EP2449063B2 - Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels - Google Patents
Ethylene/vinyl acetate/unsaturated esters terpolymer as an additive for improving the resistance to cold of liquid hydrocarbons such as middle distillates and fuels Download PDFInfo
- Publication number
- EP2449063B2 EP2449063B2 EP10734559.7A EP10734559A EP2449063B2 EP 2449063 B2 EP2449063 B2 EP 2449063B2 EP 10734559 A EP10734559 A EP 10734559A EP 2449063 B2 EP2449063 B2 EP 2449063B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- terpolymer
- fuels
- ppm
- vinyl acetate
- 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.)
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- 239000000654 additive Substances 0.000 title claims description 51
- 229920001897 terpolymer Polymers 0.000 title claims description 35
- 239000000446 fuel Substances 0.000 title claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 21
- 239000005977 Ethylene Substances 0.000 title claims description 20
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims description 19
- 229930195733 hydrocarbon Natural products 0.000 title claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 15
- 230000000996 additive effect Effects 0.000 title claims description 9
- 239000007788 liquid Substances 0.000 title description 2
- -1 demulsifiers Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 241001465754 Metazoa Species 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003225 biodiesel Substances 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000010763 heavy fuel oil Substances 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000003139 biocide Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000004071 soot Substances 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 230000007797 corrosion Effects 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 claims 1
- 239000012748 slip agent Substances 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- 239000000295 fuel oil Substances 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 241000861223 Issus Species 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-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
- 150000001732 carboxylic acid derivatives 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
- 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
- 239000000314 lubricant Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IJRVDOPVQJSPRP-UHFFFAOYSA-N octan-4-yl prop-2-enoate Chemical compound CCCCC(CCC)OC(=O)C=C IJRVDOPVQJSPRP-UHFFFAOYSA-N 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
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 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 compound 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 206010001052 Acute respiratory distress syndrome Diseases 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
- 241000209504 Poaceae Species 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
- 201000000028 adult respiratory distress syndrome Diseases 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- VWPSMBNJBFOTME-UHFFFAOYSA-N but-3-enoic acid;4-ethyl-2-methylideneoctanoic acid Chemical compound OC(=O)CC=C.CCCCC(CC)CC(=C)C(O)=O VWPSMBNJBFOTME-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940082150 encore Drugs 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002238 fumaric acids Chemical class 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
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 239000003208 petroleum Substances 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
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
-
- 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 copolymers of ethylene, vinyl acetate and ethyl-2-hexyl acrylate as additives improving the cold behavior of fuels and lubricants as well as fuel oils and packages containing these copolymers.
- the hydrocarbon compositions in particular based on middle distillate type containing paraffin waxes, such as, for example, diesel fuels and heating oils exhibit a significant reduction in their flow properties. It is well known that the crystallization of paraffins is a limiting factor in the use of middle distillates. Also, it is important to prepare diesel fuels adapted to the temperatures at which they will be used in motor vehicles, that is to say to the surrounding climate. Generally, cold operability of fuels at -10 ° C is sufficient in many warm or temperate countries. But in countries with cold climates, such as the Scandinavian countries, Canada and the countries of North Asia, one can reach temperatures of use of fuels well below -20 ° C.
- CFI cold flow improvers
- CFI additives see for example US 3,048,479 , US 3,627,838 , US 3,790,359 , US 3,961,961 , EP 261 957 ) which are in general copolymers of ethylene and unsaturated ester, such as ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / vinyl methacrylate copolymers methyl (EMMA), and ethylene / alkyl fumarate.
- EVA ethylene / vinyl acetate
- EVE ethylene / vinyl propionate
- EVE ethylene / vinyl ethanoate
- EMMA ethylene / vinyl methacrylate copolymers methyl
- alkyl fumarate ethylene / alkyl fumarate
- the prior art also provides mixtures of conventional CFI additives of ethylene / unsaturated ester type with lubricating agents (esters of mono- or polycarboxylic acid and of mono- or polyalcohols (see for example EP 721 492 ), with anti-sedimentation agents (see for example FR 2 490 669 ), with ethers (see for example US 3,999,960 , EP187 488 ).
- lubricating agents esters of mono- or polycarboxylic acid and of mono- or polyalcohols
- anti-sedimentation agents see for example FR 2 490 669
- ethers see for example US 3,999,960 , EP187 488 .
- CFI additives are also found which are terpolymers or copolymers derived from more than 3 distinct monomers.
- US 6,509,424 describes a process for preparing ethylene terpolymers and at least two compounds containing ethylenic unsaturations, such as vinyl esters, (meth) acrylic esters, alkyl vinyl ethers in a tubular reactor. These terpolymers can be used as additives to improve the cold flow of oils and petroleum distillates.
- terpolymers comprising 40 to 89% by weight of ethylene, 10 to 40% by weight of vinyl ester derived from short chain carboxylic acid (C2-C4), 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-wax agents and to improve their filterability.
- C2-C4 short chain carboxylic acid
- unsaturated monoesters having a C10-C22 alkyl chain unsaturated monoesters having a C10-C22 alkyl chain
- WO 2005/054314 discloses useful alpha olefin, vinyl ester and alpha-beta unsaturated monocarboxylic acid ester terpolymers. Exemplified are terpolymers, particularly preferred by Applicant, which contain more than 80 mole% ethylene and less than 9 mole% vinyl acetate. However, these terpolymers containing less than 9% by moles of vinyl acetate, although having an effect on the reduction of the TLF for middle distillates containing more than 18% of n-paraffins, are not satisfactory as far as concerns on the one hand solubility and on the other apart from the tendency to clogging (or filterability at room temperature): damaging filter clogging is observed.
- EP 1,391,498 describes additives improving the low temperature fluidity of middle distillates which are vinyl polymers (A), preferably ethylene-vinyl ester copolymers, in which the amount of material insoluble in hexane exceeds 60% by weight at -20 ° C and is less than 30% by weight at 10 ° C;
- the examples of EP 1,391,498 clearly show that the filterability temperature (CFPP) is lowered for copolymers and terpolymers in which the amount of material insoluble in hexane exceeds 60% by weight at -20 ° C and is less than 30% by weight at 10 ° C by compared to copolymers and terpolymers having the same repeating units present in the same proportions but in which the amount of material insoluble in hexane is outside the claimed range;
- the exemplified copolymers 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 are terpolymers of ethylene, vinyl acetate and 2-ethylhexyl acrylate.
- the copolymers according to the invention which are random copolymers have a number molecular mass (Mw) measured by GPC generally between 3,000 and 30,000, and a number average molecular mass (Mn) measured by GPC generally between 1,000 and 15,000.
- copolymers can be prepared in a known manner by any polymerization process, (see for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, "Waxes", Vol. A 28, p.146 ; US 3,627,838 ; EP 7,590 ) in particular by radical polymerization, preferably under high pressure, typically of the order of 1000 to 3000 bars (100 to 300 MPa), preferably from 1500 to 2000 bars (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 generally chosen from organic peroxides and / or oxygen or nitrogen compounds, and a molecular weight regulator (ketone or aliphatic aldehyde, ).
- the copolymers can for example be prepared in a tubular 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, domestic fuel oils for heating installations (FOD), kerosene, aviation fuel oils, heavy fuel oils, etc.
- fuel oils or fuels such as diesel fuels, domestic fuel oils for heating installations (FOD), kerosene, aviation fuel oils, heavy fuel oils, 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 advantageously 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 can for example be chosen from the distillates obtained by direct distillation of crude hydrocarbons, the vacuum distillates, the hydrotreated distillates, the distillates resulting from the catalytic cracking and / or the hydrocracking of vacuum distillates, the distillates resulting from ARDS-type conversion processes (by desulfurization of atmospheric residue) and / or visbreaking, distillates resulting from the upgrading of Fischer Tropsch cuts, distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination and / or the esters of vegetable and animal oils or their mixtures.
- BTL biomass to liquid
- the hydrocarbon compositions can also contain distillates resulting from more complex refining operations than those resulting from the direct distillation of hydrocarbons which can for example come from cracking, hydrocracking and / or catalytic cracking processes and visbreaking processes.
- These new fuel bases can be used alone or as a mixture with conventional petroleum middle distillates as fuel base and / or domestic fuel oil base; they generally comprise long paraffinic chains greater than or equal to 10 carbon atoms and preferably from C14 to C30.
- copolymers as defined above with Mw between 5,000 and 27,000 and with Mn between 1,500 and 22,000, preferably with Mw between 5,000 and 25,000 and Mn between 1,500 and 20,000 are particularly effective. when they are incorporated into light middle distillates and / or low sulfur content (typically less than 50 ppm) and / or low starting crystallization temperature (typically up to -20 ° C).
- light middle distillates distillates in which the content of n-paraffins having 24 carbon atoms or more ranges from 0 to approximately less than 0.7% by weight of the total fuel composition; in which the C18-C23 n-paraffins represent approximately 3 to approximately 5% of the total weight of the fuel and in which the mass ratio of the C18-C23 n-paraffins relative to the C24 and more paraffins generally ranges from 10 to 35.
- Copolymers of Mw between 5,000 and 10,000 and with Mn between 1,500 and 8,000, preferably with Mw between 5,000 and 8,000 and Mn between 1,500 and 5,000 are particularly effective when they are used.
- heavy middle distillates distillates in which the content of n-paraffins having 24 carbon atoms or more ranges from about 0.7 to about 2% by weight of the total fuel composition; in which the C18-C23 n-paraffins represent approximately 1 to approximately 10% of the total weight of the fuel and in which the mass ratio of C18-C23 n-paraffins to C24 + paraffins generally ranges from 1 to 10.
- copolymers can 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 solvent, such as aliphatic or aromatic hydrocarbons, alone or as a mixture (naphtha, kerosene, hydrocarbon fractions, such as Solvesso solvent, paraffinic hydrocarbons, such as pentane, hexane.
- a solvent such as aliphatic or aromatic hydrocarbons, alone or as a mixture (naphtha, kerosene, hydrocarbon fractions, such as Solvesso solvent, paraffinic hydrocarbons, such as pentane, hexane.
- the hydrocarbon compositions comprise from 10 to 5,000 ppm by weight of at least one copolymer described above optionally, preferably from 100 to 1,000 ppm, and advantageously from 150 to 500 ppm.
- the hydrocarbon compositions may also contain one or more other additives other than the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and soot promoters) , agents improving the cloud point, the pour point, the limit temperature of filterability, anti-sedimentation agents, anti-wear agents and / or agents modifying the conductivity.
- additives other additives other than the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and soot promoters) , agents improving the cloud point, the pour point
- additives are generally added in an amount ranging from 100 to 1000 ppm (each).
- the improved cold resistance additives according to the invention can be added to the hydrocarbon compositions within the refinery, and / or be incorporated downstream of the refinery, optionally as a mixture with other additives, in the form of a package. or package of additives.
- GOM 1 and GOM 2 The ability to improve the cold resistance of these terpolymers is evaluated by incorporating them into 2 distillates of motor diesel type called GOM 1 and GOM 2, the characteristics of which are given in Table 2 below.
- Table 2 Fuel characteristics ASTM D86 Distillation GOM 1 GOM 2 T90-T20 (° C) 129.6 100.4 PF-T90 (° C) 19.5 24.9 T95 (° C) 353.5 362.4 Cloud point (° C) NF EN 23015 -6 -4 TLF (° C) EN 116 -6 -7 Pour point (° C) NF T 60105 -15 -10 Paraffin content (% mass) Chromatography 14.72 14.68 TCC (° C) IP 389 -6.2 -6.3 Sulfur content (ppm) EN ISO 20846 18.6 38
- the terpolymer 17 according to the invention is the most effective on gas oil GOM 1. Moreover, from the results of Table 3, it is noted that the terpolymer 17 added at a rate of 400 ppm in GOM 1 does not degrade. the tendency to clogging. This is not the case with the comparative terpolymers 6; 7; 16 and 18 according to WO 2005/054314 which strongly degrade the tendency to clogging measured according to IP 387 and are not as effective in TLF as additive 17 of the invention.
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Description
L'invention concerne l'utilisation de copolymères d'éthylène, d'acétate de vinyle et d'acrylate d'éthyl-2-hexyle comme additifs améliorant la tenue à froid de carburants et lubrifiants ainsi que les fuel-oils et les packages contenant ces copolymères.The invention relates to the use of copolymers of ethylene, vinyl acetate and ethyl-2-hexyl acrylate as additives improving the cold behavior of fuels and lubricants as well as fuel oils and packages containing these copolymers.
A température réduite, les compositions d'hydrocarbures, notamment à base de type distillats moyens contenant des cires paraffiniques, tels que par exemple les carburants diesel et les fiouls pour chauffage présentent une diminution significative de leurs propriétés d'écoulement. Il est bien connu que la cristallisation des paraffines est un facteur limitatif de l'utilisation des distillats moyens. Aussi, il est important de préparer des carburants diesel adaptés aux températures auxquelles ils seront utilisés dans les véhicules motorisés, c'est-à-dire au climat environnant. Généralement, une opérabilité à froid des carburants à -10°C est suffisante dans de nombreux pays chauds ou tempérés. Mais dans des pays de climat froid, comme les pays scandinaves, le Canada et les pays d'Asie du Nord, on peut atteindre des températures d'utilisation des carburants bien inférieures à -20°C. Il en est de même pour les fiouls domestiques stockés à l'extérieur des bâtiments (maisons, immeubles, ...). Cette adéquation de l'opérabilité à froid des carburants de type distillats moyen est importante, notamment au démarrage à froid des moteurs. Si les paraffines sont cristallisées au fond du réservoir, elles peuvent être entraînées au démarrage dans le circuit de carburant et colmater notamment les filtres et préfiltres disposés en amont des systèmes d'injection (pompe et injecteurs). De même pour le stockage des fiouls domestiques, les paraffines précipitent en fond de cuve et peuvent être entraînées et obstruer les conduites en amont de la pompe et du système d'alimentation de la chaudière (gicleur et filtre). Il est évident que la présence de solides, tels que les cristaux de paraffines, empêche la circulation normale du distillat moyen.At reduced temperature, the hydrocarbon compositions, in particular based on middle distillate type containing paraffin waxes, such as, for example, diesel fuels and heating oils exhibit a significant reduction in their flow properties. It is well known that the crystallization of paraffins is a limiting factor in the use of middle distillates. Also, it is important to prepare diesel fuels adapted to the temperatures at which they will be used in motor vehicles, that is to say to the surrounding climate. Generally, cold operability of fuels at -10 ° C is sufficient in many warm or temperate countries. But in countries with cold climates, such as the Scandinavian countries, Canada and the countries of North Asia, one can reach temperatures of use of fuels well below -20 ° C. The same is true for domestic fuel oils stored outside buildings (houses, buildings, etc.). This suitability of the cold operability of fuels of the middle distillate type is important, in particular at cold starting of engines. If the paraffins are crystallized at the bottom of the tank, they can be entrained on start-up in the fuel circuit and in particular clog the filters and prefilters placed upstream of the injection systems (pump and injectors). Likewise for the storage of domestic fuel oils, paraffins precipitate at the bottom of the tank and can be entrained and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter). It is evident that the presence of solids, such as paraffin crystals, prevents the normal circulation of the middle distillate.
Pour améliorer leur circulation soit dans le moteur, soit vers les chaudières, plusieurs types d'additifs ont vu le jour.To improve their circulation either in the engine or to the boilers, several types of additives have emerged.
Dans un premier temps, l'industrie pétrolière s'est attachée au développement des additifs dits fluidifiants à froid (en anglais cold flow improvers ou CFI) favorisant la dispersion des cristaux de paraffines et les empêchant ainsi de s'organiser en réseaux de grande taille, responsables de l'obstruction des pores de filtre. Ces additifs agissent essentiellement sur la température limite de filtrabilité (TLF) et le point d'écoulement, mais ne modifient pas le point de trouble.Initially, the oil industry focused on the development of so-called cold flow improvers (CFI) additives, which promote the dispersion of paraffin crystals and thus prevent them from being organized into large networks. , responsible for clogging the filter pores. These additives essentially act on the limit filterability temperature (TLF) and the pour point, but do not modify the cloud point.
L'art antérieur a décrit de nombreux additifs CFI (voir par exemple
Pour améliorer les propriétés des CFI conventionnels, l'art antérieur propose également des mélanges d'additifs conventionnels CFI de type éthylène/ester insaturé avec des agents lubrifiants (esters d'acide mono- ou polycarboxylique et de mono- ou polyalcools (voir par exemple
On trouve également des additifs CFI améliorés qui sont des terpolymères ou des copolymères dérivant de plus de 3 monomères distincts.Improved CFI additives are also found which are terpolymers or copolymers derived from more than 3 distinct monomers.
Par exemple,
Il existe un besoin non résolu d'additifs pour améliorer la tenue à froid des carburants (TLF et point d'écoulement) tout en réduisant voire en éliminant le risque de colmatage, de manière à éviter de boucher les filtres des systèmes d'alimentation des moteurs ou chaudières (système d'injection et réservoirs).There is an unresolved need for additives to improve the cold behavior of fuels (TLF and pour point) while reducing or even eliminating the risk of clogging, so as to avoid clogging the filters of fuel supply systems. engines or boilers (injection system and tanks).
La présente invention concerne l'utilisation de copolymères comme additifs améliorant la tenue à froid des carburants (additifs CFI) ; ces copolymères sont des terpolymères d'éthylène, d'acétate de vinyle et d'acrylate d'éthyl-2-hexyle.The present invention relates to the use of copolymers as additives improving the cold resistance of fuels (CFI additives); these copolymers are terpolymers of ethylene, vinyl acetate and 2-ethylhexyl acrylate.
Les copolymères selon l'invention utilisables comme additifs CFI comprennent:
- ▪ de 81 à 87 % en moles d'éthylène,
- ▪ de 10,5 à moins de 12 % en moles d'acétate de vinyle,
- ▪ de 1 à 8,5 % en moles d'acrylate d'éthyl-2-hexyle.
- ▪ from 81 to 87% by moles of ethylene,
- ▪ from 10.5 to less than 12% by moles of vinyl acetate,
- ▪ from 1 to 8.5 mol% of ethyl-2-hexyl acrylate.
Lesdits terpolymères sont inscrits dans un quadrilatère A1BC1D dans lequel A1, B, C1 et D représentent les sommets dudit quadrilatère et correspondent aux pourcentages molaires d'acétate de vinyle et d'acrylate d'éthyl-2-hexyle :
- A1: 12 ; 2
- B: 12 ; 6
- C1: 10,5 ; 5
- D: 10,5 ; 8,5.
- A 1: 12; 2
- B: 12; 6
- C 1 : 10.5; 5
- D: 10.5; 8.5.
Les copolymères selon l'invention qui sont des copolymères statistiques ont une masse moléculaire en nombre (Mw) mesurée par GPC en général comprise entre 3 000 et 30 000, et une masse moléculaire moyenne en nombre (Mn) mesurée par GPC en général comprise entre 1 000 et 15 000.The copolymers according to the invention which are random copolymers have a number molecular mass (Mw) measured by GPC generally between 3,000 and 30,000, and a number average molecular mass (Mn) measured by GPC generally between 1,000 and 15,000.
Ces copolymères peuvent être préparés de manière connue par tout procédé de polymérisation, (voir par exemple,
Les compositions à base d'hydrocarbures dans lesquels les copolymères selon l'invention sont incorporés, sont choisis parmi tous types de fiouls ou carburants, tels carburants diesel, fiouls domestiques pour installations de chauffage (FOD), kérosène, fiouls d'aviation, fiouls lourds, etc ...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, domestic fuel oils for heating installations (FOD), kerosene, aviation fuel oils, heavy fuel oils, etc.
En général la teneur en soufre des compositions d'hydrocarbures est inférieure à 5000 ppm, de préférence inférieure à 500 ppm, et plus préférentiellement inférieure à 50 ppm, voire même inférieure à 10 ppm et avantageuse sans soufre.In general, 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 advantageously without sulfur.
Les compositions à base d'hydrocarbures comprennent des distillats moyens de température d'ébullition comprise entre 100 et 500°C ; leur température de cristallisation commençante Tcc est souvent supérieure ou égale à -20°C, en général comprise entre -15°C et + 10°C. Ces distillats peuvent par exemple être choisis parmi les distillats obtenus par distillation directe d'hydrocarbures bruts, les distillats sous vide, les distillats hydrotraités, des distillats issus du craquage catalytique et/ou de l'hydrocraquage de distillats sous vide, les distillats résultant de procédés de conversion type ARDS (par désulfuration de résidu atmosphérique) et/ou de viscoréduction, les distillats issus de la valorisation des coupes Fischer Tropsch, les distillats résultant de la conversion BTL (biomass to liquid) de la biomasse végétale et/ou animale, prise seule ou en combinaison et/ou les esters d'huiles végétales et animales ou leurs mélanges.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 can for example be chosen from the distillates obtained by direct distillation of crude hydrocarbons, the vacuum distillates, the hydrotreated distillates, the distillates resulting from the catalytic cracking and / or the hydrocracking of vacuum distillates, the distillates resulting from ARDS-type conversion processes (by desulfurization of atmospheric residue) and / or visbreaking, distillates resulting from the upgrading of Fischer Tropsch cuts, distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination and / or the esters of vegetable and animal oils or their mixtures.
Les compositions d'hydrocarbures peuvent également contenir des distillats issus des opérations de raffinage plus complexes que ceux issus de la distillation directe des hydrocarbures qui peuvent par exemple provenir des procédés de craquage, hydrocraquage et/ou craquage catalytique et des procédés de viscoréduction.The hydrocarbon compositions can also contain distillates resulting from more complex refining operations than those resulting from the direct distillation of hydrocarbons which can for example come from cracking, hydrocracking and / or catalytic cracking processes and visbreaking processes.
Elles peuvent également contenir de nouvelles sources de distillats, parmi lesquelles on peut notamment citer :
- les coupes les plus lourdes issues des procédés de craquage et de viscoréduction concentrées en paraffines lourdes, comprenant plus de 18 atomes de carbone,
- les distillats synthétiques issus de la transformation du gaz tels que ceux issus du procédé Fischer Tropsch,
- les distillats synthétiques résultant du traitement de la biomasse d'origine végétale et/ou animale, comme notamment le NexBTL,
- et les huiles et/ou esters d'huiles végétales et/ou animales,
- ou encore les biodiesel d'origine animale et/ou végétale.
- the heaviest cuts resulting from the cracking and visbreaking processes concentrated in heavy paraffins, comprising more than 18 carbon atoms,
- synthetic distillates resulting from the transformation of gas such as those resulting from the Fischer Tropsch process,
- synthetic distillates resulting from the treatment of biomass of plant and / or animal origin, such as in particular NexBTL,
- and oils and / or esters of vegetable and / or animal oils,
- or else biodiesel of animal and / or vegetable origin.
Ces nouvelles bases carburants peuvent être utilisées seules ou en mélange avec des distillats moyens pétroliers classiques comme base carburant et/ou base de fioul domestique ; elles comprennent en général de longues chaînes paraffiniques supérieures ou égales à 10 atomes de carbone et préférentiellement de C14 à C30.These new fuel bases can be used alone or as a mixture with conventional petroleum middle distillates as fuel base and / or domestic fuel oil base; they generally comprise long paraffinic chains greater than or equal to 10 carbon atoms and preferably from C14 to C30.
Les copolymères tels que définis précédemment de Mw comprise entre 5 000 et 27 000 et de Mn comprise entre 1 500 et 22 000, de préférence de Mw comprise entre 5 000 et 25 000 et de Mn comprise entre 1 500 et 20 000 sont particulièrement efficaces lorsqu'ils sont incorporés à des distillats moyens légers et/ou à basse teneur en soufre (typiquement inférieure à 50 ppm) et/ou à température de cristallisation commençante basse (typiquement pouvant aller jusqu'à - 20°C). Par distillats moyens légers, on entend des distillats dont le contenu en n-paraffines ayant 24 atomes de carbone ou plus va de 0 à environ inférieur à 0,7 % en poids de la composition totale de carburant ; dont les n-paraffines en C18-C23 représentent environ 3 à environ 5 % du poids total du carburant et dont le rapport massique des n-paraffines en C18-C23 par rapport aux paraffines en C24 et plus va en général de 10 à 35.The copolymers as defined above with Mw between 5,000 and 27,000 and with Mn between 1,500 and 22,000, preferably with Mw between 5,000 and 25,000 and Mn between 1,500 and 20,000 are particularly effective. when they are incorporated into light middle distillates and / or low sulfur content (typically less than 50 ppm) and / or low starting crystallization temperature (typically up to -20 ° C). By light middle distillates is meant distillates in which the content of n-paraffins having 24 carbon atoms or more ranges from 0 to approximately less than 0.7% by weight of the total fuel composition; in which the C18-C23 n-paraffins represent approximately 3 to approximately 5% of the total weight of the fuel and in which the mass ratio of the C18-C23 n-paraffins relative to the C24 and more paraffins generally ranges from 10 to 35.
Les copolymères de Mw comprise entre 5 000 et 10 000 et de Mn comprise entre 1 500 et 8 000, de préférence de Mw comprise entre 5 000 et 8 000 et de Mn comprise entre 1 500 et 5 000 sont particulièrement efficaces lorsqu'ils sont incorporés à des distillats moyens lourds et/ou à température de cristallisation commençante plutôt élevée (typiquement pouvant aller de 0 à 15°C). Par distillats moyens lourds, on entend des distillats dont le contenu en n-paraffines ayant 24 atomes de carbone ou plus va d'environ 0,7 à environ 2% en poids de la composition totale de carburant ; dont les n-paraffines en C18-C23 représentent environ 1 à environ 10 % du poids total du carburant et dont le rapport massique des n-paraffines en C18-C23 aux paraffines en C24+ va en général de 1 à 10.Copolymers of Mw between 5,000 and 10,000 and with Mn between 1,500 and 8,000, preferably with Mw between 5,000 and 8,000 and Mn between 1,500 and 5,000 are particularly effective when they are used. incorporated in heavy middle distillates and / or at a rather high starting crystallization temperature (typically ranging from 0 to 15 ° C). By heavy middle distillates is meant distillates in which the content of n-paraffins having 24 carbon atoms or more ranges from about 0.7 to about 2% by weight of the total fuel composition; in which the C18-C23 n-paraffins represent approximately 1 to approximately 10% of the total weight of the fuel and in which the mass ratio of C18-C23 n-paraffins to C24 + paraffins generally ranges from 1 to 10.
Les copolymères peuvent être ajoutés tels quels dans les compositions d'hydrocarbures ou de manière préférentielle sous forme de solutions concentrées, en particulier des solutions contenant de 50 à 80 %, de préférence de 60 à 70 % en poids de copolymère(s) dans un solvant, tel que les hydrocarbures aliphatiques ou aromatiques, seuls ou en mélange (naphta, kérosène, fractions d'hydrocarbures, telles que solvant Solvesso, hydrocarbures paraffiniques, tels que pentane, hexane.The copolymers can 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 solvent, such as aliphatic or aromatic hydrocarbons, alone or as a mixture (naphtha, kerosene, hydrocarbon fractions, such as Solvesso solvent, paraffinic hydrocarbons, such as pentane, hexane.
Selon un mode de réalisation préféré de l'invention, les compositions d'hydrocarbures comprennent de 10 à 5 000 ppm en poids d'au moins un copolymère décrit plus haut éventuellement, de préférence de 100 à 1 000 ppm, et avantageusement de 150 à 500 ppm.According to a preferred embodiment of the invention, the hydrocarbon compositions comprise from 10 to 5,000 ppm by weight of at least one copolymer described above optionally, preferably from 100 to 1,000 ppm, and advantageously from 150 to 500 ppm.
Outre les additifs CFI ou additifs de tenue à froid décrits plus haut, les compositions d'hydrocarbures peuvent également contenir un ou plusieurs autres additifs différents des copolymères selon l'invention, choisis parmi les détergents, les agents anti-corrosion, les dispersants, les désémulsifiants, des agents anti-mousse, des biocides, des réodorants, des additifs procétane, les modificateurs de friction, les additifs de lubrifiance ou additifs d'onctuosité, des agents d'aide à la combustion (promoteurs catalytiques de combustion et de suie), les agents améliorant le point de trouble, le point d'écoulement, la température limite de filtrabilité, des agents anti-sédimentation, les agents anti-usure et/ou les agents modifiant la conductivité.In addition to the CFI additives or cold resistance additives described above, the hydrocarbon compositions may also contain one or more other additives other than the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and soot promoters) , agents improving the cloud point, the pour point, the limit temperature of filterability, anti-sedimentation agents, anti-wear agents and / or agents modifying the conductivity.
Parmi ces additifs, on peut citer particulièrement :
- a) les additifs procétane, notamment (mais non limitativement) choisis parmi les nitrates d'alkyle, de préférence le nitrate de 2-éthyl hexyle, les peroxydes d'aroyle, de préférence le peroxyde de benzyle, et les peroxydes d'alkyle, de préférence le peroxyde de ter-butyle ;
- b) les additifs anti-mousse, notamment (mais non limitativement) choisis parmi les polysiloxanes, les polysiloxanes oxyalkylés, et les amides d'acides gras issus d'huiles végétales ou animales. Des exemples de tels additifs sont donnés dans
EP 861 882 EP 663 000 EP 736 590 - c) les additifs détergents et/ou anti-corrosion, notamment (mais non limitativement) choisis dans le groupe constitué par les amines, les succinimides, les alkénylsuccinimides, les polyalkylamines, les polyalkyles polyamines et les polyétheramines. Des exemples de tels additifs sont donnés dans
EP 938 535 - d) additif de lubrifiance ou agent anti-usure, notamment (mais non limitativement) choisi dans le groupe constitué par les acides gras et leurs dérivés ester ou amide, notamment le monooléate de glycérol, et les dérivés d'acides carboxyliques mono- et polycycliques. Des exemples de tels additifs sont donnés dans les documents suivants:
EP 680 506 EP 860 494 WO 98/04656 EP 915 944 FR2 772 783 FR 2 772 784 - e) les additifs de point de trouble, notamment (mais non limitativement) choisis dans le groupe constitué par les terpolymères oléfine à chaîne longue/ester (méth)acrylique /maléimide, et les polymères d'esters d'acides fumarique /maléique. Des exemples de tels additifs sont donnés dans
EP 71 513 EP 100 248 FR 2 528 051 FR 2 528 051 FR 2 528 423 EP1 12 195 EP 1 727 58 EP 271 385 EP 291367 - f) les additifs d'anti-sédimentation et/ou dispersants de paraffines notamment (mais non limitativement) choisis dans le groupe constitué par les copolymères acide (méth)acrylique/(méth)acrylate d'alkyle amidifié par une polyamine, les alkénylsuccinimides de polyamine, les dérivés d'acide phtalamique et d'amine grasse à double chaîne ; des résines alkyl phénol. Des exemples de tels additifs sont donnés dans
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 - g) les additifs polyfonctionnels d'opérabilité à froid choisis dans le groupe constitué par les polymères à base d'oléfine et de nitrate d'alkényle tels que décrits dans
EP 573 490 - h) d'autres additifs CFI améliorant la tenue à froid et la filtrabilité, tels que les copolymères EVA et/ou EVP.
- a) procetane additives, in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethylhexyl nitrate, aroyl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably tert-butyl peroxide;
- b) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides obtained from vegetable or animal oils. Examples of such additives are given in
EP 861 882 EP 663,000 EP 736 590 - c) detergent and / or anti-corrosion additives, in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines and polyetheramines. Examples of such additives are given in
EP 938 535 - d) lubricity additive or anti-wear agent, in particular (but not limited to) chosen 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 FR2 772 783 FR 2 772 784 - e) cloud point additives, in particular (but not limited to) chosen from the group consisting of long-chain olefin / (meth) acrylic ester / maleimide terpolymers, and polymers of esters of fumaric / maleic acids. 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 EP1 12 195 EP 1 727 58 EP 271 385 EP 291367 - f) anti-sedimentation additives and / or paraffin dispersants, in particular (but not limited to) chosen from the group consisting of (meth) acrylic acid / (meth) acrylate copolymers of alkyl amidated with a polyamine, alkenylsuccinimides of polyamine, phthalamic acid 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 - g) polyfunctional cold operability additives chosen from the group consisting of olefin-based polymers and alkenyl nitrate as described in
EP 573 490 - h) other CFI additives improving cold resistance and filterability, such as EVA and / or EVP copolymers.
Ces autres additifs sont en général ajoutés en quantité allant de 100 à 1 000 ppm (chacun).These other additives are generally added in an amount ranging from 100 to 1000 ppm (each).
Les additifs de tenue à froid améliorés selon l'invention peuvent être ajoutés dans les compositions d'hydrocarbures au sein de la raffinerie, et/ou être incorporés en aval de la raffinerie, éventuellement en mélange avec d'autres additifs, sous forme de package ou paquet d'additifs.The improved cold resistance additives according to the invention can be added to the hydrocarbon compositions within the refinery, and / or be incorporated downstream of the refinery, optionally as a mixture with other additives, in the form of a package. or package of additives.
Dans un réacteur tubulaire, on synthétise par polymérisation radicalaire sous haute pression (1 400 à 2 500 bars (140 à 250 MPa) et à une température de polymérisation de 200 à 280°C des terpolymères d'éthylène, d'acétate de vinyle et d'acrylate d'éthyl-2, hexyle. La synthèse est réalisée en utilisant un aldéhyde aliphatique (propanal) pour contrôler les masses moléculaires et en utilisant des peroxydes comme initiateurs de polymérisation. Dans le tableau 1 ci-dessous, sont indiquées les Mn et Mw des terpolymères synthétisés ainsi que leurs pourcentages des monomères.
On évalue l'aptitude à l'amélioration de la tenue à froid de ces terpolymères en les incorporant dans des 2 distillats de type gazole moteur appelé GOM 1 et GOM 2 dont les caractéristiques sont réunies dans le tableau 2 ci-dessous.
On incorpore 400 ppm en poids de chaque copolymère ci-dessous dans le distillat de type gazole moteur appelé GOM 1 puis on mesure l'indice de colmatage FBT (Filter Blocking Tendency) selon la norme IP 387. Le GOM 1 non additivé présente un indice de colmatage FBT de 1,01. On constate que le terpolymère 17 selon l'invention permet de ne pas dégrader la tendance au colmatage du GOM 1 c'est-à-dire que le GOM 1 additivé avec 400 ppm de terpolymère présente un FBT inférieur à 1,41. Les résultats sont présentés dans le tableau 3 ci-dessous.
On mesure l'efficacité en tenue à froid TLF des terpolymères incorporés dans les GOM 1 et GOM 2 à la concentration de 210 ppm ; les résultats sont réunis dans le tableau 4.
On constate que le terpolymère 17 selon l'invention est le plus efficace sur le gazole GOM 1. Par ailleurs, à partir des résultats du tableau 3, on constate que le terpolymère 17 ajouté à raison de 400 ppm dans le GOM 1 ne dégrade pas la tendance au colmatage. Ceci, n'est pas le cas des terpolymères comparatifs 6 ; 7 ; 16 et 18 selon
Claims (9)
- Use, as additive which improves the resistance to cold and the filterability of fuels, of at least one terpolymer comprising units derived from ethylene, units derived from vinyl acetate and units derived from 2-ethylhexyl acrylate, comprising:- from 81 mol% to 87 mol% of ethylene,- from 10.5 mol% to less than 12 mol% of vinyl acetate,- from 1 mol% to 8.5 mol% of 2-ethylhexyl acrylate, the said terpolymer being included in a quadrilateral A1BC1D in which A1, B, C1 and D represent the apexes of the said quadrilateral and correspond to the molar percentages of vinyl acetate and 2-ethylhexyl acrylate:A1: 12; 2B: 12; 6C1: 10.5; 5D: 10.5; 8.5.
- Use according to Claim 1 of at least one terpolymer with a number-average molecular weight (Mw), measured by GPC, of between 3000 and 30 000, preferably 3000 to 20 000, and a number-average molecular weight (Mn), measured by GPC, in general of between 1000 and 20 000, preferably ranging from 1500 to 15 000.
- Use according to either one of Claims 1 and 2 of at least one terpolymer as additive which improves the resistance to cold and the filterability without damaging the tendency towards clogging of middle distillates, such as diesel fuels, domestic heating oils, kerosene, aviation fuels or heavy fuel oils.
- Use according to any one of Claims 1 to 3 of at least one terpolymer as additive which improves the resistance to cold and the filterability of fuels, the sulfur content of which is less than 5000 ppm, preferably less than 500 ppm, more preferably less than 50 ppm, indeed even less than 10 ppm, and advantageously of fuels without sulfur.
- Hydrocarbon composition comprising a major amount of a middle distillate with a boiling point ranging from 100 to 500°C and of 10 to 5000 ppm by weight of at least one terpolymer comprising units derived from ethylene, units derived from vinyl acetate and units derived from 2-ethylhexyl acrylate, comprising:- from 81 mol% to 87 mol% of ethylene,- from 10.5 mol% to less than 12 mol% of vinyl acetate,- from 1 mol% to 8.5 mol% of 2-ethylhexyl acrylate, the said terpolymer being included in a quadrilateral A1BC1D in which A1, B, C1 and D represent the apexes of the said quadrilateral and correspond to the molar percentages of vinyl acetate and 2-ethylhexyl acrylate:A1: 12; 2B: 12; 6C1: 10.5; 5D: 10.5; 8.5.
- Composition according to Claim 5, characterized in that it contains biodiesel of animal and/or vegetable origin.
- Composition according to Claim 5 or 6, characterized in that it is chosen from diesel fuels, domestic heating oils, kerosene, aviation fuels or heavy fuel oils.
- Composition according to any one of Claims 5 to 7, characterized in that it comprises from 100 to 1000 ppm by weight of the said terpolymer, preferably from 150 to 500 ppm.
- Composition according to any one of Claims 5 to 8, characterized in that it comprises one or more other additives, different from the terpolymers according to the invention, chosen from detergents, corrosion inhibitors, dispersants, demulsifiers, antifoam agents, biocides, reodorants, cetane number improvers, friction modifiers, slip agents or lubricity additives, combustion aids (catalytic promoters of combustion and of soot), agents which improve the cloud point, the pour point or the cold filter plugging point, antisettling agents, antiwear agents and/or conductivity modifiers.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0903278A FR2947558B1 (en) | 2009-07-03 | 2009-07-03 | TERPOLYMER AND ETHYLENE / VINYL ACETATE / UNSATURATED ESTERS AS ADDITIVES TO ENHANCE COLD LIQUID HYDROCARBONS LIKE MEDIUM DISTILLATES AND FUELS OR COMBUSTIBLES |
PCT/IB2010/052922 WO2011001352A1 (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 |
Publications (3)
Publication Number | Publication Date |
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EP2449063A1 EP2449063A1 (en) | 2012-05-09 |
EP2449063B1 EP2449063B1 (en) | 2018-11-21 |
EP2449063B2 true EP2449063B2 (en) | 2021-07-28 |
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EP10734559.7A Active EP2449063B2 (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 |
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US (1) | US20120102825A1 (en) |
EP (1) | EP2449063B2 (en) |
JP (1) | JP2012532225A (en) |
KR (1) | KR102002887B1 (en) |
CN (1) | CN102549120A (en) |
AR (1) | AR077631A1 (en) |
AU (1) | AU2010267626B2 (en) |
BR (1) | BRPI1016080B1 (en) |
CA (1) | CA2765245C (en) |
CL (1) | CL2011003342A1 (en) |
EA (1) | EA201270129A1 (en) |
ES (1) | ES2706903T5 (en) |
FR (1) | FR2947558B1 (en) |
MX (1) | MX363328B (en) |
PT (1) | PT2449063T (en) |
SG (1) | SG177381A1 (en) |
TW (1) | TWI496883B (en) |
WO (1) | WO2011001352A1 (en) |
ZA (1) | ZA201109307B (en) |
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SG193907A1 (en) * | 2011-03-25 | 2013-11-29 | Evonik Oil Additives Gmbh | A composition to improve oxidation stability of fuel oils |
FR2987052B1 (en) | 2012-02-17 | 2014-09-12 | Total Raffinage Marketing | ADDITIVES ENHANCING WEAR AND LACQUERING RESISTANCE OF GASOLINE OR BIOGAZOLE FUEL |
FR3005061B1 (en) | 2013-04-25 | 2016-05-06 | Total Raffinage Marketing | ADDITIVE FOR IMPROVING THE STABILITY OF OXIDATION AND / OR STORAGE OF LIQUID HYDROCARBON FUELS OR FUELS |
AR100387A1 (en) * | 2014-02-18 | 2016-10-05 | Basf Se | COPOLYMERS UNDERSTANDING ETHYLENE, VINYL ESTERS AND ACRYLIC ACID (MET) ESTERS, THEIR FORMULATIONS AND USES AS A FLUIDITY POINT DEPRESSOR, WAX INHIBITOR AND FLOW OIL POTENTIATOR |
TWI576384B (en) * | 2014-11-25 | 2017-04-01 | 鴻明環保科技股份有限公司 | High plant-sources content eva polymer foam material, producing method and application thereof |
CN105733712B (en) * | 2014-12-08 | 2017-12-05 | 中国石油天然气股份有限公司 | Lubricating antifriction additive for aviation biofuel |
FR3113063B1 (en) | 2020-07-31 | 2022-08-12 | Total Marketing Services | Use of copolymers with specific molar mass distribution for lowering the filterability limit temperature of fuels or fuels |
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- 2010-06-25 ES ES10734559T patent/ES2706903T5/en active Active
- 2010-06-25 KR KR1020117031259A patent/KR102002887B1/en active IP Right Grant
- 2010-06-25 BR BRPI1016080A patent/BRPI1016080B1/en active IP Right Grant
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CA2765245A1 (en) | 2011-01-06 |
EP2449063B1 (en) | 2018-11-21 |
EA201270129A1 (en) | 2012-05-30 |
WO2011001352A1 (en) | 2011-01-06 |
CN102549120A (en) | 2012-07-04 |
AU2010267626B2 (en) | 2016-05-12 |
PT2449063T (en) | 2019-02-04 |
BRPI1016080B1 (en) | 2018-10-16 |
JP2012532225A (en) | 2012-12-13 |
TWI496883B (en) | 2015-08-21 |
MX363328B (en) | 2019-03-20 |
US20120102825A1 (en) | 2012-05-03 |
BRPI1016080A2 (en) | 2016-05-10 |
CA2765245C (en) | 2017-07-25 |
KR20120040161A (en) | 2012-04-26 |
CL2011003342A1 (en) | 2012-07-06 |
AR077631A1 (en) | 2011-09-14 |
ES2706903T3 (en) | 2019-04-01 |
FR2947558B1 (en) | 2011-08-19 |
ES2706903T5 (en) | 2021-12-14 |
KR102002887B1 (en) | 2019-07-23 |
SG177381A1 (en) | 2012-02-28 |
ZA201109307B (en) | 2012-09-26 |
FR2947558A1 (en) | 2011-01-07 |
MX2012000172A (en) | 2012-02-28 |
EP2449063A1 (en) | 2012-05-09 |
AU2010267626A1 (en) | 2012-02-02 |
TW201116617A (en) | 2011-05-16 |
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