WO2011001352A1 - Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles - Google Patents
Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles Download PDFInfo
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- WO2011001352A1 WO2011001352A1 PCT/IB2010/052922 IB2010052922W WO2011001352A1 WO 2011001352 A1 WO2011001352 A1 WO 2011001352A1 IB 2010052922 W IB2010052922 W IB 2010052922W WO 2011001352 A1 WO2011001352 A1 WO 2011001352A1
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- Prior art keywords
- fuels
- ppm
- copolymer
- additives
- filterability
- Prior art date
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- 239000000654 additive Substances 0.000 title claims abstract description 55
- 239000000446 fuel Substances 0.000 title claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000005977 Ethylene Substances 0.000 title claims abstract description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 230000000996 additive effect Effects 0.000 title claims abstract description 12
- 229920001897 terpolymer Polymers 0.000 title claims description 27
- 229930195733 hydrocarbon Natural products 0.000 title claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 16
- 239000007788 liquid Substances 0.000 title description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- -1 monocarboxylic acid ester Chemical class 0.000 claims abstract description 18
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 13
- 239000004711 α-olefin Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 239000000295 fuel oil Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000002283 diesel fuel Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 239000003225 biodiesel Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000002781 deodorant agent Substances 0.000 claims description 2
- 239000004071 soot Substances 0.000 claims description 2
- 239000010763 heavy fuel oil Substances 0.000 claims 2
- 239000004129 EU approved improving agent Substances 0.000 claims 1
- 230000006866 deterioration Effects 0.000 claims 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 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
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 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
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- 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
- 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
- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/043—Kerosene, jet fuel
-
- 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
-
- 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 invention relates to the use of alpha-olefin, vinyl ester and alpha, beta-unsaturated carboxylic acid ester copolymers as additives for improving the cold-running performance of fuels and lubricants, as well as fuel oils and lubricants. packages containing these copolymers.
- the hydrocarbon compositions especially those based on middle distillate type containing paraffin waxes, such as for example diesel fuels and heating fuel oils have a significant decrease in their flow properties. It is well known that the crystallization of paraffins is a limiting factor for the use of middle distillates. Also, it is important to prepare diesel fuels adapted to the temperatures at which they will be used in motorized vehicles, that is to say to the surrounding climate. Generally, cold operability of fuels at -10 0 C is sufficient in many hot or temperate countries. But in countries with a cold climate, such as the Scandinavian countries, Canada and the countries of North Asia, it is possible to reach fuel consumption temperatures well below -20 0 C.
- paraffins are crystallized at the bottom of the tank, they can be driven to start in the fuel system and particularly clog filters and prefilters arranged upstream of the injection systems (pump and injectors).
- paraffins precipitate at the bottom of the tank and can be driven and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents the normal circulation of the middle distillate.
- CFI cold flow improvers
- the prior art also provides conventional CFI ethylene / unsaturated ester additive mixtures with lubricating agents (mono- or polycarboxylic acid esters and mono- or polyalcohols (see, for example EP 721 492), with anti-settling agents (see, for example, FR 2 490 669), with ethers (see for example US Pat. No. 3,999,960, EP 1 87 488).
- lubricating agents mono- or polycarboxylic acid esters and mono- or polyalcohols
- anti-settling agents see, for example, FR 2 490 669
- ethers see for example US Pat. No. 3,999,960, EP 1 87 488).
- CFI additives which are terpolymers or copolymers derived from more than 3 different monomers.
- US Pat. No. 6,509,424 describes a process for the preparation of terpolymers of ethylene and at least two compounds containing ethylenic unsaturations, such as vinyl esters, (meth) acrylic esters and alkyl vinyl ethers in a tubular reactor. .
- terpolymers can be used as additives improving the cold flow of oils and petroleum distillates.
- No. 3,642,459 describes terpolymers comprising 40 to 89% by weight of ethylene, 10 to
- vinyl ester derived from short chain (C2-C4) carboxylic acid such as vinyl acetate, and unsaturated monoesters having a C10-C22 alkyl chain; these terpolymers are used as additives to lower the pour point of petroleum distillates and as anti-waxing agents and to improve their filterability.
- WO 2005/054314 describes terpolymers of alpha olefin, vinyl ester and alpha-beta unsaturated mono carboxylic acid ester used.
- Terpolymers particularly preferred by the applicant, which contain more than 80 mol% of ethylene and less than 9 mol% of vinyl acetate are exemplified.
- these terpolymers containing less than 9 mol% of vinyl acetate although having an effect on the reduction of TLF for middle distillates containing more than 18% of n-paraffins, are not satisfactory for on the one hand solubility and secondly the tendency to clogging (or filterability at room temperature): there is harmful filter clogging.
- EP 1,391,498 discloses additives improving the low temperature fluidity of middle distillates which are vinyl polymers (A), preferably ethylene-vinyl ester copolymers, the amount of hexane insoluble materials exceeding 60% by weight at -20 0 C and is less than 30% by weight at 10 0 C; the examples of EP 1.391.498 clearly show that the filterability temperature (CFPP) is lowered for copolymers and terpolymers whose amount of hexane-insoluble matter exceeds 60% by weight at -20 ° C.
- CFPP filterability temperature
- copolymers and terpolymers having the same units of recurrence present in the same proportions but the amount of hexane insoluble material is outside the range claimed;
- copolymers exemplified are EVA copolymers and ethylene-vinyl acetate-neodecanoate or 2-ethylhexanoate vinyl terpolymers.
- the present invention relates to the use of copolymers as additives improving the cold resistance of fuels (CFI additives); these copolymers contain units derived from at least one alpha-olefin, at least one vinyl ester and at least one alpha-beta unsaturated mono carboxylic acid ester, and are preferably terpolymers of ethylene, vinyl acetate and ethyl-2-acrylate, hexyl.
- copolymers according to the invention which can be used as CFI additives comprise:
- the copolymers that can be used as CFI additives are inscribed in a quadrilateral ABCD in which A, B, C and D represent the vertices of said quadrilateral and correspond to the molar percentages of at least the vinyl ester and at least one of alpha-beta unsaturated mono carboxylic acid ester:
- the copolymers that can be used as CFI additives are inscribed in a quadrilateral AiBCiD in which A 1 , B, Ci and D represent the vertices of said quadrilateral and correspond to the molar percentages of at least the vinyl ester and of at least 1 alpha-beta unsaturated mono carboxylic acid ester:
- the copolymers according to the invention which are random copolymers have a number-average molecular weight (Mw) measured by GPC in general of between 3,000 and 30,000, and a number-average molecular weight (Mn) measured by GPC in general between 1,000 and 15,000.
- copolymers can be prepared in known manner by any polymerization process (see for example, Ullmann's Encyclopedia of Industrial Chemistry, 5 th Edition, "Waxes” Vol A 28, p.146;. US 3,627,838; EP 7590 ) in particular by radical polymerization, preferably under high pressure, typically of the order of 1000 to 3000 bar (100 to 300 MPa), preferably from 1500 to 2000 bar (150 to 200 MPa), the temperatures of reaction generally ranging from 160 to 320 ° C., preferably from 200 to 280 ° C., and in the presence of at least one radical initiator chosen in general from organic peroxides and / or oxygenated or nitrogen compounds, and from molecular weight regulator (ketone or aliphatic aldehyde, ).
- the copolymers may for example be prepared in a tabular reactor according to the process described in US 6,509,424.
- hydrocarbon-based compositions in which the copolymers according to the invention are incorporated are chosen from all types of fuel oils or fuels, such as diesel fuels, heating oil for heating installations (FOD), kerosene, aviation fuel oil, fuel oil. heavy, etc.
- fuel oils or fuels such as diesel fuels, heating oil for heating installations (FOD), kerosene, aviation fuel oil, fuel oil. heavy, etc.
- the sulfur content of the hydrocarbon compositions is less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm and advantageous without sulfur.
- the hydrocarbon-based compositions comprise middle distillates with a boiling point of between 100 and 500 ° C. their starting crystallization temperature Tcc is often greater than or equal to -20 ° C., generally between -15 ° C. and + 10 ° C.
- These distillates may, 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 conversion processes such as ARDS (by atmospheric residue desulphurisation) and / or visbreaking, distillates from the recovery of Fischer Tropsch cuts, distillates resulting from BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination and / or esters of vegetable and animal oils or mixtures thereof.
- ARDS by atmospheric residue desulphurisation
- BTL biomass to liquid
- the hydrocarbon compositions may also contain distillates resulting from more complex refining operations than those resulting from the direct distillation of hydrocarbons which may for example be derived from cracking, hydrocracking and / or catalytic cracking processes and visbreaking processes.
- distillates may also contain new sources of distillates, among which may be mentioned in particular:
- oils and / or esters of vegetable and / or animal oils
- These new fuel bases can be used alone or in combination with conventional middle oil distillates as fuel base and / or base of domestic fuel oil; they generally comprise long paraffinic chains greater than or equal to 10 carbon atoms and preferably C14 to C30.
- copolymers as defined previously of Mw between 5,000 and 27,000 and Mn between 1,500 and 22,000, preferably Mw between 5,000 and 25,000 and Mn between 1,500 and 20,000 are particularly effective. when incorporated into light and / or low-sulfur middle distillates (typically less than 50 ppm) and / or low starting crystallization temperature (typically up to
- Light middle distillates means distillates whose n-paraffin content
- C18-C23 n-paraffins represent about 3 to about 5% of the total weight of the fuel and whose weight ratio of C18-C23 n-paraffins to paraffins C24 and higher is generally from 10 to 35.
- heavy middle distillates distillates having a n-paraffin content of 24 or more carbon atoms ranging from about 0.7 to about 2% by weight of the total fuel composition; wherein the C18-C23 n-paraffins represent about 1 to about 10% of the total weight of the fuel and whose mass ratio of C18-C23 n-paraffins to C24 + paraffins is generally from 1 to 10.
- copolymers may be added as such in the hydrocarbon compositions or, preferably, in the form of concentrated solutions, in particular solutions containing from 50 to 80%, preferably from 60 to 70% by weight of copolymer (s) in a mixture.
- solvent such as aliphatic or aromatic hydrocarbons, alone or as a mixture (naphtha, kerosene, hydrocarbon fractions, such as solvent Solvesso, paraffinic hydrocarbons, such as pentane, hexane.
- the hydrocarbon compositions comprise from 10 to 5000 ppm by weight of at least one copolymer described above, preferably from 100 to 1000 ppm, and advantageously from 150 to 500 ppm.
- the hydrocarbon compositions may also contain one or more other additives different from the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot) , cloud point improvers, pour point, filterability limit temperature, anti-settling agents, anti-wear agents and / or conductivity modifiers.
- additives different from the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot) , cloud point improvers, pour point, filterability limit temperature, anti-settling agents, anti-wear agents and
- procetane additives in particular (but not limited to) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aroyl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
- anti-foam additives in particular (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides from vegetable or animal oils.
- anti-foam additives examples are given in EP 861 882, EP 663 000, EP 736 590;
- detergent and / or anti-corrosion additives in particular (but not limited to) selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines and polyetheramines. Examples of such additives are given in EP 938,535.
- lubricant additive or anti-wear agent in particular (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- and polycyclic carboxylic acid derivatives .
- lubricant additive or anti-wear agent selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- and polycyclic carboxylic acid derivatives .
- examples of such additives are given in the following documents: EP 680 506, EP 860 494, WO 98/04656, EP 915 944, FR 2 772 783, FR 2 772 784.
- cloud point additives including (but not limited to) selected from the group consisting of long-chain olefin terpolymers / (meth) acrylic ester / maleimide, and fumaric acid / maleic acid ester polymers. Examples of such additives are given in EP 71 513, EP 100 248, FR 2 528 051, FR 2 528 051, FR 2 528 423, EP 1 12 195, EP 1 727 58, EP 271 385, EP 291367;
- anti-sedimentation additives and / or paraffin dispersants in particular (but not limited to) selected from the group consisting of scolymers (meth) acrylic acid / polyamine amidated alkyl (meth) acrylate; polyamine alkenyl succinimides, phthalamic acid derivatives and double chain fatty amine derivatives; alkyl phenol resins.
- scolymers meth) acrylic acid / polyamine amidated alkyl (meth) acrylate
- polyamine alkenyl succinimides, phthalamic acid derivatives and double chain fatty amine derivatives alkyl phenol resins.
- Examples of such additives are given in EP 261,959, EP593,331, EP 674,689, EP 327,423, EP 512,889, EP 832,172; US 2005/0223631; US 5,998,530; WO 93/14178.
- polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate polymers as described in EP 573,490;
- additives are generally added in an amount ranging from 100 to 1000 ppm (each).
- the improved cold-strength additives according to the invention may be added to the hydrocarbon compositions within the refinery, and / or may be incorporated downstream of the refinery, optionally mixed with other additives, in the form of a package. or package of additives.
- high-pressure radical polymerization (1400 to 2500 bar (140 to 250 MPa) and a polymerization temperature of 200 to 280 ° C. are synthesized by terpolymers of ethylene, vinyl acetate and The synthesis is carried out using an aliphatic aldehyde (propanal) to control the molecular weights and using peroxides as polymerization initiators
- Mn are indicated.
- Table 1 Characteristics of synthesized polymers
- Table 4 TLF efficiency tests on 2 gas oils with low sulfur content.
- the terpolymer 17 according to the invention is the most effective on the GOM 1 gas oil. Moreover, from the results of Table 3, it can be seen that the terpolymer 17 added at the rate of 400 ppm in the GOM 1 does not degrade. the tendency to clogging. This is not the case of comparative terpolymers 6; 7; 16 and 18 according to WO 2005/054314 which greatly degrade the clogging tendency measured according to IP 387 and are not as effective in TLF as the additive 17 of the invention.
Abstract
Description
Claims
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2010267626A AU2010267626B2 (en) | 2009-07-03 | 2010-06-25 | Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels |
SG2011096435A SG177381A1 (en) | 2009-07-03 | 2010-06-25 | Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels |
US13/381,554 US20120102825A1 (en) | 2009-07-03 | 2010-06-25 | Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels |
MX2012000172A MX363328B (es) | 2009-07-03 | 2010-06-25 | Terpolimero estileno/acetato de vinilo/esteres insaturados como aditivo mejorador de la resistencia en frio de hidrocarburos liquidos tales como los destilados medios y los carburantes o combustibles. |
CN2010800296922A CN102549120A (zh) | 2009-07-03 | 2010-06-25 | 乙烯/醋酸乙烯酯/不饱和酯三元共聚物作为改善液态烃如中间馏分和燃料的耐低温性能的添加剂 |
CA2765245A CA2765245C (fr) | 2009-07-03 | 2010-06-25 | Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles |
EA201270129A EA201270129A1 (ru) | 2009-07-03 | 2010-06-25 | Терполимер этилена, винилацетата и ненасыщенных сложных эфиров в качестве добавки для улучшения стойкости при низких температурах жидких углеводородов, таких как средние дистилляты и моторные топлива |
ES10734559T ES2706903T5 (es) | 2009-07-03 | 2010-06-25 | Terpolímero de etileno/acetato de vinilo/esteres insaturados como aditivo que mejora la resistencia al frío de los hidrocarburos líquidos, tales como los destilados medios y los carburantes o combustibles |
BRPI1016080A BRPI1016080B1 (pt) | 2009-07-03 | 2010-06-25 | etileno/acetato de vinila/ésteres insaturados do terpolímero como aditivos que aumentam a resistência à baixa temperatura de hidrocarbonetos líquidos como destilados intermediários e combustíveis. |
KR1020117031259A KR102002887B1 (ko) | 2009-07-03 | 2010-06-25 | 중간 증류액 및 연료와 같은 액체 탄화수소의 저온 저항성을 향상시키는 첨가제로서의 에틸렌/비닐 아세테이트/불포화 에스테르 삼원공중합체 |
JP2012518141A JP2012532225A (ja) | 2009-07-03 | 2010-06-25 | 中間留分及び燃料のような液体炭化水素の低温耐性を改善するための添加剤としての、エチレン/酢酸ビニル/不飽和エステルターポリマー |
EP10734559.7A EP2449063B2 (fr) | 2009-07-03 | 2010-06-25 | Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles |
ZA2011/09307A ZA201109307B (en) | 2009-07-03 | 2011-12-19 | Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0903278 | 2009-07-03 | ||
FR0903278A FR2947558B1 (fr) | 2009-07-03 | 2009-07-03 | Terpolymere et ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles |
Publications (1)
Publication Number | Publication Date |
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WO2011001352A1 true WO2011001352A1 (fr) | 2011-01-06 |
Family
ID=41716191
Family Applications (1)
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PCT/IB2010/052922 WO2011001352A1 (fr) | 2009-07-03 | 2010-06-25 | Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles |
Country Status (19)
Country | Link |
---|---|
US (1) | US20120102825A1 (fr) |
EP (1) | EP2449063B2 (fr) |
JP (1) | JP2012532225A (fr) |
KR (1) | KR102002887B1 (fr) |
CN (1) | CN102549120A (fr) |
AR (1) | AR077631A1 (fr) |
AU (1) | AU2010267626B2 (fr) |
BR (1) | BRPI1016080B1 (fr) |
CA (1) | CA2765245C (fr) |
CL (1) | CL2011003342A1 (fr) |
EA (1) | EA201270129A1 (fr) |
ES (1) | ES2706903T5 (fr) |
FR (1) | FR2947558B1 (fr) |
MX (1) | MX363328B (fr) |
PT (1) | PT2449063T (fr) |
SG (1) | SG177381A1 (fr) |
TW (1) | TWI496883B (fr) |
WO (1) | WO2011001352A1 (fr) |
ZA (1) | ZA201109307B (fr) |
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WO2015124529A1 (fr) * | 2014-02-18 | 2015-08-27 | Basf Se | Copolymères comprenant de l'éthylène, des esters de vinyle et des esters d'acide (méth)acrylique, leurs formulations et leur utilisation a titre d'abaisseurs du point d'écoulement, inhibiteurs de cires et améliorateurs d'écoulement pour huiles brutes |
WO2022023636A1 (fr) | 2020-07-31 | 2022-02-03 | Totalenergies Marketing Services | Utilisation de copolymères à distribution de masse molaire spécifique pour abaisser la température limite de filtrabilité de carburants ou de combustibles |
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DE10356595A1 (de) * | 2003-12-04 | 2005-06-30 | Basf Ag | Brennstoffölzusammensetzungen mit verbesserten Kaltfließeigenschaften |
FR2925916B1 (fr) * | 2007-12-28 | 2010-11-12 | Total France | Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles |
KR20140020933A (ko) * | 2011-03-25 | 2014-02-19 | 에보니크 오일 아디티페스 게엠베하 | 연료 오일의 산화 안정성을 개선시키기 위한 조성물 |
FR2987052B1 (fr) | 2012-02-17 | 2014-09-12 | Total Raffinage Marketing | Additifs ameliorant la resistance a l'usure et au lacquering de carburants de type gazole ou biogazole |
FR3005061B1 (fr) | 2013-04-25 | 2016-05-06 | Total Raffinage Marketing | Additif pour ameliorer la stabilite a l'oxydation et/ou au stockage de carburants ou combustibles hydrocarbones liquides |
TWI576384B (zh) * | 2014-11-25 | 2017-04-01 | 鴻明環保科技股份有限公司 | 高植物源含量之乙烯-醋酸乙烯共聚物混合物發泡材料、其製造方法及應用 |
CN105733712B (zh) * | 2014-12-08 | 2017-12-05 | 中国石油天然气股份有限公司 | 用于航空生物燃料的润滑减磨添加剂 |
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- 2010-06-25 EA EA201270129A patent/EA201270129A1/ru unknown
- 2010-06-25 US US13/381,554 patent/US20120102825A1/en not_active Abandoned
- 2010-06-25 WO PCT/IB2010/052922 patent/WO2011001352A1/fr active Application Filing
- 2010-06-25 AU AU2010267626A patent/AU2010267626B2/en active Active
- 2010-06-25 SG SG2011096435A patent/SG177381A1/en unknown
- 2010-06-25 JP JP2012518141A patent/JP2012532225A/ja active Pending
- 2010-06-25 BR BRPI1016080A patent/BRPI1016080B1/pt active IP Right Grant
- 2010-06-25 ES ES10734559T patent/ES2706903T5/es active Active
- 2010-06-25 MX MX2012000172A patent/MX363328B/es unknown
- 2010-06-25 KR KR1020117031259A patent/KR102002887B1/ko active IP Right Grant
- 2010-06-25 PT PT10734559T patent/PT2449063T/pt unknown
- 2010-06-29 TW TW099121257A patent/TWI496883B/zh not_active IP Right Cessation
- 2010-07-01 AR ARP100102360A patent/AR077631A1/es not_active Application Discontinuation
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2011
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WO2015124529A1 (fr) * | 2014-02-18 | 2015-08-27 | Basf Se | Copolymères comprenant de l'éthylène, des esters de vinyle et des esters d'acide (méth)acrylique, leurs formulations et leur utilisation a titre d'abaisseurs du point d'écoulement, inhibiteurs de cires et améliorateurs d'écoulement pour huiles brutes |
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US10208192B2 (en) | 2014-02-18 | 2019-02-19 | Basf Se | Copolymers comprising ethylene, vinyl esters and esters of (meth)acrylic acid, their formulations and use as pour point depressant, wax inhibitor and flow enhancer for crude oils |
EA032565B1 (ru) * | 2014-02-18 | 2019-06-28 | Басф Се | Сополимеры, включающие этилен, сложные виниловые эфиры и сложные эфиры (мет)акриловой кислоты, их составы и применение в качестве депрессантов точки текучести, ингибиторов воска и усилителей текучести для сырых нефтей |
US10619038B2 (en) | 2014-02-18 | 2020-04-14 | Basf Se | Copolymers comprising ethylene vinyl esters and esters of (meth)acrylic acid, their formulations and use as pour point depressant, wax inhibitor and flow enhancer for crude oils |
WO2022023636A1 (fr) | 2020-07-31 | 2022-02-03 | Totalenergies Marketing Services | Utilisation de copolymères à distribution de masse molaire spécifique pour abaisser la température limite de filtrabilité de carburants ou de combustibles |
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KR102002887B1 (ko) | 2019-07-23 |
EA201270129A1 (ru) | 2012-05-30 |
AR077631A1 (es) | 2011-09-14 |
SG177381A1 (en) | 2012-02-28 |
AU2010267626A1 (en) | 2012-02-02 |
BRPI1016080B1 (pt) | 2018-10-16 |
AU2010267626B2 (en) | 2016-05-12 |
ZA201109307B (en) | 2012-09-26 |
MX363328B (es) | 2019-03-20 |
MX2012000172A (es) | 2012-02-28 |
KR20120040161A (ko) | 2012-04-26 |
CA2765245C (fr) | 2017-07-25 |
FR2947558A1 (fr) | 2011-01-07 |
US20120102825A1 (en) | 2012-05-03 |
CA2765245A1 (fr) | 2011-01-06 |
FR2947558B1 (fr) | 2011-08-19 |
TWI496883B (zh) | 2015-08-21 |
ES2706903T3 (es) | 2019-04-01 |
JP2012532225A (ja) | 2012-12-13 |
TW201116617A (en) | 2011-05-16 |
EP2449063B2 (fr) | 2021-07-28 |
ES2706903T5 (es) | 2021-12-14 |
CN102549120A (zh) | 2012-07-04 |
PT2449063T (pt) | 2019-02-04 |
BRPI1016080A2 (pt) | 2016-05-10 |
EP2449063A1 (fr) | 2012-05-09 |
EP2449063B1 (fr) | 2018-11-21 |
CL2011003342A1 (es) | 2012-07-06 |
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