EP0239320B1 - Liquid fuel compositions - Google Patents
Liquid fuel compositions Download PDFInfo
- Publication number
- EP0239320B1 EP0239320B1 EP87302351A EP87302351A EP0239320B1 EP 0239320 B1 EP0239320 B1 EP 0239320B1 EP 87302351 A EP87302351 A EP 87302351A EP 87302351 A EP87302351 A EP 87302351A EP 0239320 B1 EP0239320 B1 EP 0239320B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuel
- alkanes
- weight
- gas oil
- wax
- 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
- 239000000446 fuel Substances 0.000 title claims description 77
- 239000000203 mixture Substances 0.000 title claims description 37
- 239000007788 liquid Substances 0.000 title claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- JXTPJDDICSTXJX-UHFFFAOYSA-N triacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 description 37
- 239000001993 wax Substances 0.000 description 33
- 230000000996 additive effect Effects 0.000 description 28
- 239000003921 oil Substances 0.000 description 20
- -1 palmityl alcohol ester Chemical class 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000005673 monoalkenes Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 3
- 101100352919 Caenorhabditis elegans ppm-2 gene Proteins 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 101100020663 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) ppm-1 gene Proteins 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- HMSWAIKSFDFLKN-UHFFFAOYSA-N hexacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC HMSWAIKSFDFLKN-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- KUPLEGDPSCCPJI-UHFFFAOYSA-N tetracontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC KUPLEGDPSCCPJI-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- QKUNKVYPGIOQNP-UHFFFAOYSA-N 4,8,11,14,17,21-hexachlorotetracosane Chemical compound CCCC(Cl)CCCC(Cl)CCC(Cl)CCC(Cl)CCC(Cl)CCCC(Cl)CCC QKUNKVYPGIOQNP-UHFFFAOYSA-N 0.000 description 1
- JDOZUYVDIAKODH-SNAWJCMRSA-N 4-o-ethyl 1-o-methyl (e)-but-2-enedioate Chemical compound CCOC(=O)\C=C\C(=O)OC JDOZUYVDIAKODH-SNAWJCMRSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 101100016994 Caenorhabditis elegans hgo-1 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class 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
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical class OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000193603 Percalates novemaculeata Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- HEJZJSIRBLOWPD-WCWDXBQESA-N didodecyl (e)-but-2-enedioate Chemical compound CCCCCCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCCCCCC HEJZJSIRBLOWPD-WCWDXBQESA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- FNMTVMWFISHPEV-WAYWQWQTSA-N dipropan-2-yl (z)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C/C(=O)OC(C)C FNMTVMWFISHPEV-WAYWQWQTSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-UHFFFAOYSA-N 0.000 description 1
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- 239000012188 paraffin wax 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
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- 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
- C10L1/16—Hydrocarbons
-
- 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
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
-
- 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
- C10L1/16—Hydrocarbons
- C10L1/1691—Hydrocarbons petroleum waxes, mineral waxes; paraffines; alkylation products; Friedel-Crafts condensation products; petroleum resins; modified waxes (oxidised)
-
- 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
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- 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
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
-
- 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
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
-
- 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
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
-
- 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
- This invention relates to distillate fuel compositions containing a flow improver.
- Heating oils and other distillate petroleum fuels e.g. diesel fuels
- the lowest temperature at which the fuel will still flow is generally known as the pour point.
- Effective wax crystal modification (as measured by CFPP and other operability tests, as well as simulated and field performance) can be achieved by flow improvers, mostly ethylene-vinyl acetate copolymer (EVA) based, in distillates containing up to 4 wt%-n-alkanes at 10°C below cloud point, as determined by gravimetric or DSC methods. Additive response in these distillates is normally stimulated by the refiner adjusting ASTM D-86 distillation characteristics of the distillates to increase the tail 90% to Final Boiling Point to deltas between 20°C and 25°C.
- EVA ethylene-vinyl acetate copolymer
- US-A-3640691 proposes that the response of the same types of middle distillate to similar additives may be improved by the addition of a paraffinic distillate fraction containing normal alkanes higher than n-hexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
- a paraffinic distillate fraction containing normal alkanes higher than n-hexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
- a paraffinic distillate fraction containing normal alkanes higher than n-hexacosane and as high as n-tetracontane to provide from 0.1 to 2 wt.% of normal alkanes of C24 and higher.
- the most difficult to treat are those fuels obtained from high wax crudes such as those from the crudes in Australia and the Far East where the total n-alkane content of the distillate can be greater than 20%, the total content being C12 and higher n-alkanes as measured by Gas Liquid Chromatography.
- a middle distillate responsive to flow improvers may be obtained by adjusting the total wax content of the fuel to between 5.5 and 12 wt.%, preferably by blending of high and low wax content fuels, the wax content being that precipitated with methyl ethyl ketone from 1 gram of the fuel at -20°C.
- This technique is not a satisfactory indication of the wax content of the fuel to be treated by the additives since it is the wax precipitated between the cloud point of the fuel and its operability point which is treated by the additive and which is important to the low temperature characteristics of the fuel.
- the ability of these fuels to respond to flow improvers is not dependent on the total wax content of the fuel.
- a typical hard to treat distillate fuel containing 5 to 10 wt.% wax at 10°C below its cloud point and/or greater than 20 wt.% n-alkanes C12+ has the following ASTM D-86 characteristics: Initial Boiling Point 212°C 5% 234°C 10% 243°C 20% 255°C 30% 263°C 40% 279°C 50% 288°C 60% 298°C 70% 303°C 80% 321°C 90% 334°C 95% 343°C Final Boiling Point 361°C
- a liquid fuel composition comprises a major proportion by weight of a distillate fuel containing between 4 and 10 wt.% wax at 10°C below cloud point and having a narrow n-alkane distribution, i.e. containing substantially no paraffins longer than n-triacontane (C30), a low temperature flow improver at 0.001 to 2.0 wt.% based on the weight of the distillate fuel and added n-alkanes which provide C24 and higher alkanes in a proportion greater than 0.35 wt.% of the fuel.
- Also according to this invention is the use as a cold flow improver for a distillate fuel containing between 4 and 10 wt.% of wax at 10°C below cloud point and having a narrow carbon distribution, i.e. containing substantially no paraffins longer than n-triacontane (C30), of a mixture of a distillate fuel low temperature flow improver and added n-alkanes whose C24 and higher is greater than 0.35 wt.% of the weight of the fuel.
- n-triacontane C30
- the flow improvers that are employed in this invention may be any of those generally available although we prefer to use the type comprising copolymers of ethylene and at least one second unsaturated monomer.
- the second unsaturated monomer can be another monoolefin, e.g. a C3 to C18 alpha-monoolefin or it can be an unsaturated ester, as for example, vinyl acetate, vinyl butyrate, vinyl propionate, lauryl methacrylate, ethyl acrylate or the like.
- the second monomer can also be a mixture of an unsaturated mono or diester and a branched or straight chain alpha monoolefin.
- copolymers can also be used, as for example mixtures of a copolymer of ethylene and vinyl acetate with an alkylated polystyrene or with an acylated polystyrene.
- Alternative materials are the amino succinic acid derivatives, esters such as polyacrylates and esterified maleic anhydride copolymers, polyalpha olefins, etc.
- the preferred distillate fuel flow improver useful in this invention is a copolymer consisting of 1 to 40, and preferably 1 to 20, more preferably 3 to 20 molar proportions of ethylene per molar proportion of the ethylenically unsaturated monomer, which latter monomer can be a single monomer or a mixture of such monomers in any proportion, said polymer being oil soluble and having a number average molecular weight in the range of about 1,000 to 50,000, preferably about 1,000 to about 5,000.
- Molecular weights can be measured by cryoscopic methods or by vapor phase osmometry, for example by using a Mechrolab Vapor Phase Osmometer Model 310A.
- the unsaturated monomers which may be homopolymerised or copolymerised with ethylene or with each other include unsaturated acids, acid anhydrides, and mono and diesters of the general formula: wherein R1 is hydrogen or methyl; R3 is a -OOCR4 or -COOR4 group wherein R4 is hydrogen or a C1 to C16, preferably C1 to C4 straight or branched chain alkyl group and R3 is hydrogen or -COOR4.
- the monomer when R1 to R3 are hydrogen and R2 is -OOCR4,includes vinyl alcohol esters of C2 to C17 monocarboxylic acids.
- esters examples include vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate, vinyl palmitate, etc.
- R2 is -COOR4
- esters include C8 oxo alcohol acrylate, methyl acrylate, methyl methacrylate, lauryl acrylate, isobutyl methacrylate, palmityl alcohol ester of alpha-methacylic acid, C13 oxo alcohol esters of methacrylic acid, etc.
- Examples of monomers wherein R1 is hydrogen and R2 and R3 are -OOCR4 groups include mono C12 oxo alcohol fumarate, di-isopropyl maleate; di-lauryl fumarate; ethyl methyl fumarate; fumaric acid, maleic acid,etc, or where R2 is H and R1 is COOR4 and R3 is CH2 COOR4 such as the itaconates.
- Other unsaturated monomers copolymerizable with ethylene to prepare pour point depressants or flow improvers useful in this invention include C3 to C16 branched chain or straight-chain alpha monoolefins, as for example, propylene, n-octene-1, 2-ethyl decene-1, n-decene-1, etc.
- a C2 to C16 branched or straight-chain alpha monoolefin e.g. propylene, n-octene-1, n-decene-1, etc.
- copolymers of 3 to 40 moles of ethylene with one mole of a mixture of 30 to 99 mole percent of unsaturated ester and 70 to 1 mole percent of olefin could be used.
- copolymers that are formed are random copolymers consisting primarily of an ethylene polymer backbone along which are distributed side chains of hydrocarbon or oxy-substituted hydrocarbon.
- the alcohols used in preparing the esters mentioned above are isomeric mixtures of branched chain aliphatic primary alcohols prepared from olefins, such as polymers and copolymers of C3 to C4 monoolefins, reacted with carbon monoxide and hydrogen in the presence of a cobalt-containing catalyst such as cobalt carbonyl, at temperatures of about 300°F to 400°F (about 150°C to 205°C), under pressures of about 1,000 to 3,000 p.s.i. (about 70 to 210 bar) to form aldehydes.
- the resulting aldenyde product is then hydrogenated to form the alcohol, the latter being recovered by distillation from the hydrogenated product.
- the copolymers have a low degree of side chain branching; particularly they contain less than 10,preferably less than 8,methyl terminated side chains (other than the ester groups) per 100 methylene groups as measured by nuclear magnetic resonance, particularly 500 megahertz proton NMR analysis.
- the flow improver is used in a concentration in the range of from about 0.001 to about 2 wt.%, preferably from about 0.005 to about 0.2 percent by weight, based on the weight of the distillate fuel being treated.
- the second additive provides the n-alkanes greater than C24 and preferably has a carbon number distribution from about 20 to about 40.
- the additive consist predominantly of linear alkanes although it may also contain a small amount of branched hydrocarbons.
- the additive may be in the form of a refinery stream such as a heavy atmospheric gas oil, vacuum gas oil or heavy cracked gas oil which provides alkanes having carbon numbers in the required range. It is believed that the additive nucleates the crystallisation of the n-alkanes in the fuel and also co-crystallises with the first n-alkanes to precipitate from the fuel.
- the preferred n-alkane distribution of the additive therefore depends upon the particular fuel. Whilst the C24 and higher n-alkane component should be greater than 0.35 wt.% based on the fuel we prefer that it be greater than 0.5 wt.%.
- additives may also be used to give further improvements in low temperature properties, for example a diamide or preferably a half amide, half amine salt of a dicarboxylic acid or anhydride such as phthalic anhydride, and a secondary amine, the alkyl groups preferably containing 12 to 20 carbon atoms,may be added.
- a particularly preferred compound is the half amide, half amine salt of phthalic acid and dihydrogenated tallow amine - Armeen 2HT (approx. 4 wt.% n-C14 alkyl, 30 wt.% n-C16 alkyl, 60 wt.% n-C18 alkyl, the remainder being unsaturated).
- the amount of diamide or half amide, half amine salt which is added is usually 0.001 to 2 wt.%, preferably 0.005 to 0.2 wt.%, based on the weight of distillate fuel.
- glycol esters such as those defined in our EP-B-0 061 895 and the esters and amines of maleic anhydride copolymers such as those defined in EP-A-0214786, and polyolefines and chlorinated polyolefines and the amines or amides of alkyl succinic anhydrides.
- the cold flow properties of the distillate fuel can be further improved by adding thereto a wax-naphthalene condensate.
- a typical condensate is prepared by chlorinating a wax containing n- and branched C18 to C39 paraffins (C26 average) to obtain a chlorinated wax containing about 15 weight % chlorine.
- the chlorowax thus obtained is polymerised with naphthalene via an alkylation reaction to give a condensate containing alternating wax and naphthalene units.
- the amount of condensate added is usually 0.00005 to 0.1 wt.% based on the weight of the distillate fuel.
- the additives of the present invention may be supplied as concentrates for incorporation into the bulk fuel , such a concentrate comprising a solution containing from 30 to 70 wt.% ,preferably 40 to 60 wt.% ,of a mixture of copolymer of ethylene and another ethylenically unsaturated monomer and the n-alkane composition.
- n-alkane distributions of the fuel and the vacuum gas oil were Fuel VGO C12 0.71 C13 1.08 C14 1.80 C15 2.59 C16 2.25 C18 2.53 0.40 C19 2.37 0.81 C20 2.19 1.81 C21 2.12 2.59 C22 1.70 3.74 C23 0.97 4.39 C24 0.43 4.29 C25 0.18 3.94 C26 0.08 3.24 C27 0.03 2.36 C28 0.02 1.95 C29 0.01 1.02 C30 0.003 0.73 C31 0.44 C32 0.26 C33 0.15 C34 0.14 C35 0.09 C36 0.03 C37 0.05 C38 0.02
- the base fuel contained 23.40 wt.% of n-alkanes of C12 and higher.
- CFPPT cold filter plugging point test
- VGO vacuum gas oil
- composition of the components was:
- the base fuel contained 27.3 wt.% of alkanes C12 and higher.
- the CFPP response to the following additives was as follows: Amount of Additive Blend 1 Blend 2 Blend 3 Additive 4 Additive 5 Additive 4 Additive 5 Additive 4 Additive 5 0 ppm -1 -1 5 5 -3 -3 500 ppm -1 -1 2 -2 -3 -3 1000 ppm -2 -2 -1 -9 -3 -3 1500 ppm -2 -2 -1 -10 -3 -3 -3
- the base fuel contained 32 wt.% of alkanes C12 and higher.
- This example illustrates the improvement in response to flow improvers by replacing heavy atmospheric gas oil (HGO) with heavy cracked gas oil (HCO), Base Fuel 1 had a cloud point of -1°C and use Fuel 2 of -2°C.
- HGO heavy atmospheric gas oil
- HCO heavy cracked gas oil
- the Base Fuel 1 contained 22.8 wt.% n-alkanes C12 and higher and Base Fuel 2 27.6 wt.%.
- the quantities of additive specified are the actual amounts of polymer.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB868606656A GB8606656D0 (en) | 1986-03-18 | 1986-03-18 | Fuel oil compositions |
GB8609293 | 1986-04-16 | ||
GB868609293A GB8609293D0 (en) | 1986-03-18 | 1986-04-16 | Liquid fuel compositions |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0239320A2 EP0239320A2 (en) | 1987-09-30 |
EP0239320A3 EP0239320A3 (en) | 1988-01-13 |
EP0239320B1 true EP0239320B1 (en) | 1993-12-29 |
Family
ID=26290507
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87302351A Expired - Lifetime EP0239320B1 (en) | 1986-03-18 | 1987-03-18 | Liquid fuel compositions |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0239320B1 (ko) |
JP (1) | JP2514199B2 (ko) |
KR (1) | KR950009004B1 (ko) |
CN (1) | CN1024014C (ko) |
AU (1) | AU590827B2 (ko) |
DE (1) | DE3788585T2 (ko) |
ES (1) | ES2048157T3 (ko) |
GB (1) | GB8609293D0 (ko) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8618397D0 (en) * | 1986-07-29 | 1986-09-03 | Exxon Chemical Patents Inc | Liquid fuel compositions |
JPH01103698A (ja) * | 1987-07-28 | 1989-04-20 | Sumitomo Chem Co Ltd | 燃料油組成物 |
JPH01103699A (ja) * | 1987-07-28 | 1989-04-20 | Sumitomo Chem Co Ltd | 燃料油組成物 |
GB9504222D0 (en) * | 1995-03-02 | 1995-04-19 | Exxon Chemical Patents Inc | Fuel oil compositions |
GB9725581D0 (en) | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Additives and oil compositions |
GB9725578D0 (en) | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Oil additives and compositions |
GB9725579D0 (en) | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Additives and oil compositions |
US6136050A (en) * | 1998-06-22 | 2000-10-24 | Tonen Corporation | Diesel fuel oil composition |
US8053614B2 (en) | 2005-12-12 | 2011-11-08 | Neste Oil Oyj | Base oil |
US7998339B2 (en) | 2005-12-12 | 2011-08-16 | Neste Oil Oyj | Process for producing a hydrocarbon component |
EP2078743A1 (en) | 2008-01-10 | 2009-07-15 | Shell Internationale Researchmaatschappij B.V. | Fuel composition |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1264638A (ko) * | 1968-09-17 | 1972-02-23 | ||
US3640691A (en) * | 1968-09-17 | 1972-02-08 | Exxon Research Engineering Co | Enhancing low-temperature flow properties of fuel oil |
US3620696A (en) * | 1968-09-17 | 1971-11-16 | Exxon Research Engineering Co | Fuel oil with improved flow properties |
US3733184A (en) * | 1971-02-09 | 1973-05-15 | Exxon Co | Composition for improving air-fuel ratio distribution in internal combustion engines |
US4153423A (en) * | 1975-03-28 | 1979-05-08 | Exxon Research & Engineering Co. | Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties |
US4464182A (en) * | 1981-03-31 | 1984-08-07 | Exxon Research & Engineering Co. | Glycol ester flow improver additive for distillate fuels |
JPS57207696A (en) * | 1981-06-17 | 1982-12-20 | Nippon Sekiyu Seisei Kk | Diesel gas oil composition |
JPS6035396A (ja) * | 1984-06-15 | 1985-02-23 | Nec Corp | 半導体メモリ装置の駆動方法 |
-
1986
- 1986-04-16 GB GB868609293A patent/GB8609293D0/en active Pending
-
1987
- 1987-03-17 CN CN87102962A patent/CN1024014C/zh not_active Expired - Fee Related
- 1987-03-18 EP EP87302351A patent/EP0239320B1/en not_active Expired - Lifetime
- 1987-03-18 ES ES87302351T patent/ES2048157T3/es not_active Expired - Lifetime
- 1987-03-18 DE DE87302351T patent/DE3788585T2/de not_active Expired - Fee Related
- 1987-03-18 KR KR1019870002443A patent/KR950009004B1/ko not_active IP Right Cessation
- 1987-03-18 AU AU70141/87A patent/AU590827B2/en not_active Ceased
- 1987-03-18 JP JP62063639A patent/JP2514199B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2514199B2 (ja) | 1996-07-10 |
ES2048157T3 (es) | 1994-03-16 |
EP0239320A3 (en) | 1988-01-13 |
EP0239320A2 (en) | 1987-09-30 |
AU590827B2 (en) | 1989-11-16 |
KR950009004B1 (ko) | 1995-08-10 |
CN1024014C (zh) | 1994-03-16 |
CN87102962A (zh) | 1987-12-16 |
AU7014187A (en) | 1987-09-24 |
KR870008998A (ko) | 1987-10-22 |
DE3788585T2 (de) | 1994-04-28 |
DE3788585D1 (de) | 1994-02-10 |
GB8609293D0 (en) | 1986-05-21 |
JPS62270687A (ja) | 1987-11-25 |
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