NO167757B - DISTILLATE PETROLEUM FUEL AND APPLICATION OF POLYMERS AND COPOLYMERS AS ADDITIVES FOR DISTILLATE FUELS. - Google Patents
DISTILLATE PETROLEUM FUEL AND APPLICATION OF POLYMERS AND COPOLYMERS AS ADDITIVES FOR DISTILLATE FUELS. Download PDFInfo
- Publication number
- NO167757B NO167757B NO854527A NO854527A NO167757B NO 167757 B NO167757 B NO 167757B NO 854527 A NO854527 A NO 854527A NO 854527 A NO854527 A NO 854527A NO 167757 B NO167757 B NO 167757B
- Authority
- NO
- Norway
- Prior art keywords
- ester
- ethylenically unsaturated
- polyoxyalkylene
- distillate
- use according
- Prior art date
Links
- 239000000654 additive Substances 0.000 title claims abstract description 76
- 239000000446 fuel Substances 0.000 title claims abstract description 61
- 229920001577 copolymer Polymers 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 239000003208 petroleum Substances 0.000 title claims description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- -1 fumarate ester Chemical class 0.000 claims description 21
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 17
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 229920001567 vinyl ester resin Polymers 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 239000001530 fumaric acid Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 description 35
- 229920001223 polyethylene glycol Polymers 0.000 description 20
- 239000003921 oil Substances 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 17
- 239000002202 Polyethylene glycol Substances 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 235000021357 Behenic acid Nutrition 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 238000002103 osmometry Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IIPCXIGUIPAGQB-OUKQBFOZSA-N (e)-4-dodecoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCCCCCCCOC(=O)\C=C\C(O)=O IIPCXIGUIPAGQB-OUKQBFOZSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DSGHFMUQANVHSK-UHFFFAOYSA-N C(C=CC(=O)OCCCCCCCCCCCCCCCC)(=O)OCCCCCCCCCCCC Chemical compound C(C=CC(=O)OCCCCCCCCCCCCCCCC)(=O)OCCCCCCCCCCCC DSGHFMUQANVHSK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 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
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 1
- 229940116224 behenate Drugs 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YZFOGXKZTWZVFN-UHFFFAOYSA-N cyclopentane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1 YZFOGXKZTWZVFN-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- NXQIBFMKDQPBGW-QNEJGDQOSA-N dihexadecyl (e)-but-2-enedioate Chemical compound CCCCCCCCCCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCCCCCCCCCC NXQIBFMKDQPBGW-QNEJGDQOSA-N 0.000 description 1
- 230000000694 effects Effects 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
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- YHPLDIMIJCPNBP-UHFFFAOYSA-N n-methyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCNC YHPLDIMIJCPNBP-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin 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
-
- 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
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
-
- 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
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- 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
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Abstract
Description
Foreliggende oppfinnelse vedrører destillatpetroleumsbrennstoff og anvendelse av polymerer og kopolymerer som additiver for destillatbrennstoffer. The present invention relates to distillate petroleum fuel and the use of polymers and copolymers as additives for distillate fuels.
Mineraloljer som inneholder voks har den egenskapen at de blir mindre flytende når temperaturen av oljen reduseres. Dette tapet av fluiditet skyldes generelt økning i viskosi-teten og/eller krystallisasjon av voksen til platelignende krystaller som eventuelt danner en svampaktig masse som fastholder oljen. Mineral oils that contain wax have the property that they become less liquid when the temperature of the oil is reduced. This loss of fluidity is generally due to an increase in viscosity and/or crystallization of the wax into plate-like crystals which eventually form a spongy mass that retains the oil.
Det har lenge vært kjent at forskjellige preparater virker som vokskrystallmodifiseringsmidler og midler som senker stivnepunktet når de blandes med voksholdige mineraloljer. Disse preparatene modifiserer størrelsen og formen av vokskrystaller og reduserer vedhengskreftene mellom voksen og oljen på en slik måte at oljen forblir flytende ved en lavere temperatur. It has long been known that various preparations act as wax crystal modifiers and agents that lower the solidification point when mixed with waxy mineral oils. These preparations modify the size and shape of wax crystals and reduce the adhesion forces between the wax and the oil in such a way that the oil remains liquid at a lower temperature.
Forskjellige midler som senker stivnepunktet er beskrevet i litteraturen og flere av disse er i kommersiell anvendelse. For eksempel beskriver US-patent nr. 3.048.479 anvendelsen av kopolymerer av etylen og C3-C5 vinylestere, f.eks. vinylacetat som middel for senking av stivnepunktet for brennstoffer, nærmere bestemt fyringsoljer, diesel og Jetbrennstoff. Polymere hydrokarbonmidler for senking av stivnepunktet basert på etylen og høyere alfa-olefiner, f.eks. propylen, er også kjente. US-patent nr. 3.961.916 beskriver anvendelsen av en blanding av kopolymerer, hvorav den ene er en vokskrystallkimdanner og den andre er et middel som kontrollerer veksten, slik at størrelsen av vokskrystallene kontrolleres. Various agents that lower the solidification point are described in the literature and several of these are in commercial use. For example, US Patent No. 3,048,479 describes the use of copolymers of ethylene and C3-C5 vinyl esters, e.g. vinyl acetate as a means of lowering the solidification point of fuels, more specifically heating oils, diesel and jet fuel. Polymeric hydrocarbon pour point depressants based on ethylene and higher alpha-olefins, e.g. propylene, are also known. US Patent No. 3,961,916 describes the use of a mixture of copolymers, one of which is a wax crystal seed former and the other a growth control agent, so that the size of the wax crystals is controlled.
Tilsvarende foreslås i britisk patent nr. 1263152 at størrelsen av vokskrystallene kan kontrolleres ved å benytte en kopolymer som har en lavere grad av sidekjedeforgrening. Det er også foreslått, f.eks. i britisk patent nr. 146 9016, at kopolymerene av di-n-alkylfumarater og vinylacetat som tidligere har vært benyttet som midler for reduksjon av stivnepunktet for smøreoljer kan benyttes som ko-tilsatsstoffer med etylen/vinylacetatkopolymerer i behandlingen av destillatbrennstoffer med høye endelige kokepunkter for å forbedre flytegenskapene ved lave temperaturer. Ifølge britisk patent nr. 146 9016 kan disse polymerene være C^, til C^g-alkylestere av umettede C4 til Cg dikarboksylsyrer, spesielt laurylfumarat; lauryl-heksadecylfumarat. Typisk blandes disse materialene med blandede estere med et gjennomsnitt på ca. 12 karbonatomer (polymer A). Similarly, it is proposed in British patent no. 1263152 that the size of the wax crystals can be controlled by using a copolymer which has a lower degree of side chain branching. It is also suggested, e.g. in British patent no. 146 9016, that the copolymers of di-n-alkyl fumarates and vinyl acetate which have previously been used as agents for reducing the pouring point of lubricating oils can be used as co-additives with ethylene/vinyl acetate copolymers in the treatment of distillate fuels with high final boiling points for to improve flow properties at low temperatures. According to British Patent No. 146 9016, these polymers can be C 1 to C 8 alkyl esters of unsaturated C 4 to C 8 dicarboxylic acids, especially lauryl fumarate; lauryl hexadecyl fumarate. Typically, these materials are mixed with mixed esters with an average of approx. 12 carbon atoms (polymer A).
De europeiske patentpublikasjonene nr. 0153176, 0153177, 0155807 og 0156577 angir at effektiviteten av materialer av denne typen kan forbedres dersom kopolymerene inneholder meget spesifikke alkylgrupper som f.eks. spesifikke di-n-alkylfumarat/vinylacetatkopolymerer. For eksempel polymerer hvor det gjennomsnittlige antallet karbonatomer i alkylgruppene i kopolymeren må være fra 12 til 14 og de må inneholde høyst 10 vekt-# av kopolymerer hvor alkylgruppene inneholder mer enn 14 karbonatomer og fortrinnsvis ikke mer enn 20 vekt-# av kopolymerer hvor alkylgrupper inneholder færre enn 12 karbonatomer, disse forbindelsene er funnet å være spesielt effektive i visse brennstoffer, og polymerer med spesifikke lengre alkylgrupper spesielt effektive i andre brennstoffer. The European Patent Publications Nos. 0153176, 0153177, 0155807 and 0156577 indicate that the efficiency of materials of this type can be improved if the copolymers contain very specific alkyl groups such as e.g. specific di-n-alkyl fumarate/vinyl acetate copolymers. For example, polymers where the average number of carbon atoms in the alkyl groups in the copolymer must be from 12 to 14 and they must contain no more than 10 wt-# of copolymers where the alkyl groups contain more than 14 carbon atoms and preferably no more than 20 wt-# of copolymers where alkyl groups contain fewer than 12 carbon atoms, these compounds have been found to be particularly effective in certain fuels, and polymers with specific longer alkyl groups particularly effective in other fuels.
Den europeiske patentpublikasjon nr. 0061895 A2 beskriver anvendelsen av polyoksyalkylenestere, -etere, -estere/-etere og blandinger derav som inneholder minst to C^q til C3Q lineære, mettede alkylgrupper og en polyoksyalkylenglykol-gruppe med molekylvekt 100 til 5000 hvor alkylgruppen i polyoksyalkylenglykolen inneholder fra 1 til 4 karbonatomer som tilsatsstoffer for destillatbrennstoffer. European Patent Publication No. 0061895 A2 describes the use of polyoxyalkylene esters, ethers, esters/ethers and mixtures thereof containing at least two C^q to C3Q linear, saturated alkyl groups and a polyoxyalkylene glycol group with a molecular weight of 100 to 5000 where the alkyl group in the polyoxyalkylene glycol contains from 1 to 4 carbon atoms as additives for distillate fuels.
Det er også vist at i mange tilfeller vil anvendelse av blandinger av to typer tilsatsstoffer gi en synergistisk forbedring av flytegenskapene ved lave temperaturer, spesielt i destillatbrennstoffer. Blanding kan imidlertid føre til problemer med vekselvirkning mellom tilsatsstoffene som i noen tilfeller fører til en reduksjon av stoffenes effek-tivitet som kan forårsake alvorlige problemer i raffinerier hvor man ofte ønsker å blande store mengder brennstoffer fra forskjellige kilder som inneholder forskjellige tilsatsstoffer for lagringsformål; en hensikt ved foreliggende oppfinnelse er å redusere dette problemet. It has also been shown that in many cases the use of mixtures of two types of additives will give a synergistic improvement of the flow properties at low temperatures, especially in distillate fuels. Mixing, however, can lead to problems with interaction between the additives which in some cases leads to a reduction of the substances' effectiveness which can cause serious problems in refineries where it is often desired to mix large quantities of fuels from different sources containing different additives for storage purposes; one purpose of the present invention is to reduce this problem.
Det er nå funnet at polyoksyalkylenglykolgrupper kan innbefattes i en umettet esterkopolymer for å tilveiebringe et effektivt flyt-forbedringsmiddel ved lave temperaturer for hydrokarboner, spesielt destillatbrennstoffer,selv om de kan benyttes i tunge dieseloljer, restoljer, råoljer og som midler for senkning av stivnepunktet i smøreoljer. Den umettede esterkopolymeren hvori polyoksyalkylengruppen inkorporeres, kan være av de typene som tidligere er foreslått som flyt-forbedringsmidler for mellomdestillat-brennstoffer. Det er også funnet at når disse kopolymerene benyttes i destillatbrennstoffer, kan problemet med ufordel-aktig vekselvirkning med andre tilsatsstoffer, som f.eks. etylenvinylacetatkopolymerer, reduseres. It has now been found that polyoxyalkylene glycol groups can be incorporated into an unsaturated ester copolymer to provide an effective low temperature flow improver for hydrocarbons, particularly distillate fuels, although they can be used in heavy diesel oils, residual oils, crude oils and as pour point depressants in lubricating oils . The unsaturated ester copolymer in which the polyoxyalkylene group is incorporated can be of the types previously proposed as flow improvers for middle distillate fuels. It has also been found that when these copolymers are used in distillate fuels, the problem of unfavorable interaction with other additives, such as e.g. ethylene vinyl acetate copolymers, is reduced.
Foreliggende oppfinnelse tilveiebringer følgelig destillatpetroleumsbrennstoff som koker i området 120°C til 400"C, kjennetegnet ved at det inneholder fra 0,0001 til 5 vekt-&, basert på vekten av destillatpetroleumsbrennstoffolJen, av en polymer eller kopolymer av vektmidlere molekylvekt fra 1000 til 200 000, fremstilt fra en etylenisk umettet ester og inneholdende fra 0,1 til 50 vekt-# polyoksyalkylengrupper av molekylvekt fra 100 til 5000. Accordingly, the present invention provides distillate petroleum fuel which boils in the range of 120°C to 400°C, characterized in that it contains from 0.0001 to 5% by weight, based on the weight of the distillate petroleum fuel oil, of a polymer or copolymer of weighting agents molecular weight from 1000 to 200 000, prepared from an ethylenically unsaturated ester and containing from 0.1 to 50 wt # of polyoxyalkylene groups of molecular weight from 100 to 5000.
Oppfinnelsen omfatter videre anvendelse av en polymer eller kopolymer av vektmidlere molekylvekt fra 1000 til 200 000, fremstilt fra en etylenisk umettet ester og inneholdende fra 0,15 til 50 vekt-# polyoksyalkylengrupper av molekylvekt 100 til 5000, for forbedring av flytegenskapene for destillat-brennstof f som koker i området fra 120<*>C til 400'C. The invention further comprises the use of a polymer or copolymer of weight agents molecular weight from 1000 to 200,000, prepared from an ethylenically unsaturated ester and containing from 0.15 to 50 wt # of polyoxyalkylene groups of molecular weight 100 to 5000, for improving the flow properties of distillate fuel f which boils in the range from 120<*>C to 400'C.
Polymerene som benyttes ved foreliggende oppfinnelse har fortrinnsvis en vektgjennomsnittlig molekylvekt i området fra 1000 til 200 000, fortrinnsvis 20 000 til 70 000, målt f.eks. ved gelgjennomtrengningskromatografi, kalibrert mot polystyrenmolekylvektstandarder. The polymers used in the present invention preferably have a weight average molecular weight in the range from 1,000 to 200,000, preferably 20,000 to 70,000, measured e.g. by gel permeation chromatography, calibrated against polystyrene molecular weight standards.
De umettede estrene som anvendes ved foreliggende oppfinnelse kan avledes fra etylenisk umettede mono-, di-, eller polykarboksylsyrer eller blandinger derav, og kan oppnås fra umettede estere eller blandinger derav med andre etylenisk umettede monomerer som f.eks. etylen, propylen eller buten. Eksempler på dikarboksylsyreestere som er nyttige for fremstilling av polymeren kan representeres ved den generelle formelen: The unsaturated esters used in the present invention can be derived from ethylenically unsaturated mono-, di- or polycarboxylic acids or mixtures thereof, and can be obtained from unsaturated esters or mixtures thereof with other ethylenically unsaturated monomers such as e.g. ethylene, propylene or butene. Examples of dicarboxylic acid esters that are useful for making the polymer can be represented by the general formula:
hvor Ri og R2 er hydrogen eller en til C4 alkylgruppe, f.eks. metyl, R3 er en C3 til C^g forbindelse i gjennomsnitt, det foretrukne gjennomsnittet avhenger av anvendelsen av polymeren. R3 kan være en blanding av en lang rekke alkylgrupper som f.eks. angitt i GB-patent nr. 1469016 for anvendelse som midler for reduksjon av stivnepunktet for en smøreolje eller området av spesifikke monomerer ifølge de europeiske patentpublikasjonene nr. 0153176, 0153177, 0155807 og 0156577 for anvendelse som destillattilsatsstoffer hvor de ikke bare kan forbedre lavtemperaturflytbarheten og filtrer- where R 1 and R 2 are hydrogen or a to C 4 alkyl group, e.g. methyl, R 3 is a C 3 to C 8 compound on average, the preferred average depending on the application of the polymer. R3 can be a mixture of a wide range of alkyl groups such as e.g. indicated in GB Patent No. 1469016 for use as agents for reducing the pour point of a lubricating oil or the range of specific monomers according to European Patent Publications Nos. 0153176, 0153177, 0155807 and 0156577 for use as distillate additives where they can not only improve low temperature flowability and filters -
barheten, men også nedsette uklarhetspunktetfor brennstoffet og R4 er COOR3, hydrogen eller en C^ til C4 alkylgruppe. Der hvor disse typene av umettede estere benyttes som råmateri-aler for fremstillingen av polymerene som anvendes ved foreliggende oppfinnelse, kan polyoksyalkylengruppen inkorporeres i molekylet under forestringen av karboksylsyr-en for fremstilling av esteren beskrevet ovenfor. F.eks. kan polyetylenglykolen blandes med alkoholen R3OH i egnet blandforhold og benyttes til å forestre f.eks. fumarsyre. Estrene av formelen ovenfor kan være homopolymeriserte eller kopolymeriserte med andre etylenisk umettede monomerer, som f.eks. kortkjedede umettede estere, f.eks. vinylestere som vinylacetat, vinylpropionat og vinylbutyrat og alkylakrylat-er og metakrylater. the bareness, but also lower the cloud point of the fuel and R4 is COOR3, hydrogen or a C^ to C4 alkyl group. Where these types of unsaturated esters are used as raw materials for the production of the polymers used in the present invention, the polyoxyalkylene group can be incorporated into the molecule during the esterification of the carboxylic acid to produce the ester described above. E.g. the polyethylene glycol can be mixed with the alcohol R3OH in a suitable mixing ratio and used to esterify e.g. fumaric acid. The esters of the formula above can be homopolymerized or copolymerized with other ethylenically unsaturated monomers, such as e.g. short-chain unsaturated esters, e.g. vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate and alkyl acrylates and methacrylates.
Typiske kopolymerer av typen beskrevet ovenfor kan oppnås ved kopolymerisasjonen av en dlkarboksylsyre mono- eller di-estermonomerer som f.eks. dialkylfumarater med forskjellige mengder, f.eks. 5 til 70 mol-%, av andre umettede estere eller olefiner. Slike andre estere innbefatter kortkjedede alkylestere av formelen: Typical copolymers of the type described above can be obtained by the copolymerization of a dicarboxylic acid mono- or diester monomers such as e.g. dialkyl fumarates with different amounts, e.g. 5 to 70 mol%, of other unsaturated esters or olefins. Such other esters include short chain alkyl esters of the formula:
hvor R<1> er hydrogen eller en til C4 alkylgruppe, R"' er -C00R"" eller -00CR"" hvor R"" er en forgrenet eller uforgrenet til C5 alkylgruppe, og R"' er R" eller hydrogen. Eksempler på slike kortkjedede estere er metakrylater, akrylater, fumarater og maleater, hvor vinylestere som f.eks. vinylacetat og vinylpropionat er foretrukket. Mer spesifikke eksempler innbefatter metylmetakrylat, isopro-penylacetat og isobutylakrylat. where R<1> is hydrogen or a to C4 alkyl group, R"' is -C00R"" or -00CR"" where R"" is a branched or unbranched to C5 alkyl group, and R"' is R" or hydrogen. Examples such short chain esters are methacrylates, acrylates, fumarates and maleates, with vinyl esters such as vinyl acetate and vinyl propionate being preferred.More specific examples include methyl methacrylate, isopropenyl acetate and isobutyl acrylate.
Den foretrukne kopolymeren av denne typen inneholder fra 40 til 60 mol-£ innhold av polyoksyalkylendelen fumarat og 60 til 40 mol-# vinylacetat. The preferred copolymer of this type contains from 40 to 60 mol-£ content of the polyoxyalkylene moiety fumarate and 60 to 40 mol-# of vinyl acetate.
Disse esterpolymerene fremstilles generelt ved å polymeri-sere estermonomerene i en oppløsning av hydrokarbonoppløs-ningsmiddel som f.eks. heptan, benzen, cykloheksan eller hvit olje, ved en temperatur som generelt ligger i området fra 20<*>C til 150<*>C, og som vanligvis fremmes med en katalysator av peroksyd eller azotypen, som f.eks. benzoylper-oksydazodiisobutyronitril under et teppe av en inert gass som f.eks. nitrogen eller karbondioksyd for å utelukke oksygen. These ester polymers are generally produced by polymerizing the ester monomers in a solution of hydrocarbon solvent such as e.g. heptane, benzene, cyclohexane or white oil, at a temperature which is generally in the range from 20<*>C to 150<*>C, and which is usually promoted with a catalyst of the peroxide or azo type, such as e.g. benzoylperoxyazodiisobutyronitrile under a blanket of an inert gas such as nitrogen or carbon dioxide to exclude oxygen.
En alternativ fremgangsmåte for inkorporering av polyoksyalkylengruppen i esterkopolymerene som anvendes ved foreliggende oppfinnelse er å kopolymerisere de ovenfor omtalte etylenisk umettede esterene med en etylenisk umettet ester av formelen: An alternative method for incorporating the polyoxyalkylene group into the ester copolymers used in the present invention is to copolymerize the above-mentioned ethylenically unsaturated esters with an ethylenically unsaturated ester of the formula:
hvor R er en etylenisk umettet hydrokarbylgruppe og R' er en polyoksyalkylengruppe. Eksempler på slike estere innbefatter polyetylenglykolmono- eller di-oleat, polyetylenglykolmono-eller di-cinamat, polyetylenglykolakrylater etc. For eksempel di-heksadecylfumarat, vinylacetat og diesteren av oleinsyre og polyoksyetylenglykol med molekylvekt 600 kan kopolymeriseres slik at man får en kopolymer som anvendes ved oppfinnelsen. where R is an ethylenically unsaturated hydrocarbyl group and R' is a polyoxyalkylene group. Examples of such esters include polyethylene glycol mono- or di-oleate, polyethylene glycol mono- or di-cinnamate, polyethylene glycol acrylates etc. For example di-hexadecyl fumarate, vinyl acetate and the diester of oleic acid and polyoxyethylene glycol with a molecular weight of 600 can be copolymerized so that a copolymer is obtained which is used in the invention .
Alternativt kan polyoksyalkylengruppen inkorporeres i esterpolymeren ved fremstilling av polymerer som inneholder frie syregrupper og deretter forestres med polyoksyalkylenalkohol eller -glykol. For eksempel kan kopolymerer av malelnsyreanhydrid med andre umettede materialer som vinylestere, dialkylfumarater, styren eller olefiner forestres med polyoksyalkylenalkoholen eller -glykolen. Polyoksyalkylenalkoholen kan selv være en mono-alkohol hvor den andre enden av gruppen er foretret eller forestret slik at det Innføres ytterligere en ønsket gruppe i polymerkjeden. Polyoksyalkylenalkoholen eller -glykolen kan blandes med andre alkoholer, spesielt de rettkjedede alkylalkoholene når produktene skal benyttes som tilsatsstoffer for destillatbrennstoffer . Alternatively, the polyoxyalkylene group can be incorporated into the ester polymer by producing polymers containing free acid groups and then esterified with polyoxyalkylene alcohol or glycol. For example, copolymers of maleic anhydride with other unsaturated materials such as vinyl esters, dialkyl fumarates, styrene or olefins can be esterified with the polyoxyalkylene alcohol or glycol. The polyoxyalkylene alcohol can itself be a mono-alcohol where the other end of the group is etherified or esterified so that a further desired group is introduced into the polymer chain. The polyoxyalkylene alcohol or glycol can be mixed with other alcohols, especially the straight-chain alkyl alcohols when the products are to be used as additives for distillate fuels.
Eksempler på polyoksyalkoholene som kan benyttes innbefatter estere, etere eller ester/etere av den generelle formelen: Examples of the polyoxy alcohols that can be used include esters, ethers or ester/ethers of the general formula:
hvor R er hydrogen, -alkyl, where R is hydrogen, -alkyl,
(CH2)n-C-, (CH2)n-C-,
A er polyoksyalkylensegmentet hvori alkylengruppen har 1 til 4 karbonatomer som f.eks. polyoksymetylen, polyoksyetylen eller polyoksytrimetylen. Det er foretrukket at polyoksyalkylensegmentet selv har en molekylvekt på 100 til 5000. A is the polyoxyalkylene segment in which the alkylene group has 1 to 4 carbon atoms such as e.g. polyoxymethylene, polyoxyethylene or polyoxytrimethylene. It is preferred that the polyoxyalkylene segment itself has a molecular weight of 100 to 5,000.
Eksempler på egnede alkoholer og glykoler, spesielt når materialene skal benyttes som tilsatsstoffer for destillatbrennstoffer, er de i det vesentlige lineære polyetylengly-koler (PEG) og polypropylenglykolene (PPG) som har en molekylvekt på 100 til 5000, fortrinnsvis 200 til 2000. Monoestrene av disse glykolene kan benyttes og estere av fettsyrer som inneholder 1-30, fortrinnsvis 2 til 30 karbonatomer er foretrukket, og det er foretrukket å benytte en C18-C24 fettsyre, spesielt behensyre eller blandinger av stearin- og behensyrer. Disse estrene kan også fremstilles ved forestring av polyetoksylerte fettsyrer eller polyetoksylerte alkoholer, f.eks. kan monometyleteren av en PEG benyttes, eller en polyetoksylert fettalkohol som de kommersielt tilgjengelige "Brij"-materialene. En spesielt foretrukket forbindelse for anvendelse som et flyt-forbedringsmiddel for et destillatbrennstoff, spesielt ved destillater ved et trangt område av kokepunkter, er en kopolymer av vinylacetat med en ekvimolar mengde av en fumaratester fremstilt ved forestring av fumarsyre med en blanding av minst 95 mol-# av en blanding av C^2/<c>14 rettkjedede alkoholer og opptil 5 mol-# av polyetylenglykol med molekylvekt 600. Examples of suitable alcohols and glycols, especially when the materials are to be used as additives for distillate fuels, are the essentially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) which have a molecular weight of 100 to 5000, preferably 200 to 2000. The monoesters of these glycols can be used and esters of fatty acids containing 1-30, preferably 2 to 30 carbon atoms are preferred, and it is preferred to use a C18-C24 fatty acid, especially behenic acid or mixtures of stearic and behenic acids. These esters can also be produced by esterification of polyethoxylated fatty acids or polyethoxylated alcohols, e.g. the monomethyl ether of a PEG can be used, or a polyethoxylated fatty alcohol such as the commercially available "Brij" materials. A particularly preferred compound for use as a flow improver for a distillate fuel, particularly in narrow boiling point distillates, is a copolymer of vinyl acetate with an equimolar amount of a fumarate ester prepared by esterification of fumaric acid with a mixture of at least 95 mol- # of a mixture of C^2/<c>14 straight chain alcohols and up to 5 mol-# of polyethylene glycol with a molecular weight of 600.
Alternativt kan en esterpolymer eller -kopolymer som inneholder frie karboksylsyre eller hydroksygrupper omsettes med etylen eller propylenoksyd slik at materialene som anvendes ved oppfinnelsen fremstilles. Alternatively, an ester polymer or copolymer containing free carboxylic acid or hydroxy groups can be reacted with ethylene or propylene oxide so that the materials used in the invention are produced.
De omtalte polymerene eller kopolymerene kan benyttes som tilsatsstoffer for forbedring av lavtemperaturegenskapene i hydrokarbonstoffer som f.eks. råoljer, restoljer og destillatbrennstoffer hvor de nedsetter stivnepunktet, kontrollerer størrelsen av vokskrystallene slik at lavtemperaturfiltrer-barheten forbedres, og de kan i noen tilfeller nedsette uklarhetspunktet for brennstoffet. Ved destillatbrennstoffer menes de brennstoffene som generelt benyttes 1 dieselmotorer °6 fyringsoljer, spesielt boligoppvarmingsoljer, som generelt koker i området 120°C til 500°C, nærmere bestemt 160°C til 400°C. I tillegg, når de benyttes i noen destillatbrennstoffer, har de en mindre tendens til negativ vekselvirkning med andre destillattilsatsstoffer enn med tilsvarende tilsatsstoffer som ikke inneholder polyoksyalkylengruppen. Forbindelsene kan benyttes alene, men det er funnet at i destillatbrennstoffer er de spesielt effektive når de benyttes sammen med andre tilsatsstoffer som tidligere er foreslått for forbedring av kaldflyt-egenskapene for destillatbrennstoffer generelt. The mentioned polymers or copolymers can be used as additives to improve the low-temperature properties of hydrocarbon substances such as e.g. crude oils, residual oils and distillate fuels where they lower the solidification point, control the size of the wax crystals so that low-temperature filterability is improved, and they can in some cases lower the cloud point of the fuel. By distillate fuels are meant the fuels that are generally used 1 diesel engines °6 heating oils, especially home heating oils, which generally boil in the range 120°C to 500°C, more specifically 160°C to 400°C. In addition, when used in some distillate fuels, they have less of a tendency to negatively interact with other distillate additives than with similar additives that do not contain the polyoxyalkylene group. The compounds can be used alone, but it has been found that in distillate fuels they are particularly effective when used together with other additives which have previously been proposed for improving the cold flow properties of distillate fuels in general.
Tilsatsstoffene som anvendes ved foreliggende oppfinnelse kan benyttes med polyoksyalkylenestrene, -etrene, ester/etrene og blandinger derav, som inneholder minst to C^g til C30 lineære mettede alkylgrupper og en polyoksyalkylenglykol med molekylvekt 100 til 5000, fortrinnsvis 200 til 5000, hvor alkylgruppen i polyoksyalkylenglykolen inneholder fra 1 til 4 karbonatomer. Disse materialene utgjør emne for europeisk patentpublikasjon nr. 0061895 A2. Eksempler på egnede ko-tilsatsstoffer av denne typen er reaksjonsproduktet av glykoler, generelt de i det vesentlige lineære polyetylen-glykolene (PEG) og polypropylenglykolene (PPG) med fettsyrer som inneholder 10-30, fortrinnsvis 18-24 karbonatomer, spesielt behensyre eller blandinger av stearin- og behensyrer, estrene kan også fremstilles ved forestring av polyetoksylerte fettsyrer eller polyetoksylerte alkoholer. Estere fremstilt ved omsetning av fettsyrer med polyalkoksy-lerte aminer eller ammoniakk kan også benyttes. The additives used in the present invention can be used with the polyoxyalkylene esters, ethers, esters/ethers and mixtures thereof, which contain at least two C^g to C30 linear saturated alkyl groups and a polyoxyalkylene glycol with a molecular weight of 100 to 5000, preferably 200 to 5000, where the alkyl group in the polyoxyalkylene glycol contains from 1 to 4 carbon atoms. These materials are the subject of European Patent Publication No. 0061895 A2. Examples of suitable co-additives of this type are the reaction product of glycols, generally the essentially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) with fatty acids containing 10-30, preferably 18-24 carbon atoms, especially behenic acid or mixtures of stearic and behenic acids, the esters can also be produced by esterification of polyethoxylated fatty acids or polyethoxylated alcohols. Esters produced by reacting fatty acids with polyalkylated amines or ammonia can also be used.
Polymerene og kopolymerene som anvendes ved foreliggende oppfinnelse kan, når de benyttes som brennstofftilsatsstoffer spesielt i destillatbrennstoffer, også benyttes med flytfor-bedringsmidler i form av etylenumettet esterkopolymer. De umettede monomerene som kan polymeriseres med etylen innbefatter umettede mono- og diestere av den generelle formelen: The polymers and copolymers used in the present invention can, when used as fuel additives especially in distillate fuels, also be used with flow improvers in the form of ethylene unsaturated ester copolymer. The unsaturated monomers that can be polymerized with ethylene include unsaturated mono- and diesters of the general formula:
hvor R3 er hydrogen eller metyl; R2 er en -OOCRs-gruppe hvor R5 er hydrogen eller en C± til C28» vanligere C^ til 0^7, og fortrinnsvis C^ til Cg, rettkjedet eller forgrenet alkylgruppe; eller R 2 er en -COORs-gruppe hvor R5 har den ovenfor angitte betydning, men ikke er hydrogen, og R4 er hydrogen eller -COOR5 som definert ovenfor. Monomeren, når R2 og R4 er hydrogen og R2 er -OOCR5, innbefatter vinylalkoholestere av Ci til C29. vanligere C± til C^g, monokarboksylsyre, og fortrinnsvis C2 til C5 monokarboksylsyre. Eksempler på vinylestere som kan kopolymeriseres med etylen innbefatter vinylacetat, vinylpropionat og vinylisobutyrat, hvor vinylacetat er den foretrukne vinylesteren. Det er foretrukket at kopolymerene inneholder fra 20 til 40 vekt-* av wherein R 3 is hydrogen or methyl; R 2 is a -OOCRs group where R 5 is hydrogen or a C± to C 28 » more commonly C 1 to 0 7 , and preferably C 1 to C 8 , straight chain or branched alkyl group; or R 2 is a -COORs group where R 5 has the above meaning, but is not hydrogen, and R 4 is hydrogen or -COOR 5 as defined above. The monomer, when R 2 and R 4 are hydrogen and R 2 is -OOCR 5 , includes vinyl alcohol esters of C 1 to C 29 . more commonly C± to C^g, monocarboxylic acid, and preferably C2 to C5 monocarboxylic acid. Examples of vinyl esters that can be copolymerized with ethylene include vinyl acetate, vinyl propionate and vinyl isobutyrate, with vinyl acetate being the preferred vinyl ester. It is preferred that the copolymers contain from 20 to 40 wt
vinylesteren, mer foretrukket fra 25 til 35 vekt-* vinylester. De kan. også være blandinger av to kopolymerer, som kopolymerene beskrevet i US-patent nr. 3961916. the vinyl ester, more preferably from 25 to 35 weight-* vinyl ester. They can. also be mixtures of two copolymers, such as the copolymers described in US patent no. 3961916.
Det er foretrukket at disse kopolymerene har en antalls-midlere molekylvekt, målt ved dampfaseosmometri (VPO), fra 1000 til 6000, fortrinnsvis 1000 til 4000. It is preferred that these copolymers have a number-average molecular weight, measured by vapor phase osmometry (VPO), from 1000 to 6000, preferably 1000 to 4000.
Polymerene og kopolymerene som anvendes ved oppfinnelsen kan også benyttes i destillatbrennstoffer sammen med polare forbindelser, enten ioniske eller ikke-ioniske, som har evnen til å virke som vekstinhibitorer for vokskrystaller i brennstoffene. Polare nitrogenholdige forbindelser er funnet å være spesielt effektive når de benyttes sammen med glykolestrene, —etrene eller —ester/etrene. Disse polare forbindelsene er generelt <C>2o_<c>300« fortrinnsvis C20~<C>lO0 aminsaltene og/eller amidene dannet ved reaksjon mellom minst en molar andel hydrokarbyl-substituerte aminer med en molar andel av hydrokarbylsyre som inneholder 1-4 karboksylsyregrupper eller anhydrider derav; ester/amider kan også benyttes. Disse nitrogenforbindelsene er beskrevet i US-patent nr. 4.211.534. Egnede aminer er vanligvis lang-kjedede Ci2-C40 primære, sekundære, tertiære eller kvaternære aminer av blandinger derav, men aminer med kortere kjede kan benyttes, forutsatt at den resulterende nitrogenforbindelsen er olje-oppløselig, og derfor normalt inneholder 20 til 300 karbonatomer. Nitrogenforbindelsen bør også inneholde minst ett rettkjedet Cg-C4g alkylsegment. The polymers and copolymers used in the invention can also be used in distillate fuels together with polar compounds, either ionic or non-ionic, which have the ability to act as growth inhibitors for wax crystals in the fuels. Polar nitrogen-containing compounds have been found to be particularly effective when used in conjunction with the glycol esters, -ethers or -ester/ethers. These polar compounds are generally <C>2o_<c>300« preferably C20~<C>lO0 the amine salts and/or amides formed by reaction between at least one molar proportion of hydrocarbyl-substituted amines with one molar proportion of hydrocarbyl acid containing 1-4 carboxylic acid groups or anhydrides thereof; ester/amides can also be used. These nitrogen compounds are described in US Patent No. 4,211,534. Suitable amines are usually long-chain C 2 -C 40 primary, secondary, tertiary or quaternary amines and mixtures thereof, but shorter chain amines may be used, provided the resulting nitrogen compound is oil-soluble, and therefore normally contains 20 to 300 carbon atoms. The nitrogen compound should also contain at least one straight-chain Cg-C4g alkyl segment.
Egnede aminer innbefatter primære, sekundære, tertiære eller kvaternære, men er fortrinnsvis sekundære aminer. Tertiære og kvaternære aminer kan bare danne aminsalter. Eksempler på aminer innbefatter tetradecylamin, kokosamin, hydrogenerte fettamlner og lignende. Eksempler på sekundære aminer innbefatter dioktadecylamin, metyl-behenylamin og lignende. Aminblandinger er også egnede og mange aminer avledet fra naturlige materialer er blandinger. Det foretrukne aminet er et sekundært hydrogenert fettamin av formelen HNR1R2, hvor R^ og R2 er alkylgrupper avledet fra hydrogenert talgfett bestående av ca. 4* (^4, 31* C^, 59* C^g. Suitable amines include primary, secondary, tertiary or quaternary, but are preferably secondary amines. Tertiary and quaternary amines can only form amine salts. Examples of amines include tetradecylamine, cocosamine, hydrogenated fatty acids and the like. Examples of secondary amines include dioctadecylamine, methyl behenylamine and the like. Amine mixtures are also suitable and many amines derived from natural materials are mixtures. The preferred amine is a secondary hydrogenated fatty amine of the formula HNR 1 R 2 , where R 1 and R 2 are alkyl groups derived from hydrogenated tallow fat consisting of approx. 4* (^4, 31* C^, 59* C^g.
Eksempler på egnede karboksylsyrer for fremstilling av disse nitrogenforbindelsene (og anhydrider derav) innbefatter cykloheksandikarboksylsyre, cykloheksendikarboksylsyre, cyklopentandikarboksylsyre, dialfa-naftyleddlksyre, nafta-lendikarboksylsyre og lignende. Generelt inneholder disse syrene 5-13 karbonatomer i den cykliske delen. Foretrukne syrer som er nyttige ved foreliggende oppfinnelse er benzen-dikarboksylsyrer som f.eks. ftalsyre, tereftalsyre, og orto-ftalsyre. Orto-ftalsyre og dens anhydrid er den spesielt foretrukne utførelsen. Examples of suitable carboxylic acids for the preparation of these nitrogen compounds (and anhydrides thereof) include cyclohexanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, dialpha-naphthyldicarboxylic acid, naphthalenedicarboxylic acid and the like. In general, these acids contain 5-13 carbon atoms in the cyclic part. Preferred acids which are useful in the present invention are benzene-dicarboxylic acids such as e.g. phthalic acid, terephthalic acid, and ortho-phthalic acid. Ortho-phthalic acid and its anhydride is the particularly preferred embodiment.
Det er foretrukket at den nitrogenholdige forbindelsen har minst ett rettkjedet alkylsegment som strekker seg fra forbindelsen som inneholder 8-40, fortrinnsvis 8-24 karbonatomer. Også minst et ammoniumsalt, aminsalt eller amidfor-bindingsledd må være tilstede i molekylet. Den spesielt foretrukne aminforbindelsen er dét amid-aminsaltet som dannes ved å omsette 1 molar andel ftalsyreanhydrld med to molare andeler di-hydrogenert fettamin. En annen foretrukket utførelse av diamidet er fremstilt ved dehydrering av dette amid-aminsaltet. It is preferred that the nitrogenous compound has at least one straight chain alkyl segment extending from the compound containing 8-40, preferably 8-24 carbon atoms. Also, at least one ammonium salt, amine salt or amide bond must be present in the molecule. The particularly preferred amine compound is the amide-amine salt which is formed by reacting 1 molar proportion of phthalic anhydride with two molar proportions of dihydrogenated fatty amine. Another preferred embodiment of the diamide is prepared by dehydrating this amide-amine salt.
Andre aminderivater som kan benyttes som ko-tilsatsstoffer er oljeoppløselige aminkarboksylsyresalter og/eller amider, f.eks. trioksylaminmyristat eller -behenat. Reaksjonspro-dukter av polyaminer med fete karboksylsyrer som f.eks. produktet som oppnås ved omsetning av tetraetylenpentamin med stearin- eller behensyrer, kan selv benyttes som fettamider. Other amine derivatives that can be used as co-additives are oil-soluble amine carboxylic acid salts and/or amides, e.g. trioxylamine myristate or behenate. Reaction products of polyamines with fatty carboxylic acids such as e.g. the product obtained by reacting tetraethylenepentamine with stearic or behenic acids can itself be used as fatty amides.
Kopolymerene kan benyttes sammen med ett eller flere tilsatsstoffer av typen omtalt ovenfor. The copolymers can be used together with one or more additives of the type mentioned above.
De relative andelene av tilsatsstoffer som benyttes i de foretrukne blandingene er fra 0,5 til 20 vektdeler av esterpolymereni som inneholder polyoksyalkylengruppen til en del av de andre tilsatsstoffene. Den totale mengden tilsatsstoffer vil avhenge av det spesielle brennstoffet, men generelt benyttes fra 0,0001 til 5 vekt-* av brennstoffet. The relative proportions of additives used in the preferred mixtures are from 0.5 to 20 parts by weight of the ester polymer containing the polyoxyalkylene group to a part of the other additives. The total amount of additives will depend on the particular fuel, but generally from 0.0001 to 5 weight-* of the fuel is used.
Tllsatsmlddelsystemet som anvendes kan med fordel tilføres som konsentrat i oljie for inkorporering i bulkbrennstoffet. Disse konsentratene kan også inneholde andre tilsatsstoffer når det er påkrevet. Konsentratene inneholder fortrinnsvis fra 3 til 75 vekt-*, mer fortetrukket 3 til 60 vekt-*, mest foretrukket 10 til 50 vekt-* av additivet. The additive system used can advantageously be added as a concentrate in oil for incorporation into the bulk fuel. These concentrates may also contain other additives when required. The concentrates preferably contain from 3 to 75 weight-*, more preferably 3 to 60 weight-*, most preferably 10 to 50 weight-* of the additive.
Foreliggende oppfinnelse er illustrert ved de følgende eksemplene hvor effektiviteten av tilsatsstoffene som anvendes ved foreliggende oppfinnelse som midler for senkning av stivnepunktet og filtrerbarhetsforbedringsmldler i destillatbrennstoffer ble sammenlignet med andre lignende tilsatsstoffer ved "kaldt filter igjenpluggingspunkt-for-søket" (CFPPT - Cold Filter Plugging Point Test) som ble utført ved fremgangsmåten beskrevet i detalj i "Journal of the Institute of Petroleum", bind 52, nummer 510, juni 1966, side 173-185. Dette forsøket er utformet for å korrelere med flytbarheten i kald tilstand av et mellomdestillatbrennstoff i automatiske dieselbrennstoffer. The present invention is illustrated by the following examples where the effectiveness of the additives used in the present invention as agents for lowering the solidification point and filterability improvement agents in distillate fuels were compared with other similar additives by the "cold filter plugging point test" (CFPPT - Cold Filter Plugging Point Test) which was carried out by the method described in detail in the "Journal of the Institute of Petroleum", Volume 52, Number 510, June 1966, pages 173-185. This test is designed to correlate with the cold flowability of a middle distillate fuel in automatic diesel fuels.
Kort oppsummert avkjøles en 40 ml prøve av oljen som skal undersøkes i et bad som holdes ved ca. -34°C slik at man får en ikke-lineær avkjøling på ca. l°C/min. Periodisk (ved hvert fall på 1°C i temperaturen med begynnelse ved minst 2°C over uklarhetspunktet) undersøkes den avkjølte oljen for evnen til å flyte gjennom en fin sikt iløpet av et forhånds-bestemt tidsrom ved å benytte en forsøksinnretning som er en pipette hvis nedre ende er koblet til en omvendt trakt som er plassert under overflaten av oljen som skal undersøkes. Strukket over åpningen av trakten er en 350 mesh sikt som har et areal definert ved en diameter på 12 mm. De peri-odiske forsøkene initieres ved at det pålegges et vakuum på den øvre enden av pipetten hvorved olje trekkes gjennom sikten opp i pipetten til et merke som indikerer 20 ml olje. Etter hver vellykket passasje returneres oljen straks til CFPP-røret. Forsøket gjentas ved hvert fall på l' C i temperaturen til oljen ikke lenger fyller pipetten iløpet av 60 sekunder. Denne temperaturen angis som CFPP-temperaturen. Forskjellen mellom CFPP-verdien for et brennstoff uten tilsatsstoffer og det samme brennstoffet som inneholder tilsatsstoffer angis som tilsatsstoffets CFPP-depresjon. En mer effektiv tilsatsstofflyt-forbedrer gir en større CFPP-depresjon ved den samme konsentrasjonen av tilsatsstoff. Briefly, a 40 ml sample of the oil to be examined is cooled in a bath maintained at approx. -34°C so that you get a non-linear cooling of approx. l°C/min. Periodically (at every 1°C drop in temperature starting at least 2°C above the cloud point) the cooled oil is examined for its ability to flow through a fine sieve during a predetermined period of time using a test device which is a pipette the lower end of which is connected to an inverted funnel which is placed below the surface of the oil to be examined. Stretched over the opening of the hopper is a 350 mesh screen which has an area defined by a diameter of 12 mm. The periodic experiments are initiated by applying a vacuum to the upper end of the pipette whereby oil is drawn through the sieve into the pipette to a mark indicating 20 ml of oil. After each successful passage, the oil is immediately returned to the CFPP pipe. The experiment is repeated with each drop of l'C in temperature until the oil no longer fills the pipette within 60 seconds. This temperature is designated as the CFPP temperature. The difference between the CFPP value for a fuel without additives and the same fuel containing additives is given as the CFPP depression of the additive. A more effective additive flow improver produces a greater CFPP depression at the same concentration of additive.
Eksempel 1 Example 1
Brennstoffene som ble benyttet i dette eksemplet var: The fuels used in this example were:
Tilsatsstoffene som ble benyttet var: The additives used were:
Tilsatsstoff l-en kopolymer av en blandet Cj^/Cj^ fumaratester oppnådd ved omsetning av en 50:50 molar blanding av normale C^2°S ^14 alkoholer med fumarsyre og oppløsningsko-polymerisasjon med vinylacetat i molforhold 1 til 1 ved 60"C ved å benytte azodiisobutyonitril som katalysator. Additive 1-a copolymer of a mixed Cj^/Cj^ fumarate ester obtained by reacting a 50:50 molar mixture of normal C^2°S^14 alcohols with fumaric acid and solution copolymerization with vinyl acetate in a molar ratio of 1 to 1 at 60" C by using azodiisobutyonitrile as catalyst.
Tilsatsstoff 2 - dibehenatesteren av polyetylenglykol med molekylvekt 600. Additive 2 - the dibehenate ester of polyethylene glycol with a molecular weight of 600.
Tilsatsstoff 3 - dibehenatesteren av polyetylenglykol med molekylvekt 400. Additive 3 - the dibehenate ester of polyethylene glycol with a molecular weight of 400.
Tilsatsstoff 4 var det samme som tilsatsstoff 1 bortsett fra at 2,5 mol-* av en polyetylenglykol med gjennomsnittlig molekylvekt 600 ble tilsatt til Ci2/Ci4 alkoholblandingen som ble benyttet for å forestre fumarsyren, og polymerisasjonen ble utført ved 80°C. Additive 4 was the same as additive 1 except that 2.5 mol-* of a polyethylene glycol with an average molecular weight of 600 was added to the Ci2/Ci4 alcohol mixture used to esterify the fumaric acid, and the polymerization was carried out at 80°C.
Tilsatsstoff 5 var det samme som tilsatsstoff 4 bortsett fra at 2,5 mol-* av monometyleteren av polyetylenglykol med molekylvekt 750 ble benyttet Isteden for polyetylenglykolen med molekylvekt 600. Additive 5 was the same as additive 4 except that 2.5 mol-* of the monomethyl ether of polyethylene glycol with a molecular weight of 750 was used instead of the polyethylene glycol with a molecular weight of 600.
CFPP-depresjonene oppnådd i brennstoffene når de ble behandlet med disse tilsatsstoffene og blandinger derav, var som følger: The CFPP depressions obtained in the fuels when treated with these additives and mixtures thereof were as follows:
I hvert tilfelle oppnås en større reduksjon i CFPP-temperaturen når polyoksyalkylensegmentet er tilstede i molekylet. In each case, a greater reduction in the CFPP temperature is obtained when the polyoxyalkylene segment is present in the molecule.
Eksempel 2 Example 2
Tilsatsstoffene fra eksempel 1 ble undersøkt i følgende brennstoffer. og mengden av tilsatsstoff (en 2:1 vektdelsblanding av tilsatsstoffene 1 eller 5 med tilsatsstoff 3) som var påkrevet for å nå den ønskede CFPP ble målt med følgende resultater: The additives from example 1 were examined in the following fuels. and the amount of additive (a 2:1 mixture by weight of additives 1 or 5 with additive 3) required to reach the desired CFPP was measured with the following results:
Eksempel 3 Example 3
CFPP-depresjonene som ble oppnådd ved å benytte 2:1 blandinger av tilsatsstoffene 1, 4 eller 5 med 3 ble funnet å være som følger: The CFPP depressions obtained using 2:1 mixtures of additives 1, 4 or 5 with 3 were found to be as follows:
Eksempel 4 Example 4
Tilsatsstoffene som anvendes ved foreliggende oppfinnelse benyttes i brennstoff G sammen med en etylenvinylacetat (EVA) kopolymer ifølge britisk patent nr. 1263152 som inneholdt 36 vekt-* vinylacetat og som hadde en antallsmid-lere molekylvekt på 2000 målt ved dampfaseosmometri. The additives used in the present invention are used in fuel G together with an ethylene vinyl acetate (EVA) copolymer according to British patent no. 1263152 which contained 36 weight-* vinyl acetate and which had a number average molecular weight of 2000 measured by vapor phase osmometry.
De andre tilsatsstoffene som ble benyttet var: The other additives used were:
Tilsatsstoff 1 fra eksempel 1. Additive 1 from example 1.
Tilsatsstoff 6 var det samme som tilsatsstoff 1 bortsett fra at 5 mol-* av en polyetylenglykol med molvekt 600 dioleat ble tilsatt til C12/C14 alkoholblandingen som ble benyttet til å forestre fumarsyren. Additive 6 was the same as additive 1 except that 5 mol-* of a polyethylene glycol with a molecular weight of 600 dioleate was added to the C12/C14 alcohol mixture used to esterify the fumaric acid.
Tilsatsstoff 7 var det samme som tilsatsstoff 1 bortsett fra at dialkylfumaratet ble oppnådd fra følgende blanding av alkoholer: Additive 7 was the same as additive 1 except that the dialkyl fumarate was obtained from the following mixture of alcohols:
Tilsatsstoff 8 var det samme som tilsatsstoff 6 bortsett fra at 2 mol-* av polyetylenglykol med molvekt 600 ble benyttet. Additive 8 was the same as additive 6 except that 2 mol-* of polyethylene glycol with a molecular weight of 600 was used.
CFPP-verdiene som ble oppnådd var som følger: The CFPP values obtained were as follows:
Eksempel 5 Example 5
Virkningen av mengden av tilsatsstoff som ble benyttet på CFPP-verdiene for brennstoffene E, F, G og I ble bestemt ved å benytte følgende blandinger av tilsatsstoffer: The effect of the amount of additive used on the CFPP values for fuels E, F, G and I was determined by using the following mixtures of additives:
Resultatene er vist i de grafiske fremstillingene i figurene 1 til 4. Figurene 3 og 4 innbefatter også resultater oppnådd ved å benytte den samme behandlingsmengden av EVA kopolymeren benyttet i eksempel 4 alene. The results are shown in the graphical representations in figures 1 to 4. Figures 3 and 4 also include results obtained by using the same treatment quantity of the EVA copolymer used in example 4 alone.
Eksempel 6 Example 6
Forbindelsene anvendt ved foreliggende oppfinnelse ble undersøkt som midler for å senke stivnepunktet i en oppløs-ningsmiddel nøytral smøreolje. Polymerene ble fremstilt ved fremgangsmåten beskrevet ovenfor fra en ekvimolar mengde av fumaratesteren fremstilt fra følgende blanding av alkoholer. og vinylacetat (tilsatsstoff 9) og en tilsvarende polymer hvor alkoholblandingen inneholdt 2,5 mol-* av polyetylenglykolen med molvekt 750 som ble benyttet i tilsatsstoff 5 (tilsatsstoff 10). The compounds used in the present invention were investigated as agents for lowering the pour point in a solvent neutral lubricating oil. The polymers were prepared by the method described above from an equimolar amount of the fumarate ester prepared from the following mixture of alcohols. and vinyl acetate (additive 9) and a corresponding polymer where the alcohol mixture contained 2.5 mol-* of the polyethylene glycol with a molecular weight of 750 which was used in additive 5 (additive 10).
Stivnepunktene ble målt ved fremgangsmåten ifølge ASTM D 97 med følgende resultater: The solidification points were measured by the method according to ASTM D 97 with the following results:
Behandlingsmengde 0 0,1 vekt-* polymer 0,2-vekt-* polymer Treatment quantity 0 0.1 weight-* polymer 0.2 weight-* polymer
Eksempel 7 Example 7
Tilsatsstoff 9 var det samme som tilsatsstoff 1 bortsett fra at en kommersiell alkoholblanding markedsført som "Dobanol 25" ble benyttet isteden for blandingen av C^- og C14 alkoholer. "Dobanol 25" er en blanding av Additive 9 was the same as Additive 1 except that a commercial alcohol mixture marketed as "Dobanol 25" was used instead of the mixture of C 14 and C 14 alcohols. "Dobanol 25" is a mixture of
hvor av 80 vekt-* er normale alkoholer og 20 vekt-* har en metylforgrening ved 1-posisjonen. of which 80 wt-* are normal alcohols and 20 wt-* have a methyl branch at the 1-position.
Tilsatsstoff 10 var det samme som tilsatsstoff 9 bortsett fra at en blanding av 1,975 mol "Dobanol 25" og 0,025 mol polyetylenglykol med molekylvekt 750 ble benyttet. Additive 10 was the same as additive 9 except that a mixture of 1.975 mol "Dobanol 25" and 0.025 mol polyethylene glycol with a molecular weight of 750 was used.
Disse tilsatsstoffene ble undersøkt som 4:1 blandinger av tilsatsstoffet med tilsatsstoff 3 i brennstoff D og brennstoff J som har en ubehandlet CFPP-verdi på -5"C og følgende resultater for ASTM D-96 destillasjon. med følgende resultater These additives were tested as 4:1 mixtures of the additive with additive 3 in fuel D and fuel J which has an untreated CFPP value of -5"C and the following results for ASTM D-96 distillation. with the following results
Eksempel 8 Example 8
Tilsatsstoffer ble undersøkt i brennstoff K som hadde et uklarhetspunkt på +5"C og følgende verdier for ASTM D-96 destillasjon Additives were investigated in fuel K which had a cloud point of +5"C and the following values for ASTM D-96 distillation
og utseende av brennstoffet ble registrert ved -5°C etter avkjøling med 1"C pr. time. 1000 ppm av tilsatsstoffene ble benyttet som 4:1 blandinger og resultatene var som følger: and appearance of the fuel was recorded at -5°C after cooling at 1°C per hour. 1000 ppm of the additives were used as 4:1 mixtures and the results were as follows:
Eksempel 9 Example 9
Tilsatsstoff 11 var det samme som tilsatsstoff 1 bortsett fra at 10 mol-* av Ci2/Cl4 alkoholen ble erstattet av monometyleteren av polyetylenglykol med molekylvekt 750. Tilsatsstoffene ble undersøkt i en blanding av 50 vekt-* brennstoff L som hadde en ubehandlet CFPP-verdi på -2°C og resultater for ASTM-D-96 destillasjon som følger Additive 11 was the same as Additive 1 except that 10 mol-* of the Ci2/Cl4 alcohol was replaced by the monomethyl ether of polyethylene glycol with a molecular weight of 750. The additives were tested in a mixture of 50 wt-* fuel L which had an untreated CFPP value at -2°C and results for ASTM-D-96 distillation as follows
og 50 vekt-* av brennstoff D som inneholdt 200 ppm av en etylenvinylacetatkopolymer av 32 vekt-* vinylacetat slik at man fikk en CFPP-verdi på -90C. Mengden av tilsatsstoff som var påkrevet for å gi blandingen en CFPP-verdi på -9°C ble bestemt å være som følger and 50 wt-* of fuel D which contained 200 ppm of an ethylene vinyl acetate copolymer of 32 wt-* vinyl acetate so that a CFPP value of -90C was obtained. The amount of additive required to give the mixture a CFPP value of -9°C was determined to be as follows
Forsøkene ble gjentatt ved at man som brennstoff anvendte en blanding av 50 vekt-* brennstoff J og 50 vekt-* brennstoff M som inneholdt 200 ppm av etylenvinylacetatkopolymeren. The experiments were repeated by using as fuel a mixture of 50 weight-* of fuel J and 50 weight-* of fuel M containing 200 ppm of the ethylene vinyl acetate copolymer.
Brennstoff M hadde en ubehandlet CFPP-verdi på -4°C og resultater fra ASTM D-96 destillasjon som følger Fuel M had an untreated CFPP value of -4°C and ASTM D-96 distillation results as follows
Mengden av tilsatsstoff som var påkrevet for å gi en CFPP-verdi på -9<e>C ble funnet å være som følger: The amount of additive required to give a CFPP value of - 9<e>C was found to be as follows:
Claims (15)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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GB848428880A GB8428880D0 (en) | 1984-11-15 | 1984-11-15 | Polyesters |
Publications (3)
Publication Number | Publication Date |
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NO854527L NO854527L (en) | 1986-05-16 |
NO167757B true NO167757B (en) | 1991-08-26 |
NO167757C NO167757C (en) | 1991-12-04 |
Family
ID=10569777
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO854527A NO167757C (en) | 1984-11-15 | 1985-11-13 | DISTILLATE PETROLEUM FUEL AND APPLICATION OF POLYMERS AND COPOLYMERS AS ADDITIVES FOR DISTILLATE FUELS. |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0183447B1 (en) |
JP (1) | JPH0689346B2 (en) |
CN (1) | CN1006399B (en) |
AT (1) | ATE51013T1 (en) |
AU (1) | AU578502B2 (en) |
DE (1) | DE3576518D1 (en) |
ES (1) | ES8705479A1 (en) |
GB (1) | GB8428880D0 (en) |
NO (1) | NO167757C (en) |
PT (1) | PT81508B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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SE463028B (en) * | 1988-02-22 | 1990-10-01 | Berol Kemi Ab | ETHANOL BRAZLE AND ITS APPLICATION AS DIESEL BRAZEN |
JPH03139192A (en) * | 1989-10-23 | 1991-06-13 | Mitsubishi Electric Corp | Motor controller |
ATE143983T1 (en) * | 1991-07-18 | 1996-10-15 | Hoechst Ag | COPOLYMERS MADE OF ETHYLENE UNSATURATED CARBOXYLIC ACID ESTERS WITH POLYOXYALKYLENE ETHERS OF LOWER UNSATURATED ALCOHOL AS FLOW IMPROVERS FOR PARAFFIN-CONTAINING OILS |
GB9315205D0 (en) † | 1993-07-22 | 1993-09-08 | Exxon Chemical Patents Inc | Additives and fuel compositions |
ATE542842T1 (en) * | 2009-12-21 | 2012-02-15 | Infineum Int Ltd | POLYMER AND POLYMER COMPOSITIONS |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US3277157A (en) * | 1956-03-29 | 1966-10-04 | Chevron Res | Polyoxyalkylene acrylates and methacrylates |
FR1146459A (en) * | 1956-04-05 | 1957-11-12 | Exxon Standard Sa | Fuel oil stabilization process |
GB798457A (en) * | 1956-05-23 | 1958-07-23 | California Research Corp | Copolymer composition |
US3347645A (en) * | 1963-12-20 | 1967-10-17 | Exxon Research Engineering Co | Multipurpose gasoline additive |
US4160459A (en) * | 1977-11-23 | 1979-07-10 | Texaco Inc. | Low pour crude oil compositions |
US4464182A (en) * | 1981-03-31 | 1984-08-07 | Exxon Research & Engineering Co. | Glycol ester flow improver additive for distillate fuels |
RU2014347C1 (en) * | 1981-03-31 | 1994-06-15 | Эксон Рисерч энд Энджиниринг Компани | Fuel composition |
CA1275403C (en) * | 1985-06-07 | 1990-10-23 | Albert Rossi | Lubricating oil composition containing dual additive combination for lowtemperature viscosity improvement |
-
1984
- 1984-11-15 GB GB848428880A patent/GB8428880D0/en active Pending
-
1985
- 1985-11-13 NO NO854527A patent/NO167757C/en unknown
- 1985-11-14 AU AU49927/85A patent/AU578502B2/en not_active Ceased
- 1985-11-14 EP EP85308322A patent/EP0183447B1/en not_active Expired - Lifetime
- 1985-11-14 AT AT85308322T patent/ATE51013T1/en not_active IP Right Cessation
- 1985-11-14 DE DE8585308322T patent/DE3576518D1/en not_active Expired - Lifetime
- 1985-11-14 CN CN85108892A patent/CN1006399B/en not_active Expired
- 1985-11-14 ES ES548867A patent/ES8705479A1/en not_active Expired
- 1985-11-15 PT PT81508A patent/PT81508B/en not_active IP Right Cessation
- 1985-11-15 JP JP60256479A patent/JPH0689346B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0689346B2 (en) | 1994-11-09 |
NO854527L (en) | 1986-05-16 |
ES548867A0 (en) | 1987-05-01 |
AU578502B2 (en) | 1988-10-27 |
AU4992785A (en) | 1986-05-22 |
GB8428880D0 (en) | 1984-12-27 |
EP0183447B1 (en) | 1990-03-14 |
EP0183447A1 (en) | 1986-06-04 |
CN1006399B (en) | 1990-01-10 |
NO167757C (en) | 1991-12-04 |
CN85108892A (en) | 1986-07-02 |
ATE51013T1 (en) | 1990-03-15 |
JPS61123698A (en) | 1986-06-11 |
PT81508A (en) | 1985-12-01 |
PT81508B (en) | 1987-11-11 |
DE3576518D1 (en) | 1990-04-19 |
ES8705479A1 (en) | 1987-05-01 |
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