EP0931824B1 - Verfahren zur Verbesserung der Kaltfliesseigenschaften von Brennstoffölen - Google Patents
Verfahren zur Verbesserung der Kaltfliesseigenschaften von Brennstoffölen Download PDFInfo
- Publication number
- EP0931824B1 EP0931824B1 EP98124678A EP98124678A EP0931824B1 EP 0931824 B1 EP0931824 B1 EP 0931824B1 EP 98124678 A EP98124678 A EP 98124678A EP 98124678 A EP98124678 A EP 98124678A EP 0931824 B1 EP0931824 B1 EP 0931824B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- weight
- copolymer
- vinyl esters
- formula
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000295 fuel oil Substances 0.000 title claims description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 40
- 239000000654 additive Substances 0.000 claims abstract description 38
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 229920001897 terpolymer Polymers 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 239000002480 mineral oil Substances 0.000 claims description 26
- 239000012188 paraffin wax Substances 0.000 claims description 17
- -1 alkyl methacrylates Chemical class 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 235000010446 mineral oil Nutrition 0.000 claims description 11
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- 229940042472 mineral oil Drugs 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 8
- 125000005396 acrylic acid ester group Chemical group 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 229920006163 vinyl copolymer Polymers 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 36
- 238000009835 boiling Methods 0.000 description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- PSABUFWDVWCFDP-UHFFFAOYSA-N 2,2-dimethylheptane Chemical compound CCCCCC(C)(C)C PSABUFWDVWCFDP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- PCVAKFVNCSPYNN-UHFFFAOYSA-N 9:0(8Me,8Me) Chemical compound CC(C)(C)CCCCCCC(O)=O PCVAKFVNCSPYNN-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RPSNJDZBVKLBES-UHFFFAOYSA-N CC(=O)OC=C.CC(C)(C)CCCCCC(O)=O Chemical compound CC(=O)OC=C.CC(C)(C)CCCCCC(O)=O RPSNJDZBVKLBES-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- QLBNZADBIKYTKU-UHFFFAOYSA-N carbonic acid;3-(2-ethylhexylperoxymethyl)heptane Chemical compound OC(O)=O.CCCCC(CC)COOCC(CC)CCCC QLBNZADBIKYTKU-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
Definitions
- the present invention relates to a method for improving the Cold flow properties of mineral oils and mineral oil distillates, while simultaneously the filterability of the oils is maintained, an additive for improving the Cold flow properties and fuel oils containing the additives.
- Crude oils and middle distillates obtained by the distillation of crude oils such as gas oil, Diesel oil or fuel oil
- Crude oils and middle distillates obtained by the distillation of crude oils contain different depending on the origin of the crude oils
- Amounts of n-paraffins the platelet-shaped when the temperature is lowered Crystals crystallize and partially agglomerate with the inclusion of oil. This leads to a deterioration of the flow properties of these oils Distillates, whereby, for example, in extraction, transport, storage and / or use of mineral oils and mineral oil distillates may occur.
- this crystallization phenomenon can occur during transport Pipelines, especially in winter to deposits on the pipe walls, in Individual cases, e.g. at standstill of a pipeline, even to its complete blockage to lead.
- the flow and cold behavior of mineral oils and mineral oil distillates is through Specification of the cloud point (determined according to ISO 3015), the pour point (determined according to ISO 3016) and the Cold Filter Plugging Point (CFPP, determined according to EN 116) described. These parameters are measured in ° C.
- Typical flow improvers for crude oils and middle distillates are copolymers of Ethylenes with carboxylic acid esters of vinyl alcohol. How to set after the DE-A-11 4 799 petroleum distillate fuels having a boiling point between about 120 and 400 ° C oil-soluble copolymers of ethylene and Vinyl acetate having a molecular weight of between about 1,000 and 3,000. Preference is given to copolymers which contain about 60 to 99 wt .-% of ethylene and about 1 to 40 wt .-% vinyl acetate. They are especially effective when they pass through radical polymerization in an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2100 atm were made (DE-A-19 14 756).
- EP-A-0 493 769 discloses terpolymers consisting of ethylene, vinyl acetate and neononane or vinyl neodecanoate, and their use as Additives for mineral oil distillates.
- DE-A-22 06 719 discloses mixtures of ethylene-vinyl acetate copolymers with different Comonomerwitz to improve the cold flow behavior of middle distillates.
- DE-A-20 37 673 discloses synergistic mixtures of ethylene-vinyl ester copolymers different molecular weights as flow improvers.
- EP-A-0 254 284 discloses blends of ethylene / vinyl acetate copolymers with Ethylene / vinyl acetate / diisobutylene terpolymers as flow improvers for mineral oils and mineral oil distillates.
- EP-A-0 648 257 discloses blends of at least 2 ethylene / vinyl ester copolymers, where the vinyl esters of carboxylic acids with 2 to 7 Derive carbon atoms.
- EP-B-0 648 258 discloses ternary mixtures of ethylene / vinyl ester copolymers, wherein one of the blend components is between 7.5 and 35 and% of the vinyl ester comonomer and another of the mixture components below 10 mol% of Contains vinyl ester comonomers.
- EP-A-0 113 581 discloses blends of two ethylene / vinyl ester copolymers, in the vinyl esters derived from carboxylic acids of 1 to 4 carbon atoms is.
- One of the copolymers is a paraffin crystal nucleating agent, while the other Copolymer is a growth inhibitor.
- EP-A-0 741 181 discloses blends of two copolymers, one of which at least one vinyl ester having alkyl or alkenyl radicals with more than 4 Contains carbon atoms as comonomers.
- EP-A-0 648 256 discloses ethylene-vinyl ester copolymers as cold flow improvers for mineral oils.
- the vinyl esters carry acid residues of C 1 to C 28 , and their molar content of the copolymer is less than 11%.
- WO-96/34073 discloses an additive as a cold flow improver for mineral oils, 10 ° C under Cloud Point have a wax content of less than 2 wt .-%.
- the Additive comprises a copolymer of ethylene and an unsaturated vinyl ester except Vinyl acetate, wherein the molar ratio of the vinyl ester is greater than 10%.
- EP-A-0 649 456 discloses copolymers of ethylene and esters of unsaturated Alcohols with which the cold flow behavior of oils with a wax content of more than 2.5 wt .-% can be improved.
- EP-A-0 706 306 discloses additives for stabilizing CFPP in middle distillates. These additives contain mixtures of copolymers and terpolymers of ethylene and Vinylestern. A disadvantage of the mixtures proposed there is the proportion of highly crystalline polymer fractions, especially at low oil and / or Additive temperatures during additivation The filterability of the additized oils above the cloud point.
- the data in% by weight relate to the total weight of the mixture of A) and B).
- Another object of the invention is a fuel oil, which defined above Composition of A and B contains.
- the mixture of the copolymers from 20 to 40 wt .-% of Components A) and 60 to 80 wt .-% of component B).
- Preferred vinyl esters for component B) are vinyl acetate, vinyl propionate, Vinylhexanoate, vinyl laurate and vinyl esters of neocarboxylic acids, here in particular of neononan, neodecane and neoundecanoic acid.
- Preferred acrylic acid esters are acrylic acid alkyl esters with alcohol radicals from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as methyl acrylate, Ethyl acrylate and 2-ethylhexyl acrylate.
- R 1 and R 2 are preferably hydrogen.
- R 3 preferably denotes a neoalkyl radical having 7 to 11 carbon atoms, in particular a neoalkyl radical having 8, 9 or 10 carbon atoms.
- the neoalkyl acids from which the abovementioned neoalkyl radicals can be derived are described by the formula 4:
- the vinyl ester used for the copolymerization therefore has the formula 5:
- Copolymer A) preferably contains 5 to 10 mol%, in particular 7 to 10 mol% of the structural units of the formula 2.
- Copolymer B) is preferably an ethylene copolymer with a Comonomer content of 10 to 20 mol%, preferably 13 to 18 mol%.
- suitable Comonomers are vinyl esters of aliphatic carboxylic acids having 2 to 15 carbon atoms, see above in that B) in particular an ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, Ethylene-vinyl acetate-neononanoic acid vinyl ester copolymer or a Ethylene-vinyl acetate-neodecanoic acid vinyl ester terpolymer.
- Comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and norbornene. Particularly preferred are ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers.
- the copolymers used in the invention are by the usual Copolymerization processes such as suspension polymerization, Solution polymerization, gas phase polymerization or High pressure mass polymerization can be produced.
- Preferred is the High-pressure bulk polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350 ° C, in particular 100 to 250 ° C.
- the reaction of the monomers is by radicals forming initiators (radical chain starter) initiated.
- radicals forming initiators radical chain starter
- Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl per-maleate, t-butyl perbenzoate, Dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile).
- the initiators are individually or as a mixture of two or more substances in amounts of from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.
- components A and B have melt viscosities at 140 ° C of 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
- component A has a higher by at least 100 mPas Melt viscosity as component B.
- the desired melt viscosity of Blends are made by selecting the individual components and varying the Blend ratio of the copolymers set.
- copolymers mentioned under A) and B) may contain up to 5% by weight of further comonomers.
- Such comonomers may be, for example, vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C 1 to C 20 alkyl radicals, isobutylene and higher olefins having at least 5 carbon atoms.
- Preferred higher olefins are hexene, isobutylene, 4-methylpentene, octene and / or diisobutylene.
- High pressure bulk polymerization is used in known high pressure reactors, e.g. Autoclaves or tube reactors, discontinuous or continuous, Tube reactors have proven particularly useful.
- Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene may be included in the reaction mixture.
- the solvent-free operation is the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and above supplied to one or more side branches.
- the monomer streams be composed differently (EP-A-0 271 738).
- the mixtures of components A and B are mineral oils or Mineral oil distillates added in the form of solutions or dispersions. These Solutions or dispersions preferably contain 1 to 90, in particular 5 to 80% by weight of the mixtures.
- Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, pentadecane, Toluene, xylene, ethylbenzene or commercial solvent mixtures such as solvent Naphtha, ®Shellsoll AB, ® Solvesso 150, ® Solvesso 200, ®Exxsol-, ®ISOPAR- and ®Shellsol D types.
- the specified solvent mixtures contain different amounts of aliphatic and / or aromatic Hydrocarbons.
- the aliphatics can be straight chain (n-paraffins) or branched his (iso-paraffins).
- Aromatic hydrocarbons can mono-, di- or be polycyclic and optionally carry one or more substituents.
- the Mixtures also together with one or more oil-soluble co-additives already used by itself the cold flow properties of crude oils, Improve lubricating oils or fuel oils.
- oil-soluble co-additives are polar Compounds which cause a paraffin dispersion (paraffin dispersants), as well as comb polymers.
- Paraffin dispersants reduce the size of the paraffin crystals and cause The paraffin particles do not settle, but colloidly with significantly reduced Sedimentation tendency, remain dispersed.
- paraffin dispersants have become oil-soluble polar compounds having ionic or polar groups, e.g. amine salts and / or amides obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained (U.S. 4,211,534).
- paraffin dispersants are copolymers of the Maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols are reacted can (EP-A-0 154 177), the reaction products of Alkenylspirobislactonen with Amines (EP-A-0 413 279) and according to EP-A-0 606 055 reaction products of Terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkenyl ether of lower unsaturated Alcohols.
- Alkylphenol-formaldehyde resins are also known as paraffin dispersants suitable.
- Comb polymers are polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. Preferably, they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30% of the monomers have side chains (compare Comb-like Polymers - Structure and Properties, NA Platé and VP Shibaev, J. Polym, Sci Macromolecular Revs 1974, 8, 117 ff).
- Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf., EP-A-0 153 176), copolymers of a C 6 -C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide (cf. A-0 320 766), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
- fumarate / vinyl acetate copolymers cf., EP-A-0 153 176
- copolymers of a C 6 -C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide cf. A-0 320 766
- further esterified olefin / maleic anhydride copolymers polymers and cop
- the mixing ratio (in parts by weight) of the mixtures according to the invention with paraffin dispersants and / or comb polymers is in each case from 1:10 to 20: 1, preferably 1: 1 to 10: 1.
- middle distillates are particularly well suited.
- Middle distillates are referred to in particular those mineral oils by Crude oil distillation and boiling in the range of 120 to 400 ° C, such as kerosene, jet fuel, diesel and heating oil.
- the invention Fuels preferably contain less than 350 ppm and especially less than 200 ppm sulfur.
- Their content of n-paraffins, the chain lengths, determined with GC of 18 carbon atoms or more, is at least 8 area%, preferably at more than 10 area%.
- EP-A-0 796 306 Compared to the nearest state of the Technology, in particular to EP-A-0 796 306, has the advantage of inventive method in an improved solubility of the additives, so that the filterability of the oils additivated with them even at low Blending temperatures of oil and / or additive is maintained. Furthermore the mixtures of the invention show pronounced synergistic effects compared to the individual components in CFPP subsidence.
- the mixtures according to the invention can be used alone or together with other additives are used, for example with Dewaxing aids, corrosion inhibitors, antioxidants, lubricity additives, Dehazem, conductivity improver, cetane improver or Sludge inhibitors.
- the determination of the boiling characteristics is carried out in accordance with ASTM D-86, the determination of the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015.
- the paraffin content is determined by gas chromatographic separation of the oil (detection by FiD) and calculation of the integral of the n paraffins ⁇ C 18 in relation to the total integral. As an approximation, this area integral of n-paraffins ⁇ C 18 is equated with wt% n-paraffins ⁇ C 18 in relation to the total integral.
- Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Test oil 6 Initial boiling point 180 ° C 169 ° C 183 ° C 183 ° C 184 ° C 182 ° C 20% 267 ° C 255 ° C 226 ° C 232 ° C 258 ° C 243 ° C 90% 350 ° C 350 ° C 330 ° C 358 ° C 329 ° C 351 ° C 95% 365 ° C 364 ° C 347 ° C 378 ° C 344 ° C 366 ° C Cloud point -0.4 ° C -1 ° C -9 ° C + 4 ° C -5 ° C -3 ° C CFPP -3 ° C -3 ° C -12 -4 ° C -9 ° C -6 ° C (90-20)% 83 ° C 95 ° C 104 ° C 126 ° C 71 ° C 108 ° C n-paraffins ⁇ C 18 /
- the CFPP value of the oil additized with the specified amount of flow improver was measured immediately after the additization and the remainder of the sample at -3 ° C, So stored below the cloud point. At weekly intervals, the Samples heated to 12 ° C, 50 ml taken for a new CFPP measurement and the remainder stored at -3 ° C on.
- the dosage rate in test oil 1 was 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A1 + B1 (1: 5) -12 -12 -10 -10 -11 A1 + B2 (1: 3) -13 -16 -12 -15 -14 A2 + B2 (1: 3) -10 -12 -10 -13 -13 A3 + B2 (1: 3) -9 -11 -12 -12 -12 A4 + B1 (1: 4) -12 -13 -11 -12 -10 A5 + B3 (1: 4) -12 -13 -13 -10 -11 B1 (comparison) -10 -4 -5 -3 -4 B2 (comparison) -11 -7 -5 -4 -5 B3 (comparison) -10 -9 -7 -7 -5
- Test Oil 2 The dosage rate in Test Oil 2 is 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A5 + B3 (1: 4) -13 -14 -15 -11 -12 A1 + B2 (1: 5) -11 -13 -13 -12 -12 B2 (comparison) -10 -9 -7 -8th -5 B3 (comparison) -10 -9 -6 -6 -5
- An ADT value ⁇ 15 is considered as an indication that the gas oil is satisfactorily usable in "normal" cold weather. Products with ADT values> 25 are referred to as non-filterable. Solubility of the additives ADT Blank value (without additive) 3.0 A5 + B3 (1: 4) 9.4 A1 + B2 (1: 5) 4.8 A1 + B1 (1: 1) 13.3 A2 + B2 (1: 3) 5.2 B2 (comparison) 5.4 B2 + 4% EVA copolymer with 13.5% by weight of vinyl acetate (according to WO 97/17905) 60 B2 + 10% EVA copolymer with 13.5% by weight of vinyl acetate (according to WO 97/17905) not filterable (115 ml in 20 minutes)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Lubrication Of Internal Combustion Engines (AREA)
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19802690A DE19802690C2 (de) | 1998-01-24 | 1998-01-24 | Additiv zur Verbesserung der Kaltfließeigenschaften von Brennstoffölen |
DE19802690 | 1998-01-24 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0931824A2 EP0931824A2 (de) | 1999-07-28 |
EP0931824A3 EP0931824A3 (de) | 1999-09-15 |
EP0931824B1 true EP0931824B1 (de) | 2005-08-31 |
Family
ID=7855580
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP98124678A Expired - Lifetime EP0931824B1 (de) | 1998-01-24 | 1998-12-24 | Verfahren zur Verbesserung der Kaltfliesseigenschaften von Brennstoffölen |
Country Status (8)
Country | Link |
---|---|
US (1) | US6110238A (no) |
EP (1) | EP0931824B1 (no) |
JP (1) | JP4370011B2 (no) |
AT (1) | ATE303426T1 (no) |
CA (1) | CA2260169C (no) |
DE (2) | DE19802690C2 (no) |
ES (1) | ES2248874T3 (no) |
NO (1) | NO990293L (no) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19729057A1 (de) * | 1997-07-08 | 1999-01-14 | Clariant Gmbh | Copolymere auf Basis von Ethylen und ungesättigten Carbonsäureestern und ihre Verwendung als Mineralöladditive |
DE19754555A1 (de) * | 1997-12-09 | 1999-06-24 | Clariant Gmbh | Verfahren zur Herstellung von Ethylen-Mischpolymerisaten und deren Verwendung als Zusatz zu Mineralöl und Mineralöldestillaten |
DE10012267B4 (de) | 2000-03-14 | 2005-12-15 | Clariant Gmbh | Copolymermischungen und ihre Verwendung als Additiv zur Verbesserung der Kaltfließeigenschaften von Mitteldestillaten |
DE10012269C2 (de) * | 2000-03-14 | 2003-05-15 | Clariant Gmbh | Verwendung von Copolymermischungen als Additiv zur Verbesserung der Kaltfließeigenschaften von Mitteldestillaten |
WO2002090470A1 (fr) * | 2001-05-08 | 2002-11-14 | Sanyo Chemical Industries, Ltd. | Agent fluidifiant et composition de mazout |
DE10208326B4 (de) * | 2002-02-27 | 2008-06-19 | Innospec Deutschland Gmbh | Additive für flüssige Kraftstoffe |
DE10245737C5 (de) * | 2002-10-01 | 2011-12-08 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur Herstellung von Additivmischungen für Mineralöle und Mineralöldestillate |
DE10260714A1 (de) * | 2002-12-23 | 2004-07-08 | Clariant Gmbh | Brennstofföle mit verbesserten Kälteeigenschaften |
DE102006022720B4 (de) * | 2006-05-16 | 2008-10-02 | Clariant International Limited | Kaltfließverbesserer für pflanzliche oder tierische Brennstofföle |
FR2947558B1 (fr) | 2009-07-03 | 2011-08-19 | Total Raffinage Marketing | Terpolymere et ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles |
AU2018404213A1 (en) | 2018-01-25 | 2020-08-13 | Petróleo Brasileiro S.A. - Petrobras | Auxiliary system and method for starting or restarting the flow of gelled fluid |
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US3048479A (en) * | 1959-08-03 | 1962-08-07 | Exxon Research Engineering Co | Ethylene-vinyl ester pour depressant for middle distillates |
DE1914756C3 (de) * | 1968-04-01 | 1985-05-15 | Exxon Research and Engineering Co., Linden, N.J. | Verwendung von Ethylen-Vinylacetat- Mischpolymerisaten für Erdöl-Destillate |
DE2037673C2 (de) * | 1970-07-16 | 1985-07-04 | Exxon Research and Engineering Co., Linden, N.J. | Polymerisatgemische als Fließpunktverbesserer für Kohlenwasserstoffe und deren Verwendung |
US3961916A (en) * | 1972-02-08 | 1976-06-08 | Exxon Research And Engineering Company | Middle distillate compositions with improved filterability and process therefor |
US4211534A (en) * | 1978-05-25 | 1980-07-08 | Exxon Research & Engineering Co. | Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils |
GB8300016D0 (en) * | 1983-01-04 | 1983-02-09 | Exxon Research Engineering Co | Middle distillate compositions |
DE3405843A1 (de) * | 1984-02-17 | 1985-08-29 | Bayer Ag, 5090 Leverkusen | Copolymere auf basis von maleinsaeureanhydrid und (alpha), (beta)-ungesaettigten verbindungen, ein verfahren zu ihrer herstellung und ihre verwendung als paraffininhibitoren |
EP0153177B1 (en) * | 1984-02-21 | 1991-11-06 | Exxon Research And Engineering Company | Middle distillate compositions with improved low temperature properties |
DE3625174A1 (de) * | 1986-07-25 | 1988-01-28 | Ruhrchemie Ag | Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten |
DE3640613A1 (de) * | 1986-11-27 | 1988-06-09 | Ruhrchemie Ag | Verfahren zur herstellung von ethylen-mischpolymerisaten und deren verwendung als zusatz zu mineraloel und mineraloelfraktionen |
DE3742630A1 (de) * | 1987-12-16 | 1989-06-29 | Hoechst Ag | Polymermischungen fuer die verbesserung der fliessfaehigkeit von mineraloeldestillaten in der kaelte |
DE3926992A1 (de) * | 1989-08-16 | 1991-02-21 | Hoechst Ag | Verwendung von umsetzungsprodukten von alkenylspirobislactonen und aminen als paraffindispergatoren |
DE4042206A1 (de) * | 1990-12-29 | 1992-07-02 | Hoechst Ag | Terpolymerisate des ethylens, ihre herstellung und ihre verwendung als additive fuer mineraloeldestillate |
US5718734A (en) * | 1992-06-30 | 1998-02-17 | Exxon Chemical Patents Inc. | Oil additives and compositions |
GB9213870D0 (en) * | 1992-06-30 | 1992-08-12 | Exxon Chemical Patents Inc | Oil additives and compositions |
GB9213854D0 (en) * | 1992-06-30 | 1992-08-12 | Exxon Chemical Patents Inc | Additives and fuel compositions |
GB9213904D0 (en) * | 1992-06-30 | 1992-08-12 | Exxon Chemical Patents Inc | Oil additives and compositions |
GB9213909D0 (en) * | 1992-06-30 | 1992-08-12 | Exxon Chemical Patents Inc | Oil additives and compositions |
DK0606055T3 (da) * | 1993-01-06 | 1998-04-14 | Clariant Gmbh | Terpolymerer på basis af alfa,beta-umættede dicarboxylsyreanhydrider, alfa-beta-umættede forbindelser og polyoxyalkylenethere af lavere umættede alkoholer |
GB9417670D0 (en) * | 1994-09-02 | 1994-10-19 | Exxon Chemical Patents Inc | Oil additives, compositions and polymers for use therein |
GB9424565D0 (en) * | 1994-12-06 | 1995-01-25 | Exxon Chemical Patents Inc | Fuel oil compositions |
CA2182993C (en) * | 1994-12-13 | 2001-08-07 | Brian William Davies | Fuel oil compositions |
GB9508644D0 (en) * | 1995-04-28 | 1995-06-14 | Exxon Chemical Patents Inc | Fuel compositions |
DE19620118C1 (de) * | 1996-05-18 | 1997-10-23 | Hoechst Ag | Terpolymerisate des Ethylens, ihre Herstellung und ihre Verwendung als Additive für Mineralöldestillate |
DE19620119C1 (de) * | 1996-05-18 | 1997-10-23 | Hoechst Ag | Terpolymerisate des Ethylens, ihre Herstellung und ihre Verwendung als Additive für Mineralöldestillate |
DE19729055C2 (de) * | 1997-07-08 | 2000-07-27 | Clariant Gmbh | Brennstofföle auf Basis von Mitteldestillaten und Copolymeren aus Ethylen und ungesättigten Carbonsäureestern |
DE19758887A1 (de) * | 1997-07-08 | 2006-10-19 | Clariant Gmbh | Fließverbesserer für Mineralöle |
-
1998
- 1998-01-24 DE DE19802690A patent/DE19802690C2/de not_active Expired - Fee Related
- 1998-12-24 AT AT98124678T patent/ATE303426T1/de not_active IP Right Cessation
- 1998-12-24 ES ES98124678T patent/ES2248874T3/es not_active Expired - Lifetime
- 1998-12-24 EP EP98124678A patent/EP0931824B1/de not_active Expired - Lifetime
- 1998-12-24 DE DE59813030T patent/DE59813030D1/de not_active Expired - Lifetime
-
1999
- 1999-01-22 CA CA002260169A patent/CA2260169C/en not_active Expired - Lifetime
- 1999-01-22 JP JP01479699A patent/JP4370011B2/ja not_active Expired - Lifetime
- 1999-01-22 NO NO990293A patent/NO990293L/no not_active Application Discontinuation
- 1999-01-22 US US09/235,723 patent/US6110238A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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ATE303426T1 (de) | 2005-09-15 |
ES2248874T3 (es) | 2006-03-16 |
DE19802690A1 (de) | 1999-07-29 |
CA2260169A1 (en) | 1999-07-24 |
JPH11256171A (ja) | 1999-09-21 |
DE19802690C2 (de) | 2003-02-20 |
JP4370011B2 (ja) | 2009-11-25 |
EP0931824A3 (de) | 1999-09-15 |
US6110238A (en) | 2000-08-29 |
NO990293L (no) | 1999-07-26 |
DE59813030D1 (de) | 2005-10-06 |
CA2260169C (en) | 2008-09-16 |
NO990293D0 (no) | 1999-01-22 |
EP0931824A2 (de) | 1999-07-28 |
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