加氢甲酰化催化剂例如Oxo催化剂存在下,通过用一氧化碳和氢气使之进行加氢甲酰化形成醛,可以将本方法的产物内烯烃转化成醛。通过仔细选择催化剂和操作条件,可由醛制备醇。
也可使用二聚的内烯烃烷基化芳烃生产烷基芳烃。这一方法包括在烷基化条件下利用烷基化催化剂使单烯烃与芳基化合物接触。例如,美国专利6111158(其在此通过参考全文引入)描述了这样一种方法,其中催化剂是具有NES沸石结构类型的沸石。
实施例
催化剂的制备
根据美国专利3405196(其在此通过参考引入)的实施例I的工序,制备实施例1的异构化催化剂,其中一些改进如下所述。将1g 80目(0.124孔隙/mm2)活化氧化铝引入到烧瓶内,在使用之前,通过将烧瓶置于真空下过夜除去水。加热含有氧化铝的烧瓶到50℃,然后冷却到室温。整个这段时间内它保持在干燥的氩气下。1g钠和钾的低共熔混合物(以重量计,0.2g Na:0.6g K)加入到该烧瓶中。在氩气下加热该混合物到80℃,保持15分钟使金属熔融。在烧瓶内的物质颜色变为暗色的固体。最后它冷却到室温。
实施例2所使用的催化剂含有钠、钾和二氧化硅。它获自于NewJersey,Cherry Hill的SiGNa Chemistry,LLC。
反应原料
用于实施例1和2的内烯烃原料是直链丁烯的混合物,具体为顺式-2-丁烯和反式-2-丁烯以及15wt%1-丁烯的混合物。该原料含有99.2%丁烯,和余量主要是丁烷。
实施例1
在室温和101kPa下,在基本上不存在空气和水的情况下,将内烯烃原料(10g)和钠/钾/氧化铝异构化催化剂引入到搅拌的反应容器内。将该混合物搅拌并冷却到0℃。在约10分钟之后,将丁烯转移到搅拌的不锈钢高压釜内,其中含有美国专利4658078的例举实施方案VIII中所述的二聚催化剂双(环戊二烯基)锆氯化氢(1.0g)。在25℃和大气压到自生压力kPa下使这一混合物反应约1小时。所得反应混合物含有2-丁烯、辛烯和小量重质低聚物(小于1wt%)的贫含1-丁烯(小于1wt%)的混合物。
接下来,将二聚体和未反应的丁烯循环回到搅拌的反应容器内。使在搅拌的反应容器内的异构化反应在70℃和自生压力kPa下继续约1小时,此刻将反应混合物转移到高压釜中,在其中在相同的条件下利用二聚催化剂进一步反应约1小时。在6个循环之后,终止反应,并分析反应混合物。冷却反应混合物到0℃,和过滤从液体产物中除去固体。通过分析,90%的原料转化成C8二聚体、三聚体等,在大气压下蒸馏从中得到纯的C8二聚体。
实施例2
在这一实施例中,只使用一个反应容器。将钠/钾/二氧化硅异构化催化剂和原料引入到反应容器内。在0℃下将1g二聚催化剂(在这一情况下为二环戊二烯基二甲基锆)加入到反应器容器中。在70℃和kPa自生压力下进行反应4小时。在这一时间段之后,冷却反应混合物到0℃,过滤除去固体,并除去液体有机产物和进行分析。87%转化成C8二聚体、三聚体等,蒸馏从中得到纯的C8二聚体。在固定温度下增加反应时间将相对于二聚体增加所产生的三聚体和重质低聚物的比例。在固定温度下减少反应时间将相对于三聚体和低聚物得到较高比例的二聚体,但减慢二聚/低聚速度。
Claims (22)
1.制备内烯烃的方法,该方法包括:在异构化催化剂存在下,异构化含一种或多种内烯烃的原料产生α-烯烃,和在二聚催化剂存在下,使所述α-烯烃反应产生具有比原料内烯烃更高碳数的内烯烃。
2.权利要求1的方法,其中由异构化反应产生的α-烯烃的量尽可能接近于异构化反应混合物中α-烯烃的平衡量。
3.权利要求1的方法,其中温度为0-200℃和压力为1-10,000kPa。
4.权利要求1的方法,其中异构化反应和在二聚催化剂存在下的反应在同一反应容器内发生。
5.权利要求3的方法,其中温度为10-150℃。
6.权利要求4的方法,其中温度为50-120℃。
7.权利要求6的方法,其中所产生的α-烯烃的量是在异构化反应混合物中α-烯烃的平衡量或者更低。
8.权利要求1的方法,其中在同一反应容器的不同区内进行异构化反应和在二聚催化剂存在下发生的反应。
9.权利要求1的方法,其中在分开的反应容器内进行异构化反应和在二聚催化剂存在下发生的反应。
10.权利要求9的方法,其中在0-500℃的温度和1-10,000kPa的压力下发生异构化反应。
11.权利要求9的方法,其中在最多200℃和1-10,000kPa的压力下发生二聚反应。
12.权利要求1的方法,其中异构化和二聚反应在同一反应容器内在分开的区中进行,其中所述区允许异构化的α-烯烃移动到二聚区内,但阻止异构化催化剂和二聚催化剂之间的接触。
13.权利要求1的方法,其中α-烯烃与原料内烯烃一起存在。
14.权利要求13的方法,其中α-烯烃选自乙烯和丙烯。
15.权利要求14的方法,其中所产生的二聚内烯烃具有6或7个碳原子。
16.权利要求1的方法,其中原料内烯烃具有4-24个碳原子,和二聚内烯烃具有6-40个碳原子。
17.权利要求16的方法,其中原料内烯烃具有4-20个碳原子,和二聚内烯烃具有8-20个碳原子。
18.权利要求17的方法,其中原料内烯烃具有4-14个碳原子,和二聚内烯烃具有12-18个碳原子。
19.权利要求1的方法,其中二聚催化剂由甲基铝氧烷、配位到铁中心上的三齿双亚胺配体或者铁中心与取代或未取代的芳环的组合以及烷基化试剂组成。
20.权利要求1的方法,其中二聚催化剂包含通式为(环戊二烯基)2MY2的茂金属和铝氧烷,其中M是锆或铪,和每一Y独立地选自氢、C1-C5烷基、C6-C20芳基和卤素,和其中催化剂内的铝与M的原子比范围为1-100。
21.生产醇的方法,该方法包括首先通过权利要求1的方法制备内烯烃,使该内烯烃与异构化催化剂接触得到异构化的烯烃,和加氢甲酰化该异构化的烯烃产生醇。
22.生产硫酸化洗涤剂的方法,该方法包括首先通过权利要求1的方法制备内烯烃,使该内烯烃与异构化催化剂接触得到异构化的烯烃,加氢甲酰化该异构化的烯烃产生醇,任选氧烷基化该醇,硫酸化该醇,和组合硫酸化产品与其它洗涤剂组分。
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