EP3844250A1 - Utilisation de copolymères spécifiques pour améliorer les propriétés à froid de carburants ou combustibles - Google Patents
Utilisation de copolymères spécifiques pour améliorer les propriétés à froid de carburants ou combustiblesInfo
- Publication number
- EP3844250A1 EP3844250A1 EP19755939.6A EP19755939A EP3844250A1 EP 3844250 A1 EP3844250 A1 EP 3844250A1 EP 19755939 A EP19755939 A EP 19755939A EP 3844250 A1 EP3844250 A1 EP 3844250A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymer
- ethylene
- formula
- copolymers
- vinyl
- 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.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 110
- 229920001577 copolymer Polymers 0.000 title claims abstract description 82
- 239000000654 additive Substances 0.000 claims abstract description 127
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 230000000996 additive effect Effects 0.000 claims abstract description 64
- 239000012188 paraffin wax Substances 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- -1 vinyl carbon Chemical compound 0.000 claims description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229920001567 vinyl ester resin Polymers 0.000 claims description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 238000004062 sedimentation Methods 0.000 claims description 15
- 229920001897 terpolymer Polymers 0.000 claims description 13
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 229920001400 block copolymer Polymers 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 8
- 229920005604 random copolymer Polymers 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 claims description 5
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 18
- 239000000178 monomer Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- 125000005250 alkyl acrylate group Chemical group 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 235000013311 vegetables Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 239000010775 animal oil Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000008158 vegetable oil Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 125000002015 acyclic group Chemical group 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 3
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000003412 degenerative effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003879 lubricant additive Substances 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000006280 diesel fuel additive Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000005670 ethenylalkyl group Chemical group 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 2
- 239000012989 trithiocarbonate Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- GVTLFGJNTIRUEG-ZHACJKMWSA-N (e)-n-(3-methoxyphenyl)-3-phenylprop-2-enamide Chemical class COC1=CC=CC(NC(=O)\C=C\C=2C=CC=CC=2)=C1 GVTLFGJNTIRUEG-ZHACJKMWSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 206010001052 Acute respiratory distress syndrome Diseases 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004165 Methyl ester of fatty acids Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 201000000028 adult respiratory distress syndrome Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZLAYEEPDSOYWBZ-UHFFFAOYSA-N octan-4-yl 2-methylprop-2-enoate Chemical compound CCCCC(CCC)OC(=O)C(C)=C ZLAYEEPDSOYWBZ-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
-
- 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
- C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
-
- 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
- C10L10/16—Pour-point depressants
-
- 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
-
- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
- C10L2200/0446—Diesel
-
- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
- C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
Definitions
- the present invention relates to the use of particular copolymers to improve the cold-keeping properties of fuels and combustibles during their storage and / or their use at low temperature.
- the present invention also relates to additive compositions (or “additive packages”) containing these copolymers, as well as fuel and fuel compositions additivated with such copolymers, preferably in combination with at least one cold-thinning additive. (CFI) and / or at least one paraffin anti-sedimentation additive (WASA).
- CFI cold-thinning additive
- WASA paraffin anti-sedimentation additive
- Fuels or combustibles containing paraffinic compounds in particular compounds containing n-alkyl, iso-alkyl or n-alkenyl groups such as paraffinic waxes, are known to exhibit deteriorated flow properties at low temperature, typically below 0 ° C.
- the middle distillates obtained by distillation from crude oils of petroleum origin such as diesel or heating oil, contain different amounts of n-alkanes or n-paraffins depending on their origin. These compounds tend to crystallize at low temperatures, clogging hoses, pipes, pumps and filters, for example in the fuel circuits of motor vehicles.
- cold flow improvers in English “cold flow improvers” or CFI
- CFI cold thinning additives
- TLF Filterability Limit Temperature
- PE pour point
- TLF additives polymers of ethylene and vinyl acetate and / or vinyl propionate
- EVA EVP
- TLF additives This type of additive, widely known to those skilled in the art, is systematically added to conventional medium distillates at the end of the refinery. These additive distillates are used as fuel for diesel engines or as heating fuel. Additional quantities of these additives can be added to the fuels sold in service stations, in particular to satisfy the so-called “Great Cold” specifications.
- Document EP0857776 proposes using alkylphenol-aldehyde resins resulting from the condensation of alkylphenol and aldehyde in combination with ethylene / vinyl ester copolymers or terpolymers, to improve the fluidity of mineral oils.
- Patent application WO 2008/006965 describes the use of a combination of a homopolymer obtained from an olefinic ester of carboxylic acid of 3 to 12 carbon atoms and a fatty alcohol comprising a chain of 16 carbon atoms and possibly an olefinic double bond and of a cold fluidizing additive (CFI) of EVA or EVP type, to increase the effectiveness of CFI additives by amplifying their effect on TLF.
- CFI cold fluidizing additive
- Patent application WO 2016/128379 describes the use, as a cold-keeping additive of a fuel or combustible, of a block copolymer comprising:
- a block A consisting of a chain of structural units derived from one or more ⁇ , b-unsaturated acrylate or alkyl methacrylate monomers
- a block B consisting of a chain of structural units derived from one or more a, b-unsaturated monomers containing at least one aromatic nucleus.
- This additive is particularly useful as a TLF booster in association with a cold fluidizing additive (CFI).
- CFI cold fluidizing additive
- Another object of the cold-keeping additives is to ensure the dispersion of the paraffin crystals, so as to delay or prevent the sedimentation of such crystals and of avoid the formation of a layer rich in paraffins at the bottom of containers, tanks or storage tanks; these paraffin dispersant additives are called anti-sedimentation additives or WASA (acronym of the English term "Wax Anti-Settling Additive").
- WASA anti-sedimentation additives
- Modified alkylphenol-aldehyde resins have been described in document FR2969620 as an anti-sedimentation additive in combination with a TLF additive.
- This need is particularly important for fuels or fuels comprising one or more paraffinic compounds, for example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.
- paraffinic compounds for example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.
- distillates used in fuels and fuels are increasingly produced from more complex refining operations than those resulting from direct petroleum distillation, and can originate in particular from cracking, hydrocracking, catalytic cracking and visbreaking processes.
- the refiner tends to introduce into these fuels cuts that are more difficult to use, such as the heavier cuts resulting from cracking and visbreaking processes which are rich in long chain paraffins.
- the present invention applies to fuels and combustibles containing not only conventional distillates such as those resulting from the direct distillation of crude oils, but also to bases obtained from other sources, such as those described above.
- the aim of the present invention is to propose new additives and concentrates containing them which can advantageously be used as additives to improve the cold-resistance properties, in particular the cold-flow properties of these fuels or combustibles, during storage and / or their use at low temperature, typically less than 0 ° C.
- the aim of the present invention is further to propose new additives for fuels and combustibles, and concentrates containing such additives, acting on the Filterability Limit Temperature (TLF), the pour point (PE), and delaying and / or preventing the sedimentation of crystals of hydrocarbon compounds, in particular paraffins.
- TEZ Filterability Limit Temperature
- PE pour point
- Another object of the invention is to provide a fuel or fuel composition having improved cold-holding properties, in particular at temperatures below 0 ° C, preferably below -5 ° C.
- the present invention thus relates to the use, to improve the cold-keeping properties of a fuel or fuel composition, of one or more copolymers comprising:
- Ri represents a hydrogen atom or a methyl group
- X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
- R2 represents a C1 to C24 alkyl group
- R represents a substituted or unsubstituted imidazole ring.
- the polymer defined above is used as an additive called “TLF booster”, that is to say in combination with a flow improvement additive or cold fluidizing additive (in English “cold flow improvers ”or CFI) which it improves performance.
- TEZ booster a flow improvement additive or cold fluidizing additive
- the subject of the invention is also an additive composition comprising such a copolymer in combination with at least one cold-keeping additive different from the copolymers according to the invention, as well as an additive concentrate containing such a composition.
- the cold-keeping additive is preferably chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
- the invention also has for its object and a fuel or fuel composition, comprising:
- At least one cut of hydrocarbons from one or more sources chosen from the group consisting of mineral (preferably petroleum), animal, vegetable and synthetic sources, and
- said composition also comprises at least one cold-keeping additive different from the copolymers according to the invention defined above.
- CN compound or group denotes a compound or group containing in its chemical structure N carbon atoms.
- copolymer The copolymer:
- the invention uses a copolymer, comprising at least one unit of formula (I) below:
- Ri represents a hydrogen atom or a methyl group
- X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
- R2 represents a C1 to C24 alkyl radical.
- the group X of formula (I) is preferably the group -O- CO-.
- the group X of formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group X is linked to the vinyl carbon by the carbon atom.
- the group X of formula (I) is preferably the group -CO-O-
- the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom.
- the group R 2 of formula (I) is a C 1 to C 24 alkyl radical.
- This alkyl radical can be linear or branched, cyclic or acyclic.
- This alkyl radical can comprise a linear or branched part and a cyclic part.
- the group R 2 of formula (I) is a linear or branched acyclic alkyl radical in C to C 1 4, preferably in Cs to C 1 4, more preferably still in C 1 2 to C 1 4.
- alkyl groups such as octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl, alkyl groups containing C 1 4.
- the group X is a group -CO-O-, X being connected to the vinyl carbon by the carbon atom, and the group R2 is a linear or branched Cs to C 1 acyclic alkyl radical 4, preferably in Cio to C 1 4, and more preferably still in C 1 2 to C 1 4.
- the patterns according to this embodiment correspond to those derived from monomers chosen from acrylates and methacrylates alkyl group having a alklyle Cs to C 4, preferably Cio to C 14, more preferably still C12 to Ci 4.
- the group R2 of formula (I) is a linear or branched acyclic alkyl radical in C14 to C24, preferably in C1 to C22, more preferably still in Cis to C22.
- the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is an acyclic linear or branched C14 to C24 alkyl radical, preferably in CI ⁇ to C22, more preferably still in Cis to C22.
- the units according to this embodiment correspond to those derived from monomers selected from acrylates and alkyl methacrylates having a alklyle group C14 to C24, preferably CI O to C 22, more preferably still C22 to Cis.
- the copolymer used in the present invention also comprises at least one unit of formula (II) below:
- R represents a substituted or unsubstituted imidazole ring.
- the substituent (s) possibly present on the imidazole cycle (s) may be saturated or unsaturated, and may in particular be chosen from hydrocarbon, oxygenated, nitrogenous, halogenated substituents, etc.
- the units of formula (II) come from one or more vinyl monomers carrying an R group as described above.
- l-vinylimidazole or N-vinylimidazole:
- the copolymer used in the present invention may or may not be crosslinked. Preferably, it is not crosslinked.
- the copolymer used in the present invention can advantageously be a random copolymer, or a block copolymer. According to a particularly preferred embodiment, it is a random copolymer.
- the copolymer according to the invention advantageously contains from 50 to 99 mol% of units of formula (I), preferably from 60 to
- the copolymer according to the invention advantageously contains from 1 to 50 mol% of units of formula (II), preferably from 5 to 40 mol%, more preferably from 10 to 30 mol%, and better still from 10 to 25 % in moles.
- the copolymer used in the present invention contains only units of formula (I) and units of formula (II).
- the copolymer used in the present invention can be obtained by copolymerization of:
- Ri, X and R 2 are as defined above, the preferred variants of Ri, X and R 2 according to formula (I) described above being also preferred variants of formula (IA), and
- the monomer of formula (IA) is preferably chosen from vinyl alkyl esters having a C 1 to C 24 alkyl group, and more preferably from vinyl alkyl esters having a C 1 2 to C 1 4 or C 1 to C 22 alkyl group.
- the alkyl radical of the vinyl ester is linear or branched, cyclic or acyclic, preferably acyclic.
- vinyl ester alkyl monomers that may be mentioned, by way of nonlimiting example, vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl 2-ethylhexanoate.
- the monomer of formula (IA) is typically chosen from alkyl acrylates and methacrylates having a C 1 to C 24 alkyl group, and more preferably from alkyl acrylates and methacrylates having a C 1 to C 14 or C 1 to C 22 alkyl group .
- alkyl (meth) acrylates which may be used as monomers in the manufacture of the copolymer of the invention
- the monomers of formula (IIA) are vinyl monomers carrying an R group as described above.
- the polymer according to the invention were obtained from monomers different from those of formula (IA) and (IIA) above, insofar as the final copolymer corresponds to a polymer comprising units of formula (I) and units of formula (II) as defined above.
- the polymer were obtained by polymerization of different monomers, followed by post-functionalization.
- the units of formula (I) can be obtained from acrylic acid, by transesterification reaction.
- the polymer according to the invention can be prepared according to any known method of polymerization.
- the various techniques and conditions of polymerization and crosslinking are widely described in literature and fall within the general knowledge of those skilled in the art.
- a polymerization is advantageously chosen from controlled radical polymerization; for example, by atomic transfer radical polymerization (ATRP in English “Atom Transfer Radical Polymerization”); radical polymerization with nitroxide (NMP in English “Nitroxide-mediated polymerization”); degenerative transfer processes (in English “degenerative transfer processes") such as degenerative iodine transfer polymerization (in English "ITRP- iodine transfer radical polymerization") or radical polymerization by reversible chain transfer by addition-fragmentation ( RAFT in English "Reversible Addition-Fragmentation Chain Transfer”); polymerizations derived from ATRP such as polymerizations using initiators for continuous regeneration of the activator (ICAR - Initiators for continuous activator regeneration) or using activators regenerated by electron transfer (ARGET in English "activators regenerated by electron transfer ”).
- ATRP atomic transfer radical polymerization
- NMP radical polymerization with nitroxide
- degenerative transfer processes in English “degenerative
- the copolymer according to the invention advantageously has a weight-average molar mass (Mw) of between 1,000 and 50,000 g. mol ⁇ 1 , more preferably between 1,000 and 20,000, even more preferably between 3,000 and 15,000 g. mol 1 .
- the copolymer according to the invention advantageously has a number-average molar mass (Mn) of between 1,000 and 50,000 g. mol 1 , more preferably between 1,000 and 20,000, even more preferably between 2,000 and 10,000 g. mol 1 .
- the number and weight average molar masses are measured by size exclusion chromatography (SEC in English “Size Exclusion Chromatography”).
- the copolymer described above is used to improve the cold-keeping properties of a fuel or fuel composition, in particular, of a composition chosen from gas oils, biodiesels, gas oils of type B x and fuel oils , preferably, domestic fuel oils (FOD).
- a fuel or fuel composition in particular, of a composition chosen from gas oils, biodiesels, gas oils of type B x and fuel oils , preferably, domestic fuel oils (FOD).
- FOD domestic fuel oils
- the fuel or fuel composition is as described below and advantageously comprises at least one section of hydrocarbons obtained from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal sources , vegetable and synthetic.
- said copolymer is used to improve the flow properties at low temperature of the fuel or fuel during its storage and / or its use at low temperature, by lowering its limit filterability temperature (or TLF, measured according to the NF standard).
- TLF limit filterability temperature
- EN 1 16 and / or its pour point or PE, measured according to standard ASTM D 7346
- PE measured according to standard ASTM D 7346
- TLF limit filterability temperature
- the copolymer according to the invention can be used to delay or prevent the sedimentation of paraffin crystals and more particularly of n-alkanes, preferably, the n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms , even more preferably preferably at least 24.
- the copolymer according to the invention is used as a TLF booster additive, that is to say in combination with at least one flow-improving additive or cold-thinning additive (in English “cold flow” improvers "or CFI).
- the cold fluidizing additive (CFI) is preferably chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
- the copolymer according to the invention is used to amplify the fluidizing effect of the cold fluidizing additive, in particular by lowering the limit filterability temperature (TLF) and / or the pour point, and / or by delaying or preventing the sedimentation of crystals, such as those containing paraffins.
- TLF limit filterability temperature
- TLF booster This effect is usually called the “TLF booster” effect insofar as the presence of the copolymer according to the invention improves the fluidizing nature of the CFI additive.
- This improvement is reflected, in particular, by a significant drop in the TLF of the fuel composition or fuel additivated with this combination compared to the same fuel composition or fuel additivated only with the additive CFI, at the same treatment rate.
- a significant drop in TLF results in a decrease of at least 3 ° C in TLF according to standard NF EN 1 16.
- the copolymer is used to amplify the fluidizing (flow) effect of the cold fluidizing additive (CFI) by improving the Limit of Filterability (TLF) of the fuel or fuel, the TLF being measured according to standard NF EN 1 16.
- CFI cold fluidizing additive
- TLF Limit of Filterability
- the copolymer can be added to the fuels or combustibles within the refinery, and / or be incorporated downstream of the refinery, possibly, in mixture with other additives, in the form of an additive concentrate, also called according to the use "additive package".
- the copolymer is advantageously used in fuel or fuel at a content of at least 0.0001% by weight, relative to the total weight of the fuel or fuel composition.
- the content of said copolymer ranges from 0.0001 to 0.01% by weight, preferably from 0.0002 to 0.005% by weight, and better still from 0.0003 to 0.003% by weight, relative to the total weight of the fuel or fuel composition.
- the subject of the invention is also an additive composition comprising a copolymer as described above, and one or more additive (s) for cold resistance different from the copolymers comprising formula (I) and units of formula (II) as described above.
- the cold-keeping additive (s) are chosen from cold-thinning additives (s), anti-sedimentation additives and / or paraffin dispersants, and mixtures of these additives .
- the cold-thinning additives can in particular be chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
- copolymers of ethylene and of an unsaturated ester such as ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE) copolymers.
- EVA ethylene / vinyl acetate
- EVE ethylene / vinyl ethanoate
- EMMA ethylene / methyl methacrylate
- Mention may also be made of terpolymers of ethylene, vinyl acetate and another vinyl ester, for example vinyl neodecanoate.
- the composition contains at least one cold-thinning additive (CFI) chosen from copolymers of ethylene and of vinyl ester (s), alone or as a mixture, in particular ethylene / vinyl acetate (EVA), ethylene vinyl propionate copolymers (TEU) and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably ethylene / vinyl acetate copolymers (EVA) and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.
- CFI cold-thinning additive
- the weight ratio between the content of copolymer (s) according to the invention on the one hand, and the content of copolymer (s) of ethylene and of vinyl ester (s) of on the other hand is advantageously included in the range from 0.01: 100 to 20: 100, preferably from 0.1: 100 to 10: 100, and better still from 0.5:
- a particularly preferred weight ratio is 1: 100 ⁇ 10%.
- the anti-sedimentation additives and / or paraffin dispersants can be in particular, but not limited to, chosen from the group consisting of (meth) acrylic acid / alkyl (meth) acrylate copolymers amidified by a polyamine, polyamine alkenyl succinimides, phthalamic acid derivatives and double chain fatty amines; optionally grafted alkylphenol resins.
- WASA paraffin dispersants
- the particularly preferred anti-sedimentation additives and / or paraffin dispersants are chosen from alkylphenol resins and alkylphenol resins grafted, for example, by functional groups such as polyamines.
- the additive composition can also comprise one or more other additives commonly used in fuels or combustibles, different from the copolymer according to the invention and the cold-keeping additives described above.
- the additive composition can typically include one or more other additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
- additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
- procetane additives in particular (but not limited to) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
- anti-foam additives in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590;
- detergent and / or anti-corrosion additives in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenyl succinimides, polyalkylamines, polyalkyl polyamines, polyetheramines, quaternary ammonium salts and triazole derivatives; examples of such additives are given in the following documents: EP0938535, US2012 / 00101 12 and W02012 / 004300. It is also advantageously possible to use block copolymers formed from at least one polar unit and one apolar unit, such as for example those described in patent application FR 1761700 in the name of the Applicant;
- the additive composition can advantageously comprise from 0.1 to 50% by weight of copolymer as described above, relative to the total weight of the additive composition.
- the present invention also relates to an additive concentrate comprising an additive composition as described above, in admixture with an organic liquid.
- the organic liquid is advantageously inert with respect to the constituents of the additive composition, and miscible with fuels or combustibles, in particular those from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic.
- the organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, only or mixed.
- aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO”
- alcohols, ethers and other oxygenated compounds such as hexane, pentane or isoparaffins, only or mixed.
- paraffinic solvents such as hexane, pentane or isoparaffins, only or mixed.
- the invention also relates to a fuel or fuel composition, comprising:
- the mineral sources are preferably petroleum.
- the fuel or fuel composition according to the invention advantageously comprises said copolymer (s) in a content of at least 0.0001% by weight, relative to the total weight of the fuel or fuel composition.
- the content of copolymer (s) ranges from 0.0001 to 0.01% by weight, preferably from 0.0002 to 0.005% by weight, and better still from 0.0003 to 0.003% by weight, relative the total weight of the fuel or fuel composition.
- said composition also comprises at least one cold-keeping additive, chosen from cold-thinning additives (CEI) and anti-sedimentation additives and / or paraffin dispersants (WASA), different (s) copolymers according to the invention comprising units of formula (I) and units of formula (II).
- cold-keeping additive chosen from cold-thinning additives (CEI) and anti-sedimentation additives and / or paraffin dispersants (WASA), different (s) copolymers according to the invention comprising units of formula (I) and units of formula (II).
- CEI cold-thinning additives
- WASA paraffin dispersants
- the composition contains advantageously at least 20 ppm, preferably at least 50 ppm, advantageously between 20 and 5000 ppm, more preferably between 50 and 1000 ppm in total of cold-keeping additive (s).
- the fuels or fuels can be chosen from liquid hydrocarbon fuels or fuels, alone or as a mixture.
- Fuels or liquid hydrocarbon fuels include in particular distillais with a boiling temperature of between 100 and 500 ° C.
- These distillates can for example be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS-type conversion processes (by desulfurization of atmospheric residue) and / or visbreaking, the distillates resulting from the recovery of Fischer Tropsch cuts, the distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination, and / or biodiesels of animal and / or vegetable origin and / or oils and / or esters of vegetable and / or animal oils.
- the sulfur content of fuels is preferably less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm, and advantageously without sulfur.
- the fuel or fuel is preferably chosen from gas oils, biodiesel, type B x gas oils and fuel oils, preferably domestic fuel oils (FOD).
- FOD domestic fuel oils
- type B x diesel for diesel engine is meant a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a process chemical called transesterification reacting this oil with an alcohol in order to obtain fatty acid esters (EAG).
- EAG fatty acid esters
- EMAG methyl esters of fatty acids
- EEAG ethyl esters of fatty acids
- B followed by a number x ranging from 0 to 100, which indicates the percentage of EAG contained in diesel.
- a B99 contains 99% of EAG and 1% of middle distillates of fossil origin, B20, 20% of EAG and 80% of middle distillates of fossil origin, etc.
- diesel fuels of type Bo which do not contain oxygenated compounds
- diesel fuels of type Bx which contain x% (v / v) of vegetable or animal oil esters or fatty acids, most often methyl esters (EMHV or EMAG).
- EAG methyl esters
- the fuel or combustible can also contain hydrogenated vegetable oils, known to a person skilled in the art under the name HVO (from the English “hydrogenated vegetable oil”) or HDRD (from the English “hydrogenation-derived renewable diesel”) .
- HVO from the English “hydrogenated vegetable oil”
- HDRD from the English “hydrogenation-derived renewable diesel”
- the fuel or fuel is chosen from gas oils, biodiesel and gas oils of type B x , hydrogenated vegetable oils (HVO), and their mixtures.
- the fuel or combustible composition can also contain one or more additional additives, different from the copolymers and cold-keeping additives described above.
- additional additives can in particular be chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or additives oiliness, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
- Additional additives can generally be present in an amount ranging from 50 to 1000 ppm (each).
- a method for improving the cold-keeping properties of a fuel or combustible composition comprises the successive steps of:
- an additive composition (s) most suitable for the fuel composition or fuel to be treated as well as treatment rate necessary to reach a given specification relating to the cold-keeping properties for the specific fuel or fuel composition, said additive composition (s) comprising at least one copolymer according to the invention and, optionally, at least one additive cold resistance, chosen from cold-thinning additives and paraffin dispersants and / or anti-sedimentation additives, different from the copolymers comprising units of formula (I) and units of formula (II);
- step b) treatment of the fuel or combustible composition with the quantity determined in step a) of said additive composition (s).
- the process for improving the cold resistance properties is typically intended for a fuel or combustible composition as described above.
- Step a) is carried out according to any known process and is part of current practice in the field of additivation of fuels or combustibles. This step involves defining a characteristic representative of the cold-keeping properties of the fuel or fuel, for example the characteristics of flow at low temperature, setting the target value and then determining the improvement which is required to reach the specification.
- a specification relating to the resistance to cold can be a European specification for Great Cold defining, in particular, a maximum TLF according to standard NF EN 1 16.
- the determination of the quantity of composition of additive (s) to be added to the composition of fuel or combustible to reach the specification will be carried out typically by comparison with the composition of fuel or combustible without said composition of additive (s).
- the amount of copolymer necessary to treat the composition of fuel or combustible can vary according to the nature and the origin of the fuel or combustible, in particular according to the rate and the nature of the paraffinic compounds which it contains. The nature and origin of the fuel or combustible can therefore also be a factor to take into account for step a).
- the process for improving the cold resistance properties may also include an additional step after step b) of verifying the target reached and / or of adjusting the treatment rate with the additive composition (s).
- Monomer 2 1 -vinylimidazole (NVI) (CAS 1072-63-5)
- Control agent Trithiocarbonate (CAS 558484-21 -2)
- the flask containing the reaction medium is heated and once the target temperature is reached (70 ° C), the initiator solution is introduced to start the polymerization.
- the reaction is left for 6 h at 70 ° C.
- the heating is switched off and the medium is exposed to air in order to stop the polymerization.
- the solvent is then evaporated under vacuum in order to recover the polymer.
- the block copolymers of the various examples were synthesized according to this protocol.
- the amount of the monomers was adapted in each case.
- the polymers were characterized by steric exclusion chromatography (SEC in English “Size Exclusion Chromatography”), in order to determine the composition and the molar mass of each copolymer.
- SEC steric exclusion chromatography
- the characteristics of the polymers synthesized according to the protocols described above are collated in Table I below:
- Example 2 Evaluation of the Cold Resistance Performance
- the polymers described in Example 1 were tested as cold resistance additives in a fuel composition G of the diesel fuel type which is particularly difficult to process, and the characteristics of which are detailed in the table. II below:
- the diesel fuel composition G was added with a package containing the following two standard commercial cold-thinning additives (CFI additives), in Solvesso 150 solvent:
- additive CP7956C sold by the company Total Additives Special Fuels, and which is an ethylene / vinyl acetate (EVA) copolymer;
- Dodiflow additive D4134 sold by the company Clariant, and which is an ethylene / vinyl acetate / vinyl neodecanoate terpolymer.
- This package was incorporated into the diesel composition G at a content of 300 ppm by weight of active material (ie 150 ppm by weight of each additive) relative to the total weight of the diesel composition.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1857716A FR3085384B1 (fr) | 2018-08-28 | 2018-08-28 | Utilisation de copolymeres specifiques pour ameliorer les proprietes a froid de carburants ou combustibles |
PCT/EP2019/072598 WO2020043618A1 (fr) | 2018-08-28 | 2019-08-23 | Utilisation de copolymères spécifiques pour améliorer les propriétés à froid de carburants ou combustibles |
Publications (2)
Publication Number | Publication Date |
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EP3844250A1 true EP3844250A1 (fr) | 2021-07-07 |
EP3844250B1 EP3844250B1 (fr) | 2024-04-03 |
Family
ID=65201180
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19755939.6A Active EP3844250B1 (fr) | 2018-08-28 | 2019-08-23 | Utilisation de copolymères spécifiques pour améliorer les propriétés à froid de carburants ou combustibles |
Country Status (5)
Country | Link |
---|---|
US (1) | US20210348073A1 (fr) |
EP (1) | EP3844250B1 (fr) |
FR (1) | FR3085384B1 (fr) |
PL (1) | PL3844250T3 (fr) |
WO (1) | WO2020043618A1 (fr) |
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US3048479A (en) | 1959-08-03 | 1962-08-07 | Exxon Research Engineering Co | Ethylene-vinyl ester pour depressant for middle distillates |
US3275427A (en) | 1963-12-17 | 1966-09-27 | Exxon Research Engineering Co | Middle distillate fuel composition |
US3627838A (en) | 1964-12-11 | 1971-12-14 | Exxon Research Engineering Co | Process for manufacturing potent pour depressants |
US3790359A (en) | 1969-03-17 | 1974-02-05 | Exxon Research Engineering Co | Middle distillate fuel having increased low temperature flowability |
US3961961A (en) | 1972-11-20 | 1976-06-08 | Minnesota Mining And Manufacturing Company | Positive or negative developable photosensitive composition |
GB8307522D0 (en) * | 1983-03-18 | 1983-04-27 | Shell Int Research | Wax-containing crude oil |
IN184481B (fr) | 1986-09-24 | 2000-08-26 | Exxon Chemical Patents Inc | |
EP0261959B1 (fr) | 1986-09-24 | 1995-07-12 | Exxon Chemical Patents Inc. | Additifs pour mazout |
FR2626578B1 (fr) | 1988-02-03 | 1992-02-21 | Inst Francais Du Petrole | Polymeres amino-substitues et leur utilisation comme additifs de modification des proprietes a froid de distillats moyens d'hydrocarbures |
GB9006315D0 (en) * | 1990-03-21 | 1990-05-16 | Shell Int Research | Polymer compositions |
TW215106B (fr) * | 1990-09-25 | 1993-10-21 | Shell Internat Res Schappej B V | |
FR2676062B1 (fr) | 1991-05-02 | 1993-08-20 | Inst Francais Du Petrole | Polymere amino-substitues et leur utilisation comme additifs de modification des proprietes a froid de distillats moyens d'hydrocarbures. |
GB9200694D0 (en) | 1992-01-14 | 1992-03-11 | Exxon Chemical Patents Inc | Additives and fuel compositions |
GB9219962D0 (en) | 1992-09-22 | 1992-11-04 | Exxon Chemical Patents Inc | Additives for organic liquids |
ES2103066T3 (es) | 1992-10-09 | 1997-08-16 | Inst Francais Du Petrole | Fosfatos de aminas que incluyen un ciclo imida terminal, su preparacion y su utilizacion como aditivos para carburantes motores. |
GB9222458D0 (en) * | 1992-10-26 | 1992-12-09 | Exxon Chemical Patents Inc | Oil additives and compositions |
FR2699550B1 (fr) | 1992-12-17 | 1995-01-27 | Inst Francais Du Petrole | Composition de distillat moyen de pétrole contenant des additifs azotés utilisables comme agents limitant la vitesse de sédimentation des paraffines. |
GB9301119D0 (en) | 1993-01-21 | 1993-03-10 | Exxon Chemical Patents Inc | Fuel composition |
ATE152138T1 (de) * | 1993-10-02 | 1997-05-15 | Basf Ag | Copolymerisate auf ethylenbasis und ihre verwendung als fliessverbesserer in erdölmitteldestillaten |
FR2735494B1 (fr) | 1995-06-13 | 1997-10-10 | Elf Antar France | Additif bifonctionnel de tenue a froid et composition de carburant |
FR2751982B1 (fr) | 1996-07-31 | 2000-03-03 | Elf Antar France | Additif d'onctuosite pour carburant moteurs et composition de carburants |
FR2753455B1 (fr) | 1996-09-18 | 1998-12-24 | Elf Antar France | Additif detergent et anti-corrosion pour carburants et composition de carburants |
EP0857776B2 (fr) | 1997-01-07 | 2007-05-02 | Clariant Produkte (Deutschland) GmbH | Amélioration de la fluidité d'huiles minérales et de distillates d'huiles minérales par l'utilisation de résines alkylphénol-aldéhyde |
US5730029A (en) | 1997-02-26 | 1998-03-24 | The Lubrizol Corporation | Esters derived from vegetable oils used as additives for fuels |
JPH10237467A (ja) | 1997-02-26 | 1998-09-08 | Tonen Corp | ディーゼルエンジン用燃料油組成物 |
FR2772783A1 (fr) | 1997-12-24 | 1999-06-25 | Elf Antar France | Additif d'onctuosite pour carburant |
FR2772784B1 (fr) | 1997-12-24 | 2004-09-10 | Elf Antar France | Additif d'onctuosite pour carburant |
US20050223631A1 (en) | 2004-04-07 | 2005-10-13 | Graham Jackson | Fuel oil compositions |
FR2903418B1 (fr) | 2006-07-10 | 2012-09-28 | Total France | Utilisation de composes revelateurs d'efficacite des additifs de filtrabilite dans des distillats hydrocarbones, et composition synergique les contenant. |
CN101691508B (zh) * | 2009-10-20 | 2012-10-03 | 济南开发区星火科学技术研究院 | 一种柴油低温流动性改进剂及其制备方法 |
US20120010112A1 (en) | 2010-07-06 | 2012-01-12 | Basf Se | Acid-free quaternized nitrogen compounds and use thereof as additives in fuels and lubricants |
CA2804322C (fr) | 2010-07-06 | 2020-02-11 | Basf Se | Composes azotes quaternises exempts d'acide et utilisation desdits composes comme additifs pour carburants ou pour lubrifiants |
FR2969620B1 (fr) | 2010-12-23 | 2013-01-11 | Total Raffinage Marketing | Resines alkylphenol-aldehyde modifiees, leur utilisation comme additifs ameliorant les proprietes a froid de carburants et combustibles hydrocarbones liquides |
EP3056526A1 (fr) | 2015-02-11 | 2016-08-17 | Total Marketing Services | Copolymeres a blocs et leur utilisation pour ameliorer les proprietes a froid de carburants ou combustibles |
FR3045658A1 (fr) * | 2015-12-22 | 2017-06-23 | Total Marketing Services | Additif detergent pour carburant |
-
2018
- 2018-08-28 FR FR1857716A patent/FR3085384B1/fr active Active
-
2019
- 2019-08-23 EP EP19755939.6A patent/EP3844250B1/fr active Active
- 2019-08-23 US US17/272,049 patent/US20210348073A1/en not_active Abandoned
- 2019-08-23 PL PL19755939.6T patent/PL3844250T3/pl unknown
- 2019-08-23 WO PCT/EP2019/072598 patent/WO2020043618A1/fr unknown
Also Published As
Publication number | Publication date |
---|---|
FR3085384B1 (fr) | 2021-05-28 |
US20210348073A1 (en) | 2021-11-11 |
PL3844250T3 (pl) | 2024-07-29 |
WO2020043618A1 (fr) | 2020-03-05 |
FR3085384A1 (fr) | 2020-03-06 |
EP3844250B1 (fr) | 2024-04-03 |
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