WO2005061447A2 - Verfahren zur herstellung von alkylaryl-verbindungen - Google Patents
Verfahren zur herstellung von alkylaryl-verbindungen Download PDFInfo
- Publication number
- WO2005061447A2 WO2005061447A2 PCT/EP2004/014444 EP2004014444W WO2005061447A2 WO 2005061447 A2 WO2005061447 A2 WO 2005061447A2 EP 2004014444 W EP2004014444 W EP 2004014444W WO 2005061447 A2 WO2005061447 A2 WO 2005061447A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- stage
- olefins
- olefin
- pentene
- catalyst
- Prior art date
Links
- 125000002877 alkyl aryl group Chemical group 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 78
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- -1 alkyl aromatic compounds Chemical class 0.000 claims abstract description 24
- 230000029936 alkylation Effects 0.000 claims abstract description 21
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 21
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 21
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 34
- 238000006471 dimerization reaction Methods 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000006277 sulfonation reaction Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000007792 addition Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000012459 cleaning agent Substances 0.000 claims description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical class CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 7
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- 238000002955 isolation Methods 0.000 abstract 5
- 239000000047 product Substances 0.000 description 25
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 21
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 20
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 235000013844 butane Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- 150000003871 sulfonates Chemical class 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005686 cross metathesis reaction Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910003449 rhenium oxide Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000012013 faujasite Substances 0.000 description 3
- 210000002196 fr. b Anatomy 0.000 description 3
- 210000000540 fraction c Anatomy 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005872 self-metathesis reaction Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 210000003918 fraction a Anatomy 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 description 1
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001481828 Glyptocephalus cynoglossus Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- OMHAAOPPMHUWJP-UHFFFAOYSA-N but-1-ene;but-2-ene;pent-2-ene;prop-1-ene Chemical compound CC=C.CCC=C.CC=CC.CCC=CC OMHAAOPPMHUWJP-UHFFFAOYSA-N 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- IQXNRWWCKRFQNB-UHFFFAOYSA-N but-2-ene;ethene;prop-1-ene Chemical compound C=C.CC=C.CC=CC IQXNRWWCKRFQNB-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000009419 refurbishment Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
- C07C309/31—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups by alkyl groups containing at least three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
- C07C5/2506—Catalytic processes
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
Definitions
- the present invention relates to processes for the preparation of alkylaryl compounds, in particular alkylarylsulfonates, alkyl aryls and alkylarylsulfonates obtainable by the process, the use of the alkylarylsulfonates as surfactants, preferably in washing and cleaning agents, and washing and cleaning agents containing them.
- Alkylbenzenesulfonates have long been used as surfactants in detergents and cleaning agents. After such surfactants based on tetrapropylene were initially used, but were poorly biodegradable, alkylbenzenesulfonates (LAS) which were as linear as possible were subsequently produced and used. However, linear alkylbenzenesulfonates do not have adequate property profiles in all areas of application.
- terminal phenylalkanes (2-phenylalkanes and 3-phenylalkanes)
- internal phenylalkanes (4-, 5-, 6- etc. phenylalkanes) plays a role in the product properties.
- a 2-phenyl content of approximately 30% and a 2- and 3-phenyl content of approximately 50% can be advantageous in terms of product quality (solubility, viscosity, washing properties).
- the process according to the invention has the significant advantage that the combination of metathesis and dimerization with intermediate isomerization of 2-pentene gives a unique olefin mixture which, after alkylation of an aromatic, sulfonation and neutralization, provides a surfactant which is characterized by its Combination of excellent application properties (solubility, viscosity, stability against water hardness, washing properties, biodegradability).
- excellent application properties solubility, viscosity, stability against water hardness, washing properties, biodegradability.
- biodegradability of alkylarylsulfonates compounds which are less strongly adsorbed on sewage sludge than conventional LAS are particularly advantageous.
- WO 99/05241 relates to cleaning agents which contain branched alkylarylsulfonates as surfactants.
- the alkylarylsulfonates are obtained by dimerization of olefins to vinylidene olefins and subsequent alkylation of benzene over a shape-selective catalyst such as MOR or BEA. This is followed by sulfonation.
- WO 02/44114 relates to a process for the preparation of alkylarylsulfonates, in which mono-branched C 1 -C 4 -olefins obtainable by different processes are reacted with an aromatic hydrocarbon in the presence of zeolites of the faujasite type as alkylation catalyst.
- the C 0- ⁇ 4 -olefins can be prepared, for example, by metathesis of a C 4 -olefin mixture, followed by dimerization of the 2-pentene and / or 3-hexene obtained on a dimerization catalyst.
- Alternative methods are extraction, Fischer-Tropsch synthesis, dimerization or isomerization of olefins.
- WO 02/14266 relates to a process for the preparation of alkylarylsulfonates, in which a metathesis of a C 4 -olefin mixture for the preparation of 2-pentene and / or 3-hexene is first carried out and the products are subjected to dimerization. An alkylation then takes place in the presence of an alkylation catalyst, followed by sulfonation and neutralization.
- the olefins hitherto used for alkylation sometimes have too high or too low a degree of branching or do not result in a non-optimal ratio of terminal to internal phenylalkanes.
- DE-A 102 61 481 which is older and not prepublished, relates to a process for the preparation of alkylarylsulfonates by
- step c) sulfonation of the alkyl aromatic compounds obtained in step c) and neutralization to alkylarylsulfonates, 0 to 60% by weight, preferably 0 to 50% by weight, based on the alkyl aromatic compounds obtained in step c), being additionally present before the sulfonation linear alkylbenzenes can be added, provided that no addition has been made in step c),
- the object of the present invention is to provide a process for the preparation of alkylaryl compounds, in particular alkylarylsulfonates, which are at least partially branched and thus have advantageous properties over the known compounds for use in detergents and cleaning agents.
- alkylarylsulfonates should have a suitable property profile from biodegradability, insensitivity to water hardness, solubility and viscosity during manufacture and use.
- the alkylarylsulfonates should be inexpensive to produce.
- Olefin mixture in the presence of a dimerization catalyst to give a mixture containing C 8 i 6 olefins, separation of the C 8 i 6 olefins and, if appropriate, separation of a partial stream thereof,
- these mixtures can advantageously be used in the alkylation of aromatic hydrocarbons, products being obtained which, after sulfonation and neutralization, give surfactants which have outstanding properties, in particular with regard to the sensitivity to hardness-forming ions, the solubility of the sulfonates, the viscosity of the sulfonates and their washing properties.
- the present method is extremely cost-effective since the product streams can be designed so flexibly that no by-products are generated.
- linear internal olefins are produced by the metathesis according to the invention, which are then converted into branched olefins via the dimerization step.
- Step a) of the process according to the invention is the reaction of a C 1 -C 6 ⁇ -olefin mixture over a metathesis catalyst for the production of a C 4-8 -olefin mixture and, if appropriate, separation of C 4-8 olefins.
- the metathesis can be carried out, for example, as described in WO 00/39058 or DE-A-100 13 253.
- homogeneous and heterogeneous transition metal compounds are suitable as metathesis catalysts, in particular those of VI. to VIII. Subgroup of the periodic table of the elements and homogeneous and heterogeneous catalyst systems in which these compounds are contained.
- DE-A-199 32 060 relates to a process for the preparation of C 5 - / C 6 -ofins by reacting an output stream which contains 1-butene, 2-butene and isobutene to give a mixture of C 2-6 -olefins.
- propene in particular is obtained from butenes.
- witches and methylpentene are removed as products.
- No ethene is added in the metathesis.
- ethene formed in the metathesis is returned to the reactor.
- a preferred process for the production of propene and hexene, if appropriate, from a raffinate-II starting stream containing oiefinic C-hydrocarbons is characterized in that
- a metathesis reaction is carried out, in the context of which butenes contained in the input stream with ethene to a mixture containing ethene, propene, butenes, 2-pentene, 3-hexene and butanes are implemented, based on the butenes up to 0.6 molar equivalents of ethene can be used,
- the discharge stream obtained in this way is first separated by distillation into a low boiler fraction A optionally containing C 2 -C 3 olefins and into a high boiler fraction containing C 4 -C 6 olefins and butanes,
- the low boiler fraction A optionally obtained from b) is then separated by distillation into an ethene-containing fraction and a propene-containing fraction, the ethene-containing fraction being returned to process step a) and the propene-containing fraction being discharged as product,
- the high boiler fraction obtained from b) is then separated by distillation into a low boiler fraction B containing butenes and butanes, a medium boiler fraction C containing 2-pentene and a high boiler fraction D containing 3-hexene,
- a) in a step a) the stream C with a metathesis catalyst which contains at least one compound of a metal of VI. b, VII. b or VIII.
- the output current C is subjected to a metathesis reaction using a method as described in EP-A 1069101.
- the metathesis reaction according to step a) is preferably carried out in the presence of heterogeneous metathesis catalysts which are not or only slightly isomerization-active and which are selected from the class of transition metal compounds of metals of VI which are applied to inorganic supports. b, VII. b or VIII. Group of the Periodic Table of the Elements are selected.
- Rhenium oxide on a support preferably on ⁇ -aluminum oxide or on Al 2 O 3 / B 2 O 3 / SiO 2 mixed supports, is preferably used as the metathesis catalyst.
- the catalyst used is Re 2 O 7 / ⁇ -Al 2 O 3 with a rhenium oxide content of 1 to 20% by weight, preferably 3 to 15% by weight, particularly preferably 6 to 12% by weight.
- the metathesis is preferably carried out at a temperature of 0 to 150 ° C., particularly preferably 20 to 80 ° C. and a pressure of 2 to 200 bar, particularly preferably 5 to 30 bar.
- the temperature is preferably 20 to 300 ° C., particularly preferably 50 to 200 ° C.
- the pressure in this case is preferably 1 to 20 bar, particularly preferably 1 to 5 bar.
- Detailed information on the metathesis reaction can again be found in EP-A 1069101.
- the individual streams and fractions may contain or consist of the compounds / olefins mentioned. In the event that they consist of the streams or compounds, the presence of smaller amounts of other hydrocarbons is not excluded.
- the external mass balance of the process can be targeted through variable use of ethene and can be influenced by shifting the equilibrium by returning certain partial flows.
- the 3-hexene yield is increased in that the return of 2-pentene to the metathesis step suppresses the cross-metathesis of 1-butene with 2-butene, so that no or as little as possible 1-butene is consumed here.
- ethene is additionally formed, which reacts in a subsequent reaction with 2-butene to give the valuable product propene.
- Olefin mixtures containing 1-butene and 2-butene and optionally isobutene are obtained as a C 4 fraction in various cracking processes such as steam cracking or FCC cracking.
- butene mixtures such as those obtained in the dehydrogenation of butanes or by dimerization of ethene, can be used.
- Butanes contained in the C 4 fraction are inert.
- dienes, alkynes or enynes are removed using customary methods such as extraction or selective hydrogenation.
- the butene content of the C 4 fraction used in the process is 1 to 100% by weight, preferably 60 to 90% by weight.
- the butene content relates to 1-butene, 2-butene and isobutene.
- a C 4 fraction is preferably used, such as is obtained in steam or FCC cracking or in the dehydrogenation of butane.
- Raffinate II is preferably used as the C 4 fraction, the C stream before the metathesis reaction being freed from disturbing impurities by appropriate treatment on protective adsorber beds, preferably on high-surface area aluminum oxides or molecular sieves.
- step d) the separation into low boiler fraction B, medium boiler fraction C and high boiler fraction D can be carried out, for example, in a dividing wall column.
- the low boiler fraction B is obtained overhead, the medium boiler fraction C via a medium discharge and the high boiler fraction D as the bottom.
- the stream preferably contains 0 to 10 mol% of butenes, 10 to 40% of pentenes, 60 to 80% of hexenes, 5 to 30% of heptenes and 0 to 15% of octenes, particularly preferably 0 to 5 mol% of butenes, 15 to 25% Pentenes, 60 to 75% hexenes, 10 to 30% heptenes and 0 to 10% octenes, the total amount being 100 mol%.
- the metathesis reaction is preferably carried out in the presence of heterogeneous, not or only slightly isomerization-active metathesis catalysts, which belong to the class of transition metal compounds of metals of the VI applied to inorganic supports. b, VII. b or VIII group of the Periodic Table of the Elements are selected.
- Rhenium oxide on a support preferably on ⁇ -aluminum oxide or on, is preferred as the metathesis catalyst used.
- the catalyst used is Re 2 O 7 / ⁇ -Al 2 O 3 with a rhenium oxide content of 1 to 20% by weight, preferably 3 to 15% by weight, particularly preferably 6 to 12% by weight.
- the metathesis is preferably carried out at a temperature of 0 to 150 ° C., particularly preferably 20 to 110 ° C. and a pressure of 2 to 200 bar, particularly preferably 5 to 40 bar.
- the temperature is preferably 20 to 300 ° C., particularly preferably 50 to 200 ° C.
- the pressure in this case is preferably 1 to 20 bar, particularly preferably 1 to 5 bar.
- the protective bed serves to dry the C 4 C 5 stream and to remove substances which can act as a catalyst poison in the subsequent metathesis step.
- the preferred adsorbent materials are Selexsorb CD and CDO as well as 3 ⁇ and NaX molecular sieves (13X). Cleaning takes place in drying towers at temperatures and pressures, which are preferably selected so that all components are in the liquid phase. If necessary, the cleaning step for preheating the feed is used for the subsequent metathesis step. It can be advantageous to combine several cleaning steps with each other or to connect them in series.
- the reaction is complete after 1 s to 1 h, preferably after 30 s to 30 min. It can be carried out continuously or batchwise in reactors, such as pressurized gas vessels, flow tubes or reactive distillation devices, flow tubes being preferred.
- reactors such as pressurized gas vessels, flow tubes or reactive distillation devices, flow tubes being preferred.
- stage b part of the 2-pentene obtained in stage a) is separated off, converted to a mixture of 2-pentene and 1-pentene on an isomerization catalyst, and the mixture thus obtained is returned to stage a).
- the isomerization of 2-pentene to 1-pentene is an equilibrium reaction. Cis-2-pentene, trans-2-pentene and 1-pentene exist side by side in equilibrium. The reaction from 2-pentene to 1-pentene is weakly endothermic, so that an increase in temperature shifts the equilibrium towards 1-pentene.
- the thermodynamic data are listed in D. Stull, "The Chemical Thermodynamics of Organic Compounds", J. Wiley, New York 1969.
- the isomerization preferably takes place at temperatures between 100 and 500 ° C.
- the isomerization catalyst There is no further restriction on the choice of the isomerization catalyst, provided that it is able to effect the intended isomerization.
- basic catalysts or zeolite-based catalysts are used for this purpose, and the isomerization can also be carried out under hydrogenating conditions on contacts containing precious metals.
- EP-A 0 718 036 specifically describes the use of alkaline earth oxides on aluminum oxide as a catalyst.
- DE-A 33 190 99 lists catalysts based on mixed aluminum oxide / silicon oxide supports which are doped with oxides of alkaline earth metals, boron group metals, lanthanides or elements of the iron group.
- EP-A 0 419 630 discloses a catalyst made from polymorphic magnesium / aluminum oxides.
- An alkali-soaked gamma alumina is disclosed in JP 57043055 as a double bond isomerization catalyst.
- An isomerization catalyst consisting of manganese oxide on aluminum oxide can be found in US 4,289,919.
- EP-A ⁇ 234 498 describes an isomerization catalyst composed of magnesium, alkali metal and zirconium oxides dispersed on an aluminum support.
- An alumina catalyst that additionally contains sodium oxide and silicon oxide is taught in US 4,229,610.
- zeolite-based contacts can be found, for example, in EP-A 0 129 899, which teaches the use of zeolites of the pentasil type.
- Mol sieves exchanged with alkali or alkaline earth metals are described in US 3,475,511.
- US 4,749,819 the use of aluminosilicates with an 8 or 10 Ring channel structure mentioned as double bond isomerization catalysts.
- Zeolites in the alkali or alkaline earth form are disclosed in US 4,992,613. Catalysts based on crystalline borosilicates are described in US 4,499,326.
- step c) the C Cs-olefin mixture obtained in step b) is dimerized in the presence of a dimerization catalyst to give a C 8-16 -olefin mixture.
- the dimer-olefin mixtures obtained according to the invention preferably have an average degree of branching in the range from 1 to 2.5, particularly preferably 1 to 2.0, in particular 1 to 1.5 and especially 1 to 1.2.
- the degree of branching of a pure olefin is defined as the number of carbon atoms which are linked to three carbon atoms, plus two times the number of carbon atoms which are linked to 4 carbon atoms.
- the degree of branching of a pure olefin can easily be measured after total hydrogenation to the alkane via 1 H-NMR via the integration of the signals of the methyl groups relative to the methylene and methine protons.
- the degrees of branching are weighted with the molar percentages, and an average degree of branching is thus calculated.
- the molar proportions are optimally determined using gas chromatography.
- the type of branching in the olefin is preferably such that, after hydrogenation, less than 10%, preferably less than 5%, particularly preferably less than 1%, alkanes are obtained which are not methyl, dimethyl or ethyl methyl. and count diethylalkanes. This means that the branches are only methyl and ethyl branches.
- the dimerization is carried out in such a way that the catalysis directly provides the desired advantageous composition in relation to the branching structures.
- C 8 i 6 olefins are formed in the dimerization. From this stream a part of current (the total current from 59 to 99 mol%), preferably separated, preferably containing less than 5 mole% C ⁇ 10, 5 to 15% C 10, 35 to 55% C11 (25 to 45% C 12 , 5 to 15%
- C 3 and ⁇ 5% C> 13 , preferably ⁇ 2 mol% C ⁇ 10 , 5 to 15% C- ⁇ 0l 40 to 50% Cn, 30 to 50% C 12 , 5 to 15% C 13 and ⁇ 2% C > 13 .
- the sum is 100 mol%.
- the stream into the isomerization unit is preferably selected such that> 70%, preferably> 80% product of value according to the composition indicated above results after the isomerization.
- This olefin stream is now used for the alkylation in stage d).
- the C 8-16 olefins obtained are separated off and 5 to 30% by weight, preferably 5 to 20% by weight, in particular up to 10 to 20% by weight, based on the separated C 8 -16-olefins, low-boiling constituents of the C 8- ⁇ 6 olefins are separated.
- the proportion of C denotes 8- ⁇ 6 -Olefingemischs which first merges at a distillation or the lowest boiling point.
- the weight fraction mentioned thus corresponds to the fraction which initially passes over in a distillation and can thus be separated off.
- the separation can also be carried out using any other suitable method. In particular, fractional distillation is carried out.
- the multiply branched olefins are partly or preferably completely separated from the C 8-16 -olefin mixture.
- the removal can also be carried out in such a way that at least 80%, preferably at least 90%, in particular at least 95% of the double or multiple-branched olefins are removed.
- the C 8- ⁇ 6 olefin mixture at the end of step c) so as to leave the linear and mono-branched olefins, and optionally minor proportions of multiply branched olefins.
- Suitable separation methods and analytical methods for determining the content of multiply branched olefins are known to the person skilled in the art.
- dimerization mixture ⁇ 30, preferably ⁇ 10% by weight alkanes and ⁇ 5% by weight. % not - C 8-16 olefins may be included.
- the internal linear pentenes, hexenes, heptenes and octenes contained in the metathesis product are preferably used for the dimerization.
- the dimerization can be carried out homogeneously or heterogeneously.
- the homogeneously catalyzed dimerization can be varied within wide limits with regard to the branching structures.
- Ti, Zr, Cr or Fe systems can be used, for example, which can be modified in a targeted manner using further cocatalysts and ligands.
- the homogeneously catalyzed dimerization is particularly preferably catalyzed with aluminum alkyl AIR 3 in the absence of transition metals. While these ⁇ -olefins selectively convert to vinylidenes under very mild conditions, the corresponding conversion of internal olefins also succeeds under more drastic conditions. Dimers with a high vinylidene content are also formed here. The proportion of double and triple branched isomers is extremely low.
- the AIR 3 -catalyzed dimerization is preferably carried out at temperatures in the range from 150 to 300.degree. C., particularly preferably 180 to 240.degree. C., in particular 210 to 230.degree. C., the catalyst is preferably separated off by distillation at the bottom and returned to the catalysis.
- Combinations of oxides of metals from subgroup VIII with aluminum oxide on support materials made of silicon and titanium oxides, as are known, for example, from DE-A-43 39 713, are advantageously used for heterogeneous catalysis.
- the heterogeneous catalyst can be used in a fixed bed - then preferably in coarse-grained form as 1 to 1.5 mm grit - or suspended (particle size 0.05 to 0.5 mm).
- the dimerization is advantageously carried out in a closed system at temperatures of 80 to 200 ° C., preferably 100 to 180 ° C., under the pressure prevailing at the reaction temperature, optionally also under a protective gas overpressure.
- the reaction mixture is circulated several times, with a certain proportion of the circulating product being continuously discharged and replaced by starting material.
- olefin mixtures obtainable by the above process represent valuable intermediates, in particular for the preparation of branched alkyl aromatics for the preparation of surfactants described below.
- step d) the C 8 -i 6 olefin mixture obtained in step c) is reacted with an aromatic hydrocarbon in the presence of an alkylation catalyst to form alkyl aromatic compounds.
- the C 8 i 6 olefin mixture used in stage d) has an optimal structure / linearity. This means that the degree of branching and the type of branching are optimally selected in order to obtain advantageous alkylaromatic compounds in stage d).
- the setting of the optimal employed in step d) C 8- ⁇ 6 olefin mixture can be carried out by admixing linear olefins. However, higher branched olefins are preferably separated off instead of admixing linear olefins.
- a suitable catalyst is particularly preferably combined with a suitable method to arrive at the optimum -olefin ⁇ 6 C 8 in the dimerization. In this procedure, the desired structures are obtained directly in the alkylation. In this case, the addition of linear olefins and the separation of higher branched olefins can be dispensed with. Combinations of the procedures described are also possible.
- stage c) If a low boiler removal is carried out in stage c), 0 to 60% by weight, preferably 0 to 50% by weight, in particular 0 to 30% by weight, based on the stage, can optionally be used in stage d) c) C 8 to 6 olefin mixtures obtained are added to linear olefins. If linear olefins are added, their amount is at least 1% by weight, preferably at least 5% by weight, in particular at least 10% by weight.
- step c) no low boiler removal is carried out in stage c), in at least one of stages d), e) and f) 5 to 60% by weight, based in each case on the mixtures obtained in the previous step, of the linear compounds.
- additional linear olefins are added in stage d) and / or additional linear alkylbenzenes are added in stage e) and / or additional linear alkylarylsulfonates are added in stage e).
- Linear compounds can thus be added in each of stages c), d) and e), as well as in individual or two of the stages.
- step c) 5 to 60% by weight preferably 10 to 50% by weight, in particular 10 to 30% by weight, based on the C 0- ⁇ 2 -olefin mixtures obtained in step c), can be linear Olefins can be added.
- stages d), e) and f) in total preferably at most 60% by weight, particularly preferably at most 40% by weight, in particular at most 30% by weight, of the linear compounds are added. If this maximum quantity has already been reached by adding one of the stages, linear connections are not added in the other stages.
- the property profile of the alkylarylsulfonates can be adapted to the particular desired field of application and requirement profile in addition to the advantageous synthesis sequence.
- An alkylation catalyst is preferably used, which leads to alkyl aromatic compounds which have one to three carbon atoms in the alkyl radical and an H / C index of 1.
- the alkylation can be carried out in the presence of any alkylation catalysts.
- heterogeneous or shape-selective catalysts offer advantages.
- solid catalysts include, for example, the fluorinated Si / Al catalyst used in the DE-TAL process, a number of shape-selective catalysts or supported metal oxide catalysts, as well as layered silicates and clays.
- the catalyst it is important, regardless of the large influence of the feedstock used, to minimize compounds formed by the catalyst, which are characterized in that they contain carbon atoms with an H / C index of 0 in the alkyl radical.
- compounds are to be formed which have an average of 1 to 3 carbon atoms in the alkyl radical with an H / C index of 1. This can be achieved in particular by selecting suitable catalysts which, on the one hand, suppress the formation of the undesired products due to their geometry and, on the other hand, permit a sufficient reaction rate.
- the alkyl aromatic compounds according to the invention have a characteristic proportion of primary, secondary, tertiary and quaternary carbon atoms in the alkyl radical (side chain). This is reflected in the number of carbon atoms in the alkyl radical with an H / C index from 0 to 3.
- the H / C index defines the number of protons per carbon atom in the alkyl radical.
- the mixtures of alkylaromatic compounds according to the invention preferably have only a small proportion of carbon atoms in the alkyl radical with an H / C index of 0.
- the proportion of carbon atoms in the alkyl radical with an H / C index of 0 on average of all compounds is preferably ⁇ 15%, particularly preferably ⁇ 10%.
- the proportion of carbon atoms in the alkyl radical with an H / C index of 0, which are simultaneously bound to the aromatics is> 80%, preferably> 90%, particularly preferably> 95% of all carbon atoms in the alkyl radical with an H / C index from 0.
- the mixtures of alkylaromatic compounds according to the invention preferably have on average 1 to 3, preferably 1 to 2.5, particularly preferably 1 to 2 carbon atoms in the side chain (ie without counting the aromatic C atoms) with an H / C index of 1 on.
- the proportion of compounds with three carbon atoms of this type is preferably ⁇ 30%, particularly preferably ⁇ 20%, in particular ⁇ 10%.
- the proportion of carbon atoms which have a specific H / C index can be controlled by a suitable choice of the catalyst used.
- Preferred catalysts with which advantageous H / C distributions are achieved are mordenite, ⁇ -zeolite, L-zeolite, MCM-58, MCM-68 and faujasite. Mordenite and faujasite are particularly preferred.
- One-dimensional pore systems usually have the disadvantage of rapid clogging of the pores by degradation or build-up products from the Process on. Catalysts with multidimensional pore systems are therefore preferred.
- the catalysts used can be of natural or synthetic origin, the properties of which can be adjusted to a certain extent by methods known from the literature (e.g. ion exchange, steaming, blocking of acidic centers, washing out of extra-lattice species, etc.). It is important for the present invention that the catalysts are at least partially acidic in character.
- the catalysts are available either as powder or as shaped bodies.
- the connections between the matrices of the shaped bodies ensure adequate mechanical stability, but free access of the molecules to the active constituents of the catalysts must be ensured by means of sufficient porosity of the matrices.
- the production of such moldings is known from the literature and is carried out according to the prior art.
- the alkylation is carried out in such a way that the aromatics (the aromatics mixture) and the olefin (mixture) are allowed to react with the catalyst in a suitable reaction zone by contacting them, the reaction mixture is worked up after the reaction and the valuable products are thus obtained.
- Suitable reaction zones are e.g. Tube reactors or stirred tanks. If the catalyst is in solid form, it can be used either as a slurry, as a fixed bed or as a fluidized bed. Execution as a catalytic distillation is also possible.
- the reactants are either in a liquid and / or in a gaseous state.
- reaction temperature is chosen so that on the one hand the conversion of the olefin is as complete as possible and on the other hand as few by-products as possible are formed.
- the choice of temperature control also depends crucially on the chosen catalyst. Reaction temperatures between 50 ° C and 500 ° C (preferably 80 to 350 ° C, particularly preferably 80-250 ° C) can be used.
- the pressure of the reaction depends on the selected procedure (reactor type) and is between 0.1 and 100 bar, the catalyst load (WHSV) is selected between 0.1 and 100. As a rule, you work at your own pressure (the vapor pressure of the system) or above.
- the reactants can optionally be diluted with inert substances.
- Inert substances are preferred paraffins.
- the molar ratio of aroma olefin is usually set between 1: 1 and 100: 1 (preferably 2: 1-20: 1).
- Ar-R All aromatic hydrocarbons of the formula Ar-R are possible, where Ar is a monocyclic or bicyclic aromatic hydrocarbon radical and R from H, C 1-5 -alkyl, preferably C 1-3 -alkyl, OH, OR etc., preferably H or C- ⁇ -3 alkyl is selected. Benzene and toluene are preferred.
- stage e the alkyl aromatic compounds obtained in stage d) are sulfonated and neutralized to alkylarylsulfonates.
- the alkylaryls are through
- sulfonation for example with SO 3 , oleum, chlorosulfonic acid, etc., preferably with S0 3
- neutralization for example with Na, K, NH 4 , Mg compounds, preferably with Na compounds
- the compounds prepared by the processes described above are either further processed as such, or previously mixed with linear alkylarylene and then sent for further processing.
- Mixtures of alkyl aryl sulfonic acids or alkyl aryl sulfonates can also be used.
- the blends are always made with a view to optimizing the product quality of the surfactants made from the alkylaryl.
- linear alkylbenzenes can also be added before the sulfonation.
- Their amount is 0 to 60% by weight, preferably 0 to 50% by weight, in particular 0 to 30% by weight. If no low boiler removal is carried out in stage c) and no linear compounds are added in stages d) and f), the minimum amount is 5% by weight, preferably 10% by weight. Reference is made to the above explanations regarding the total amount of linear compounds added.
- the chain length of the alkyl radicals preferably corresponds to the chain length of the alkyl radicals as obtained from step c) in the alkylaromatic compounds.
- Linear (C 10 alkyl) benzenes are preferably added to (C 10 alkyl) benzenes, corresponding to linear (C 1 2 alkyl) benzenes corresponding to (C 1 -C 2 alkyl) benzenes.
- alkylation, sulfonation, neutralization is given e.g. "Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties” in Surf. Sci. Ser. 56 (1996) Chapter 2, Marcel Dekker, New York and references contained therein.
- the alkylarylsulfonates contained in stage e) can additionally be mixed with linear alkylarylsulfonates.
- step f) preferably 0 to 60% by weight, particularly preferably 0 to 50% by weight, in particular 0 to 30% by weight, linear alkylarylsulfonates are mixed in.
- the minimum amount is preferably 5% by weight, preferably at least 10% by weight. Reference is made to the preferred total amounts given above for the addition of linear compounds.
- the invention also relates to alkylarylsulfonates which can be obtained by a process as described above.
- alkylarylsulfonates according to the invention are preferably used as surfactants, in particular in detergents and cleaning agents.
- the invention also relates to a washing and cleaning agent containing alkylarylsulfonates, as described above, in addition to conventional ingredients.
- Non-exclusive examples of common ingredients of the washing and cleaning agents according to the invention are e.g. listed in WO 02/44114 and WO 02/14266.
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Abstract
Description
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Priority Applications (4)
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US10/583,140 US20070142258A1 (en) | 2003-12-19 | 2004-12-17 | Method for producing alkylaryl compounds |
CA002544867A CA2544867A1 (en) | 2003-12-19 | 2004-12-17 | Process for the preparation of alkylaryl compounds |
BRPI0417365-1A BRPI0417365A (pt) | 2003-12-19 | 2004-12-17 | proceso para preparação de compostos, compostos, uso dos mesmos, e, agentes de lavagem e de limpeza |
EP04804045A EP1697314A2 (de) | 2003-12-19 | 2004-12-17 | Verfahren zur herstellung von alkylaryl-verbindungen |
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DE10360026.4 | 2003-12-19 | ||
DE10360026A DE10360026A1 (de) | 2003-12-19 | 2003-12-19 | Verfahren zur Herstellung von Alkylaryl-Verbindungen |
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PCT/EP2004/014444 WO2005061447A2 (de) | 2003-12-19 | 2004-12-17 | Verfahren zur herstellung von alkylaryl-verbindungen |
Country Status (11)
Country | Link |
---|---|
US (1) | US20070142258A1 (de) |
EP (1) | EP1697314A2 (de) |
KR (1) | KR20060134966A (de) |
CN (1) | CN1997611A (de) |
BR (1) | BRPI0417365A (de) |
CA (1) | CA2544867A1 (de) |
DE (1) | DE10360026A1 (de) |
MY (1) | MY136695A (de) |
TW (1) | TW200530147A (de) |
WO (1) | WO2005061447A2 (de) |
ZA (1) | ZA200604943B (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009017497A2 (en) * | 2007-07-31 | 2009-02-05 | Chevron Oronite Company Llc | A method of making a synthetic alkylaryl sulfonate |
US7598414B2 (en) * | 2006-06-01 | 2009-10-06 | Chevron Oronite Company Llc | Method of making a synthetic alkylaryl sulfonate |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005041349A1 (de) * | 2005-08-31 | 2007-03-01 | Basf Ag | Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate |
EP2330091A4 (de) * | 2008-08-28 | 2013-02-06 | Mitsui Chemicals Inc | Herstellungsverfahren für olefin |
US9174891B2 (en) * | 2013-06-20 | 2015-11-03 | Uop Llc | Detergent alkylation process for controlling alkylation exotherm with paraffins |
CN104557407B (zh) * | 2013-10-11 | 2017-10-27 | 中国石油化工股份有限公司 | 一种2‑戊烯异构化为1‑戊烯的方法 |
CN108569944B (zh) * | 2017-03-14 | 2021-03-30 | 中国石油化工股份有限公司 | 支链烷基苯的生产方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999005241A1 (en) * | 1997-07-21 | 1999-02-04 | The Procter & Gamble Company | Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof |
WO1999007656A2 (en) * | 1997-08-08 | 1999-02-18 | The Procter & Gamble Company | Improved processes for making surfactants via adsorptive separation and products thereof |
WO2002014266A1 (de) * | 2000-08-11 | 2002-02-21 | Basf Aktiengesellschaft | Verfahren zur herstellung von alkylarylsulfonaten |
WO2002044114A1 (de) * | 2000-11-30 | 2002-06-06 | Basf Aktiengesellschaft | Verfahren zur herstellung von alkylarylsulfonaten |
-
2003
- 2003-12-19 DE DE10360026A patent/DE10360026A1/de not_active Withdrawn
-
2004
- 2004-12-16 MY MYPI20045180A patent/MY136695A/en unknown
- 2004-12-17 WO PCT/EP2004/014444 patent/WO2005061447A2/de not_active Application Discontinuation
- 2004-12-17 US US10/583,140 patent/US20070142258A1/en not_active Abandoned
- 2004-12-17 CA CA002544867A patent/CA2544867A1/en not_active Abandoned
- 2004-12-17 BR BRPI0417365-1A patent/BRPI0417365A/pt not_active IP Right Cessation
- 2004-12-17 CN CNA2004800378132A patent/CN1997611A/zh active Pending
- 2004-12-17 EP EP04804045A patent/EP1697314A2/de not_active Withdrawn
- 2004-12-17 KR KR1020067013610A patent/KR20060134966A/ko not_active Application Discontinuation
- 2004-12-17 TW TW093139445A patent/TW200530147A/zh unknown
-
2006
- 2006-06-15 ZA ZA200604943A patent/ZA200604943B/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999005241A1 (en) * | 1997-07-21 | 1999-02-04 | The Procter & Gamble Company | Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof |
WO1999007656A2 (en) * | 1997-08-08 | 1999-02-18 | The Procter & Gamble Company | Improved processes for making surfactants via adsorptive separation and products thereof |
WO2002014266A1 (de) * | 2000-08-11 | 2002-02-21 | Basf Aktiengesellschaft | Verfahren zur herstellung von alkylarylsulfonaten |
WO2002044114A1 (de) * | 2000-11-30 | 2002-06-06 | Basf Aktiengesellschaft | Verfahren zur herstellung von alkylarylsulfonaten |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7598414B2 (en) * | 2006-06-01 | 2009-10-06 | Chevron Oronite Company Llc | Method of making a synthetic alkylaryl sulfonate |
WO2009017497A2 (en) * | 2007-07-31 | 2009-02-05 | Chevron Oronite Company Llc | A method of making a synthetic alkylaryl sulfonate |
WO2009017497A3 (en) * | 2007-07-31 | 2009-09-17 | Chevron Oronite Company Llc | A method of making a synthetic alkylaryl sulfonate |
Also Published As
Publication number | Publication date |
---|---|
CN1997611A (zh) | 2007-07-11 |
ZA200604943B (en) | 2007-12-27 |
MY136695A (en) | 2008-11-28 |
WO2005061447A3 (de) | 2007-01-04 |
US20070142258A1 (en) | 2007-06-21 |
CA2544867A1 (en) | 2005-07-07 |
BRPI0417365A (pt) | 2007-04-10 |
EP1697314A2 (de) | 2006-09-06 |
TW200530147A (en) | 2005-09-16 |
KR20060134966A (ko) | 2006-12-28 |
DE10360026A1 (de) | 2005-07-21 |
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