US3442964A - Production of detergent alkylate - Google Patents
Production of detergent alkylate Download PDFInfo
- Publication number
- US3442964A US3442964A US425059A US42505965A US3442964A US 3442964 A US3442964 A US 3442964A US 425059 A US425059 A US 425059A US 42505965 A US42505965 A US 42505965A US 3442964 A US3442964 A US 3442964A
- Authority
- US
- United States
- Prior art keywords
- catalyst
- salt
- transition metal
- detergent alkylate
- silica
- 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.)
- Expired - Lifetime
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- 239000003599 detergent Substances 0.000 title description 21
- 238000004519 manufacturing process Methods 0.000 title description 11
- 239000003054 catalyst Substances 0.000 description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 229910052723 transition metal Inorganic materials 0.000 description 21
- 238000005336 cracking Methods 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 20
- 150000001336 alkenes Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 150000003624 transition metals Chemical class 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005804 alkylation reaction Methods 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- 230000029936 alkylation Effects 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- -1 alkylbenzene sulphonate Chemical class 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000005120 petroleum cracking Methods 0.000 description 7
- 230000000447 dimerizing effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000002152 alkylating effect Effects 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 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 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical class [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- NYIQECIYDUSNRC-UHFFFAOYSA-N 1,2,3,5-tetrapropylbenzene Chemical compound CCCC1=CC(CCC)=C(CCC)C(CCC)=C1 NYIQECIYDUSNRC-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- ADOQBZAVKYCFOI-UHFFFAOYSA-N 2-dodecene Chemical compound CCCCCCCCCC=CC ADOQBZAVKYCFOI-UHFFFAOYSA-N 0.000 description 1
- UIIMVYYDGLHIAO-UHFFFAOYSA-N 2-methylnon-2-ene Chemical class CCCCCCC=C(C)C UIIMVYYDGLHIAO-UHFFFAOYSA-N 0.000 description 1
- SMDXUIYTBVHJNX-UHFFFAOYSA-N 2-methylundec-2-ene Chemical class CCCCCCCCC=C(C)C SMDXUIYTBVHJNX-UHFFFAOYSA-N 0.000 description 1
- BNFCIDFHWFDEAB-UHFFFAOYSA-N 3-methylundec-3-ene Chemical class CCCCCCCC=C(C)CC BNFCIDFHWFDEAB-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 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 class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- UXQPRXPNOJXOQO-UHFFFAOYSA-N sulfuric acid;hydrobromide Chemical compound Br.OS(O)(=O)=O UXQPRXPNOJXOQO-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/16—Acids of sulfur; Salts thereof; Sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/14—Silica and magnesia
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to the production of detergent alkylate.
- a process for the production of detergent alkylate comprises dimerising in the liquid phase straight chain monoolefines in the C to C carbon number range in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and a salt of a transition metal, which is heat stable under catalyst activation and regeneration conditions, and alkylating with a fraction of the dimerisation product in the C to C carbon number range an aromatic hydrocarbon in the presence of an alkylation catalyst.
- Benzene is the preferred aromatic hydrocarbon.
- the starting materials for the process of the present invention are straight chain monoolefines having carbon numbers in the range C -C
- the feedstock may be obtained in any suitable manner, for instance as a fraction of the products of thermally cracking a high molecular weight parafi'inic hydrocarbon, preferably after purification of the cracked fraction to remove sulphur compounds, diolefines and acetylenic hydrocarbons.
- Other suitable feedstocks are obtained by polymerisation of lower olefines, especially ethylene, propylene or butene and isolation of a fraction from the polymer consisting of straight chain monoolefines having 5 to 8 carbon atoms. Suitable fractions can also be made by dehydrogenation of C to C normal parafiins.
- the olefineparaffin mixture from the dehydrogenation may be used as feedstock, and unreacted olefine and parafiin recycled in part to the dimerisation and in part to the dehydrogenation.
- the position of the double bond in the molecule is not critical, but the starting material. should not contain an appreciable proportion of branched chain olefines.
- feedstocks not containing substantial amounts of such hydrocarbons particularly if it is desired to recycle monomeric olefine separated from the dimerisation product.
- Small amounts of aromatic hydrocarbons can be tolerated in the feedstock, but the proportion must be small, since these tend to form undesirable alkylated aromatics by reaction with olefine in the feed.
- Aromatic free feedstocks are generally to be preferred. It is preferred to operate at relatively low olefine conversion per pass, and to recycle recovered monomer, since this gives higher yields of the required detergent olefine fraction.
- the flow rate of ethylene may conveniently be between 0.1 and 10 volumes of liquid olefine per volume of catalyst per hour.
- the catalysts which may be used in the process of the invention comprise synthetic cracking catalysts used in the cracking of petroleum and a salt of a transition metal which is heat-stable under catalyst activation and regeneration conditions.
- Typical examples of the cracking catalysts are silica/alumina, silica/magnesia, silica/zirconia, silica/boria, and silica/titania catalysts.
- the preferred cracking catalyst is silica/ alumina, suitably containing from to 90% and preferably about by weight of silica, although the proportion of silica to alumina may vary within moderately wide limits.
- the dimerisation catalyst may be suitably produced by impregnation of the cracking catalyst with a salt of a transition metal which does not decompose on heating with the formation of the oxide or the metal and removal of the acid radical (chloride, bromide sulphate etc.) from combination with the metal.
- Suitable salts include the halides and sulphates of nickel, cobalt, manganese and chromium or mixtures of any of these salts but the fluorides and iodides are less satisfactory. It is particularly preferred to impregnate the cracking catalyst with the chlorides of nickel, cobalt or manganese.
- the impregnation of the cracking catalyst is conveniently carried out with a solution of the transition metal salt in an ionising solvent, such as water.
- the catalyst is then preferably activated initially by heating in inert gas, nitrogen or air to temperatures in the range 350 to 850 C.
- the air or nitrogen used should be dry, and for catalysts impregnated with sulphates the use of air for activation is preferred.
- Transition metal salts may be introduced into the cracking catalyst by other means than impregnation with a solution of a transition metal salt. Mixtures of transition metal sulphide and the cracking catalyst may be heated in the presence of free oxygen to oxidise the sulphide to sulphate. Thus nickel sulphate catalysts may be obtained from cracking catalyst containing nickel sulphide.
- Transition metal halides may be introduced into the cracking by treating synthetic silica/ alumina cracking catalyst comprising a transition metal or a transition metal oxide with a halogenating agent.
- nickel chloride catalysts may be prepared by heating nickel or nickel oxide containing cracking catalysts with chlorine, hydrogen chloride, or ammonium chloride.
- the incorporation of the transition metal salt increases the selectivity of the catalyst for the production of dimers.
- the activity of the catalyst tends to decline with long continued use, owing largely to the deposition of carbon on the catalyst surface, and may be restored in the conventional way, for instance by heating the catalyst in oxygen containing gases to temperatures in the range 300 to 600 C.
- the selectivity of the catalyst for the dimerisation reaction remains at a high level.
- the required C to C olefine fraction is suitably recovered from the dimerisation product by fractional distillation, preferably under reduced pressure.
- the C to C olefines contained in the dimerisation product can be separated and recycled to the dimerisation step since no significant skeletal isomerisation occurs during the-dimerisation.
- the products of the dimerisation step are mostly olefines containing two or more branch chains, with only a small proportion of singly branched or normal olefines, such as n-dodecene. The production of biologically degradable alkylbenzene sulphonates from these products is therefore surprising.
- the recovered C to C olefine fraction is condensed preferably with benzene in the presence of a suitable alkylation catalyst, such as aluminum chloride or anhydrous hydrogen fiuoride.
- a suitable alkylation catalyst such as aluminum chloride or anhydrous hydrogen fiuoride.
- aluminum chloride or anhydrous hydrogen fiuoride is preferred.
- the condensation is suitably carried out in the liquid phase at a temperature in the range of about 20 C. to +100 C.
- the alkylation product after separation of the catalyst, is suitably fractionated to recover unreacted benzene for recycle, a small light alkylate fraction, and a distillate detergent alkylate fraction, leaving a small residue of heavy alkylate.
- Example 1 A silica-alumina cracking catalyst containing 13% by weight of alumina was heated in air at 550 C., allowed to cool and heated with an aqueous solution of nickel chloride. After standing, excess solution was removed from the solid, which was then dried in air at 80 C. to give a product containing nickel chloride equivalent to 2.4% by weight of nickel in the solid. This dried catalyst was charged to a tubular reactor, through which air was passed at 55 C. After this treatment the air was replaced with nitrogen and the catalyst allowed to cool to the reaction temperature.
- a hexene feedstock containing 40% of hexene-l and 60% of hexene-Z plus hexene-3 was then pumped over the catalyst at a temperature of 80-90 C., a pressure of 400 p.s.i.g. and at a rate of 1 liquid volume per volume of catalyst per hour.
- the product was collected and fractionated to recover unpolymerised hexenes and a hexenefree polymer.
- the recovered hexenes amounted to 89.9% of the total liquid product and contained 4% of hexene-l and 96% of hexene-Z plus hexene-3.
- the hexene-free polymer contained 91% of C olefines, the remainder being high polymer (mainly C)
- the catalyst was regenerated by passing a current of air over the catalyst at 550 C., the air then being replaced by nitrogen and the catalyst cooled to reaction temperature.
- a hexene feedstock containing 29% of hexene-l and 71% of hexene2 plus hexene-3 was then processed over the regenerated catalyst under the same conditions as before, the product from this test containing 87.9% of unpolymerised hexenes (again containing 96% hexene-Z plus heXene-3 and 4% of hexenel) and 13.1 wt.
- the C product contained only traces of normal dodecene, less than of methylundecene, and was largely dimethyldecenes, methylethylnonenes and dimethyloctenes.
- the C olefine fraction from this second test was reacted with benzene, using moles of benzene to 1 mole of olefine, with 20 moles of anhydrous hydrogen fluoride as catalyst, this alkylation reaction being carried out at 10l5 C. in the liquid phase.
- the HP catalyst layer was separated and the hydrocarbon layer washed with aqueous potassium hydroxide and water. After drying, the hydrocarbon product was fractionated to separate unreacted benzene, a very small light alkylate fraction, and a distillate detergent alkylate (recovered under reduced pressure) of boiling range 255-2985 C./76O mm. A small residue of heavy alkylate remained.
- the yield of detergent alkylate was 130 parts by weight per 100 parts of this olefine consumed, and this product was 98.3% sulphonatable.
- the sodium salt of the sulphonic acid derived from this detergent alkylate degraded much more rapidly and completely in biological degradation tests than the sulphonate derived from conventional tetrapropylene benzene alkylate.
- Example 2 This example shows the preparation of dimer su1table for the preparation of detergent alkylate and illustrates the operation of the C dimerisation step with three different catalysts, containing nickel, manganese, and cobalt chlorides respectively.
- a silica-alumina cracking catalyst containing 13% of alumina which had been heated in air for 16 hours at 550 C. prior to use was employed as catalyst base.
- This base was impregnated with an aqueous solution of the metallic chloride as described in Example 1 to give in each case 10% by weight of the chloride on the dry catalyst.
- Each of the catalysts was then charged to a tubular reactor and activated by heating in a stream of nitrogen at 450 C. for 16 hours. Hexene-l was then pumped over each catalyst at a temperature of 63 C. in the liquid phase, and the product recovered and separated into unpolymerised C to C and higher polymers. The conversions and yields obtained are shown in the following table.
- the C fraction of the dimerisation product was suitable for condensation with benzene in the presence of an alkylation catalyst to produce detergent alkylate.
- a process for production of C to C olefins having two or more branches which comprises dimerizing in the liquid phase straight chain C to C monoolefins in the presence of -a catalyst comprising a synthetic petroleum cracking catalyst and at least one salt of a transition metal, the salt being heat stable under catalyst activation and regeneration conditions, and recovering the C to C olefins formed.
- the at least one salt of a transition metal is selected from the group consisting of the halides and sulphides of nickel, cobalt, manganese and chromium.
- a process as claimed in claim 2 wherein the salt of a transition metal is nickel chloride.
- a process as claimed in claim 2 wherein the salt of a transition metal is manganese chloride.
- cracking catalyst is selected from the group consisting of silica/ alumina, silica/magnesia, silica/zirconia and silica/boria.
- a process as claimed in claim 1 wherein the cracking catalyst is silica/alumina containing from about -90% by weight of silica.
- dimerisation catalyst is activated by heating in a gas selected from the group consisting of molecular oxygen containing gases and inert gases.
- a process as claimed in claim 1 wherein the dimeri- 5 sation reaction is carried out at a temperature in the range 50 to 100 C.
- a process as claimed in claim 1 wherein the olefine flow rate in the dimerisation reaction is in the range 0.1 to 10 volumes of liquid olefine per volume of catalyst per hour.
- a process for the production of detergent alkylate which is biodegradable upon sulphonation which comprises alkylating an aromatic hydrocarbon in the presence of an alkylation catalyst with an olefin and recovering the detergent alkylate formed
- the olefin is a C to C olefin having two or more branches produced by dimerizing in the liquid phase straight chain C to C monoolefins in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and at least one salt of a transition metal, the salt being heat stable under catalyst activation and regeneration conditions.
- the olefin is a C to C olefin having two or more branches produced by dimerizing in the liquid phase straight chain C to C monoolefins in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and at least one salt of a transition metal selected from the group consisting of nickel, cobalt, manganese and chromium.
- a process for the production of a C olefin having two or more branches from a straight chain hexene feedstock which comprises dimerizing the hexene feedstock in the liquid phase in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and a transition metal salt which is heat stable under catalyst activation and regeneration conditions, and recovering the formed C olefin.
- a process for the production of detergent alkylate which is biodegradable upon sulphonation which comprises alkylating an aromatic hydrocarbon in the presence of an alkylation catalyst with an olefin and recovering the detergent alkylate formed
- the olefin is a C olefin having two or more branches produced by dimerizing straight chain hexene feedstock in the liquid phase in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and a. transition met-a1 salt which is heat stable under catalyst activation and regeneration conditions.
Description
United States Patent 3,442,964 PRODUCTION OF DETERGENT ALKYLATE Wilfred John Oldham, Falkirk, Scotland, assignor, by mesne assignments, to British Hydrocarbon Chemicals Limited, London, England No Drawing. Filed Jan. 12, 1965, Ser. No. 425,059 Claims priority, application Great Britain, Jan. 17, 1964, 2,197/64 Int. Cl. C07c 3/52, 15/00, 143/24 US. Cl. 260671 19 Claims ABSTRACT OF THE DISCLOSURE Detergent alkylates are prepared by the alkylation of aromatic hydrocarbons with C C olefins. The olefins are prepared by dimerizing C -C olefins with a catalyst comprised of a synthetic petroleum cracking catalyst and a stable salt of a transition metal.
The present invention relates to the production of detergent alkylate.
The preparation of detergent alkylate fractions having an alkyl chain length of about C to C which give alkylbenzene sulphonate detergents, which can be readily metabolised by sewage bacteria, has recently assumed considera-ble importance. Hitherto, it has been thought that the use of straight chain alkylbenzenes was necessary to give biologically degradable alkylbenzene sulphonates, in contrast to the conventional highly branched-chain alkylbenzene sulphonates, derived for instance from propylene tetramer.
It has now been discovered that detergent alkylate fractions can be produced, which give biologically degradable alkylbenzene sulphonates, but which do not consist predominantly of straight chain alkylbenzenes.
According to the present invention a process for the production of detergent alkylate comprises dimerising in the liquid phase straight chain monoolefines in the C to C carbon number range in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and a salt of a transition metal, which is heat stable under catalyst activation and regeneration conditions, and alkylating with a fraction of the dimerisation product in the C to C carbon number range an aromatic hydrocarbon in the presence of an alkylation catalyst.
Benzene is the preferred aromatic hydrocarbon.
The starting materials for the process of the present invention are straight chain monoolefines having carbon numbers in the range C -C The feedstock may be obtained in any suitable manner, for instance as a fraction of the products of thermally cracking a high molecular weight parafi'inic hydrocarbon, preferably after purification of the cracked fraction to remove sulphur compounds, diolefines and acetylenic hydrocarbons. Other suitable feedstocks are obtained by polymerisation of lower olefines, especially ethylene, propylene or butene and isolation of a fraction from the polymer consisting of straight chain monoolefines having 5 to 8 carbon atoms. Suitable fractions can also be made by dehydrogenation of C to C normal parafiins. In this case the olefineparaffin mixture from the dehydrogenation may be used as feedstock, and unreacted olefine and parafiin recycled in part to the dimerisation and in part to the dehydrogenation. The position of the double bond in the molecule is not critical, but the starting material. should not contain an appreciable proportion of branched chain olefines. The
presence of saturated hydrocarbons in the feedstock can be tolerated, since these do not materlally affect the dimerisation step; it is however preferred to use feedstocks not containing substantial amounts of such hydrocarbons particularly if it is desired to recycle monomeric olefine separated from the dimerisation product. Small amounts of aromatic hydrocarbons can be tolerated in the feedstock, but the proportion must be small, since these tend to form undesirable alkylated aromatics by reaction with olefine in the feed. Aromatic free feedstocks are generally to be preferred. It is preferred to operate at relatively low olefine conversion per pass, and to recycle recovered monomer, since this gives higher yields of the required detergent olefine fraction. The flow rate of ethylene may conveniently be between 0.1 and 10 volumes of liquid olefine per volume of catalyst per hour.
The catalysts which may be used in the process of the invention comprise synthetic cracking catalysts used in the cracking of petroleum and a salt of a transition metal which is heat-stable under catalyst activation and regeneration conditions. Typical examples of the cracking catalysts are silica/alumina, silica/magnesia, silica/zirconia, silica/boria, and silica/titania catalysts. The preferred cracking catalyst is silica/ alumina, suitably containing from to 90% and preferably about by weight of silica, although the proportion of silica to alumina may vary within moderately wide limits. The dimerisation catalyst may be suitably produced by impregnation of the cracking catalyst with a salt of a transition metal which does not decompose on heating with the formation of the oxide or the metal and removal of the acid radical (chloride, bromide sulphate etc.) from combination with the metal. Suitable salts include the halides and sulphates of nickel, cobalt, manganese and chromium or mixtures of any of these salts but the fluorides and iodides are less satisfactory. It is particularly preferred to impregnate the cracking catalyst with the chlorides of nickel, cobalt or manganese. The impregnation of the cracking catalyst is conveniently carried out with a solution of the transition metal salt in an ionising solvent, such as water. The catalyst is then preferably activated initially by heating in inert gas, nitrogen or air to temperatures in the range 350 to 850 C. The air or nitrogen used should be dry, and for catalysts impregnated with sulphates the use of air for activation is preferred.
Transition metal salts may be introduced into the cracking catalyst by other means than impregnation with a solution of a transition metal salt. Mixtures of transition metal sulphide and the cracking catalyst may be heated in the presence of free oxygen to oxidise the sulphide to sulphate. Thus nickel sulphate catalysts may be obtained from cracking catalyst containing nickel sulphide.
Transition metal halides may be introduced into the cracking by treating synthetic silica/ alumina cracking catalyst comprising a transition metal or a transition metal oxide with a halogenating agent. Thus nickel chloride catalysts may be prepared by heating nickel or nickel oxide containing cracking catalysts with chlorine, hydrogen chloride, or ammonium chloride.
It has been found that the incorporation of the transition metal salt increases the selectivity of the catalyst for the production of dimers. The activity of the catalyst tends to decline with long continued use, owing largely to the deposition of carbon on the catalyst surface, and may be restored in the conventional way, for instance by heating the catalyst in oxygen containing gases to temperatures in the range 300 to 600 C. However, the selectivity of the catalyst for the dimerisation reaction remains at a high level.
The required C to C olefine fraction is suitably recovered from the dimerisation product by fractional distillation, preferably under reduced pressure. The C to C olefines contained in the dimerisation product can be separated and recycled to the dimerisation step since no significant skeletal isomerisation occurs during the-dimerisation. The products of the dimerisation step are mostly olefines containing two or more branch chains, with only a small proportion of singly branched or normal olefines, such as n-dodecene. The production of biologically degradable alkylbenzene sulphonates from these products is therefore surprising.
The recovered C to C olefine fraction is condensed preferably with benzene in the presence of a suitable alkylation catalyst, such as aluminum chloride or anhydrous hydrogen fiuoride. The use of anhydrous hydrogen fluoride is preferred. The condensation is suitably carried out in the liquid phase at a temperature in the range of about 20 C. to +100 C.
The alkylation product, after separation of the catalyst, is suitably fractionated to recover unreacted benzene for recycle, a small light alkylate fraction, and a distillate detergent alkylate fraction, leaving a small residue of heavy alkylate.
Example 1 A silica-alumina cracking catalyst containing 13% by weight of alumina was heated in air at 550 C., allowed to cool and heated with an aqueous solution of nickel chloride. After standing, excess solution was removed from the solid, which was then dried in air at 80 C. to give a product containing nickel chloride equivalent to 2.4% by weight of nickel in the solid. This dried catalyst was charged to a tubular reactor, through which air was passed at 55 C. After this treatment the air was replaced with nitrogen and the catalyst allowed to cool to the reaction temperature.
A hexene feedstock containing 40% of hexene-l and 60% of hexene-Z plus hexene-3 was then pumped over the catalyst at a temperature of 80-90 C., a pressure of 400 p.s.i.g. and at a rate of 1 liquid volume per volume of catalyst per hour. The product was collected and fractionated to recover unpolymerised hexenes and a hexenefree polymer. The recovered hexenes amounted to 89.9% of the total liquid product and contained 4% of hexene-l and 96% of hexene-Z plus hexene-3. The hexene-free polymer contained 91% of C olefines, the remainder being high polymer (mainly C After this reaction the catalyst was regenerated by passing a current of air over the catalyst at 550 C., the air then being replaced by nitrogen and the catalyst cooled to reaction temperature. A hexene feedstock containing 29% of hexene-l and 71% of hexene2 plus hexene-3 was then processed over the regenerated catalyst under the same conditions as before, the product from this test containing 87.9% of unpolymerised hexenes (again containing 96% hexene-Z plus heXene-3 and 4% of hexenel) and 13.1 wt. percent of C and higher olefines, of which 91.5 percent was C olefines. The C product contained only traces of normal dodecene, less than of methylundecene, and was largely dimethyldecenes, methylethylnonenes and dimethyloctenes.
The C olefine fraction from this second test was reacted with benzene, using moles of benzene to 1 mole of olefine, with 20 moles of anhydrous hydrogen fluoride as catalyst, this alkylation reaction being carried out at 10l5 C. in the liquid phase. The HP catalyst layer was separated and the hydrocarbon layer washed with aqueous potassium hydroxide and water. After drying, the hydrocarbon product was fractionated to separate unreacted benzene, a very small light alkylate fraction, and a distillate detergent alkylate (recovered under reduced pressure) of boiling range 255-2985 C./76O mm. A small residue of heavy alkylate remained. The yield of detergent alkylate was 130 parts by weight per 100 parts of this olefine consumed, and this product was 98.3% sulphonatable. The sodium salt of the sulphonic acid derived from this detergent alkylate degraded much more rapidly and completely in biological degradation tests than the sulphonate derived from conventional tetrapropylene benzene alkylate.
Example 2 This example shows the preparation of dimer su1table for the preparation of detergent alkylate and illustrates the operation of the C dimerisation step with three different catalysts, containing nickel, manganese, and cobalt chlorides respectively. A silica-alumina cracking catalyst containing 13% of alumina which had been heated in air for 16 hours at 550 C. prior to use was employed as catalyst base. This base was impregnated with an aqueous solution of the metallic chloride as described in Example 1 to give in each case 10% by weight of the chloride on the dry catalyst. Each of the catalysts was then charged to a tubular reactor and activated by heating in a stream of nitrogen at 450 C. for 16 hours. Hexene-l was then pumped over each catalyst at a temperature of 63 C. in the liquid phase, and the product recovered and separated into unpolymerised C to C and higher polymers. The conversions and yields obtained are shown in the following table.
The C fraction of the dimerisation product was suitable for condensation with benzene in the presence of an alkylation catalyst to produce detergent alkylate.
I claim:
1. A process for production of C to C olefins having two or more branches which comprises dimerizing in the liquid phase straight chain C to C monoolefins in the presence of -a catalyst comprising a synthetic petroleum cracking catalyst and at least one salt of a transition metal, the salt being heat stable under catalyst activation and regeneration conditions, and recovering the C to C olefins formed.
2. A process as claimed in claim 1 wherein the at least one salt of a transition metal is selected from the group consisting of the halides and sulphides of nickel, cobalt, manganese and chromium.
3. A process as claimed in claim 2 wherein the salt of a transition metal is nickel chloride.
4. A process as claimed in claim 2 wherein the salt of a transition metal is manganese chloride.
5. A process as claimed in claim 2 wherein the salt of a transition metal is cobalt chloride.
6. A process as claimed in claim 1 wherein the cracking catalyst is impregnated with a salt of a transition metal by a solution of the salt in an ionising solvent.
7. A process as claimed in claim 6 wherein the cracking catalyst is impregnated with a salt of a transition metal by a solution of the salt in water.
8. A process as claimed in claim 1 wherein the cracking catalyst is selected from the group consisting of silica/ alumina, silica/magnesia, silica/zirconia and silica/boria.
9. A process as claimed in claim 1 wherein the cracking catalyst is silica/alumina containing from about -90% by weight of silica.
10. A process as claimed in claim 1 wherein the dimerisation catalyst is activated by heating in a gas selected from the group consisting of molecular oxygen containing gases and inert gases.
11. A process as claimed in claim 10 wherein the gas is air.
12. A process as claimed in claim 10 wherein the gas is nitrogen.
13. A process as claimed in claim 1 wherein the dimeri- 5 sation reaction is carried out at a temperature in the range 50 to 100 C.
14. A process as claimed in claim 1 wherein the dimerisation reaction is carried out at a pressure in the range 20 to 500 p.s.i.g.
15. A process as claimed in claim 1 wherein the olefine flow rate in the dimerisation reaction is in the range 0.1 to 10 volumes of liquid olefine per volume of catalyst per hour.
'16. In a process for the production of detergent alkylate which is biodegradable upon sulphonation, which comprises alkylating an aromatic hydrocarbon in the presence of an alkylation catalyst with an olefin and recovering the detergent alkylate formed, the improvement wherein the olefin is a C to C olefin having two or more branches produced by dimerizing in the liquid phase straight chain C to C monoolefins in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and at least one salt of a transition metal, the salt being heat stable under catalyst activation and regeneration conditions.
17. In a process for the production of detergent alkylate which is biodegradable upon sulphonation, which comprises alkylating an aromatic hydrocarbon in the presence of an alkylation catalyst with an olefin and recovering the detergent alkylate formed, the improve ment wherein the olefin is a C to C olefin having two or more branches produced by dimerizing in the liquid phase straight chain C to C monoolefins in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and at least one salt of a transition metal selected from the group consisting of nickel, cobalt, manganese and chromium.
18. A process for the production of a C olefin having two or more branches from a straight chain hexene feedstock which comprises dimerizing the hexene feedstock in the liquid phase in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and a transition metal salt which is heat stable under catalyst activation and regeneration conditions, and recovering the formed C olefin.
-19. In a process for the production of detergent alkylate which is biodegradable upon sulphonation, which comprises alkylating an aromatic hydrocarbon in the presence of an alkylation catalyst with an olefin and recovering the detergent alkylate formed, the improvement wherein the olefin is a C olefin having two or more branches produced by dimerizing straight chain hexene feedstock in the liquid phase in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and a. transition met-a1 salt which is heat stable under catalyst activation and regeneration conditions.
References Cited UNITED STATES PATENTS 3,196,174 7/1965 Cohen 260-671 XR 3,3 17,628 5/1967 Schuck et a1 260683.15 3,351,654 11/1967 Gudelis 260671 XR 2,718,526 9/1955 Mammen 260-671 X 3,109,869 11/1963 Chambers et a1. 260671 X 3,214,462 10/1965 Swenson et a1. 260671 X 3,238,249 3/1966 Mirviss et al. 260-671 X FOREIGN PATENTS 852,079 10/ 1960 Great Britain.
910,540 1 1/ 1962 Great Britain.
913,795 12/ 1962 Great Britain.
DELBERT E. GANTZ, Primary Examiner.
CURTIS R. DAVIS, Assistant Examiner.
US. Cl X.R. 260-505, 683.15
Applications Claiming Priority (1)
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GB2197/64A GB1078572A (en) | 1964-01-17 | 1964-01-17 | Improvements relating to the production of detergent alkylate |
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US5012020A (en) * | 1989-05-01 | 1991-04-30 | Mobil Oil Corporation | Novel VI enhancing compositions and Newtonian lube blends |
US5015795A (en) * | 1989-02-21 | 1991-05-14 | Mobil Oil Corporation | Novel synthetic lube composition and process |
US5026948A (en) * | 1989-02-21 | 1991-06-25 | Mobil Oil Corporation | Disproportionation of alpha-olefin dimer to liquid lubricant basestock |
US5132478A (en) * | 1989-01-06 | 1992-07-21 | Mobil Oil Corporation | Alkylaromatic lubricant fluids |
US5132477A (en) * | 1991-04-29 | 1992-07-21 | Mobil Oil Corporation | Process for producing alkylaromatic lubricant fluids |
US5171915A (en) * | 1989-02-21 | 1992-12-15 | Mobil Oil Corporation | Alkylaromatic lubricants from alpha-olefin dimer |
US5254274A (en) * | 1989-01-06 | 1993-10-19 | Mobil Oil Corporation | Alkylaromatic lubricant fluids |
WO1999005244A1 (en) * | 1997-07-21 | 1999-02-04 | The Procter & Gamble Company | Improved alkyl aryl sulfonate surfactants |
US6274540B1 (en) | 1997-07-21 | 2001-08-14 | The Procter & Gamble Company | Detergent compositions containing mixtures of crystallinity-disrupted surfactants |
AU737736B2 (en) * | 1997-07-21 | 2001-08-30 | Procter & Gamble Company, The | Improved alkylbenzenesulfonate surfactants |
US6303556B1 (en) | 1999-01-20 | 2001-10-16 | The Procter & Gamble Company | Hard surface cleaning compositions comprising modified alkybenzene sulfonates |
US6342473B1 (en) | 1999-01-20 | 2002-01-29 | The Procter & Gamble Company | Hard surface cleaning compositions comprising modified alkylbenzene sulfonates |
WO2002014266A1 (en) * | 2000-08-11 | 2002-02-21 | Basf Aktiengesellschaft | Method for producing alkyl aryl sulphonates |
US6498134B1 (en) | 1999-01-20 | 2002-12-24 | The Procter & Gamble Company | Dishwashing compositions containing alkylbenzenesulfonate surfactants |
US6514926B1 (en) | 1998-10-20 | 2003-02-04 | The Procter & Gamble Company | Laundry detergents comprising modified alkylbenzene sulfonates |
US6525233B1 (en) | 1997-08-08 | 2003-02-25 | The Procter & Gamble Company | Process for preparing a modified alkylaryl |
US6566319B1 (en) | 1997-07-21 | 2003-05-20 | The Procter & Gamble Company | Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof |
US6583096B1 (en) | 1998-10-20 | 2003-06-24 | The Procter & Gamble Company | Laundry detergents comprising modified alkylbenzene sulfonates |
US6602840B1 (en) | 1997-07-21 | 2003-08-05 | The Procter & Gamble Company | Processes for making alkylbenzenesulfonate surfactants and products thereof |
US6774099B1 (en) | 1999-01-20 | 2004-08-10 | The Procter & Gamble Company | Dishwashing detergent compositions containing mixtures or crystallinity-disrupted surfactants |
US20040254411A1 (en) * | 2001-10-01 | 2004-12-16 | Ulrich Steinbrenner | Method for producing alkylaryl compounds and sulfonates thereof |
US7202205B1 (en) | 1999-09-01 | 2007-04-10 | Daniel Stedman Connor | Processes for making surfactants via adsorptive separation and products thereof |
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Also Published As
Publication number | Publication date |
---|---|
FR1429340A (en) | 1966-02-25 |
DE1518527A1 (en) | 1969-04-10 |
NL6500287A (en) | 1965-07-19 |
BE658263A (en) | 1965-07-13 |
GB1078572A (en) | 1967-08-09 |
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