EP1196362A1 - Method for the production of alcohol mixtures - Google Patents
Method for the production of alcohol mixturesInfo
- Publication number
- EP1196362A1 EP1196362A1 EP00956211A EP00956211A EP1196362A1 EP 1196362 A1 EP1196362 A1 EP 1196362A1 EP 00956211 A EP00956211 A EP 00956211A EP 00956211 A EP00956211 A EP 00956211A EP 1196362 A1 EP1196362 A1 EP 1196362A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- alcohol
- reaction
- mixtures
- olefin fraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 138
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 77
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 61
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 239000011541 reaction mixture Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000005674 acyclic monoalkenes Chemical class 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 150000005673 monoalkenes Chemical class 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 230000019635 sulfation Effects 0.000 claims description 16
- 238000005670 sulfation reaction Methods 0.000 claims description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 239000011630 iodine Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 238000005858 glycosidation reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 44
- -1 acyclic olefin Chemical class 0.000 description 42
- 229910052799 carbon Inorganic materials 0.000 description 36
- 238000007037 hydroformylation reaction Methods 0.000 description 22
- 125000002947 alkylene group Chemical group 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 150000001298 alcohols Chemical class 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001720 carbohydrates Chemical group 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005686 cross metathesis reaction Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052703 rhodium Inorganic materials 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007306 functionalization reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000004678 hydrides Chemical class 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000001180 sulfating effect Effects 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000004508 fractional distillation Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000011552 falling film Substances 0.000 description 3
- 229930182470 glycoside Natural products 0.000 description 3
- 150000002338 glycosides Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical class CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- YNWSXIWHOSSPCO-UHFFFAOYSA-N rhodium(2+) Chemical compound [Rh+2] YNWSXIWHOSSPCO-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- IGDNJMOBPOHHRN-UHFFFAOYSA-N 5h-benzo[b]phosphindole Chemical compound C1=CC=C2C3=CC=CC=C3PC2=C1 IGDNJMOBPOHHRN-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000005677 ethinylene group Chemical class [*:2]C#C[*:1] 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical class [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- MTNKRTXSIXNCAP-UHFFFAOYSA-N 1-(4-butoxyphenyl)-n-[4-[2-[4-[(4-butoxyphenyl)methylideneamino]phenyl]ethyl]phenyl]methanimine Chemical compound C1=CC(OCCCC)=CC=C1C=NC(C=C1)=CC=C1CCC1=CC=C(N=CC=2C=CC(OCCCC)=CC=2)C=C1 MTNKRTXSIXNCAP-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006820 Bouveault-Blanc reduction reaction Methods 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- HDTOJNWTFZFLPZ-UHFFFAOYSA-J [K+].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [K+].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDTOJNWTFZFLPZ-UHFFFAOYSA-J 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 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
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- BNGNANCNFVQZBM-UHFFFAOYSA-N cobalt;ethyl hexanoate Chemical compound [Co].CCCCCC(=O)OCC BNGNANCNFVQZBM-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 150000002243 furanoses Chemical class 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 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
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 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 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003215 pyranoses Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005872 self-metathesis reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 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
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/38—Alcohols, e.g. oxidation products of paraffins
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
Definitions
- the present invention relates to a process for the preparation of alcohol mixtures and the mixtures obtained by this process. It further relates to a process for the functionalization of these alcohol mixtures, the functionalized alcohol mixtures thus obtained and their use.
- fatty alcohols with about 8 to 20 carbon atoms for the production of nonionic and anionic surfactants.
- the alcohols are subjected to a corresponding functionalization, for example by alkoxylation or glycosidation.
- the resulting alkoxylates can either be used directly as nonionic surface-active substances or by further functionalization, e.g. can be converted into anionic surface-active substances by sulfation or phosphating.
- the application properties of this side e.g. their wetting capacity, foaming, fat-dissolving capacity, biodegradability etc. are essentially determined by the chain length and the degree of branching of the hydrophilic hydrocarbon residue of the alcohol used.
- Alcohols that are well suited for further processing into effective surfactants are also known as surfactant alcohols.
- Fatty alcohols can be obtained both from native sources and synthetically, for example by building up from starting materials with a lower number of carbon atoms.
- SHOP process Shell higher olefine process
- ethene gives olefin fractions with a carbon number suitable for further processing into surfactants.
- the functionalization of the olefins to give the corresponding alcohols takes place, for example, by hydroformylation and hydrogenation, it being possible, depending on the reaction procedure, to work in one stage or in two separate reaction stages.
- An overview of hydroformylation processes and suitable catalysts can be found in Beller et al. Journal of Molecular Catalysis A 104 (1995), pp. 17-85.
- a disadvantage of the ethylene-based processes for the production of fatty alcohols the high cost of the raw material, which makes these processes economically disadvantageous.
- a hydrocarbon mixture called a Cs cut with a total olefin content of, for example, about 50% is obtained, of which approx. 15% is based on cyclopentene and the rest on acyclic monoolefins, especially n-pentene ( approx. 15% by weight) and further isomeric methylbutenes (approx. 20% by weight) are omitted.
- the industrial processing of the C 5 cut has been carried out essentially by distillation to obtain the cyclopentane contained therein. Processes of this type are very complex in terms of process engineering. There is therefore a need for the non-distillative removal of the cyclopentene and optionally further acyclic monoolefins from the Cs cut to obtain valuable products.
- DE-A-196 54 166 describes oligomer mixtures with ethylenically unsaturated double bonds which are derived from cyclopentene and which are obtained by metathesis reaction of a Cs cut in the presence of a transition metal catalyst.
- DE-A-196 54 167 describes a process for the functionalization of such oligomer mixtures derived from cyclopentene, e.g. by hydroformylation and, if appropriate, subsequent hydrogenation. This results in alcohol mixtures with a high proportion of dihydric and higher alcohols. Such alcohol mixtures are not suitable for use as surfactant alcohols.
- the object of the present invention is to provide a process for the preparation of surfactant alcohols.
- a large-scale starting hydrocarbon mixture is to be used in the process according to the invention.
- the object is achieved by a process in which a hydrocarbon mixture which contains cyclopentene and at least one aeyclic monoolefin is subjected to a metathesis, a Cs-C o-01efin fraction is isolated from the metathesis mixture and then one undergoes catalytic hydroformylation and hydrogenation.
- the invention thus relates to a process for the preparation of alcohol mixtures, wherein a) reacting a hydrocarbon mixture which contains cyclopentene and at least one acyclic monoolefin in a metathesis reaction,
- the, optionally selectively hydrogenated, olefin fraction is catalytically hydroformylated and hydrogenated by reaction with carbon monoxide and hydrogen.
- the total olefin content of the hydrocarbon mixture used for the metathesis is preferably at least 30% by weight, preferably at least 40% by weight, in particular at least 50% by weight. Hydrocarbon mixtures with a total olefin content of up to 100% by weight are suitable.
- the hydrocarbon mixtures used for metathesis preferably contain at least one acyclic monoolefin.
- Preferred acyclic monoolefins are selected from Cs-monoolefins, such as 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene and mixtures thereof.
- the proportion of Cs-monoolefins in the acyclic monoolefins is preferably at least 70% by weight, preferably at least 80% by weight, in particular at least 90% by weight.
- a hydrocarbon mixture which is obtained on a large industrial scale in petroleum processing is preferably used. If desired, such mixtures can be subjected to a catalytic partial hydrogenation to remove dienes beforehand. For example, a mixture enriched in saturated and unsaturated Cs hydrocarbons, in particular a C 5 cut, is particularly suitable.
- pyrolysis gasoline is preferably suitable, for example occurs when steam cracking naphtha. If desired, this pyrolysis gasoline can first be subjected to a selective hydrogenation in order to essentially convert the dienes and acetylenes contained therein into the corresponding alkanes and alkenes.
- step a) of the process according to the invention is followed by a separation step, for example a fractional distillation, on the one hand the C 6 -C 8 cut which is important for further chemical syntheses and which contains the aromatic hydrocarbons and on the other hand a Cs cut which can be used in step a) of the process according to the invention ,
- a total olefin content of e.g. 50 to 60% by weight such as 56%
- a cyclopentene content of e.g. 10 to 20% by weight such as about 15% by weight
- Cs monoolefins e.g. 33 to 43% by weight
- a hydrocarbon mixture which comprises a cyclopentene-containing hydrocarbon mixture, in particular the Cs cut, and a mixture containing acyclic C 4 -01efins.
- the C 4 -01efin mixture is preferably a petroleum fraction, in particular raffinate II. Raffinate II can be obtained, for example, by cracking high molecular weight hydrocarbons, such as crude oil.
- a C 4 -01efin mixture is preferably used which contains 60 to 85% by volume of butene-1 and butene-2.
- the C 4 -01efin mixture preferably contains at most 40% by volume, preferably at most 20% by volume, of saturated hydrocarbons, such as n-butane, isobutane, Cs-alkanes, etc.
- the metathesis reaction of the hydrocarbon mixture in step a) preferably comprises i) the disproportionation of acyclic monoolefins by cross metathesis, ii) the oligomerization of cyclopentene by ring-opening metathesis, iii) chain termination by reaction of an oligomer from ii) with an acyclic olefin of the hydrocarbon mixture or a product from i), steps i) and / or ii) and / or iii) being able to be carried out several times on their own or in combination.
- Step i) Combinations of cross-metathesis of different and self-metathesis of the same acyclic olefins and repeated runs of this reaction result in a large number of monoolefins with different structure and number of carbon atoms, which form the end groups of the oligomers in the reaction mixture resulting from the metathesis.
- a catalyst is used for the metathesis, which enables the formation of cross-metathesis products.
- These preferably include the metathesis catalysts described below as being particularly active. According to this embodiment, metathesis mixtures with a higher proportion of oligomers without terminal double bonds are obtained than when using a less active catalyst.
- the average number of cyclopentene insertions in the growing chain in the sense of a ring-opening metathesis polymerization determines the average molecular weight of the cyclopentene-oligomer mixture formed.
- Oligomer mixtures with an average molecular weight in a range from about 138 to 206 are preferably formed by the process according to the invention, which corresponds to an average number of one to two cyclopentene units per oligomer.
- the chain is terminated by reacting an oligomer which still has an active chain end in the form of a catalyst complex (alkylidene complex) with an acyclic olefin, an active catalyst complex generally being recovered.
- a catalyst complex alkylidene complex
- the acyclic olefin may originate unchanged from the hydrocarbon mixture originally used for the reaction or may have been modified beforehand in a cross metathesis according to stage i).
- Suitable catalysts for metathesis are known and include homogeneous and heterogeneous catalyst systems.
- catalysts based on a transition metal of the 6th, 7th or 8th subgroup of the periodic table are suitable for the process according to the invention, preference being given to using catalysts based on Mo, W, Re and Ru.
- Catalyst / cocatalyst systems based on W, Mo and Re are preferably used, which can comprise at least one soluble transition metal compound and / or an alkylating agent.
- These include, for example, MoCl 2 (NO) 2 (PR 3 ) 2 / Al 2 (CH 3 ) 3 Cl 3 ; WCl 6 / BuLi; WCl 6 / EtAlCl 2 (Sn (CH 3 ) 4 ) / EtOH; WOCl 4 / Sn (CH 3 ) 4 ; WOCl 2 (0- [2,6-Br 2 -C 6 H 3 ]) / Sn (CH 3 ) 4 and CH 3 Re0 3 / C 2 H 5 AlCl 2 .
- Preferred catalysts are furthermore four-coordinate Mo and W alkylidene complexes, which additionally have two bulky alkoxy and one imido ligands, in particular
- a particularly preferred heterogeneous catalyst is Re 2 0 on Al 2 0 3 as the support material.
- oligomer mixtures with changing double bond proportions and changing proportions of terminal double bonds can be obtained in the metathesis.
- the metathesis reaction mixtures obtained in step a) have an iodine value in the range of about 200 to 400 g I 2/100 g oligomers.
- the metathesis reaction in step a) preferably results in an oligomer mixture that essentially contains cyclopentene-derived oligomers of the general formula I.
- n is an integer from 1 to 15, and
- R 1 , R 2 , R 3 , R 4 are independently hydrogen or alkyl.
- the radicals R 1 , R 2 , R 3 and R 4 in the formula I independently of one another represent hydrogen or alkyl, the term "alkyl” encompassing straight-chain and branched alkyl groups.
- Ci-Cis-alkyl preferably C ⁇ -C ⁇ o-alkyl, particularly preferably C ⁇ -C 5 alkyl groups.
- alkyl groups are in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2 -Dimethylpropyl, 1, 1-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl , 1, 3-dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3, 3-dimethylbuty
- n in formula I stands for the number of cyclopentene units introduced into the oligomer mixtures derived from cyclopentene by ring-opening metathesis reaction.
- the value n and thus the degree of ring-opening metathesis can be influenced by the activity of the metathesis catalyst used and the ratio of acyclic to cyclic olefins.
- n is preferably in a range from approximately 1 to 4, in particular 1 to 2.
- Preferred oligomer mixtures of the formula I are those in which at least 50% by weight, in particular at least 70% by weight (determined by the area integration of the gas chromatograms) of the components has a value of n> 1.
- the reaction mixture from step a) is subjected to one or more separation steps.
- Suitable separation devices are the usual apparatuses known to the person skilled in the art. These include e.g. B. distillation columns, such as tray columns which, if desired, can be equipped with bells, sieve plates, sieve trays, valves, side draws, etc., Evaporators such as thin film evaporators, falling film evaporators, wiper blade evaporators, Sambay evaporators etc. and combinations thereof.
- the olefin fraction is preferably isolated by fractional distillation.
- an olefin fraction is isolated which essentially contains olefins having 9 to 18 carbon atoms, preferably 10 to 15 carbon atoms.
- the olefin fraction isolated in step b) preferably has the highest possible olefin content.
- the olefin content is preferably at least 40% by weight, preferably at least 50% by weight. According to a particularly preferred embodiment, the olefin content is about 100% by weight.
- a hydrocarbon mixture can be used for the metathesis in step a) which, in addition to cyclopentene and acyclic monoolefins, also has saturated compounds. If the olefin fraction isolated in step b) contains part of these saturated compounds, this is generally not critical for the further processing to the olefin mixtures according to the invention.
- the olefin fraction isolated in step b) preferably has a proportion of saturated compounds in the range from approximately 0 to 60% by weight, preferably approximately 0.1 to 50% by weight.
- the metathesis in step a) generally results in reaction mixtures which, in addition to monoolefins and optionally saturated compounds from the reactant hydrocarbon mixture, also contain two- and polyunsaturated compounds.
- the olefin fraction isolated in step b) preferably has a proportion of di- and polyunsaturated compounds in the range from about 60 to 100% by weight.
- At least one further olefin fraction can be isolated from the reaction mixture of the metathesis in step b). These are preferably fractions which are present in the reaction mixture obtained in step a) in an amount of at least 5% by weight, based on the total amount of the mixture.
- step b) at least one further olefin fraction is preferably isolated, which essentially contains olefins having more than 20, preferably more than 18, in particular more than 15 carbon atoms.
- This fraction preferably contains essentially olefins with at most 75, particularly preferably at most 50, in particular at most 40 carbon atoms.
- these olefin fractions can preferably be subjected to cross metathesis with at least one acyclic olefin which has at most 9, preferably at most 8, in particular at most 7 carbon atoms.
- Low molecular weight olefins and olefin mixtures suitable for cross metathesis are, for example, ethene, raffinate II or corresponding olefin fractions from the metathesis from step a).
- these higher molecular weight further olefin fractions can, if desired, also be partially or completely fed back in step a) of the process according to the invention.
- step b) at least one further olefin fraction is preferably isolated, which essentially has olefins having at most 9, preferably at most 8, in particular at most 7 carbon atoms.
- This fraction preferably contains essentially olefins having at least 5, preferably at least 6, carbon atoms.
- these low molecular weight further olefin fractions can preferably be subjected to cross metathesis with at least one acyclic olefin which contains more than 20, preferably more than 18, in particular more than 15 carbon atoms.
- Suitable higher molecular weight olefins and olefin mixtures are e.g. the previously described higher molecular weight further olefin fractions from the metathesis from step a).
- cross-metathesis reactions of the further olefin fractions isolated in step b) preferably result in turn in fractions which essentially contain olefins having 8 to 20, preferably 9 to 18, in particular 10 to 15 carbon atoms. These can be used for further processing in step c) of the method according to the invention.
- the olefin fraction isolated in step b) by the process according to the invention can also contain, in addition to monoolefins, a proportion of two- or polyunsaturated compounds.
- the olefin fraction is further processed to the alcohol mixtures according to the invention, the corresponding di- or polyhydric alcohols result from these di- and polyunsaturated compounds. Too high a proportion of these dihydric and polyhydric alcohols may be undesirable if the alcohol mixtures according to the invention are used for the preparation of surface-active compounds.
- the olefin fraction from step b) can therefore be subjected to a selective hydrogenation.
- the di- and polyunsaturated compounds are at least partially in Monoolefins convicted. The proportion of monoolefins in the olefin fraction is thus advantageously increased.
- Suitable catalysts for the selective hydrogenation are known from the prior art and include conventional homogeneous and heterogeneous hydrogenation catalyst systems.
- the catalysts suitable for the process according to the invention are preferably based on a transition metal of the 8th or 1st subgroup, preference being given to using catalysts based on Ni, Pd, Pt, Ru or Cu. Catalysts based on Cu or Pd are particularly preferably used.
- Suitable heterogeneous catalyst systems generally comprise one of the aforementioned transition metal compounds on an inert support.
- Suitable inorganic carriers are the oxides customary for this, in particular silicon and aluminum oxides, aluminosilicates, zeolites, carbides, nitrides etc. and mixtures thereof. Al 2 O 3 , Si0 2 and mixtures thereof are preferably used as carriers.
- heterogeneous catalysts are used in the process according to the invention, such as those described in US Pat. Nos. 4,587,369; US-A-4,704,492 and US-A-4, 493, 906, which are incorporated by reference in their entirety.
- Suitable Cu-based catalyst systems are sold by Dow Chemical as KLP catalysts.
- olefin fractions which have a proportion of di- and polyunsaturated compounds in the range from 60 to 100% by weight.
- an olefin fraction isolated in step b) and optionally selectively hydrogenated in step c) is hydroformylated and hydrogenated.
- the alcohol mixtures can be prepared in one step or in two separate reaction steps.
- the step in) d olefin used has an iodine value in the range of 175 to 350 g I 2/100 g.
- the olefin fraction used in step d) preferably has a proportion of unbranched olefins in the range from 10 to 90% by weight, preferably 30 to 70% by weight.
- Suitable catalysts for hydroformylation are known and generally comprise a salt or a complex compound of an element of subgroup VIII of the periodic table.
- the metal of subgroup VIII is preferably selected from cobalt, ruthenium, iridium, rhodium, nickel, palladium and platinum. Salts and in particular complex compounds of rhodium or cobalt are preferably used for the process according to the invention.
- Suitable salts are, for example, the hydrides, halides, nitrates, sulfates, oxides, sulfides or the salts with alkyl or aryl carboxylic acids or alkyl or aryl sulfonic acids.
- Suitable complex compounds are, for example, the carbonyl compounds and carbonyl hydrides of the metals mentioned and complexes with amines, amides, triarylphosphines, trialkylphosphines, tricycloalkylphosphines, olefins, or dienes as ligands.
- the ligands can also be used in polymeric or polymer-bound form. Catalyst systems can also be prepared in situ from the salts mentioned and the ligands mentioned.
- Suitable alkyl residues of the ligands are the linear or branched Ci-Cis-alkyl described above, in particular Ci-Cs-alkyl residues.
- Cycloalkyl is preferably C 3 -C ⁇ o-cycloalkyl, in particular cyclopentyl and cyclohexyl, which can optionally also be substituted with C ⁇ -C 4 alkyl groups.
- Aryl is preferably understood to mean phenyl (Ph) or naphthyl, optionally with 1, 2, 3 or 4 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, for example methoxy, halogen, preferably chloride, or hydroxy, the may optionally also be ethoxylated.
- Suitable rhodium catalysts or catalyst precursors are rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate (rhodium alum), rhodium (II) and Rhodium (III) carboxylate, preferably rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid and trisammonium hexachloro-rhodate (III).
- rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate (
- rhodium complexes of the general formula RhX m L 1 L 2 (L 3 ) n , where X is halide, preferably chloride or bromide, alkyl or aryl carboxylate, acetylacetonate, aryl or alkyl sulfonate, in particular phenyl sulfonate and toluenesulfonate, hydride or the diphenyltriazine anion,
- L 1 , L 2 , L 3 independently of one another for CO, olefins, cycloolefins, preferably cyclooctadiene (COD), dibenzophosphole, benzonitrile, PR 3 or R 2 PA-PR 2 , m for 1, 2 or 3 and n for 0.1 or 2 stand.
- R (the radicals R can be the same or different) are to be understood as meaning alkyl, cycloalkyl and aryl radicals, preferably phenyl, p-tolyl, m-tolyl, p-ethylphenyl, p-cumyl, pt.-Butylphenyl, p -C-C -alkoxyphenyl, preferably p-anisyl, xylyl, mesityl, p-Hydroxyphenyl, which may also be ethoxylated, isopropyl, C 1 -C 4 alkoxy, cyclopentyl or cyclohexyl.
- A stands for 1,2-ethylene or 1,3-propylene.
- L 1 , L 2 or L 3 are preferably independently of one another CO, COD, P (phenyl) 3 , P (i-propyl) 3 , P (anisyl) 3 , P (OC 2 H 5 ) 3 , P ( Cyclohexyl) 3 , dibenzophosphole or benzonitrile.
- X preferably represents hydride, chloride, bromide, acetate, tosylate, acetylacetonate or the diphenyltriazine anion, in particular hydride, chloride or acetate.
- Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates such as cobalt acetate, cobalt ethyl hexanoate, cobalt naphthanoate, and the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tecacoblobium and hexacobalt hexadecacarbonyl.
- the cobalt carbonyl complexes and in particular dicobalt octacarbonyl are preferably used for the process according to the invention.
- a hydroformylation catalyst based on rhodium is used, it is generally used in an amount of 1 to 150 ppm, preferably 1 to 100 ppm.
- the reaction temperature for a hydroformylation catalyst based on rhodium is generally in the range from room temperature to 200 ° C., preferably 50 to 150 ° C.
- hydroformylation catalyst based on cobalt it is generally used in an amount of 0.0001 to 0.5
- reaction temperature for a hydroformylation catalyst based on cobalt is generally in the range from about 100 to 250 ° C., preferably 150 to 200 ° C.
- the reaction can be carried out at an elevated pressure of about 10 to 650 bar.
- the molar ratio of H 2 : CO is generally about 1: 5 to about 5: 1.
- the aldehydes or aldehyde / alcohol mixtures resulting from the hydroformylation can, if desired, be isolated and, if appropriate, purified by conventional methods known to the person skilled in the art before the hydrogenation.
- the hydroformylation catalyst is preferably removed from the reaction mixture before the hydrogenation. In general, if necessary after working up, it can be used again for the hydroformylation.
- the reaction mixtures obtained in the hydroformylation are reacted with hydrogen in the presence of a hydrogenation catalyst.
- Suitable hydrogenation catalysts are generally transition metals such as e.g. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., or their mixtures, which increase the activity and stability on supports, such as Activated carbon, aluminum oxide, diatomaceous earth, etc., can be applied.
- transition metals such as e.g. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc.
- supports such as Activated carbon, aluminum oxide, diatomaceous earth, etc.
- Fe, Co, and preferably Ni can also be used in the form of the Raney catalysts as a metal sponge with a very large surface area.
- a Co / Mo catalyst is preferably used for the process according to the invention.
- the hydrogenation of the oxo aldehydes is preferably carried out at elevated temperatures and elevated pressure.
- the reaction temperature is preferably about 80 to 250.degree.
- the pressure is preferably about 50 to 350 bar.
- the alcohol mixtures according to the invention are prepared in a one-step reaction.
- an olefin fraction is reacted with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst which is also suitable for the further hydrogenation to the oxo alcohols.
- a hydroformylation catalyst which is also suitable for the further hydrogenation to the oxo alcohols.
- all hydroformylation catalysts are also suitable for carrying out catalytic hydrogenations, although, depending on the catalytic activity, generally higher temperatures and / or higher pressures and / or longer reaction times and a larger amount of catalyst than for an exclusive hydroformylation are used.
- a cobalt carbonyl catalyst and in particular Co 2 (CO) 8 are preferably used.
- the reaction temperature is generally 100 to 220 ° C, preferably 150 to 200 ° C, at an increased pressure of 50 to 650 bar, preferably 100 to 600 bar.
- the invention further relates to the alcohol mixtures obtained by the process according to the invention.
- the alcohol mixtures preferably have an OH number in the range from about 200 to 400 mg KOH / g product, preferably 250 to 350 mg KOH / g product.
- the alcohol mixtures preferably have a degree of branching determined by means of NMR in the range from 0.5 to 2.5, preferably 0.7 to 2.0.
- the hydrogenation preferably takes place as completely as possible so that the carbonyl number of the alcohol mixtures obtained by the process according to the invention is generally low.
- the alcohol mixtures according to the invention have a carbonyl number of at most 5.
- the alcohol mixtures according to the invention are preferably suitable for the functionalization for the preparation of surface-active mixtures.
- Another object of the invention is a process for the preparation of functionalized alcohol mixtures, wherein one of the previously described alcohol mixtures according to the invention is subjected to alkoxylation, glycosidation, sulfation, phosphating, alkoxylation and subsequent sulfation or alkoxylation and subsequent phosphating.
- the invention thus relates to a process for the preparation of functionalized alcohol mixtures, wherein
- the, optionally selectively hydrogenated, olefin fraction is catalytically hydroformylated and hydrogenated by reaction with carbon monoxide and hydrogen,
- step d) the alcohol mixture from step d) is subjected to alkoxylation, glycosidation, sulfation, phosphating, alkoxylation and subsequent sulfation or alkoxylation and subsequent phosphating.
- the alcohol mixtures are alkoxylated by reaction with at least one alkylene oxide.
- the alkylene oxides are preferably selected from compounds of the general formula II or CH ⁇ - CH R 7 (II)
- R 7 represents hydrogen or a straight-chain or branched Ci to Ci 6 alkyl radical, and mixtures thereof.
- the radical R 7 in the formula II preferably represents a straight-chain or branched C 1 -C 4 -alkyl radical, in particular C 1 -C 3
- the alkylene oxides are preferably selected from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
- the alcohol mixtures are reacted with the alkylene oxide (s) by customary methods known to the person skilled in the art and in equipment customary for this.
- the average chain length of the polyether chains of the alcohol mixtures thus functionalized can be determined by the molar ratio of alcohol to alkylene oxide.
- Alkoxylated alcohol mixtures having about 1 to 200, preferably about 1 to 50, in particular 1 to 10, alkylene oxide units are preferably prepared. If desired, the alcohol mixtures can only be reacted with one alkylene oxide or with two or more different alkylene oxides. When the alcohol mixtures are reacted with a mixture of two or more alkylene oxides, the resulting alkoxylates contain the alkylene oxide units essentially randomly distributed. If the alkylene oxides are used separately one after the other, this results in alkoxylates which, in the order in which they are added, contain the alkylene oxide units in the form of blocks in copolymerized form.
- the alkoxylation can be catalyzed by strong bases, such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AICI 3 , BF 3 etc.
- strong bases such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AICI 3 , BF 3 etc.
- the alkoxylation is preferably carried out at temperatures in the range from approximately 80 to 250 ° C., preferably approximately 100 to 220 ° C.
- the pressure is preferably between ambient pressure and 600 bar.
- the alkylene oxide may contain an inert gas admixture, e.g. from about 5 to 60%.
- the functionalized alcohol mixtures obtained by alkoxylation have a very good surface activity and can be used advantageously as nonionic surfactants in a large number of fields of application.
- the alcohol mixtures are glycosidated by one, two or more reactions of the alcohol mixtures according to the invention with mono-, di- or polysaccharides.
- the reaction is carried out using customary methods known to those skilled in the art. On the one hand, this includes acid-catalyzed conversion with dehydration.
- Acids are, for example, mineral acids, such as HCl and H 2 S0 4 .
- oligosaccharides with statistical chain length distribution are obtained.
- the average degree of oligomerization is preferably 1 to 3 saccharide residues.
- the saccharide can first be acetalized by reaction with a low molecular weight C ⁇ ⁇ to C 8 alkanol, such as ethanol, propanol or butanol.
- the acetalization is preferably acid-catalyzed.
- the resulting glycoside with the low molecular weight alcohol can then be reacted with the alcohol mixture according to the invention to give the corresponding glycosides.
- Aqueous saccharide solutions are generally also suitable for this reaction.
- the saccharide can first be converted into the corresponding O-acetylhalosaccharide by reaction with a hydrogen halide and then with a sen alcohol mixture in the presence of acid-binding compounds are glycosidated.
- Monosaccharides are preferably used for the glycosidation.
- hexoses such as glucose, fructose, galactose, mannose etc. and pentoses such as arabinose, xylose, ribose etc.
- Glucose is particularly preferably used.
- the saccharides can be used individually or in the form of mixtures. Saccharide mixtures generally result in glycosides with randomly distributed sugar residues. With multiple addition of saccharide to an alcoholic hydroxide group, polyglycosides of the alcohol mixtures according to the invention result.
- saccharides can also be used in succession or as a mixture for polyglycosidation, so that the resulting functionalized alcohol mixtures contain the saccharides in the form of blocks or incorporated in a statistically distributed manner.
- reaction conditions in particular reaction temperature, furanose or pyranose structures can result.
- Suitable methods and reaction conditions for glycosidation are e.g. in Ulimann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A25 (1994), pp. 792-793 and the documents cited therein.
- the functionalized alcohol mixtures obtained by glycosidation have a very good surface activity and can be used advantageously as a nonionic surfactant in a large number of fields of application.
- alcohol mixtures or alkoxylated alcohol mixtures are sulfated or phosphated by reaction with sulfuric acid or sulfuric acid derivatives to give acidic alkyl sulfates or alkyl ether sulfates or by reaction with phosphoric acid or or phosphoric acid derivatives to give acidic alkyl phosphates or alkyl ether phosphates.
- Suitable processes for the sulfation of alcohols are the customary ones known to the person skilled in the art, such as e.g. in US 3,462,525, US 3,420,875 or US 3,524,864, which are incorporated herein by reference. Suitable processes for sulfation are also described in Ulimann's Encyclopedia of Industrial Chemistry, 5th edition vol. A25 (1994), pp. 779-783 and the literature cited therein.
- sulfuric acid is used to sulfate the alcohol mixtures according to the invention, this is preferably 75 to 100% by weight, in particular 85 to 98% by weight.
- sulfur Acid is available under the names concentrated sulfuric acid and monohydrate.
- a solvent or diluent can be used for sulfation with sulfuric acid.
- Suitable solvents are e.g. those that form an azeotrope with water, e.g. Toluene.
- the alcohol mixture is placed in a reaction vessel and the sulfating agent is added with constant mixing.
- the molar ratio of alkanol to sulfating agent is preferably about 1: 1 to 1: 1.5, in particular 1: 1 to 1: 1.2.
- the sulfating agent can also be used in a molar deficit, e.g. in the sulfation of alkoxylated alcohol mixtures if mixtures of nonionic and anionic surface-active compounds are to be produced.
- the sulfation is preferably carried out at a temperature in the range from ambient temperature to 80 ° C., in particular 40 to 75 ° C.
- Suitable sulfating agents are e.g. Sulfur trioxide, sulfur trioxide complexes, solutions of sulfur trioxide in sulfuric acid (oleum), chlorosulfonic acid, sulfuryl chloride, amidosulfonic acid etc. If sulfur trioxide is used as the sulfating agent, the reaction can advantageously be carried out in a falling film evaporator, preferably in countercurrent. The reaction can be carried out batchwise or continuously.
- reaction mixtures formed in the sulfation are worked up by customary processes known to the person skilled in the art. This includes e.g. neutralization, separation of any solvents used, etc.
- the phosphation of the alcohol mixtures and alkoxylated alcohol mixtures described above is generally carried out in an analogous manner to the sulfation.
- Suitable processes for the phosphating of alcohols are the customary, known to the person skilled in the art, as described, for example, in Synthesis 1985, pp. 449 to 488, to which reference is made in full here.
- Suitable phosphating agents are, for example, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, P0C1 3 etc.
- POCI 3 the remaining acid chloride functions are hydrolyzed after the esterification.
- the functionalized alcohol mixtures and their salts obtained by sulfation or phosphation show a very good surface activity and can be used advantageously as anionic surfactants in a large number of application areas.
- the invention further relates to the functionalized alcohol mixtures and their salts obtainable by the process described above.
- Another object of the invention is the use of the functionalized alcohol mixtures as surfactants, dispersants, paper auxiliaries, soil solvents, corrosion inhibitors, auxiliaries for dispersions, incrustation inhibitors.
- the mixtures of functionalized alcohols according to the invention are advantageously distinguished by very good surface-active properties.
- the aqueous solutions of these mixtures show e.g. good surface tension values and / or cloud points.
- a 5890 gas chromatograph from Hewlett Packard with a DB 5.30 mx 0.32 mm glass capillary acid and a flame ionization detector with connected integration unit was used to record the gas chromatograms.
- the iodine number is defined as g iodine / 100 g product and was determined according to Kaufmann. For this purpose, about 0.2 g of test substance is precisely weighed into a 300 ml Erlenmeyer flask, dissolved in 20 ml of chloroform, mixed with exactly 20.00 ml of bromine solution and left to stand in the dark for 2 hours. Then 10 ml of potassium iodide solution and about 2 g of potassium iodate are added. The iodine which is excreted is titrated with sodium thiosulphate solution against starch solution until the blue color disappears.
- acetylation reagent 810 ml of pyridine, 100 ml of acetic anhydride and 9 ml of acetic acid are mixed.
- a 1: 1 mixture of cyclopentene and 1-pentene was pumped continuously at 60 ° C., 5 bar and residence times of 1-3 h into a tube reactor equipped with Re0 7 / Al 2 0 3 .
- the reaction product was then separated into a light and a high boiler fraction and the former was returned to the metathesis process.
- the high boiler fraction was freed from residual amounts of low boilers in vacuo.
- space-time yields of 50-500 g 1 _1 h _1 slightly yellowish liquids were obtained, which were then chromatographed on Al 2 O 3 .
- a sample taken had the following composition (GC area percent):
- a metathesis reaction mixture according to Example 4 was subjected to fractional distillation under reduced pressure (60 theoretical plates; reflux ratio 5; fraction isolated at 100 mbar, top temperature 96-124 ° C, bottom temperature
- the alcohol mixture was worked up by distillation and a fraction with a boiling range from 99 ° C./9 mbar to 144 ° C./40 mbar was isolated (40% by weight based on crude hydroformylation product). This fraction has an OH number of 296 mg KOH / g. An average degree of branching of 1.02 was determined using ⁇ -NMR.
- olefin fraction from example 5 was subjected to a further fractional distillation (apparatus as example 5; fraction isolated at 200 mbar, top temperature 95-110 ° C., bottom temperature 130 ° C.).
- An olefin fraction of the following composition (GC area percent) was isolated:
- the iodine value was 295 g I 2/100 g. 2260 g of this olefin fraction were mixed with 8.5 g of Co 2 (CO) 8 at 185 ° C. and 280 bar with synthesis gas (CO / H 2 1: 1) with the addition of 226 g of water and 1.5 kg of heptane in a 20 l Rotary stirring autoclave hydroformylated, the reaction time was 7.5 hours. After cooling and releasing the pressure in the autoclave, the reaction mixture was decobtained with 10% acetic acid with introduction of air at 90 ° C. The resulting hydroformylation mixture was hydrogenated in a 2.5 1 tubular reactor in a trickle mode over a Co / Mo fixed bed catalyst at 175 ° C. and 280 bar with hydrogen with the addition of 10% by weight of water.
- the alcohol mixture was worked up by distillation and a fraction with a boiling range from 80 ° C./2 mbar to 114 ° C./2 mbar was isolated (71% by weight based on crude hydroformylation product). This fraction has an OH number of 310 mg KOH / g. By means ! H-NMR showed an average degree of branching of 1.14.
- Example 5 380 g of the alcohol mixture obtained in Example 5 were introduced into a dry 2 l autoclave with 1.5 g of NaOH. The contents of the autoclave were heated to 150 ° C. and 616 g of ethylene oxide were pressed into the autoclave under pressure. After filling the entire amount of ethylene oxide, the autoclave was at 150 ° C for 30 minutes held. After cooling, the reactor discharge was neutralized with sulfuric acid.
- the surfactant mixture obtained had a cloud point of 46 ° C., measured in accordance with DIN 53917 on a 1% strength solution in water.
- Example 6 270 g of the alcohol mixture obtained in Example 6 were introduced into a dry 2-1 autoclave with 1.5 g of NaOH. The contents of the autoclave were heated to 150 ° C. and 726 g of ethylene oxide were pressed into the autoclave under pressure. After the entire amount of ethylene oxide had been introduced, the autoclave was kept at 150 ° C. for a further 30 minutes. After cooling, the reactor discharge was neutralized with sulfuric acid. The mixture obtained had a cloud point of 95.5 ° C., measured in accordance with DIN 53917 on a 1% strength solution in water. The surface tension, measured according to DIN 53914, at a concentration of 1 g / 1, was 31.2 mN / m.
- Example 6 360 g of the alcohol mixture obtained in Example 6 were heated to 60 ° C. in a stirred vessel under a nitrogen atmosphere and 167 g of polyphosphoric acid were slowly added. A temperature of 65 ° C was not exceeded. At the end of the addition, the temperature was raised to 70 ° C. and the reaction mixture was stirred at this temperature for another hour. A surfactant mixture was obtained with a surface tension determined according to DIN 53914 of 32.1 mN / m at a concentration of 1 g / 1.
- Example 7 490 g of the fatty alcohol ethoxylate obtained in Example 7 were heated to 60 ° C. in a stirred vessel under a nitrogen atmosphere and 85 g of polyphosphoric acid were slowly added. A temperature of 65 ° C was not exceeded. At the end of the addition, the temperature was raised to 70 ° C. and the batch was stirred at this temperature for a further hour. A surfactant mixture was obtained with a surface tension of 35.7 m / N / m, measured according to DIN 53914, measured at a concentration of 1 g / 1.
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Abstract
The invention relates to a method for the production of alcohol mixtures, wherein a) a hydrocarbon mixture containing cyclopentene and at least one acyclic monoolefin is transformed in a metathesis reaction, b) an olefin fraction containing essentially olefins with 8-20 carbon atoms is isolated from the metathesis reaction mixture, c) optionally, the bi or multi-saturated compounds contained in the olefin fractions undergo at least partially selective hydrogenation in order to form monoolefins, and d) the optionally selectively hydrogenated olefin fraction is catalytically hydroformulated and hydrogenated by reacting it with carbon monoxide and hydrogen. The invention also relates to alcohol mixtures that can be obtained according to said method, in addition to a method for the production of functionalized alcohol mixtures and the use thereof.
Description
Verfahren zur Herstellung von AlkoholgemischenProcess for the preparation of alcohol mixtures
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Alkoholgemischen und die nach diesem Verfahren erhaltenen Gemische. Sie betrifft weiter ein Verfahren zur Funktionalisierung dieser Alkoholgemische, die so erhaltenen funktionalisierten Al- koholgemische und deren Verwendung.The present invention relates to a process for the preparation of alcohol mixtures and the mixtures obtained by this process. It further relates to a process for the functionalization of these alcohol mixtures, the functionalized alcohol mixtures thus obtained and their use.
Es ist bekannt, Fettalkohole mit etwa 8 bis 20 Kohlenstoffatomen zur Herstellung von nichtionischen und anionischen Tensiden einzusetzen. Dazu werden die Alkohole einer entsprechenden Funktio- nalisierung, z.B durch Alkoxilierung oder Glycosidierung unterworfen. Die resultierenden Alkoxilate können entweder direkt als nichtionische oberflächenaktive Substanzen eingesetzt oder durch eine weitere Funktionalisierung, z.B. durch Sulfatierung oder Phosphatierung, in anionische oberflächenaktive Substanzen über- führt werden. Die anwendungstechnischen Eigenschaften dieser Ten- side, z.B. deren Netzvermögen, Schaumbildung, Fettlösevermögen, biologische Abbaubarkeit etc., werden wesentlich durch die Kettenlänge und den Verzweigungsgrad des hydrophilen Kohlenwasserstoffrestes des eingesetzten Alkohols bestimmt. Alkohole, die sich gut für die Weiterverarbeitung zu wirksamen Tensiden eignen werden auch als Tensidalkohole bezeichnet.It is known to use fatty alcohols with about 8 to 20 carbon atoms for the production of nonionic and anionic surfactants. For this purpose, the alcohols are subjected to a corresponding functionalization, for example by alkoxylation or glycosidation. The resulting alkoxylates can either be used directly as nonionic surface-active substances or by further functionalization, e.g. can be converted into anionic surface-active substances by sulfation or phosphating. The application properties of this side, e.g. their wetting capacity, foaming, fat-dissolving capacity, biodegradability etc. are essentially determined by the chain length and the degree of branching of the hydrophilic hydrocarbon residue of the alcohol used. Alcohols that are well suited for further processing into effective surfactants are also known as surfactant alcohols.
In Kosswig/Stache, "Die Tenside", Carl Hanser Verlag, München, Wien, 1993, Kapitel 2.2 und 2.3, ist die Umsetzung von Fettalko- holen mit Alkylenoxiden zu den entsprechenden Fettalkoholalkoxi- laten sowie deren Sulfatierung und Phosphatierung beschrieben.Kosswig / Stache, "Die Tenside", Carl Hanser Verlag, Munich, Vienna, 1993, chapters 2.2 and 2.3, describes the conversion of fatty alcohols with alkylene oxides to the corresponding fatty alcohol alkoxylates as well as their sulfation and phosphating.
Fettalkohole sind sowohl aus nativen Quellen als auch auf synthetischem Weg, z.B. durch Aufbau aus Edukten mit einer geringeren Zahl an Kohlenstoffatomen erhältlich. So erhält man z.B. nach dem SHOP-Prozess (Shell higher olefine process), ausgehend von Ethen, Olefinfraktionen mit einer für die Weiterverarbeitung zu Tensiden geeigneten Kohlenstoffanzahl. Die Funktionalisierung der Olefine zu den entsprechenden Alkoholen erfolgt dabei z.B. durch Hydro- formylierung und Hydrierung, wobei je nach Reaktionsführung einstufig oder in zwei separaten Reaktionsstufen gearbeitet werden kann. Eine Übersicht von Hydroformylierungsverfahren und geeigneten Katalysatoren findet sich in Beller et al. Journal of Molecu- lar Catalysis A 104 (1995), S. 17-85. Nachteilig an den auf Ethy- len basierenden Verfahren zur Herstellung von Fettalkoholen sind
die hohen Kosten des Ausgangsmaterials, wodurch diese Verfahren wirtschaftlich benachteiligt sind.Fatty alcohols can be obtained both from native sources and synthetically, for example by building up from starting materials with a lower number of carbon atoms. For example, the SHOP process (Shell higher olefine process), based on ethene, gives olefin fractions with a carbon number suitable for further processing into surfactants. The functionalization of the olefins to give the corresponding alcohols takes place, for example, by hydroformylation and hydrogenation, it being possible, depending on the reaction procedure, to work in one stage or in two separate reaction stages. An overview of hydroformylation processes and suitable catalysts can be found in Beller et al. Journal of Molecular Catalysis A 104 (1995), pp. 17-85. A disadvantage of the ethylene-based processes for the production of fatty alcohols the high cost of the raw material, which makes these processes economically disadvantageous.
Bei der Aufarbeitung von Erdöl durch Steamcracken fällt unter an- derem ein als Cs-Schnitt bezeichnetes Kohlenwasserstoffgemisch mit einem Gesamtolefinanteil von z.B. etwa 50% an, von denen ca. 15% auf Cyclopenten und der Rest auf acyclische Monoolefine, vor allem n-Penten (ca. 15 Gew.-%) und weitere isomere Methylbutene (ca. 20 Gew.-%) entfallen. Bislang erfolgte die großtechnische Aufarbeitung des C5-Schnittes im Wesentlichen destillativ zur Gewinnung des darin enthaltenen Cyclopentans. Derartige Verfahren sind verfahrenstechnisch sehr aufwendig. Es besteht daher ein Bedarf zur nicht-destillativen Entfernung des Cyclopentens und gegebenenfalls weiterer acyclischer Monoolefine aus dem Cs-Schnitt unter Gewinnung von Wertprodukten.When petroleum is worked up by steam cracking, a hydrocarbon mixture called a Cs cut with a total olefin content of, for example, about 50% is obtained, of which approx. 15% is based on cyclopentene and the rest on acyclic monoolefins, especially n-pentene ( approx. 15% by weight) and further isomeric methylbutenes (approx. 20% by weight) are omitted. So far, the industrial processing of the C 5 cut has been carried out essentially by distillation to obtain the cyclopentane contained therein. Processes of this type are very complex in terms of process engineering. There is therefore a need for the non-distillative removal of the cyclopentene and optionally further acyclic monoolefins from the Cs cut to obtain valuable products.
Die DE-A-196 54 166 beschreibt Oligomerengemische mit ethylenisch ungesättigten Doppelbindungen, die von Cyclopenten abgeleitet sind und die durch Metathesereaktion eines Cs-Schnittes in Gegen- wart eines Übergangsmetallkatalysators erhalten werden.DE-A-196 54 166 describes oligomer mixtures with ethylenically unsaturated double bonds which are derived from cyclopentene and which are obtained by metathesis reaction of a Cs cut in the presence of a transition metal catalyst.
Die DE-A-196 54 167 beschreibt ein Verfahren zur Funktionalisierung solcher Oligomerengemische, die von Cyclopenten abgeleitet sind, z.B. durch Hydroformylierung und gegebenenfalls anschlies- sende Hydrierung. Dabei resultieren Alkoholgemische mit einem hohen Anteil an zwei- und höherwertigen Alkoholen. Derartige Alkoholgemische eignen sich nicht für einen Einsatz als Tensidalko- hole.DE-A-196 54 167 describes a process for the functionalization of such oligomer mixtures derived from cyclopentene, e.g. by hydroformylation and, if appropriate, subsequent hydrogenation. This results in alcohol mixtures with a high proportion of dihydric and higher alcohols. Such alcohol mixtures are not suitable for use as surfactant alcohols.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Tensidalkoholen zur Verfügung zu stellen. Dabei soll möglichst auf einen Einsatz von Edukten mit hohen Produktionskosten, wie insbesondere Ethen, verzichtet werden. Vorzugsweise soll in dem erfindungsgemässen Verfahren ein gross- technisch anfallendes Ausgangskohlenwasserstoffgemisch eingesetzt werden.The object of the present invention is to provide a process for the preparation of surfactant alcohols. The use of starting materials with high production costs, such as ethene in particular, should be avoided as far as possible. Preferably, a large-scale starting hydrocarbon mixture is to be used in the process according to the invention.
Überraschenderweise wurde nun gefunden, dass die Aufgabe durch ein Verfahren gelöst wird, bei dem man ein Kohlenwasserstoffgemi- seh, das Cyclopenten und wenigstens ein aeyclisches Monoolefin enthält, einer Metathese unterzieht, aus dem Metathesegemisch eine Cs-C o-01efinfraktion isoliert und diese anschliessend einer katalytischen Hydroformylierung und Hydrierung unterzieht. Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung von Alkoholgemischen, wobei man
a) ein Kohlenwasserstoffgemisch, das Cyclopenten und wenigstens ein acyclisches Monoolefin enthält, in einer Metathesereaktion umsetzt,Surprisingly, it has now been found that the object is achieved by a process in which a hydrocarbon mixture which contains cyclopentene and at least one aeyclic monoolefin is subjected to a metathesis, a Cs-C o-01efin fraction is isolated from the metathesis mixture and then one undergoes catalytic hydroformylation and hydrogenation. The invention thus relates to a process for the preparation of alcohol mixtures, wherein a) reacting a hydrocarbon mixture which contains cyclopentene and at least one acyclic monoolefin in a metathesis reaction,
b) aus dem Reaktionsgemisch der Metathese eine Olefinfraktion isoliert, die im Wesentlichen Olefine mit 8 bis 20 Kohlenstoffatomen enthält,b) an olefin fraction which essentially contains olefins having 8 to 20 carbon atoms is isolated from the reaction mixture of the metathesis,
c) gegebenenfalls die in der Olefinfraktion enthaltenen zwei- oder mehrfach ungesättigten Verbindungen zumindest teilweise einer selektiven Hydrierung zu Monoolefinen unterwirft,c) if appropriate, subjecting the di- or polyunsaturated compounds contained in the olefin fraction at least partially to a selective hydrogenation to monoolefins,
d) die, gegebenenfalls selektiv hydrierte, Olefinfraktion durch Umsetzung mit Kohlenmonoxid und Wasserstoff katalytisch hy- droformyliert und hydriert.d) the, optionally selectively hydrogenated, olefin fraction is catalytically hydroformylated and hydrogenated by reaction with carbon monoxide and hydrogen.
Schritt a)Step a)
Bevorzugt wird für die Metathesereaktion ein Kohlenwasserstoffge- misch mit einem Cyclopentengesamtgehalt im Bereich von etwa 5 bis 40 Gew.-%, bevorzugter 10 bis 30 Gew.-%, insbesondere 12 bis 20 Gew.-%, eingesetzt.A hydrocarbon mixture with a total cyclopentene content in the range from about 5 to 40% by weight, more preferably 10 to 30% by weight, in particular 12 to 20% by weight, is preferably used for the metathesis reaction.
Vorzugsweise beträgt der Gesamtolefingehalt des zur Metathese eingesetzten Kohlenwasserstoffgemisches mindestens 30 Gew.-%, bevorzugt mindestens 40 Gew.-%, insbesondere mindestens 50 Gew.-%. Geeignet sind Kohlenwasserstoffgemische mit einem Gesamtolefingehalt von bis zu 100 Gew.-%.The total olefin content of the hydrocarbon mixture used for the metathesis is preferably at least 30% by weight, preferably at least 40% by weight, in particular at least 50% by weight. Hydrocarbon mixtures with a total olefin content of up to 100% by weight are suitable.
Vorzugsweise enthalten die zur Metathese eingesetzten Kohlenwasserstoffgemische wenigstens ein acyclisches Monoolefin. Bevorzugte acyclische Monoolefine sind ausgewählt unter Cs-Monoolefi- nen, wie 1-Penten, 2-Penten, 2-Methyl-l-buten, 3-Methyl-1-buten, 2-Methyl-2-buten und Gemischen davon. Bevorzugt beträgt der An- teil von Cs-Monoolefinen an den acyclischen Monoolefinen mindestens 70 Gew.-%, bevorzugt mindestens 80 Gew.-%, insbesondere mindestens 90 Gew.-%.The hydrocarbon mixtures used for metathesis preferably contain at least one acyclic monoolefin. Preferred acyclic monoolefins are selected from Cs-monoolefins, such as 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene and mixtures thereof. The proportion of Cs-monoolefins in the acyclic monoolefins is preferably at least 70% by weight, preferably at least 80% by weight, in particular at least 90% by weight.
Vorzugsweise wird für die Metathesereaktion in Schritt a) ein bei der Erdölverarbeitung großtechnisch anfallendes Kohlenwasserstoffgemisch verwendet. Derartige Gemische können gewünschten- falls zuvor einer katalytischen Teilhydrierung zur Entfernung von Dienen unterzogen werden kann. Besonders geeignet ist z.B. ein an gesättigten und ungesättigten Cs-Kohlenwasserstoffen angereicher- tes Gemisch, insbesondere ein C5-Schnitt. Zur Gewinnung eines für den Einsatz in dem erfindungsgemäßen Verfahren geeigneten C5-Schnittes eignet sich vorzugsweise Pyrolysebenzin, das z.B.
beim Steamcracken von Naphtha anfällt. Dieses Pyrolysebenzin kann gewünschtenfalls zuerst einer Selektivhydrierung unterzogen werden, um enthaltene Diene und Acetylene im Wesentlichen selektiv in die entsprechenden Alkane und Alkene zu überführen. Anschlie- ßend erfolgt ein Trennschritt, z.B. eine fraktionierte Destillation, wobei zum einen der für weitere chemische Synthesen wichtige C6-C8-Schnitt, der die aromatischen Kohlenwasserstoffe enthält und zum anderen ein in Schritt a) des erfindungsgemässen Verfahrens einsetzbarer Cs-Schnitt anfallen.For the metathesis reaction in step a), a hydrocarbon mixture which is obtained on a large industrial scale in petroleum processing is preferably used. If desired, such mixtures can be subjected to a catalytic partial hydrogenation to remove dienes beforehand. For example, a mixture enriched in saturated and unsaturated Cs hydrocarbons, in particular a C 5 cut, is particularly suitable. To obtain a C 5 cut suitable for use in the process according to the invention, pyrolysis gasoline is preferably suitable, for example occurs when steam cracking naphtha. If desired, this pyrolysis gasoline can first be subjected to a selective hydrogenation in order to essentially convert the dienes and acetylenes contained therein into the corresponding alkanes and alkenes. This is followed by a separation step, for example a fractional distillation, on the one hand the C 6 -C 8 cut which is important for further chemical syntheses and which contains the aromatic hydrocarbons and on the other hand a Cs cut which can be used in step a) of the process according to the invention ,
Bevorzugt wird zur Metathese ein großtechnisch anfallender Cs-Schnitt mit einem Gesamtolefinanteil von z.B. 50 bis 60 Gew.-%, wie etwa 56%, einem Cyclopentenanteil von z.B. 10 bis 20 Gew.-%, wie etwa 15 Gew.-% und einem Anteil an Cs-Monoolefinen von z.B. 33 bis 43 Gew.-%, wie etwa 38 Gew.-%, eingesetzt. Dabei entfallen bevorzugt etwa 16 Gew.-% auf das n-Penten und etwa 22 Gew.-% auf isomere Pentene .For metathesis, a large-scale Cs cut with a total olefin content of e.g. 50 to 60% by weight, such as 56%, a cyclopentene content of e.g. 10 to 20% by weight, such as about 15% by weight and a proportion of Cs monoolefins of e.g. 33 to 43% by weight, such as about 38% by weight. About 16% by weight is preferably attributable to the n-pentene and about 22% by weight to isomeric pentenes.
In Schritt a) des erfindungsgemässen Verfahrens kann auch vor- teilhaft ein Kohlenwasserstoffgemisch verwendet werden, welches ein Cyclopenten-haltiges Kohlenwasserstoffgemisch, insbesondere den Cs-Schnitt, und ein acyclische C4-01efine enthaltendes Gemisch umfasst. Bevorzugt handelt es sich bei dem C4-01efingemisch um eine Erdölfraktion, insbesondere um Raffinat II. Raffinat II ist z.B. durch Cracken hochmolekularer Kohlenwasserstoffe, wie Rohöl, erhältlich. Bevorzugt wird ein C4-01efingemisch eingesetzt, das 60 bis 85 Vol.-% Buten-1 und Buten-2 enthält. Vorzugsweise enthält das C4-01efingemisch höchstens 40 Vol.-%, bevorzugt höchstens 20 Vol.-%, gesättigte Kohlenwasserstoffe, wie n-Butan, Isobutan, Cs-Alkane etc .In step a) of the process according to the invention, it is also advantageously possible to use a hydrocarbon mixture which comprises a cyclopentene-containing hydrocarbon mixture, in particular the Cs cut, and a mixture containing acyclic C 4 -01efins. The C 4 -01efin mixture is preferably a petroleum fraction, in particular raffinate II. Raffinate II can be obtained, for example, by cracking high molecular weight hydrocarbons, such as crude oil. A C 4 -01efin mixture is preferably used which contains 60 to 85% by volume of butene-1 and butene-2. The C 4 -01efin mixture preferably contains at most 40% by volume, preferably at most 20% by volume, of saturated hydrocarbons, such as n-butane, isobutane, Cs-alkanes, etc.
Die Metathesereaktion des Kohlenwasserstoffgemisches in Schritt a) umfasst vorzugsweise i) die Disproportionierung von acyclischen Monoolefinen durch Kreuzmetathese, ii) die Oligomerisation von Cyclopenten durch ringöffnende Metathese, iii)den Kettenabbruch durch Umsetzung eines Oligomers aus ii) mit einem acyclischen Olefin des Kohlenwasserstoffgemisches oder einem Produktes aus i), wobei die Schritte i) und/oder ii) und/oder iii) mehrmals für sich alleine oder in Kombination durchlaufen werden können.The metathesis reaction of the hydrocarbon mixture in step a) preferably comprises i) the disproportionation of acyclic monoolefins by cross metathesis, ii) the oligomerization of cyclopentene by ring-opening metathesis, iii) chain termination by reaction of an oligomer from ii) with an acyclic olefin of the hydrocarbon mixture or a product from i), steps i) and / or ii) and / or iii) being able to be carried out several times on their own or in combination.
Schritt i)
Durch Kombinationen aus Kreuzmetathese verschiedener und Selbstmetathese gleicher acyclischer Olefine sowie durch mehrmaliges Durchlaufen dieser Reaktion werden eine Vielzahl von Monoolefinen mit unterschiedlicher Struktur und Kohlenstoffatomanzahl erhal- ten, die die Endgruppen der Oligomere in dem bei der Metathese resultierenden Reaktionsgemisch bilden. Nach einer bevorzugten Ausführungsform des erfindungsgemässen Verfahrens wird für die Metathese ein Katalysator eingesetzt, der die Bildung von Kreuzmetatheseprodukten ermöglicht. Dazu zählen bevorzugt die im Folgenden als besonders aktiv beschriebenen Metathesekatalysatoren. Nach dieser Ausführungsform werden Metathesegemische mit einem höheren Anteil an Oligomeren ohne terminale Doppelbindungen erhalten, als bei Einsatz eines weniger aktiven Katalysators.Step i) Combinations of cross-metathesis of different and self-metathesis of the same acyclic olefins and repeated runs of this reaction result in a large number of monoolefins with different structure and number of carbon atoms, which form the end groups of the oligomers in the reaction mixture resulting from the metathesis. According to a preferred embodiment of the method according to the invention, a catalyst is used for the metathesis, which enables the formation of cross-metathesis products. These preferably include the metathesis catalysts described below as being particularly active. According to this embodiment, metathesis mixtures with a higher proportion of oligomers without terminal double bonds are obtained than when using a less active catalyst.
Schritt ii)Step ii)
Die durchschnittliche Anzahl an Cyclopenten-Insertionen in die wachsende Kette im Sinne einer ringöffnenden Metathesepolymerisation bestimmt das mittlere Molekulargewicht des gebildeten Cyclo- penten-Oligomerengemisches. Vorzugsweise werden durch das erfindungsgemäße Verfahren Oligomerengemische mit einem mittleren Molekulargewicht in einem Bereich von etwa 138 bis 206 gebildet, was einer durchschnittlichen Anzahl von einer bis zwei Cyclopen- teneinheiten pro Oligomer entspricht.The average number of cyclopentene insertions in the growing chain in the sense of a ring-opening metathesis polymerization determines the average molecular weight of the cyclopentene-oligomer mixture formed. Oligomer mixtures with an average molecular weight in a range from about 138 to 206 are preferably formed by the process according to the invention, which corresponds to an average number of one to two cyclopentene units per oligomer.
Schritt iii)Step iii)
Der Kettenabbruch erfolgt durch Umsetzung eines Oligomeren, welches noch ein aktives Kettenende in Form eines Katalysatorkom- plexes (Alkylidenkomplexes) aufweist, mit einem acyclischen Olefin, wobei im Allgemeinen ein aktiver Katalysatorkomplex zurückgewonnen wird. Dabei kann das acyclische Olefin unverändert aus dem ursprünglich zur Reaktion eingesetzten Kohlenwasserstoffgemisch stammen oder zuvor in einer Kreuzmetathese nach Stufe i) modifiziert worden sein.The chain is terminated by reacting an oligomer which still has an active chain end in the form of a catalyst complex (alkylidene complex) with an acyclic olefin, an active catalyst complex generally being recovered. The acyclic olefin may originate unchanged from the hydrocarbon mixture originally used for the reaction or may have been modified beforehand in a cross metathesis according to stage i).
Geeignete Katalysatoren für die Metathese sind bekannt und umfassen homogene und heterogene Katalysatorsysteme. Im Allgemeinen eignen sich für das erfindungsgemäße Verfahren Katalysatoren auf Basis eines Übergangsmetalls der 6., 7. oder 8. Nebengruppe des Periodensystems, wobei vorzugsweise Katalysatoren auf Basis von Mo, W, Re und Ru verwendet werden.Suitable catalysts for metathesis are known and include homogeneous and heterogeneous catalyst systems. In general, catalysts based on a transition metal of the 6th, 7th or 8th subgroup of the periodic table are suitable for the process according to the invention, preference being given to using catalysts based on Mo, W, Re and Ru.
Bevorzugt werden Katalysator/Cokatalysator-Systeme auf Basis von W, Mo und Re eingesetzt, die mindestens eine lösliche Übergangs- metallverbindung und/oder ein alkylierendes Agens umfassen können. Dazu zählen z.B. MoCl2(NO)2(PR3)2/Al2(CH3)3Cl3; WCl6/BuLi;
WCl6/EtAlCl2(Sn(CH3)4)/EtOH; WOCl4/Sn(CH3)4; WOCl2(0-[2,6-Br2-C6H3] )/Sn(CH3)4 und CH3Re03/C2H5AlCl2.Catalyst / cocatalyst systems based on W, Mo and Re are preferably used, which can comprise at least one soluble transition metal compound and / or an alkylating agent. These include, for example, MoCl 2 (NO) 2 (PR 3 ) 2 / Al 2 (CH 3 ) 3 Cl 3 ; WCl 6 / BuLi; WCl 6 / EtAlCl 2 (Sn (CH 3 ) 4 ) / EtOH; WOCl 4 / Sn (CH 3 ) 4 ; WOCl 2 (0- [2,6-Br 2 -C 6 H 3 ]) / Sn (CH 3 ) 4 and CH 3 Re0 3 / C 2 H 5 AlCl 2 .
Bevorzugte Katalysatoren sind weiterhin vierfach koordinierte Mo- und W-Alkylidenkomplexe, die zusätzlich zwei sperrige Alkoxy- und einen Imido-Liganden aufweisen, insbesonderePreferred catalysts are furthermore four-coordinate Mo and W alkylidene complexes, which additionally have two bulky alkoxy and one imido ligands, in particular
((CH3)3CO)2Mθ(=N-[2,6-(i-C3H7)2-C6H3])(=CHC(CH3)2C6H5) und [ (CF3)2C(CH3)0]2Mo(=N-[2,5-(i-C3H7)-C6H3] ) (=CH(CH3 )2C6H5 ) .((CH 3 ) 3 CO) 2 Mθ (= N- [2,6- (iC 3 H 7 ) 2 -C 6 H 3 ]) (= CHC (CH 3 ) 2 C 6 H 5 ) and [(CF 3 ) 2 C (CH 3 ) 0] 2 Mo (= N- [2.5- (iC 3 H 7 ) -C 6 H 3 ]) (= CH (CH 3 ) 2 C 6 H 5 ).
Weiterhin bevorzugt werden homogene Metathesekatalysatoren eingesetzt, die in der Angew. Chem. 107, S. 2179 ff. (1995), in J. Am. Chem. Soc. 118, S. 100 ff. (1996) sowie in J. Chem. Soc . , Chem. Commun., S. 1127 ff. (1995) beschrieben sind. Dazu zählen insbesondere Katalysatoren der allgemeinen Formel RuCl2 (=CHR) (PR'3)2, wieHomogeneous metathesis catalysts which are used in Angew. Chem. 107, pp. 2179 ff. (1995), in J. Am. Chem. Soc. 118, pp. 100 ff. (1996) and in J. Chem. Soc. , Chem. Commun., P. 1127 ff. (1995). These include in particular catalysts of the general formula RuCl 2 (= CHR) (PR ' 3 ) 2 , such as
RUC12 ( =CHCH3 ) ( P ( C6Hu ) 3 ) 2 ,RUC1 2 (= CHCH 3 ) (P (C 6 Hu) 3 ) 2 ,
(η6-p-Cymol ) RuCl2 ( P ( C6HU ) 3 ) / ( CH3 ) 3SiCHN2 und(η 6 -p-Cymol) RuCl 2 (P (C 6 H U ) 3 ) / (CH 3 ) 3 SiCHN 2 and
( η6-p-Cymol ) RuCl2 ( P ( C6Hι1 ) 3 ) /C6H5CHN2 .(η 6 -p-Cymol) RuCl 2 (P (C 6 Hι 1 ) 3 ) / C 6 H 5 CHN 2 .
Ein besonders bevorzugter heterogener Katalysator ist Re20 auf Al203 als Trägermaterial.A particularly preferred heterogeneous catalyst is Re 2 0 on Al 2 0 3 as the support material.
Gewünschtenfalls können je nach verwendetem Katalysator bei der Metathese Oligomerengemische mit wechselnden Doppelbindungsantei- len und wechselnden Anteilen an terminalen Doppelbindungen erhalten werden. Vorzugsweise wird ein Katalysator mit hoher katalyti- scher Aktivität, wie RuCl2(=CHC6H5) (P(C6Hn)3)2 oder Re207 auf Al203 eingesetzt, wobei Metatheseprodukte mit einem möglichst geringen Anteil an Doppelbindungen und einer geringen Jodzahl erhalten werden.If desired, depending on the catalyst used, oligomer mixtures with changing double bond proportions and changing proportions of terminal double bonds can be obtained in the metathesis. A catalyst with high catalytic activity, such as RuCl 2 (= CHC 6 H 5 ) (P (C 6 Hn) 3 ) 2 or Re 2 0 7 on Al 2 0 3 , is preferably used, with metathesis products having the lowest possible proportion of double bonds and a low iodine number.
Bevorzugt weisen die in Schritt a) erhaltenen Metathese-Reaktionsgemische eine Jodzahl im Bereich von etwa 200 bis 400 g I2/100 g Oligomere auf.Preferably, the metathesis reaction mixtures obtained in step a) have an iodine value in the range of about 200 to 400 g I 2/100 g oligomers.
Vorzugsweise resultiert bei der Metathesereaktion in Schritt a) ein Oligomerengemisch, dass im Wesentlichen von Cyclopenten abgeleitete Oligomere der allgemeinen Formel IThe metathesis reaction in step a) preferably results in an oligomer mixture that essentially contains cyclopentene-derived oligomers of the general formula I.
umfasst, worin n für eine ganze Zahl von 1 bis 15 steht, undwherein n is an integer from 1 to 15, and
R1, R2, R3, R4 unabhängig voneinander für Wasserstoff oder Alkyl stehen.
Die Reste R1, R2, R3 und R4 in der Formel I stehen unabhängig voneinander für Wasserstoff oder Alkyl, wobei der Ausdruck "Alkyl" geradkettige und verzweigte Alkylgruppen umfaßt.R 1 , R 2 , R 3 , R 4 are independently hydrogen or alkyl. The radicals R 1 , R 2 , R 3 and R 4 in the formula I independently of one another represent hydrogen or alkyl, the term "alkyl" encompassing straight-chain and branched alkyl groups.
Vorzugsweise handelt es sich dabei um geradkettige oder verzweigte Ci-Cis-Alkyl-, bevorzugt Cι-Cιo-Alkyl-, insbesondere bevorzugt Cι-C5-Alkylgruppen. Beispiele für Alkylgruppen sind insbesondere Methyl, Ethyl, Propyl, 1-Methylethyl, Butyl, 1-Methylpropyl, 2-Methylpropyl, 1, 1-Dimethylethyl, n-Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 1, 2-Dimethylpropyl, 1, 1-Dimethyl- propyl, 2 , 2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 1-Methyl- pentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,2-Di- methylbutyl, 1, 3-Dimethylbutyl, 2,3-Dimethylbutyl, 1, 1-Dimethyl- butyl, 2,2-Di-methylbutyl, 3, 3-Dimethylbutyl, 1, 1, 2-Trimethyl- propyl, 1, 2,2-Trimethylpropyl, 1-Ethylbutyl, 2-Ethylbutyl, l-Ethyl-2-methylpropyl, n-Heptyl, 1-Methylhexyl, 1-Ethylpentyl, 2-Ethylpentyl, 1-Propylbutyl, Octyl, Decyl, Dodecyl, etc.These are preferably straight-chain or branched Ci-Cis-alkyl, preferably Cι-Cιo-alkyl, particularly preferably Cι-C 5 alkyl groups. Examples of alkyl groups are in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2 -Dimethylpropyl, 1, 1-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl , 1, 3-dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3, 3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2.2 -Trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl, etc.
Der Wert n in der Formel I steht für die Anzahl der in die von Cyclopenten abgeleiteten Oligomerengemische durch ringöffnende Metathesereaktion eingeführten Cyclopenten-Einheiten. Der Wert n und somit der Grad der ringöffnenden Metathese kann durch die Aktivität des verwendeten Metathesekatalysators und das Verhältnis von acyclischen zu cyclischen Olefinen beeinflusst werden.The value n in formula I stands for the number of cyclopentene units introduced into the oligomer mixtures derived from cyclopentene by ring-opening metathesis reaction. The value n and thus the degree of ring-opening metathesis can be influenced by the activity of the metathesis catalyst used and the ratio of acyclic to cyclic olefins.
Vorzugsweise liegt der Wert für n in einem Bereich von etwa 1 bis 4 , insbesondere 1 bis 2.The value for n is preferably in a range from approximately 1 to 4, in particular 1 to 2.
Bevorzugt sind Oligomerengemische der Formel I, bei denen minde- stens 50 Gew.-%, insbesondere mindestens 70 Gew.-% (ermittelt durch die Flächenintegration der Gaschromatogramme ) der Komponenten einen Wert von n > 1 aufweist.Preferred oligomer mixtures of the formula I are those in which at least 50% by weight, in particular at least 70% by weight (determined by the area integration of the gas chromatograms) of the components has a value of n> 1.
Für Schritt a) des erfindungsgemässen Verfahrens geeignete Reak- tionsbedingungen und Katalysatoren sind in der DE-A-196 54 166 und DE-A-196 54 167 beschrieben, auf die hier in vollem Umfang Bezug genommen wird.Reaction conditions and catalysts suitable for step a) of the process according to the invention are described in DE-A-196 54 166 and DE-A-196 54 167, to which reference is made in full here.
Schritt blStep bl
Zur Isolierung einer Olefinfraktion, die im Wesentlichen Olefine mit 8 bis 20 Kohlenstoffatomen aufweist, wird das Reaktionsgemisch aus Schritt a) einem oder mehreren Trennschritten unterworfen. Geeignete Trennvorrichtungen sind die üblichen, dem Fachmann bekannten Apparaturen. Dazu zählen z. B. Destillationskolonnen, wie Bodenkolonnen, die gewünschtenfalls mit Glocken, Siebplatten, Siebböden, Ventilen, Seitenabzügen etc. ausgerüstet sein können,
Verdampfer, wie Dünnschichtverdampfer, Fallfilmverdampfer, Wischblattverdampfer, Sambay-Verdampfer etc. und Kombinationen davon. Bevorzugt erfolgt die Isolierung der Olefinfraktion durch fraktionierte Destillation.To isolate an olefin fraction which essentially has olefins having 8 to 20 carbon atoms, the reaction mixture from step a) is subjected to one or more separation steps. Suitable separation devices are the usual apparatuses known to the person skilled in the art. These include e.g. B. distillation columns, such as tray columns which, if desired, can be equipped with bells, sieve plates, sieve trays, valves, side draws, etc., Evaporators such as thin film evaporators, falling film evaporators, wiper blade evaporators, Sambay evaporators etc. and combinations thereof. The olefin fraction is preferably isolated by fractional distillation.
Vorzugsweise isoliert man in Schritt b) eine Olefinfraktion, die im Wesentlichen Olefine mit 9 bis 18 Kohlenstoffatomen, bevorzugt 10 bis 15 Kohlenstoffatomen, enthält.Preferably in step b) an olefin fraction is isolated which essentially contains olefins having 9 to 18 carbon atoms, preferably 10 to 15 carbon atoms.
Vorzugsweise weist die in Schritt b) isolierte Olefinfraktion einen möglichst hohen Olefinanteil auf. Bevorzugt beträgt der Ole- finanteil mindestens 40 Gew.-%, bevorzugt mindestens 50 Gew.-%. Nach einer besonders bevorzugten Ausführungsform liegt der Olefinanteil bei etwa 100 Gew.-%.The olefin fraction isolated in step b) preferably has the highest possible olefin content. The olefin content is preferably at least 40% by weight, preferably at least 50% by weight. According to a particularly preferred embodiment, the olefin content is about 100% by weight.
Wie zuvor beschrieben, kann zur Metathese in Schritt a) ein Kohlenwasserstoffgemisch eingesetzt werden, das neben Cyclopenten und acyclischen Monoolefinen auch gesättigte Verbindungen aufweist. Enthält die in Schritt b) isolierte Olefinfraktion einen Teil dieser gesättigten Verbindungen, so ist dies für die Weiterverarbeitung zu den erfindungsgemäßen Olefingemischen im Allgemeinen unkritisch. Vorzugsweise weist die in Schritt b) isolierte Olefinfraktion einen Anteil an gesättigten Verbindungen im Bereich von etwa 0 bis 60 Gew.-%, bevorzugt etwa 0,1 bis 50 Gew.-%, auf.As described above, a hydrocarbon mixture can be used for the metathesis in step a) which, in addition to cyclopentene and acyclic monoolefins, also has saturated compounds. If the olefin fraction isolated in step b) contains part of these saturated compounds, this is generally not critical for the further processing to the olefin mixtures according to the invention. The olefin fraction isolated in step b) preferably has a proportion of saturated compounds in the range from approximately 0 to 60% by weight, preferably approximately 0.1 to 50% by weight.
Wie zuvor beschrieben, resultieren bei der Metathese in Schritt a) im Allgemeinen Reaktionsgemische, die neben Monoolefinen und gegebenenfalls gesättigten Verbindungen aus dem Eduktkohlenwas- serstoffgemisch auch zwei- und mehrfach ungesättigte Verbindungen aufweisen. Vorzugsweise weist die in Schritt b) isolierte Olefinfraktion einen Anteil an zwei- und mehrfach ungesättigten Verbindungen im Bereich von etwa 60 bis 100 Gew.-% auf.As described above, the metathesis in step a) generally results in reaction mixtures which, in addition to monoolefins and optionally saturated compounds from the reactant hydrocarbon mixture, also contain two- and polyunsaturated compounds. The olefin fraction isolated in step b) preferably has a proportion of di- and polyunsaturated compounds in the range from about 60 to 100% by weight.
Gewünschtenfalls kann in Schritt b) noch wenigstens eine weitere Olefinfraktion aus dem Reaktionsgemisch der Metathese isoliert werden. Vorzugsweise handelt es sich dabei um Fraktionen, die in dem in Schritt a) erhaltenen Reaktionsgemisch in einer Menge von mindestens 5 Gew.-%, bezogen auf die Gesamtmenge des Gemisches, enthalten sind.If desired, at least one further olefin fraction can be isolated from the reaction mixture of the metathesis in step b). These are preferably fractions which are present in the reaction mixture obtained in step a) in an amount of at least 5% by weight, based on the total amount of the mixture.
Bevorzugt wird in Schritt b) wenigstens eine weitere Olefinfraktion isoliert, die im Wesentlichen Olefine mit mehr als 20, bevorzugt mehr als 18, insbesondere mehr als 15 Kohlenstoffatomen enthält. Vorzugsweise enthält diese Fraktion im Wesentlichen Olefine mit höchstens 75, besonders bevorzugt höchstens 50, insbesondere höchstens 40 Kohlenstoffatomen. Zur weiteren Verarbeitung
können diese Olefinfraktionen vorzugsweise einer Kreuzmetathese mit wenigsten einem acyclischen Olefin unterzogen werden, dass höchstens 9, bevorzugt höchstens 8, insbesondere höchstens 7 Kohlenstoffatome aufweist. Für die Kreuzmetathese geeignete nieder- molekulare Olefine und Olefingemische sind z.B. Ethen, Raffinat II oder entsprechende Olefinfraktionen aus der Metathese aus Schritt a) . Zur weiteren Verarbeitung können diese höhermolekularen weiteren Olefinfraktionen gewünschtenfalls auch teilweise oder vollständig erneut in Schritt a) des erfindungsgemässen Ver- fahrens eingespeist werden.In step b), at least one further olefin fraction is preferably isolated, which essentially contains olefins having more than 20, preferably more than 18, in particular more than 15 carbon atoms. This fraction preferably contains essentially olefins with at most 75, particularly preferably at most 50, in particular at most 40 carbon atoms. For further processing these olefin fractions can preferably be subjected to cross metathesis with at least one acyclic olefin which has at most 9, preferably at most 8, in particular at most 7 carbon atoms. Low molecular weight olefins and olefin mixtures suitable for cross metathesis are, for example, ethene, raffinate II or corresponding olefin fractions from the metathesis from step a). For further processing, these higher molecular weight further olefin fractions can, if desired, also be partially or completely fed back in step a) of the process according to the invention.
Bevorzugt wird in Schritt b) wenigstens eine weitere Olefinfraktion isoliert, die im Wesentlichen Olefine mit höchstens 9, bevorzugt höchstens 8, insbesondere höchstens 7 Kohlenstoff tomen aufweist. Vorzugsweise enthält diese Fraktion im Wesentlichen Olefine mit mindestens 5, bevorzugt mindestens 6 Kohlenstoffatomen. Zur weiteren Verarbeitung können diese niedermolekularen weiteren Olefinfraktionen vorzugsweise einer Kreuzmetathese mit wenigsten einem acyclischen Olefin unterzogen werden, dass mehr als 20, bevorzugt mehr als 18, insbesondere mehr als 15 Kohlenstoffatome enthält. Geeignete höhermolekulare Olefine und Olefingemische sind z.B. die zuvor beschriebenen höhermolekularen weiteren Olefinfraktionen aus der Metathese aus Schritt a) .In step b), at least one further olefin fraction is preferably isolated, which essentially has olefins having at most 9, preferably at most 8, in particular at most 7 carbon atoms. This fraction preferably contains essentially olefins having at least 5, preferably at least 6, carbon atoms. For further processing, these low molecular weight further olefin fractions can preferably be subjected to cross metathesis with at least one acyclic olefin which contains more than 20, preferably more than 18, in particular more than 15 carbon atoms. Suitable higher molecular weight olefins and olefin mixtures are e.g. the previously described higher molecular weight further olefin fractions from the metathesis from step a).
Vorzugsweise resultieren bei den zuvor beschriebenen Kreuzmetathesereaktionen der weiteren in Schritt b) isolierten Olefinfraktionen wiederum Fraktionen, die im Wesentlichen Olefine mit 8 bis 20, bevorzugt 9 bis 18, insbesondere 10 bis 15 Kohlenstoffatomen enthalten. Diese können zur Weiterverarbeitung in Schritt c) des erfindungsgemässen Verfahrens eingesetzt werden.The cross-metathesis reactions of the further olefin fractions isolated in step b) preferably result in turn in fractions which essentially contain olefins having 8 to 20, preferably 9 to 18, in particular 10 to 15 carbon atoms. These can be used for further processing in step c) of the method according to the invention.
Schritt c)Step c)
Wie zuvor beschrieben kann die nach dem erfindungsgemäßen Verfah- ren in Schritt b) isolierte Olefinfraktion neben Monoolefinen auch noch einen Anteil an zwei- oder mehrfach ungesättigte Verbindungen enthalten. Bei der Weiterverarbeitung der Olefinfraktion zu den erfindungsgemässen Alkoholgemischen resultieren aus diesen zwei- und mehrfach ungesättigten Verbindungen die entspre- chenden zwei- bzw. mehrwertigen Alkohole. Ein zu hoher Anteil dieser zwei- und mehrwertigen Alkohole ist unter Umständen unerwünscht, wenn die erfindungsgemässen Alkoholgemische zur Herstellung von grenzflächenaktiven Verbindungen eingesetzt werden. Gewünschtenfalls kann die Olefinfraktion aus Schritt b) daher einer selektiven Hydrierung unterzogen werden. Dabei werden die zwei- und mehrfach ungesättigten Verbindungen zumindest teilweise in
Monoolefine überführt. Vorteilhafterweise wird somit der Anteil von Monoolefinen an der Olefinfraktion erhöht.As described above, the olefin fraction isolated in step b) by the process according to the invention can also contain, in addition to monoolefins, a proportion of two- or polyunsaturated compounds. When the olefin fraction is further processed to the alcohol mixtures according to the invention, the corresponding di- or polyhydric alcohols result from these di- and polyunsaturated compounds. Too high a proportion of these dihydric and polyhydric alcohols may be undesirable if the alcohol mixtures according to the invention are used for the preparation of surface-active compounds. If desired, the olefin fraction from step b) can therefore be subjected to a selective hydrogenation. The di- and polyunsaturated compounds are at least partially in Monoolefins convicted. The proportion of monoolefins in the olefin fraction is thus advantageously increased.
Geeignete Katalysatoren für die selektive Hydrierung sind aus dem Stand der Technik bekannt und umfassen übliche homogene und heterogene Hydrierkatalysatorsysteme. Vorzugsweise basieren die für das erfindungsgemäße Verfahren geeigneten Katalysatoren auf einem Übergangsmetall der 8. oder 1. Nebengruppe, wobei vorzugsweise Katalysatoren auf Basis von Ni, Pd, Pt, Ru oder Cu verwendet wer- den. Insbesondere bevorzugt werden Katalysatoren auf Basis von Cu oder Pd verwendet .Suitable catalysts for the selective hydrogenation are known from the prior art and include conventional homogeneous and heterogeneous hydrogenation catalyst systems. The catalysts suitable for the process according to the invention are preferably based on a transition metal of the 8th or 1st subgroup, preference being given to using catalysts based on Ni, Pd, Pt, Ru or Cu. Catalysts based on Cu or Pd are particularly preferably used.
Geeignete heterogene Katalysatorsysteme umfassen im Allgemeinen eine der zuvor genannten Übergangsmetallverbindungen auf einem inerten Träger. Geeignete anorganische Träger sind die hierfür üblichen Oxide, insbesondere Silicium- und Aluminiumoxide, Alumo- silikate, Zeolithe, Carbide, Nitride etc. und deren Mischungen. Bevorzugt werden als Träger AI2O3, Si02 und deren Mischungen verwendet. Insbesondere werden im erfindungsgemäßen Verfahren hete- rogene Katalysatoren verwendet, wie die in der US-A-4 ,587,369; US-A-4,704,492 und US-A-4 ,493, 906 beschriebenen, auf die hier in vollem Umfang Bezug genommen wird. Weiterhin geeignete Katalysatorsysteme auf Cu-Basis werden von der Fa. Dow Chemical als KLP- Katalysator vertrieben.Suitable heterogeneous catalyst systems generally comprise one of the aforementioned transition metal compounds on an inert support. Suitable inorganic carriers are the oxides customary for this, in particular silicon and aluminum oxides, aluminosilicates, zeolites, carbides, nitrides etc. and mixtures thereof. Al 2 O 3 , Si0 2 and mixtures thereof are preferably used as carriers. In particular, heterogeneous catalysts are used in the process according to the invention, such as those described in US Pat. Nos. 4,587,369; US-A-4,704,492 and US-A-4, 493, 906, which are incorporated by reference in their entirety. Suitable Cu-based catalyst systems are sold by Dow Chemical as KLP catalysts.
Bevorzugt werden für die selektive Hydrierung Olefinfraktionen eingesetzt, die einen Anteil an zwei- und mehrfach ungesättigten Verbindungen im Bereich von 60 bis 100 Gew.-% aufweisen.For the selective hydrogenation it is preferred to use olefin fractions which have a proportion of di- and polyunsaturated compounds in the range from 60 to 100% by weight.
Schritt d)Step d)
Zur erfindungsgemässen Herstellung von Alkoholgemischen wird eine in Schritt b) isolierte und gegebenenfalls in Schritt c) selektivhydrierte Olefinfraktion hydroformyliert und hydriert. Dabei kann die Herstellung der Alkoholgemische einstufig oder in zwei separaten Reaktionsschritten erfolgen.For the production of alcohol mixtures according to the invention, an olefin fraction isolated in step b) and optionally selectively hydrogenated in step c) is hydroformylated and hydrogenated. The alcohol mixtures can be prepared in one step or in two separate reaction steps.
Bevorzugt weist die in Schritt d) eingesetzte Olefinfraktion eine Jodzahl im Bereich von 175 bis 350 g I2/100 g auf.Preferably, the step in) d olefin used has an iodine value in the range of 175 to 350 g I 2/100 g.
Bevorzugt weist die in Schritt d) eingesetzte Olefinfraktion einen Anteil an unverzweigten Olefinen im Bereich von 10 bis 90 Gew.-%, bevorzugt 30 bis 70 Gew.-%, auf.The olefin fraction used in step d) preferably has a proportion of unbranched olefins in the range from 10 to 90% by weight, preferably 30 to 70% by weight.
Geeignete Katalysatoren für die Hydroformylierung sind bekannt und umfassen im Allgemeinen ein Salz oder eine Komplexverbindung eines Elementes der VIII. Nebengruppe des Periodensystems. Vor-
zugsweise ist das Metall der VIII. Nebengruppe ausgewählt unter Cobalt, Ruthenium, Iridium, Rhodium, Nickel, Palladium und Platin. Für das erfindungsgemäße Verfahren werden bevorzugt Salze und insbesondere Komplexverbindungen des Rhodiums oder des Co- balts verwendet.Suitable catalysts for hydroformylation are known and generally comprise a salt or a complex compound of an element of subgroup VIII of the periodic table. In front- the metal of subgroup VIII is preferably selected from cobalt, ruthenium, iridium, rhodium, nickel, palladium and platinum. Salts and in particular complex compounds of rhodium or cobalt are preferably used for the process according to the invention.
Geeignete Salze sind beispielsweise die Hydride, Halogenide, Nitrate, Sulfate, Oxide, Sulfide oder die Salze mit Alkyl- oder Arylcarbonsäuren oder Alkyl- oder Arylsulfonsäuren. Geeignete Komplexverbindungen sind beispielsweise die Carbonylverbindungen und Carbonylhydride der genannten Metalle sowie Komplexe mit Ami- nen, Amiden, Triarylphosphinen, Trialkylphosphinen, Tricycloal- kylphosphinen, Olefinen, oder Dienen als Liganden. Die Liganden können auch in polymerer oder polymergebundener Form eingesetzt werden. Auch können Katalysatorsysteme in situ aus den obengenannten Salzen und den genannten Liganden hergestellt werden.Suitable salts are, for example, the hydrides, halides, nitrates, sulfates, oxides, sulfides or the salts with alkyl or aryl carboxylic acids or alkyl or aryl sulfonic acids. Suitable complex compounds are, for example, the carbonyl compounds and carbonyl hydrides of the metals mentioned and complexes with amines, amides, triarylphosphines, trialkylphosphines, tricycloalkylphosphines, olefins, or dienes as ligands. The ligands can also be used in polymeric or polymer-bound form. Catalyst systems can also be prepared in situ from the salts mentioned and the ligands mentioned.
Geeignete Alkylreste der Liganden sind die zuvor beschriebenen linearen oder verzweigten Ci-Cis-Alkyl, insbesondere Ci-Cs-Alkyl- reste. Cycloalkyl steht vorzugsweise für C3-Cιo-Cycloalkyl, insbesondere Cyclopentyl und Cyclohexyl, die gegebenenfalls auch mit Cι-C4-Alkylgruppen substituiert sein können. Unter Aryl versteht man vorzugsweise Phenyl (Ph) oder Naphthyl, das gegebenenfalls mit 1, 2, 3 oder 4 Cι-C4-Alkyl, Cι-C4-Alkoxy, z.B. Methoxy, Halo- gen, vorzugsweise Chlorid, oder Hydroxy, das gegebenenfalls auch ethoxyliert sein kann, substituiert ist.Suitable alkyl residues of the ligands are the linear or branched Ci-Cis-alkyl described above, in particular Ci-Cs-alkyl residues. Cycloalkyl is preferably C 3 -Cιo-cycloalkyl, in particular cyclopentyl and cyclohexyl, which can optionally also be substituted with Cι-C 4 alkyl groups. Aryl is preferably understood to mean phenyl (Ph) or naphthyl, optionally with 1, 2, 3 or 4 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, for example methoxy, halogen, preferably chloride, or hydroxy, the may optionally also be ethoxylated.
Geeignete Rhodiumkatalysatoren bzw. -katalysatorvorstufen sind Rhodium(II)- und Rhodium( III ) salze wie Rhodium(III)chlorid, Rhodium( III)nitrat, Rhodium( III)sulfat, Kalium-Rhodiumsulfat (Rhodiumalaun), Rhodium(II)- bzw. Rhodium( III)carboxylat, vorzugsweise Rhodium(II)- und Rhodium(III)acetat, Rhodium(III)oxid, Salze der Rhodium( III) säure und Trisammoniumhexachloro- rhodat(III) .Suitable rhodium catalysts or catalyst precursors are rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate (rhodium alum), rhodium (II) and Rhodium (III) carboxylate, preferably rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid and trisammonium hexachloro-rhodate (III).
Weiterhin eignen sich Rhodiumkomplexe der allgemeinen Formel RhXmL1L2 (L3)n, worin X für Halogenid, vorzugsweise Chlorid oder Bromid, Alkyl- oder Arylcarboxylat, Acetylacetonat, Aryl- oder Alkylsulfonat , insbesondere Phenylsulfonat und Toluolsulfonat, Hydrid oder das Diphenyltriazin-Anion,Also suitable are rhodium complexes of the general formula RhX m L 1 L 2 (L 3 ) n , where X is halide, preferably chloride or bromide, alkyl or aryl carboxylate, acetylacetonate, aryl or alkyl sulfonate, in particular phenyl sulfonate and toluenesulfonate, hydride or the diphenyltriazine anion,
L1, L2, L3 unabhängig voneinander für CO, Olefine, Cycloolefine, vorzugsweise Cyclooctadien (COD), Dibenzophosphol, Benzonitril, PR3 oder R2P-A-PR2, m für 1, 2 oder 3 und n für 0, 1 oder 2 stehen. Unter R (die Reste R können gleich oder verschieden sein) sind Alkyl-, Cycloalkyl- und Arylreste zu verstehen, vorzugsweise Phenyl, p-Tolyl, m-Tolyl, p-Ethylphenyl, p-Cumyl, p-t .-Butylphe- nyl, p-Cι-C -Alkoxyphenyl, vorzugsweise p-Anisyl, Xylyl, Mesityl,
p-Hydroxyphenyl, das gegebenenfalls auch ethoxyliert vorliegen kann, Isopropyl, C1-C4-Alkoxy, Cyclopentyl oder Cyclohexyl. A steht für 1,2-Ethylen oder 1,3-Propylen. Bevorzugt stehen L1, L2 oder L3 unabhängig voneinander für CO, COD, P(Phenyl) 3, P(i-Pro- pyl)3, P(Anisyl)3, P(OC2H5)3, P(Cyclohexyl)3, Dibenzophosphol oder Benzonitril. X steht bevorzugt für Hydrid, Chlorid, Bromid, Ace- tat, Tosylat, Acetylacetonat oder das Diphenyltriazin-Anion, insbesondere für Hydrid, Chlorid oder Acetat.L 1 , L 2 , L 3 independently of one another for CO, olefins, cycloolefins, preferably cyclooctadiene (COD), dibenzophosphole, benzonitrile, PR 3 or R 2 PA-PR 2 , m for 1, 2 or 3 and n for 0.1 or 2 stand. R (the radicals R can be the same or different) are to be understood as meaning alkyl, cycloalkyl and aryl radicals, preferably phenyl, p-tolyl, m-tolyl, p-ethylphenyl, p-cumyl, pt.-Butylphenyl, p -C-C -alkoxyphenyl, preferably p-anisyl, xylyl, mesityl, p-Hydroxyphenyl, which may also be ethoxylated, isopropyl, C 1 -C 4 alkoxy, cyclopentyl or cyclohexyl. A stands for 1,2-ethylene or 1,3-propylene. L 1 , L 2 or L 3 are preferably independently of one another CO, COD, P (phenyl) 3 , P (i-propyl) 3 , P (anisyl) 3 , P (OC 2 H 5 ) 3 , P ( Cyclohexyl) 3 , dibenzophosphole or benzonitrile. X preferably represents hydride, chloride, bromide, acetate, tosylate, acetylacetonate or the diphenyltriazine anion, in particular hydride, chloride or acetate.
Geeignete Cobaltverbindungen sind beispielsweise Cobalt ( II )chlo- rid, Cobalt (II) sulfat, Cobalt( II) nitrat, deren Amin- oder Hydratkomplexe, Cobaltcarboxylate, wie Cobaltacetat, Cobaltethylhexa- noat, Cobaltnaphthanoat, sowie die Carbonylkomplexe des Cobalts wie Dicobaltoctacarbonyl, Tetracobaltdodecacarbonyl und Hexa- cobalthexadecacarbonyl. Bevorzugt werden für das erfindungsgemäße Verfahren die Cobaltcarbonylkomplexe und insbesondere Dicobaltoctacarbonyl verwendet.Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates such as cobalt acetate, cobalt ethyl hexanoate, cobalt naphthanoate, and the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tecacoblobium and hexacobalt hexadecacarbonyl. The cobalt carbonyl complexes and in particular dicobalt octacarbonyl are preferably used for the process according to the invention.
Die genannten Verbindungen des Rhodiums und Cobalts sind im Prin- zip bekannt und in der Literatur hinreichend beschrieben oder sie können vom Fachmann analog zu den bereits bekannten Verbindungen hergestellt werden. Diese Herstellung kann auch in situ erfolgen, wobei die katalytisch aktive Spezies auch aus den zuvor genannten Verbindungen als Katalysatorvorstufen erst unter den Hydroformy- lierungsbedingungen gebildet werden kann.The compounds of rhodium and cobalt mentioned are known in principle and adequately described in the literature, or they can be prepared by a person skilled in the art analogously to the compounds already known. This production can also take place in situ, the catalytically active species also being able to be formed from the aforementioned compounds as catalyst precursors only under the hydroformylation conditions.
Wird ein Hydroformylierungskatalysator auf Basis von Rhodium eingesetzt, so im Allgemeinen in einer Menge von 1 bis 150 ppm, bevorzugt bei 1 bis 100 ppm. Die Reaktionstemperatur liegt für ei- nen Hydroformylierungskatalysator auf Basis von Rhodium im Allgemeinen im Bereich von Raumtemperatur bis 200°C, bevorzugt 50 bis 150°C.If a hydroformylation catalyst based on rhodium is used, it is generally used in an amount of 1 to 150 ppm, preferably 1 to 100 ppm. The reaction temperature for a hydroformylation catalyst based on rhodium is generally in the range from room temperature to 200 ° C., preferably 50 to 150 ° C.
Wird ein Hydroformylierungskatalysator auf Basis von Cobalt ein- gesetzt, so im Allgemeinen in einer Menge von 0,0001 bis 0,5If a hydroformylation catalyst based on cobalt is used, it is generally used in an amount of 0.0001 to 0.5
Gew.-%, bezogen auf die Menge der zu hydroformylierenden Olefine. Die Reaktionstemperatur liegt für einen Hydroformylierungskatalysator auf Basis von Cobalt im Allgemeinen im Bereich von etwa 100 bis 250°C, bevorzugt 150 bis 200°C.% By weight, based on the amount of the olefins to be hydroformylated. The reaction temperature for a hydroformylation catalyst based on cobalt is generally in the range from about 100 to 250 ° C., preferably 150 to 200 ° C.
Die Reaktion kann bei einem erhöhten Druck von etwa 10 bis 650 bar durchgeführt werden.The reaction can be carried out at an elevated pressure of about 10 to 650 bar.
Das Molmengenverhältnis von H2:CO beträgt im Allgemeinen etwa 1:5 bis etwa 5:1.
Die bei der Hydroformylierung resultierenden Aldehyde bzw. Aldehyd/Alkohol-Gemische können vor der Hydrierung gewünschtenfalls nach üblichen, dem Fachmann bekannten Verfahren isoliert und gegebenenfalls gereinigt werden. Vorzugsweise wird vor der Hydrie- rung der Hydroformylierungskatalysator aus dem Reaktionsgemisch entfernt. Er kann im Allgemeinen, gegebenenfalls nach Aufarbeitung, erneut zur Hydroformylierung eingesetzt werden. Zur Hydrierung werden die bei der Hydroformylierung erhaltenen Reaktionsgemische mit Wasserstoff in Gegenwart eines Hydrierungskatalysators umsetzt.The molar ratio of H 2 : CO is generally about 1: 5 to about 5: 1. The aldehydes or aldehyde / alcohol mixtures resulting from the hydroformylation can, if desired, be isolated and, if appropriate, purified by conventional methods known to the person skilled in the art before the hydrogenation. The hydroformylation catalyst is preferably removed from the reaction mixture before the hydrogenation. In general, if necessary after working up, it can be used again for the hydroformylation. For the hydrogenation, the reaction mixtures obtained in the hydroformylation are reacted with hydrogen in the presence of a hydrogenation catalyst.
Geeignete Hydrierungskatalysatoren sind im Allgemeinen Übergangsmetalle wie z.B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., oder deren Mischungen, die zur Erhöhung der Aktivität und Stabi- lität auf Trägern, wie z.B. Aktivkohle, Aluminiumoxid, Kieselgur, etc., aufgebracht werden können. Zur Erhöhung der katalytischen Aktivität können Fe, Co, und bevorzugt Ni auch in Form der Raney- Katalysatoren als Metallschwamm mit einer sehr großen Oberfläche verwendet werden.Suitable hydrogenation catalysts are generally transition metals such as e.g. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., or their mixtures, which increase the activity and stability on supports, such as Activated carbon, aluminum oxide, diatomaceous earth, etc., can be applied. To increase the catalytic activity, Fe, Co, and preferably Ni can also be used in the form of the Raney catalysts as a metal sponge with a very large surface area.
Bevorzugt wird für das erfindungsgemäße Verfahren ein Co/Mo-Kata- lysator eingesetzt.A Co / Mo catalyst is preferably used for the process according to the invention.
Die Hydrierung der Oxo-Aldehyde erfolgt in Abhängigkeit von der Aktivität des Katalysators vorzugsweise bei erhöhten Temperaturen und erhöhtem Druck. Vorzugsweise liegt die Reaktionstemperatur bei etwa 80 bis 250°C. Bevorzugt liegt der Druck bei etwa 50 bis 350 bar.Depending on the activity of the catalyst, the hydrogenation of the oxo aldehydes is preferably carried out at elevated temperatures and elevated pressure. The reaction temperature is preferably about 80 to 250.degree. The pressure is preferably about 50 to 350 bar.
Nach einer besonderen Ausführungsform des erfindungsgemäßen Verfahrens erfolgt die Herstellung der erfindungsgemässen Alkoholgemische in einer einstufigen Reaktion. Dazu wird eine Olefinfraktion mit Kohlenmonoxid und Wasserstoff in Gegenwart eines Hydro- formylierungskatalysators, der auch für die weitere Hydrierung zu den Oxo-Alkoholen geeignet ist, umgesetzt. Allgemein sind alle Hydroformylierungskatalysatoren auch zur Durchführung katalyti- scher Hydrierungen geeignet, wobei jedoch in Abhängigkeit von der katalytischen Aktivität im Allgemeinen höhere Temperaturen und/ oder höhere Drücke und/oder längere Reaktionszeiten sowie eine größere Katalysatormenge als für eine ausschließliche Hydroformylierung verwendet werden.According to a particular embodiment of the process according to the invention, the alcohol mixtures according to the invention are prepared in a one-step reaction. For this purpose, an olefin fraction is reacted with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst which is also suitable for the further hydrogenation to the oxo alcohols. In general, all hydroformylation catalysts are also suitable for carrying out catalytic hydrogenations, although, depending on the catalytic activity, generally higher temperatures and / or higher pressures and / or longer reaction times and a larger amount of catalyst than for an exclusive hydroformylation are used.
Für das erfindungsgemäße Verfahren zur Hydroformylierung mit gleichzeitiger Hydrierung wird bevorzugt ein Cobaltcarbonyl-Kata- lysator und insbesondere Co2(CO)8 verwendet. Die Reaktionstemperatur liegt im Allgemeinen bei 100 bis 220°C, bevorzugt bei 150 bis
200°C, bei einem erhöhten Druck von 50 bis 650 bar, bevorzugt 100 bis 600 bar.For the process according to the invention for hydroformylation with simultaneous hydrogenation, a cobalt carbonyl catalyst and in particular Co 2 (CO) 8 are preferably used. The reaction temperature is generally 100 to 220 ° C, preferably 150 to 200 ° C, at an increased pressure of 50 to 650 bar, preferably 100 to 600 bar.
Auch andere Verfahren können zur Reduktion der Aldehyde zu den Alkoholen verwendet werden. Dazu zählen z.B. die Reduktion mit komplexen Hydriden, wie z.B. LiAlH4 und NaBH , die Reduktion mit Natrium in Ethanol nach Bouveault-Blanc sowie weitere bekannte Verfahren.Other methods can also be used to reduce the aldehydes to the alcohols. These include, for example, the reduction with complex hydrides, such as LiAlH 4 and NaBH, the reduction with sodium in ethanol according to Bouveault-Blanc and other known processes.
Ein weiterer Gegenstand der Erfindung sind die nach dem erfin- dungsgemässen Verfahren erhaltenen Alkoholgemische.The invention further relates to the alcohol mixtures obtained by the process according to the invention.
Vorzugsweise weisen die Alkoholgemische eine OH-Zahl im Bereich von etwa 200 bis 400 mg KOH/g Produkt, bevorzugt 250 bis 350 mg KOH/g Produkt, auf.The alcohol mixtures preferably have an OH number in the range from about 200 to 400 mg KOH / g product, preferably 250 to 350 mg KOH / g product.
Vorzugsweise weisen die Alkoholgemische einen mittels NMR ermittelten Verzweigungsgrad im Bereich von 0,5 bis 2,5, bevorzugt 0,7 bis 2,0, auf.The alcohol mixtures preferably have a degree of branching determined by means of NMR in the range from 0.5 to 2.5, preferably 0.7 to 2.0.
Vorzugsweise findet bei der Hydrierung ein möglichst vollständiger Umsatz statt, so dass die Carbonylzahl der nach dem erfindungsgemäßen Verfahren erhaltenen Alkoholgemische im Allgemeinen gering ist. Im Allgemeinen weisen die erfindungsgemässen Alkohol- gemische eine Carbonylzahl von höchstens 5 auf.The hydrogenation preferably takes place as completely as possible so that the carbonyl number of the alcohol mixtures obtained by the process according to the invention is generally low. In general, the alcohol mixtures according to the invention have a carbonyl number of at most 5.
Die erfindungsgemässen Alkoholgemische eignen sich vorzugsweise für die Funktionalisierung zur Herstellung grenzflächenaktiver Gemische.The alcohol mixtures according to the invention are preferably suitable for the functionalization for the preparation of surface-active mixtures.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung funktionalisierter Alkoholgemische, wobei man eines der zuvor beschriebenen erfindungsgemässen Alkoholgemische einer Alkoxilierung, Glycosidierung, Sulfatierung, Phosphatierung, Alko- xilierung und nachfolgender Sulfatierung oder Alkoxilierung und nachfolgender Phosphatierung unterwirft.Another object of the invention is a process for the preparation of functionalized alcohol mixtures, wherein one of the previously described alcohol mixtures according to the invention is subjected to alkoxylation, glycosidation, sulfation, phosphating, alkoxylation and subsequent sulfation or alkoxylation and subsequent phosphating.
Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung von funktionalisierten Alkoholgemischen, wobei manThe invention thus relates to a process for the preparation of functionalized alcohol mixtures, wherein
a) ein Kohlenwasserstoffgemisch, das Cyclopenten und wenigstens ein acyclisches Monoolefin enthält, in einer Metathesereaktion umsetzt,
b) aus dem Reaktionsgemisch der Metathese eine Olefinfraktion isoliert, die im Wesentlichen Olefine mit 8 bis 20 Kohlenstoffatomen enthält,a) reacting a hydrocarbon mixture which contains cyclopentene and at least one acyclic monoolefin in a metathesis reaction, b) an olefin fraction which essentially contains olefins having 8 to 20 carbon atoms is isolated from the reaction mixture of the metathesis,
c) gegebenenfalls die in der Olefinfraktion enthaltenen zwei- oder mehrfach ungesättigten Verbindungen zumindest teilweise einer selektiven Hydrierung zu Monoolefinen unterwirft,c) if appropriate, subjecting the di- or polyunsaturated compounds contained in the olefin fraction at least partially to a selective hydrogenation to monoolefins,
d) die, gegebenenfalls selektiv hydrierte, Olefinfraktion durch Umsetzung mit Kohlenmonoxid und Wasserstoff katalytisch hydroformyliert und hydriert,d) the, optionally selectively hydrogenated, olefin fraction is catalytically hydroformylated and hydrogenated by reaction with carbon monoxide and hydrogen,
e) das Alkoholgemisch aus Schritt d) einer Alkoxilierung, Glyco- sidierung, Sulfatierung, Phosphatierung, Alkoxilierung und nachfolgender Sulfatierung oder Alkoxilierung und nachfolgender Phosphatierung, unterwirft.e) the alcohol mixture from step d) is subjected to alkoxylation, glycosidation, sulfation, phosphating, alkoxylation and subsequent sulfation or alkoxylation and subsequent phosphating.
Die Alkoxilierung der Alkoholgemische erfolgt durch Umsetzung mit mindestens einem Alkylenoxid. Bevorzugt sind die Alkylenoxide ausgewählt unter Verbindungen der allgemeinen Formel II o CH^— CH R7 (II)The alcohol mixtures are alkoxylated by reaction with at least one alkylene oxide. The alkylene oxides are preferably selected from compounds of the general formula II or CH ^ - CH R 7 (II)
worinwherein
R7 für Wasserstoff oder einen geradkettigen oder verzweigten Ci- bis Ci6-Alkylrest steht, und Mischungen davon.R 7 represents hydrogen or a straight-chain or branched Ci to Ci 6 alkyl radical, and mixtures thereof.
Bevorzugt steht der Rest R7 in der Formel II für einen geradketti- gen oder verzweigten Ci- bis Cs-Alkylrest, insbesondere Ci- bisThe radical R 7 in the formula II preferably represents a straight-chain or branched C 1 -C 4 -alkyl radical, in particular C 1 -C 3
C -Alkylrest .C alkyl group.
Bevorzugt sind die Alkylenoxide ausgewählt unter Ethylenoxid, Propylenoxid, Butylenoxid und Mischungen davon.The alkylene oxides are preferably selected from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
Die Umsetzung der Alkoholgemische mit dem/den Alkylenoxid(en) erfolgt nach üblichen, dem Fachmann bekannten Verfahren und in dafür üblichen Apparaturen.The alcohol mixtures are reacted with the alkylene oxide (s) by customary methods known to the person skilled in the art and in equipment customary for this.
Die mittlere Kettenlänge der Polyetherketten der so funktionali- sierten Alkoholgemische kann durch das Molmengenverhältnis von Alkohol zu Alkylenoxid bestimmmt werden. Bevorzugt werden alkoxi- lierte Alkoholgemische mit etwa 1 bis 200, bevorzugt etwa 1 bis 50, insbesondere 1 bis 10 Alkylenoxideinheiten hergestellt.
Die Alkoholgemische können gewünschtenfalls nur mit einem Alkylenoxid oder mit zwei oder mehreren verschiedenen Alkylenoxiden umgesetzt werden. Bei der Umsetzung der Alkoholgemische mit einem Gemisch aus zwei oder mehreren Alkylenoxiden enthalten die resultierenden Alkoxilate die Alkylenoxideinheiten im Wesentlichen statistisch verteilt. Werden die Alkylenoxide getrennt nacheinander eingesetzt, so resultieren Alkoxilate, die entsprechen der Zugabereihenfolge die Alkylenoxideinheiten in Form von Blöcken einpolymerisiert enthalten.The average chain length of the polyether chains of the alcohol mixtures thus functionalized can be determined by the molar ratio of alcohol to alkylene oxide. Alkoxylated alcohol mixtures having about 1 to 200, preferably about 1 to 50, in particular 1 to 10, alkylene oxide units are preferably prepared. If desired, the alcohol mixtures can only be reacted with one alkylene oxide or with two or more different alkylene oxides. When the alcohol mixtures are reacted with a mixture of two or more alkylene oxides, the resulting alkoxylates contain the alkylene oxide units essentially randomly distributed. If the alkylene oxides are used separately one after the other, this results in alkoxylates which, in the order in which they are added, contain the alkylene oxide units in the form of blocks in copolymerized form.
Die Alkoxilierung kann durch starke Basen, wie Alkalihydroxide und Erdalkalihydroxide, Brönstedsäuren oder Lewissäuren, wie AICI3, BF3 etc. katalysiert werden.The alkoxylation can be catalyzed by strong bases, such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AICI 3 , BF 3 etc.
Die Alkoxilierung erfolgt vorzugsweise bei Temperaturen im Bereich von etwa 80 bis 250 °C, bevorzugt etwa 100 bis 220 °C. Der Druck liegt vorzugsweise zwischen Umgebungsdruck und 600 bar. Gewünschtenfalls kann das Alkylenoxid eine Inertgasbeimischung, z.B von etwa 5 bis 60 %, enthalten.The alkoxylation is preferably carried out at temperatures in the range from approximately 80 to 250 ° C., preferably approximately 100 to 220 ° C. The pressure is preferably between ambient pressure and 600 bar. If desired, the alkylene oxide may contain an inert gas admixture, e.g. from about 5 to 60%.
Die durch Alkoxilierung erhaltenen funktionalisierten Alkoholgemische zeigen eine sehr gute Oberflächenaktivität und können als nichtionische Tenside in einer Vielzahl von Anwendungsbereichen vorteilhaft eingesetzt werden.The functionalized alcohol mixtures obtained by alkoxylation have a very good surface activity and can be used advantageously as nonionic surfactants in a large number of fields of application.
Die Glycosidierung der Alkoholgemische erfolgt durch ein-, zwei- oder mehrfache Umsetzung der erfindungsgemässen Alkoholgemische mit Mono-, Di- oder Polysacchariden. Die Umsetzung erfolgt nach üblichen, dem Fachmann bekannten Verfahren. Dazu zählt zum einen die säurekatalysierte Umsetzung unter Wasserentzug. GeeigneteThe alcohol mixtures are glycosidated by one, two or more reactions of the alcohol mixtures according to the invention with mono-, di- or polysaccharides. The reaction is carried out using customary methods known to those skilled in the art. On the one hand, this includes acid-catalyzed conversion with dehydration. suitable
Säuren sind z.B. Mineralsäuren, wie HCl und H2S04. Dabei werden in der Regel Oligosaccharide mit statistischer Kettenlängenvertei- lung erhalten. Vorzugsweise liegt der durchschnittliche Oligome- risierungsgrad bei 1 bis 3 Saccharidresten. Nach einem weiteren geeigneten Verfahren kann das Saccharid zunächst durch Umsetzung mit einem niedermolekularen Cχ~ bis C8-Alkanol, wie z.B. Ethanol, Propanol oder Butanol, acetalisiert werden. Die Acetalisierung erfolgt vorzugsweise säurekatalysiert. Das dabei resultierende Glycosid mit dem niedermolekularen Alkohol kann anschließend mit eimem erfindungsgemässen Alkoholgemisch zu den entsprechenden Glycosiden umgesetzt werden. Für diese Reaktion eignen sich im Allgemeinen auch wässrige Saccharidlösungen. Nach einem weiteren geeigneten Verfahren kann das Saccharid zunächst durch Umsetzung mit einem Halogenwasserstoff in das entsprechende O-Acetylhalo- saccharid überführt und anschliessend mit einem erfindungsgemäs-
sen Alkoholgemisch in Gegenwart säurebindender Verbindungen gly- cosidiert werden.Acids are, for example, mineral acids, such as HCl and H 2 S0 4 . As a rule, oligosaccharides with statistical chain length distribution are obtained. The average degree of oligomerization is preferably 1 to 3 saccharide residues. According to a further suitable method, the saccharide can first be acetalized by reaction with a low molecular weight Cχ ~ to C 8 alkanol, such as ethanol, propanol or butanol. The acetalization is preferably acid-catalyzed. The resulting glycoside with the low molecular weight alcohol can then be reacted with the alcohol mixture according to the invention to give the corresponding glycosides. Aqueous saccharide solutions are generally also suitable for this reaction. According to a further suitable method, the saccharide can first be converted into the corresponding O-acetylhalosaccharide by reaction with a hydrogen halide and then with a sen alcohol mixture in the presence of acid-binding compounds are glycosidated.
Vorzugsweise werden zur Glycosidierung Monosaccharide eingesetzt. Insbesondere werden Hexosen, wie Glucose, Fructose, Galactose, Mannose etc. und Pentosen, wie Arabinose, Xylose, Ribose etc. eingesetzt. Besonders bevorzugt wird Glucose eingesetzt. Die Saccharide können einzeln oder in Form von Gemischen eingesetzt werden. Bei Saccharidgemischen resultieren im Allgemeinen Glycoside mit statistisch verteilten Zuckerresten. Bei mehrfacher Saccha- ridanlagerung an eine alkoholische Hydroxidgruppe resultieren Po- lyglycoside der erfindungsgemässen Alkoholgemische. Auch zu Poly- glycosidierung können mehrere Saccharide nacheinander oder als Gemisch eingesetzt werden, so dass die resultierenden funktiona- lisierten Alkoholgemische die Saccharide in Form von Blöcken oder statistisch verteilt eingebaut enthalten. Es können je nach Reaktionbedingungen, insbesondere Reaktionstemperatur, Furanose- oder Pyranosestrukturen resultieren.Monosaccharides are preferably used for the glycosidation. In particular, hexoses such as glucose, fructose, galactose, mannose etc. and pentoses such as arabinose, xylose, ribose etc. are used. Glucose is particularly preferably used. The saccharides can be used individually or in the form of mixtures. Saccharide mixtures generally result in glycosides with randomly distributed sugar residues. With multiple addition of saccharide to an alcoholic hydroxide group, polyglycosides of the alcohol mixtures according to the invention result. Several saccharides can also be used in succession or as a mixture for polyglycosidation, so that the resulting functionalized alcohol mixtures contain the saccharides in the form of blocks or incorporated in a statistically distributed manner. Depending on the reaction conditions, in particular reaction temperature, furanose or pyranose structures can result.
Geeignete Verfahren und Reaktionsbedingungen zur Glycosidierung sind z.B. in Ulimanns Encyclopedia of Industrial Chemistry, 5. Aufl., Bd. A25 (1994), S. 792-793 und den dort zitierten Dokumenten beschrieben.Suitable methods and reaction conditions for glycosidation are e.g. in Ulimann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A25 (1994), pp. 792-793 and the documents cited therein.
Die durch Glycosidierung erhaltenen funktionalisierten Alkoholgemische zeigen eine sehr gute Oberflächenaktivität und können als nichtionische Tensid in einer Vielzahl von Anwendungsbereichen vorteilhaft eingesetzt werden.The functionalized alcohol mixtures obtained by glycosidation have a very good surface activity and can be used advantageously as a nonionic surfactant in a large number of fields of application.
Die Sulfatierung oder Phosphatierung der zuvor beschriebenen Alkoholgemische oder alkoxilierten Alkoholgemische erfolgt durch Umsetzung mit Schwefelsäure oder Schwefelsäurederivaten zu sauren Alkylsulfaten oder Alkylethersulfaten oder durch Umsetzung mit Phosphorsäure oder oder Phosphorsäurederivaten zu sauren Alkyl- phosphaten oder Alkyletherphosphaten.The above-described alcohol mixtures or alkoxylated alcohol mixtures are sulfated or phosphated by reaction with sulfuric acid or sulfuric acid derivatives to give acidic alkyl sulfates or alkyl ether sulfates or by reaction with phosphoric acid or or phosphoric acid derivatives to give acidic alkyl phosphates or alkyl ether phosphates.
Geeignete Verfahren zur Sulfatierung von Alkoholen sind die üblichen, dem Fachmann bekannten, wie sie z.B. in der US 3,462,525, US 3,420,875 oder US 3,524,864 beschrieben werden, worauf hier in vollem Umfang Bezug genommen wird. Geeignete Verfahren zur Sulfatierung sind auch in Ulimanns Encyclopedia of Industrial Chemistry, 5. Aufl. Bd A25 (1994), S. 779-783 und der dort zitierten Literatur beschrieben.Suitable processes for the sulfation of alcohols are the customary ones known to the person skilled in the art, such as e.g. in US 3,462,525, US 3,420,875 or US 3,524,864, which are incorporated herein by reference. Suitable processes for sulfation are also described in Ulimann's Encyclopedia of Industrial Chemistry, 5th edition vol. A25 (1994), pp. 779-783 and the literature cited therein.
Wird zur Sulfatierung der erfindungsgemässen Alkoholgemische Schwefelsäure eingesetzt, so ist diese vorzugsweise 75 bis 100 gew.-%ig, insbesondere 85 bis 98 gew.-%ig. Derartige Schwefel-
säure ist unter den Bezeichnungen konzentrierte Schwefelsäure und Monohydrat erhältlich.If sulfuric acid is used to sulfate the alcohol mixtures according to the invention, this is preferably 75 to 100% by weight, in particular 85 to 98% by weight. Such sulfur Acid is available under the names concentrated sulfuric acid and monohydrate.
Gewünschtenfalls kann zur Sulfatierung mit Schwefelsäure ein Lö- sungs- oder Verdünnungsmittel eingesetzt werden. Geeignete Lösungsmittel sind z.B. solche, die mit Wasser ein Azeotrop bilden, wie z.B. Toluol.If desired, a solvent or diluent can be used for sulfation with sulfuric acid. Suitable solvents are e.g. those that form an azeotrope with water, e.g. Toluene.
Nach einer geeigneten Ausführungsform zur Herstellung sulfatier- ter Alkoholgemische wird das Alkoholgemisch in einem Reaktionsge- fäss vorgelegt und das Sulfatierungsmittel unter ständigem Durchmischen zugegeben. Zur Erzielung einer möglichst vollständigen Veresterung des Alkoholgemischs beträgt das Molmengenverhältnis von Alkanol zu Sulfatierungsmittel bevorzugt etwa 1:1 bis 1:1,5, insbesondere 1:1 bis 1:1,2. Gewünschtenfalls kann das Sulfatierungsmittel auch in einem molaren Unterschuss eingesetzt werden, z.B. bei der Sulfatierung alkoxilierter Alkoholgemische, wenn Gemische aus nichtionischen und anionischen grenzflächenaktiven Verbindungen hergestellt werden sollen. Die Sulfatierung erfolgt bevorzugt bei einer Temperatur im Bereich von Umgebungstemperatur bis 80°C, insbesondere 40 bis 75°C.According to a suitable embodiment for the production of sulfated alcohol mixtures, the alcohol mixture is placed in a reaction vessel and the sulfating agent is added with constant mixing. To achieve the most complete esterification of the alcohol mixture, the molar ratio of alkanol to sulfating agent is preferably about 1: 1 to 1: 1.5, in particular 1: 1 to 1: 1.2. If desired, the sulfating agent can also be used in a molar deficit, e.g. in the sulfation of alkoxylated alcohol mixtures if mixtures of nonionic and anionic surface-active compounds are to be produced. The sulfation is preferably carried out at a temperature in the range from ambient temperature to 80 ° C., in particular 40 to 75 ° C.
Weitere geeignete Sulfatierungsmittel sind z.B. Schwefeltrioxid, Schwefeltrioxid-Komplexe, Lösungen von Schwefeltrioxid in Schwe- feisäure (Oleum), Chlorsulfonsäure, Sulfurylchlorid, Amidosulfon- säure etc . Bei Einsatz von Schwefeltrioxid als Sulfatierungsmittel kann die Umsetzung vorteilhaft in einem Fallfilmverdampfer, bevorzugt im Gegenstrom, durchgeführt werden. Dabei kann die Umsetzung diskontinuierlich oder kontinuierlich erfolgen.Other suitable sulfating agents are e.g. Sulfur trioxide, sulfur trioxide complexes, solutions of sulfur trioxide in sulfuric acid (oleum), chlorosulfonic acid, sulfuryl chloride, amidosulfonic acid etc. If sulfur trioxide is used as the sulfating agent, the reaction can advantageously be carried out in a falling film evaporator, preferably in countercurrent. The reaction can be carried out batchwise or continuously.
Die Aufarbeitung der bei der Sulfatierung entstehenden Reaktionsgemische erfolgt nach üblichen, dem Fachmann bekannten Verfahren. Dazu zählt z.B. die Neutralisierung, Abtrennung ggf. eingesetzter Lösungsmittel etc.The reaction mixtures formed in the sulfation are worked up by customary processes known to the person skilled in the art. This includes e.g. neutralization, separation of any solvents used, etc.
Die Phosphatierung der zuvor beschriebenen Alkoholgemische und alkoxilierten Alkoholgemische erfolgt im Allgemeinen in analoger Weise zur Sulfatierung.The phosphation of the alcohol mixtures and alkoxylated alcohol mixtures described above is generally carried out in an analogous manner to the sulfation.
Geeignete Verfahren zur Phosphatierung von Alkoholen sind die üblichen, dem Fachmann bekannten, wie sie z.B. in Synthesis 1985, S. 449 bis 488 beschrieben werden, worauf hier in vollem Umfang Bezug genommen wird.
Geeignete Phosphatierungsmittel sind z.B. Phosphorsäure, Poly- phosphorsäure, Phosphorpentoxid, P0C13 etc. Bei Einsatz von POCI3 werden die verbleibenden Säurechloridfunktionen nach der Veresterung hydrolysiert .Suitable processes for the phosphating of alcohols are the customary, known to the person skilled in the art, as described, for example, in Synthesis 1985, pp. 449 to 488, to which reference is made in full here. Suitable phosphating agents are, for example, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, P0C1 3 etc. When using POCI 3 , the remaining acid chloride functions are hydrolyzed after the esterification.
Die durch Sulfatierung oder Phosphatierung erhaltenen funktiona- lisierten Alkoholgemische und deren Salze zeigen eine sehr gute Oberflächenaktivität und können als anionische Tenside in einer Vielzahl von Anwendungsbereichen vorteilhaft eingesetzt werden.The functionalized alcohol mixtures and their salts obtained by sulfation or phosphation show a very good surface activity and can be used advantageously as anionic surfactants in a large number of application areas.
Ein weiterer Gegenstand der Erfindung sind die durch das zuvor beschriebene Verfahren erhältlichen funktionalisierten Alkoholgemische und deren Salze.The invention further relates to the functionalized alcohol mixtures and their salts obtainable by the process described above.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der funktionalisierten Alkoholgemische als Tenside, Dispergiermittel, Papierhilfsmittel, Schmutzlösungsmittel, Korrosionsinhibitoren, Hilfsmittel für Dispersionen, Inkrustierungsinhibitoren.Another object of the invention is the use of the functionalized alcohol mixtures as surfactants, dispersants, paper auxiliaries, soil solvents, corrosion inhibitors, auxiliaries for dispersions, incrustation inhibitors.
Vorteilhafterweise zeichnen sich die erfindungsgemässen Gemische funktionalisierter Alkohole durch sehr gute oberflächenaktive Eigenschaften aus. So zeigen die wässrigen Lösungen dieser Gemische z.B. gute Oberflächungsspannungswerte und/oder Trübungspunkte.The mixtures of functionalized alcohols according to the invention are advantageously distinguished by very good surface-active properties. The aqueous solutions of these mixtures show e.g. good surface tension values and / or cloud points.
Die Erfindung wird anhand der folgenden nicht einschränkenden Beispiele erläutert.The invention is illustrated by the following non-limiting examples.
BeispieleExamples
Für die Aufnahme der Gaschromatogramme wurde ein 5890 Gaschromatograph der Fa. Hewlett Packard mit einer DB 5,30 m x 0,32 mm Glaskapillarsäure und einem Flammionisationsdetektor mit angeschlossener Integriereinheit verwendet.A 5890 gas chromatograph from Hewlett Packard with a DB 5.30 mx 0.32 mm glass capillary acid and a flame ionization detector with connected integration unit was used to record the gas chromatograms.
Die Iodzahl ist definiert als g Iod/100 g Produkt und wurde ermittelt nach Kaufmann. Dazu werden in einen 300 ml Erlenmeyerkol- ben ca. 0,2 g PrüfSubstanz exakt eingewogen, in 20 ml Chloroform gelöst, mit genau 20,00 ml Brom-Lösung versetzt und 2 Stunden im Dunkeln stehen gelassen. Danach werden 10 ml Kaliumiodid-Lösung und ca. 2 g Kaliumiodat hinzugegeben. Das ausgeschiedene lod wird mit Natriumthiosulfatmaßlösung gegen Stärkelösung bis zum Verschwinden der Blaufärbung titriert. Zur Herstellung der verwendeten Bromlösung nach Kaufmann werden 120 g Natriumbromid in ca. 900 ml Methanol gelöst. Hierzu gibt man 6,5 ml Brom und füllt mit Methanol auf 1000 ml auf. Die Lösung ist dann ca. 0,25 molar und wird in braunen Glasflaschen aufbewahrt.
Die Alkoholzahl ist definiert als mg KOH/g Produkt. Zur Bestimmung werden ca. 1 g PrüfSubstanz exakt eingewogen, 9,8 ml Acety- lierungsreagenz hinzugefügt und 24 Stunden bei Raumtemperatur stehen gelassen. Danach werden 25 ml dest. Wasser zugefügt und 15 min. gerührt, 25 ml Isopropanol zugesetzt und mit Natronlauge- Maßlösung gegen den Wendepunkt potentiometrisch titriert. Zur Herstellung des Acetylierungsreagenzes werden 810 ml Pyridin, 100 ml Essigsäureanhydrid und 9 ml Essigsäure vermischt.The iodine number is defined as g iodine / 100 g product and was determined according to Kaufmann. For this purpose, about 0.2 g of test substance is precisely weighed into a 300 ml Erlenmeyer flask, dissolved in 20 ml of chloroform, mixed with exactly 20.00 ml of bromine solution and left to stand in the dark for 2 hours. Then 10 ml of potassium iodide solution and about 2 g of potassium iodate are added. The iodine which is excreted is titrated with sodium thiosulphate solution against starch solution until the blue color disappears. To prepare the bromine solution used according to Kaufmann, 120 g of sodium bromide are dissolved in about 900 ml of methanol. For this purpose, 6.5 ml of bromine are added and the volume is made up to 1000 ml with methanol. The solution is then approximately 0.25 molar and is stored in brown glass bottles. The alcohol number is defined as mg KOH / g product. For the determination, approx. 1 g of test substance is weighed exactly, 9.8 ml of acetylene reagent added and left to stand for 24 hours at room temperature. Then 25 ml of dist. Water added and 15 min. stirred, 25 ml isopropanol added and titrated potentiometrically with sodium hydroxide solution against the turning point. To prepare the acetylation reagent, 810 ml of pyridine, 100 ml of acetic anhydride and 9 ml of acetic acid are mixed.
I. MetatheseI. Metathesis
Beispiel 1:Example 1:
Ein l:l-Gemisch aus je 17,1 mol Cyclopenten und 1-Penten wurde bei Raumtemperatur und Normaldruck mit einer "in situ"-erzeugten Katalysatormischung aus 8,6 mmol (p-Cymol)RuCl (PCV3) und 2 ml Me3SiCHN2 in 50 ml CH2CI2 versetzt. Hierbei wurde eine schwache Gasentwicklung beobachtet. Nach 3 Stunden Rühren wurde die Lösung über neutrales Al203 chromatographiert und das farblose Filtrat destillativ von nicht umgesetzten Leichtsiedern befreit. Es verblieben 956 g einer farblosen, niederviskosen Flüssigkeit nachfolgender Zusammensetzung (GC-Flächenprozent) :A 1: 1 mixture of 17.1 mol of cyclopentene and 1-pentene was mixed at room temperature and normal pressure with an “in situ” catalyst mixture of 8.6 mmol (p-cymene) RuCl (PCV 3 ) and 2 ml of Me 3 SiCHN 2 in 50 ml CH 2 CI 2 added. Weak gas evolution was observed. After stirring for 3 hours, the solution was chromatographed over neutral Al 2 O 3 and the colorless filtrate was freed from unconverted low boilers by distillation. There remained 956 g of a colorless, low-viscosity liquid of the following composition (GC area percent):
26% Cι0H18, 22% Cι5H26, 17% C20H3 , 13% C25H42, 10% C30H50, 7% C35H58, 5% C oH66- Jodzahl: 351 g J2/100 g26% C 0 H 18 , 22% C 5 H 26 , 17% C 20 H 3 , 13% C 25 H 42 , 10% C 30 H 50 , 7% C 35 H 58 , 5% C oH 6 6 iodine number : 351 g I 2/100 g
Beispiel 2:Example 2:
1 1 C5-Schnitt (Cyclopenten-Gehalt : 15% ) wurde bei Raumtemperatur unter Normaldruck mit einer Lösung von 0,6 mmol1 1 C 5 cut (cyclopentene content: 15%) was at room temperature under normal pressure with a solution of 0.6 mmol
RuCl2(=CHPh) (PCy3)2 in 20 ml CH2C1 umgesetzt. Hierbei wurde eine schwache Gasentwicklung beobachtet. Nach 1 h Rühren wurde die Lösung über Al 03 chromatographiert und das farblose Filtrat destillativ von nicht umgesetzten Leichsiedern befreit. Man er- hielt 96 g einer farblosen, niederviskosen Flüssigkeit folgender Zusammensetzung (GC-Flächenprozent) :RuCl 2 (= CHPh) (PCy 3 ) 2 implemented in 20 ml CH 2 C1. Weak gas evolution was observed. After stirring for 1 h, the solution was chromatographed over Al 3 and the colorless filtrate was freed from unconverted low boilers by distillation. 96 g of a colorless, low-viscosity liquid of the following composition (GC area percent) were obtained:
4% C7Hi2, 11% C8H16, 14% Cι0H18, 3% C12H20, 8% C13H24, 12% Cι5H26, 2% Cι7H28, 5% C18H32, 9% C20H34, 1% C22H36, 4% C23H40, 7% C25H42, 3% C28H48, 6% C30H50, 1% C33H56, 4% C35H58, 3% C40H58, 3% C40H66, 2% C40H66, 1% C40H66.4% C 7 Hi2, 11% C 8 H 16 , 14% Cι 0 H 18 , 3% C 12 H 20 , 8% C 13 H 24 , 12% Cι 5 H 26 , 2% Cι 7 H 28 , 5% C 18 H 32.9 % C 20 H 34.1 % C 22 H 36.4 % C 23 H 40.7 % C 25 H 42.3 % C 28 H 48.6 % C 30 H 50.1 % C 33 H 56 , 4% C 35 H 58 , 3% C 40 H 58 , 3% C 40 H 66 , 2% C 40 H 66 , 1% C 40 H 66 .
Jodzahl: 329 g J2/100 gIodine value: 329 g I 2/100 g
Beispiel 3 :Example 3:
Ein l:l-Gemisch aus Cyclopenten und 1-Penten wurde bei 60°C, 5 bar und Verweilzeiten von 1-3 h kontinuierlich in einen mit Re07/Al203 bestückten Rohrreaktor gepumpt. Mit Hilfe eines bei 115°C und
Normaldruck betriebenen Fallfilmverdampfers wurde das Reaktionsprodukt anschließend in eine Leicht- und eine Hochsiederfraktion getrennt und erstere in den Metatheseprozess zurückgeführt. Die Hochsiederfraktion wurde im Vakuum von Restmengen an Leichtsie- 5 dern befreit. Man erhielt bei Raum-Zeit-Ausbeuten von 50-500 g 1_1 h_1 leicht gelbliche Flüssigkeiten, die abschließend über AI2O3 chromatographiert wurden. Eine entnommene Probe hatte folgende Zusammensetzung (GC-Flächenprozent) :A 1: 1 mixture of cyclopentene and 1-pentene was pumped continuously at 60 ° C., 5 bar and residence times of 1-3 h into a tube reactor equipped with Re0 7 / Al 2 0 3 . With the help of at 115 ° C and Fall film evaporator operated at normal pressure, the reaction product was then separated into a light and a high boiler fraction and the former was returned to the metathesis process. The high boiler fraction was freed from residual amounts of low boilers in vacuo. With space-time yields of 50-500 g 1 _1 h _1, slightly yellowish liquids were obtained, which were then chromatographed on Al 2 O 3 . A sample taken had the following composition (GC area percent):
3% C7H12, 9% C8H16, 16% C10H18, 2% Cι2H20, 8% Cι3H24, 13% Cι5H26, 10 2% C17H28, 6% Cι8H32, 11% C20H34, 1% C22H36r 4% C23H40, 9% C25H42, 2% C28H48, 6% C30H50, 3% CssHss, 2% C4oH66r 1% c oH66f 1* C45H74 • Jodzahl: 349 g J2/100 g3% C 7 H 12 , 9% C 8 H 16 , 16% C 10 H 18 , 2% Cι 2 H 20 , 8% Cι 3 H 24 , 13% Cι 5 H 26 , 10 2% C 17 H 28 , 6% Cι 8 H 32 , 11% C 20 H 34 , 1% C 22 H 3 6r 4% C 23 H 40 , 9% C 25 H 42 , 2% C 28 H 48 , 6% C30H50, 3% CssHss, 2% C 4% oH66r 1 c 1 * oH66f C45 H 74 • iodine value: 349 g I 2/100 g
Beispiel 4 :Example 4:
1515
1 1 Cs-Schnitt wurde bei 60°C, 5 bar und einer Verweilzeit von 1,2 h kontinuierlich in einen mit Re207/Al2θ3 bestückten Rohrreaktor gepumpt. Mit Hilfe eines bei 115°C und Normaldruck betriebenen Fallfilmverdampfers wurde das Reaktionsprodukt in eine Leicht-1 1 Cs cut was pumped continuously at 60 ° C., 5 bar and a residence time of 1.2 h into a tube reactor equipped with Re 2 0 7 / Al 2 θ 3 . With the help of a falling film evaporator operated at 115 ° C and normal pressure, the reaction product was
20 und eine Hochsiederfraktion getrennt. Letztere wurde durch Destillation im Vakuum von Restmengen an Leichtsiedern befreit. Man erhielt bei Raum-Zeit-Ausbeuten von 85 g l-1 h_1 und Cyclopenten- Umsätzen bis 70% eine leicht gelbliche Flüssigkeit, die abschließend über AI2O3 chromatographiert wurde. Eine entnommene Probe20 and a high boiler fraction separated. The latter was freed from residual amounts of low boilers by distillation in vacuo. A slightly yellowish liquid was obtained with space-time yields of 85 gl -1 h _1 and cyclopentene conversions up to 70%, which was then chromatographed on Al 2 O 3 . A sample taken
25 hatte folgende Zusammensetzung (GC-Flächenprozent) :25 had the following composition (GC area percent):
47% isomere C6Hι2, C7HX2, C7H14, C8Hι4, C8Hι6, C9H16, C9Hι8,47% isomeric C 6 Hι 2, C 7 H X2, C 7 H 14, C 8 Hι 4, C 8 Hι 6, C 9 H 16, C 9 Hι 8,
44% isomere Cι0Hι8, CnH2o, Cι2H20, C12H22, C13H22, Cι3H24, CX4H24, 14H26, 9% isomere C15H26 _ C2sH 2. 30 Jodzahl: 325 g J2/100 g44% isomeric Cι 0 Hι 8, C n H 2 O, Cι 2 H 20, C 12 H 22, C 13 H 22, Cι 3 H 24, C X4 H 24, 14 H 26, 9% isomeric C1 5 H2 6 _ C 2 sH 2 . 30 iodine value: 325 g I 2/100 g
II. AlkoholherstellungII. Alcohol production
Beispiel 5Example 5
3535
Ein Metathese-Reaktionsgemisch gemäss Beispiel 4 wurde einer fraktionierten Destillation unter verringertem Druck unterzogen (60 theoretische Trennstufen; RücklaufVerhältnis 5; Fraktion isoliert bei 100 mbar, Kopftemperatur 96-124°C, SumpftemperaturA metathesis reaction mixture according to Example 4 was subjected to fractional distillation under reduced pressure (60 theoretical plates; reflux ratio 5; fraction isolated at 100 mbar, top temperature 96-124 ° C, bottom temperature
40 126-173°C). Dabei wurde eine Olefinfraktion folgender Zusammensetzung (GC-Flächenprozent) isoliert:40 126-173 ° C). An olefin fraction of the following composition (GC area percent) was isolated:
52,2% C10, 15,0% Cu, 1,5% C12 , 1,4% C13, 8,9% Cχ4, 21,1% C15. Die Jodzahl betrug 284 g J2/100 g. 4960 g dieser Olefinfraktion wurden mit 18,9 g Co2(CO)8 bei 185°C und 280 bar mit Synthesegas (C0/H2 52.2% C 10 , 15.0% Cu, 1.5% C 12 , 1.4% C 13 , 8.9% Cχ 4 , 21.1% C 15 . The iodine value was 284 g I 2/100 g. 4960 g of this olefin fraction were treated with 18.9 g of Co 2 (CO) 8 at 185 ° C and 280 bar with synthesis gas (C0 / H 2
45 1:1) unter Zusatz von 496 g Wasser und 6 1 Heptan in einem 20 1 Drehrührautoklaven hydroformyliert, die Reaktionszeit betrug 7,5 Stunden. Nach Abkühlen und Entspannen des Autoklaven wurde der
Reaktionsaustrag mit 10%iger Essigsäure unter Lufteinleitung bei 90°C entcobaltet. Das resultierende Hydroformylierungsgemisch wurde in einem 2,5 1 Rohrreaktor in Rieselfahrweise an einem Co/ Mo-Festbettkatalysator bei 175°C und 280 bar mit Wasserstoff unter Zusatz von 10 Gew.-% Wasser hydriert. Nach destillativer Abtrennung des Heptans wurde ein Alkoholgemisch mit einer OH-Zahl von 326 mg KOH/g erhalten.45 1: 1) with the addition of 496 g of water and 6 l of heptane in a 20 l rotary autoclave hydroformylated, the reaction time was 7.5 hours. After the autoclave had cooled and relaxed, the Reaction discharge with 10% acetic acid with introduction of air at 90 ° C decobtained. The resulting hydroformylation mixture was hydrogenated in a 2.5 1 tubular reactor in a trickle mode over a Co / Mo fixed bed catalyst at 175 ° C. and 280 bar with hydrogen with the addition of 10% by weight of water. After separation of the heptane by distillation, an alcohol mixture with an OH number of 326 mg KOH / g was obtained.
Das Alkoholgemisch wurde destillativ aufgearbeitet und eine Fraktion mit einem Siedebereich von 99°C/9 mbar bis 144°C/40 mbar iso- liert (40 Gew.-% bezogen auf rohes Hydroformylierungsprodukt) . Diese Fraktion hat eine OH-Zahl von 296 mg KOH/g. Mittels ^-NMR wurde ein mittlerer Verzweigungsgrad von 1,02 ermittelt.The alcohol mixture was worked up by distillation and a fraction with a boiling range from 99 ° C./9 mbar to 144 ° C./40 mbar was isolated (40% by weight based on crude hydroformylation product). This fraction has an OH number of 296 mg KOH / g. An average degree of branching of 1.02 was determined using ^ -NMR.
Beispiel 6Example 6
Die Olefinfraktion aus Beispiel 5 Beispiel wurde einer weiteren fraktionierten Destillation (Apparatur wie Beispiel 5; Fraktion isoliert bei 200 mbar, Kopftemperatur 95-110°C, Sumpftemperatur 130°C)unterzogen. Dabei wurde eine Olefinfraktion folgender Zu- sammensetzung (GC-Flächenprozent) isoliert:The olefin fraction from example 5 was subjected to a further fractional distillation (apparatus as example 5; fraction isolated at 200 mbar, top temperature 95-110 ° C., bottom temperature 130 ° C.). An olefin fraction of the following composition (GC area percent) was isolated:
72,5% Cio, 23,0% Cu, 3,9% Cι2. Die Jodzahl betrug 295 g J2/100 g. 2260 g dieser Olefinfraktion wurden mit 8,5 g Co2(CO)8 bei 185°C und 280 bar mit Synthesegas (CO/H2 1:1) unter Zusatz von 226 g Wasser und 1,5 kg Heptan in einem 20 1 Drehrührautoklaven hydro- formyliert, die Reaktionszeit betrug 7,5 Stunden. Nach Abkühlen und Entspannen des Autoklaven wurde der Reaktionsaustrag mit 10%iger Essigsäure unter Lufteinleitung bei 90°C entcobaltet. Das resultierende Hydroformylierungsgemisch wurde in einem 2,5 1 Rohrreaktor in Rieselfahrweise an einem Co/Mo-Festbettkatalysator bei 175°C und 280 bar mit Wasserstoff unter Zusatz von 10 Gew.-% Wasser hydriert.72.5% Cio, 23.0% Cu, 3.9% Cι 2 . The iodine value was 295 g I 2/100 g. 2260 g of this olefin fraction were mixed with 8.5 g of Co 2 (CO) 8 at 185 ° C. and 280 bar with synthesis gas (CO / H 2 1: 1) with the addition of 226 g of water and 1.5 kg of heptane in a 20 l Rotary stirring autoclave hydroformylated, the reaction time was 7.5 hours. After cooling and releasing the pressure in the autoclave, the reaction mixture was decobtained with 10% acetic acid with introduction of air at 90 ° C. The resulting hydroformylation mixture was hydrogenated in a 2.5 1 tubular reactor in a trickle mode over a Co / Mo fixed bed catalyst at 175 ° C. and 280 bar with hydrogen with the addition of 10% by weight of water.
Das Alkoholgemisch wurde destillativ aufgearbeitet und eine Fraktion mit einem Siedebereich von 80°C/2 mbar bis 114°C/2 mbar isoliert (71 Gew.-% bezogen auf rohes Hydroformylierungsprodukt) . Diese Fraktion hat eine OH-Zahl von 310 mg KOH/g. Mittels !H-NMR wurde ein mittlerer Verzweigungsgrad von 1,14 ermittelt.The alcohol mixture was worked up by distillation and a fraction with a boiling range from 80 ° C./2 mbar to 114 ° C./2 mbar was isolated (71% by weight based on crude hydroformylation product). This fraction has an OH number of 310 mg KOH / g. By means ! H-NMR showed an average degree of branching of 1.14.
III. Herstellung grenzflächenaktiver GemischeIII. Production of surface-active mixtures
Beispiel 7Example 7
(Herstellung eines Fettalkoholethoxylates mit 7 mol Ethylenoxid)(Production of a fatty alcohol ethoxylate with 7 mol ethylene oxide)
380 g des in Beispiel 5 erhaltenen Alkoholgemisches wurden mit 1,5 g NaOH in einen trockenen 2 1-Autoklaven eingefüllt. Der Au- toklaveninhalt wurde auf 150 °C erhitzt und 616 g Ethylenoxid unter Druck in den Autoklaven gepresst. Nach Einfüllen der gesamten Ethylenoxidmenge wurde der Autoklave noch 30 Minuten bei 150 °C
gehalten. Nach dem Abkühlen wurde der Reaktoraustrag mit Schwefelsäure neutralisiert. Das erhaltene Tensidgemisch wies einen nach DIN 53917 an einer l-%igen Lösung in Wasser gemessenen Trübungspunkt von 46 °C auf. Die Oberflächenspannung, gemessen nach DIN 53914, betrug bei einer Konzentration von 1 g/1 26,8 mN/m.380 g of the alcohol mixture obtained in Example 5 were introduced into a dry 2 l autoclave with 1.5 g of NaOH. The contents of the autoclave were heated to 150 ° C. and 616 g of ethylene oxide were pressed into the autoclave under pressure. After filling the entire amount of ethylene oxide, the autoclave was at 150 ° C for 30 minutes held. After cooling, the reactor discharge was neutralized with sulfuric acid. The surfactant mixture obtained had a cloud point of 46 ° C., measured in accordance with DIN 53917 on a 1% strength solution in water. The surface tension, measured according to DIN 53914, was 26.8 mN / m at a concentration of 1 g / 1.
Beispiel 8Example 8
(Herstellung eines Fettalkoholethoxylates mit 11 mol Ethylenoxid)(Production of a fatty alcohol ethoxylate with 11 mol ethylene oxide)
270 g des in Beispiel 6 erhaltenen Alkoholgemisches wurden mit 1,5 g NaOH in einen trockenen 2-1-Autoklaven eingefüllt. Der Autoklaveninhalt wurde auf 150 °C erhitzt und 726 g Ethylenoxid unter Druck in den Autoklaven gepresst. Nach Einfüllen der gesamten Ethylenoxidmenge wurde der Autoklave noch 30 Minuten bei 150 °C gehalten. Nach dem Abkühlen wurde der Reaktoraustrag mit Schwefelsäure neutralisiert. Das erhaltene Gemisch wies einen nach DIN 53917 an einer l-%igen Lösung in Wasser gemessenen Trübungspunkt von 95,5 °C auf. Die Oberflächenspannung, gemessen nach DIN 53914, bei einer Konzentration von 1 g/1, betrug 31,2 mN/m.270 g of the alcohol mixture obtained in Example 6 were introduced into a dry 2-1 autoclave with 1.5 g of NaOH. The contents of the autoclave were heated to 150 ° C. and 726 g of ethylene oxide were pressed into the autoclave under pressure. After the entire amount of ethylene oxide had been introduced, the autoclave was kept at 150 ° C. for a further 30 minutes. After cooling, the reactor discharge was neutralized with sulfuric acid. The mixture obtained had a cloud point of 95.5 ° C., measured in accordance with DIN 53917 on a 1% strength solution in water. The surface tension, measured according to DIN 53914, at a concentration of 1 g / 1, was 31.2 mN / m.
Beispiel 9Example 9
(Herstellung eines Alkylphosphates )(Preparation of an alkyl phosphate)
360 g des in Beispiel 6 erhaltenen Alkoholgemisches wurden in ei- nem Rührgefäß unter Stickstoffatmosphäre auf 60 °C erwärmt und langsam mit 167 g Polyphosphorsäure versetzt. Dabei wurde eine Temperatur von 65 °C nicht überschritten. Zum Ende der Zugabe wurde die Temperatur auf 70 °C erhöht und der Reaktionsansatz noch eine Stunde bei dieser Temperatur gerührt. Man erhielt ein Ten- sidgemisch mit einer nach DIN 53914 bestimmten Oberflächenspannung von 32,1 mN/m bei einer Konzentration von 1 g/1.360 g of the alcohol mixture obtained in Example 6 were heated to 60 ° C. in a stirred vessel under a nitrogen atmosphere and 167 g of polyphosphoric acid were slowly added. A temperature of 65 ° C was not exceeded. At the end of the addition, the temperature was raised to 70 ° C. and the reaction mixture was stirred at this temperature for another hour. A surfactant mixture was obtained with a surface tension determined according to DIN 53914 of 32.1 mN / m at a concentration of 1 g / 1.
Beispiel 10Example 10
(Herstellung eines Alkyletherphosphates)(Preparation of an alkyl ether phosphate)
490 g des in Beispiel 7 erhaltenen Fettalkoholethoxylates wurden in einem Rührgefäß unter Stickstoffatmosphäre auf 60 °C erwärmt und langsam mit 85 g Polyphosphorsäure versetzt. Dabei wurde eine Temperatur von 65 °C nicht überschritten. Zum Ende der Zugabe wurde die Temperatur auf 70 °C erhöht und der Ansatz noch 1 Stunde bei dieser Temperatur gerührt. Man erhielt ein Tensidgemisch mit einer nach DIN 53914 gemessenen Oberflächenspannung von 35,7 m/ N/m, gemessen bei einer Konzentration von 1 g/1.
490 g of the fatty alcohol ethoxylate obtained in Example 7 were heated to 60 ° C. in a stirred vessel under a nitrogen atmosphere and 85 g of polyphosphoric acid were slowly added. A temperature of 65 ° C was not exceeded. At the end of the addition, the temperature was raised to 70 ° C. and the batch was stirred at this temperature for a further hour. A surfactant mixture was obtained with a surface tension of 35.7 m / N / m, measured according to DIN 53914, measured at a concentration of 1 g / 1.
Claims
1. Verfahren zur Herstellung von Alkoholgemischen, wobei man1. A process for the preparation of alcohol mixtures, wherein one
a) ein Kohlenwasserstoffgemisch, das Cyclopenten und wenigstens ein acyclisches Monoolefin enthält, in einer Metathesereaktion umsetzt,a) reacting a hydrocarbon mixture which contains cyclopentene and at least one acyclic monoolefin in a metathesis reaction,
b) aus dem Reaktionsgemisch der Metathese eine Olefinfraktion isoliert, die im Wesentlichen Olefine mit 8 bis 20 Kohlenstoffatomen enthält,b) an olefin fraction which essentially contains olefins having 8 to 20 carbon atoms is isolated from the reaction mixture of the metathesis,
c) gegebenenfalls die in der Olefinfraktion enthaltenen zwei- oder mehrfach ungesättigten Verbindungen zumindest teilweise einer selektiven Hydrierung zu Monoolefinen unterwirft,c) if appropriate, subjecting the di- or polyunsaturated compounds contained in the olefin fraction at least partially to a selective hydrogenation to monoolefins,
d) die, gegebenenfalls selektiv hydrierte, Olefinfraktion durch Umsetzung mit Kohlenmonoxid und Wasserstoff kataly- tisch hydroformyliert und hydriert.d) the, optionally selectively hydrogenated, olefin fraction is catalytically hydroformylated and hydrogenated by reaction with carbon monoxide and hydrogen.
2. Verfahren nach Anspruch 1, wobei man in Schritt a) ein Kohlenwasserstoffgemisch mit einem Cyclopentengehalt im Bereich von 5 bis 40 Gew.-%, bevorzugt 10 bis 30 Gew.-%, einsetzt.2. The method according to claim 1, wherein in step a) a hydrocarbon mixture with a cyclopentene content in the range of 5 to 40 wt .-%, preferably 10 to 30 wt .-%, is used.
3. Verfahren nach einem der Ansprüche 1 oder 2 , wobei man in Schritt b) eine Olefinfraktion isoliert, die im Wesentlichen Olefine mit 9 bis 18 Kohlenstoffatomen, bevorzugt 10 bis 15 Kohlenstoffatomen, enthält.3. The method according to any one of claims 1 or 2, wherein in step b) an olefin fraction is isolated which essentially contains olefins having 9 to 18 carbon atoms, preferably 10 to 15 carbon atoms.
4. Verfahren nach einem der vorhergehenden Ansprüche, wobei die in Schritt d) eingesetzte Olefinfraktion eine Jodzahl im Bereich von 175 bis 350 g I2/100 g aufweist.4. The method according to any one of the preceding claims, wherein the at in step d) olefin fraction used has a iodine value in the range of 175 to 350 g I 2/100 g.
5. Verfahren nach einem der vorhergehenden Ansprüche, wobei die in Schritt d) eingesetzte Olefinfraktion einen Anteil an unverzweigten Olefinen im Bereich von 10 bis 90 Gew.-%, bevor- zugt 30 bis 70 Gew.-%, aufweist.5. The method according to any one of the preceding claims, wherein the olefin fraction used in step d) has a proportion of unbranched olefins in the range from 10 to 90% by weight, preferably 30 to 70% by weight.
6. Alkoholgemisch, erhältlich durch ein Verfahren nach einem der Ansprüche 1 bis 5. 6. alcohol mixture obtainable by a process according to any one of claims 1 to 5.
7. Alkoholgemisch nach Anspruch 6, das eine OH-Zahl im Bereich von 200 bis 400 mg KOH/g Produkt, bevorzugt 250 bis 350 mg KOH/g, aufweist.7. Alcohol mixture according to claim 6, which has an OH number in the range from 200 to 400 mg KOH / g product, preferably 250 to 350 mg KOH / g.
5 8. Alkoholgemisch nach einem der Ansprüche 6 oder 7, das einen mittleren Verzweigungsgrad im Bereich von 0,5 bis 2,5, bevorzugt 0,7 bis 2,0, aufweist.5 8. Alcohol mixture according to one of claims 6 or 7, which has an average degree of branching in the range of 0.5 to 2.5, preferably 0.7 to 2.0.
9. Verfahren zur Herstellung funktionalisierter Alkoholgemische, 10 wobei man ein Alkoholgemisch nach einem der Ansprüche 6 bis 8 einer Alkoxilierung, Glycosidierung, Sulfatierung, Phosphatierung, Alkoxilierung und nachfolgender Sulfatierung oder Alkoxilierung und nachfolgender Phosphatierung unterwirft.9. A process for the preparation of functionalized alcohol mixtures, wherein an alcohol mixture according to one of claims 6 to 8 is subjected to alkoxylation, glycosidation, sulfation, phosphation, alkoxylation and subsequent sulfation or alkoxylation and subsequent phosphation.
15 10. Funktionalisiertes Alkoholgemisch, erhältlich durch ein Verfahren nach Anspruch 9.15 10. Functionalized alcohol mixture, obtainable by a process according to claim 9.
11. Verwendung der funktionalisierten Alkoholgemische nach Anspruch 10 als Tenside, Dispergiermittel, Papierhilfsmittel, 20 Schmutzlösungsmittel, Korrosionsinhibitoren, Hilfsmittel für Dispersionen, Inkrustierungsinhibitoren.11. Use of the functionalized alcohol mixtures according to claim 10 as surfactants, dispersants, paper auxiliaries, 20 soil solvents, corrosion inhibitors, auxiliaries for dispersions, incrustation inhibitors.
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Applications Claiming Priority (3)
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DE19933828 | 1999-07-20 | ||
DE19933828A DE19933828A1 (en) | 1999-07-20 | 1999-07-20 | Process for the preparation of alcohol mixtures |
PCT/EP2000/006896 WO2001005735A1 (en) | 1999-07-20 | 2000-07-19 | Method for the production of alcohol mixtures |
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EP1196362A1 true EP1196362A1 (en) | 2002-04-17 |
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EP00956211A Withdrawn EP1196362A1 (en) | 1999-07-20 | 2000-07-19 | Method for the production of alcohol mixtures |
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EP (1) | EP1196362A1 (en) |
JP (1) | JP2003505354A (en) |
CN (1) | CN1361757A (en) |
DE (1) | DE19933828A1 (en) |
WO (1) | WO2001005735A1 (en) |
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US7041864B2 (en) | 2002-12-11 | 2006-05-09 | Shell Oil Company | Linear and branched olefin production from cyclic olefin feedstocks |
US10183899B2 (en) | 2016-11-10 | 2019-01-22 | Chevron Phillips Chemical Company Lp | Normal alpha olefin synthesis using metathesis and dehydroformylation |
EP3759063A1 (en) | 2018-02-26 | 2021-01-06 | Bischof, Steven M. | Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation |
US11123723B2 (en) | 2018-02-26 | 2021-09-21 | The Regents Of The University Of California | Oxidative dehydroxymethylation of alcohols to produce olefins |
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CA2261821A1 (en) * | 1996-07-20 | 1998-01-29 | Basf Aktiengesellschaft | Process for preparing alcohols and/or aldehydes from olefins |
DE19629369A1 (en) * | 1996-07-20 | 1998-01-22 | Basf Ag | Alcohol and aldehyde preparation with good selectivity for normal isomers by adding single carbon atom |
DE19654166A1 (en) * | 1996-12-23 | 1998-06-25 | Basf Ag | Mixtures of oligomers derived from cyclopentene, process for their preparation and their use |
DE19654167A1 (en) * | 1996-12-23 | 1998-06-25 | Basf Ag | Functionalized cyclopentene-derived oligomer mixtures, process for their preparation and their use |
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1999
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2000
- 2000-07-19 WO PCT/EP2000/006896 patent/WO2001005735A1/en not_active Application Discontinuation
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WO2001005735A1 (en) | 2001-01-25 |
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