EP2449063B1 - 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
- EP2449063B1 EP2449063B1 EP10734559.7A EP10734559A EP2449063B1 EP 2449063 B1 EP2449063 B1 EP 2449063B1 EP 10734559 A EP10734559 A EP 10734559A EP 2449063 B1 EP2449063 B1 EP 2449063B1
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- EP
- European Patent Office
- Prior art keywords
- mol
- fuels
- copolymer
- cold
- ppm
- 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 53
- 239000000446 fuel Substances 0.000 title claims description 26
- 229920001897 terpolymer Polymers 0.000 title claims description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 18
- 239000005977 Ethylene Substances 0.000 title claims description 17
- 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 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims description 12
- 239000007788 liquid Substances 0.000 title description 2
- 229920001577 copolymer Polymers 0.000 claims description 38
- -1 monocarboxylic acid ester Chemical class 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- 229920001567 vinyl ester resin Polymers 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 9
- 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
- 239000004711 α-olefin Substances 0.000 claims description 7
- 241001465754 Metazoa Species 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 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 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 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
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000004071 soot Substances 0.000 claims description 2
- 239000010763 heavy fuel oil Substances 0.000 claims 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
- 230000000052 comparative effect Effects 0.000 description 17
- 150000002148 esters Chemical class 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 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
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920001296 polysiloxane 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
- 239000000314 lubricant Substances 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
- 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 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
- 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
- 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
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000004062 sedimentation 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
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002781 deodorant agent Substances 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
- 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
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000009434 installation Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 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
- 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
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 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
- 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 ° C is sufficient in many hot or temperate countries. But in cold climate countries, such as the Scandinavian countries, Canada, and Northeast Asian countries, fuel usage temperatures well below -20 ° C can be achieved. It is the same for domestic fuel stored outside buildings (houses, buildings, ).
- 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). Similarly for the storage of domestic fuel oils, 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
- 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 generally copolymers of ethylene and unsaturated ester, such as ethylene / vinyl acetate copolymers (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methacrylate methyl (EMMA), and ethylene / alkyl fumarate.
- EVA ethylene / vinyl acetate copolymers
- EVE ethylene / vinyl propionate
- EMMA ethylene / vinyl ethanoate
- EMMA ethylene / methacrylate methyl
- 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-sedimentation agents (see for example FR 2,490,669 ), with ethers (see for example US 3,999,960 , EP187488 ).
- lubricating agents mono- or polycarboxylic acid esters and mono- or polyalcohols
- anti-sedimentation agents see for example FR 2,490,669
- ethers see for example US 3,999,960 , EP187488 .
- CFI additives which are terpolymers or copolymers derived from more than 3 different monomers.
- US 6,509,424 discloses a process for preparing terpolymers of ethylene 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 improving the cold flow of oils and petroleum distillates.
- US 3,642,459 describes terpolymers comprising 40 to 89% by weight of ethylene, 10 to 40% by weight of 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.
- C2-C459 long chain (C2-C4) carboxylic acid, such as vinyl acetate, and unsaturated monoesters having a C10-C22 alkyl chain
- WO 2005/054314 discloses terpolymers of alpha olefin, vinyl ester and alpha-beta unsaturated mono carboxylic acid ester useful.
- 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 matter exceeds 60% by weight at -20 ° C and is less than 30% by weight at 10 ° C; 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 and is less than 30% by weight at 10 ° C by copolymers and terpolymers having the same units of recurrence present in the same proportions but the amount of hexane insoluble material is outside the claimed range; the copolymers exemplified are EVA copolymers and ethylene-vinyl acetate-neodecanoate or 2-ethylhexanoate vinyl terpolymers.
- A vinyl polymers
- CFPP
- 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.
- 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 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 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 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, 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 having 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 obtained 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.
- 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.
- 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 they are incorporated in light middle distillates and / or low sulfur (typically less than 50 ppm) and / or low initial crystallization temperature (typically up to - 20 ° C).
- light middle distillates distillates whose n-paraffin content having 24 or more carbon atoms ranges from 0 to about less than 0.7% by weight of the total fuel composition; wherein the 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.
- Copolymers of Mw between 5,000 and 10,000 and Mn between 1,500 and 8,000, preferably Mw between 5,000 and 8,000 and Mn between 1,500 and 5,000 are particularly effective when they are incorporated in heavy middle distillates and / or at a rather high starting crystallization temperature (typically ranging from 0 to 15 ° C.).
- Heavy middle distillates are distillates whose n-paraffin content with 24 or more carbon atoms ranges 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
- 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.
- GOM 1 and GOM 2 The ability to improve the cold strength of these terpolymers is evaluated by incorporating them into two distillates of the diesel engine 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 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.
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Description
L'invention concerne l'utilisation de copolymères d'alpha-oléfine, d'ester vinylique et d'ester d'acide carboxylique alpha, beta insaturé 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 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.
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, 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 ° C is sufficient in many hot or temperate countries. But in cold climate countries, such as the Scandinavian countries, Canada, and Northeast Asian countries, fuel usage temperatures well below -20 ° C can be achieved. It is the same for domestic fuel stored outside buildings (houses, buildings, ...). This adequacy of the cold operability of the middle distillate type fuels is important, especially when the engines start cold. If the 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). Similarly for the storage of domestic fuel oils, 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.
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), which promotes the dispersion of paraffin crystals and prevents them from organizing into large networks. , responsible for clogging the filter pores. These additives act essentially on the Filterability limit (TLF) and pour point, but do not change 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.There are also improved CFI additives which are terpolymers or copolymers derived from more than 3 different 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 holding of fuels (TLF and pour point) while reducing or even eliminating the risk of clogging, so as to avoid clogging the filters of fuel 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 contiennent des unités dérivés d'au moins une alpha-oléfine, d'au moins un ester vinylique et d'au moins un ester d'acide mono carboxylique alpha-beta insaturé, et sont de préférence 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 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.
Les copolymères selon l'invention utilisables comme additifs CFI comprennent :
- ▪ de 81 à 87 % en moles d'au moins une alpha-oléfine, de préférence d'au moins l'éthylène,
- ▪ de 10,5 à moins de 12 % en moles d'au moins un ester vinylique, de préférence d'au moins l'acétate de vinyle,
- ▪ de 1 à 8,5 % en moles d'au moins un ester d'acide mono carboxylique alpha-beta insaturé, de préférence d'au moins l'acrylate d'éthyl-2, hexyle
- A: 12 ; 1
- B: 12 ; 6
- C: 10,5 ; 4
- D: 10,5 ; 8,5.
- From 81 to 87 mol% of at least one alpha-olefin, preferably at least ethylene,
- From 10.5 to less than 12 mol% of at least one vinyl ester, preferably at least vinyl acetate,
- From 1 to 8.5 mol% of at least one unsaturated alpha-beta mono carboxylic acid ester, preferably at least 2-ethylhexyl acrylate,
- AT 12 ; 1
- B: 12; 6
- C, 10.5; 4
- D, 10.5; 8.5.
De manière avantageuse, les copolymères utilisables comme additifs CFI sont inscrits dans un quadrilatère A1BC1D dans lequel A1, B, C1 et D représentent les sommets dudit quadrilatère et correspondent aux pourcentages molaires d'au moins l'ester vinylique et d'au moins l'ester d'acide mono carboxylique alpha-beta insaturé :
- 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-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.
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 ...The 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.
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 advantageous 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 having 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 obtained 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.
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 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.
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 heavier cuts resulting from heavy paraffinic cracking and visbreaking processes comprising more than 18 carbon atoms,
- synthetic distillates resulting from the transformation of the 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 NexBTL,
- and oils and / or esters of vegetable and / or animal oils,
- or 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 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.
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 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 they are incorporated in light middle distillates and / or low sulfur (typically less than 50 ppm) and / or low initial crystallization temperature (typically up to - 20 ° C). By light middle distillates are meant distillates whose n-paraffin content having 24 or more carbon atoms ranges from 0 to about less than 0.7% by weight of the total fuel composition; wherein the 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.
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 Mn between 1,500 and 8,000, preferably Mw between 5,000 and 8,000 and Mn between 1,500 and 5,000 are particularly effective when they are incorporated in heavy middle distillates and / or at a rather high starting crystallization temperature (typically ranging from 0 to 15 ° C.). Heavy middle distillates are distillates whose n-paraffin content with 24 or more carbon atoms ranges 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.
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 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.
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 5000 ppm by weight of at least one copolymer described above, preferably from 100 to 1000 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-holding additives described above, 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.
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) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aroyl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
- b) anti-foam additives, in particular (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides 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) selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylamines and polyetheramines. Examples of such additives are given in
EP 938 535 - d) 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 . 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, 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 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) selected from the group consisting of (meth) acrylic acid / polyamine-amidated alkyl (meth) acrylate copolymers, alkenylsuccinimides of polyamine, phthalamic acid derivatives and double chain fatty amine; 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) the polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate polymers as described in
EP 573,490 - h) other CFI additives improving the cold resistance and the filterability, such as the 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-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.
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 (12)
- Use, as additive which improves the resistance to cold and the filterability of fuels, of at least one copolymer comprising- from 81 mol% to 87 mol% of at least one α-olefin,- from 10.5 mol% to less than 12 mol% of at least vinyl ester,- from 1 mol% to 8.5 mol% of at least one α,β-unsaturated monocarboxylic acid ester, the said copolymer being included in a quadrilateral ABCD in which A, B, C and D represent the apexes of the said quadrilateral and correspond to the molar percentages of at least the vinyl ester and at least the α,β-unsaturated monocarboxylic acid ester:A: 12; 1B: 12; 6C: 10.5; 4D: 10.5; 8.5.
- Use, as additive which improves the resistance to cold and the filterability of fuels, of at least one copolymer according to Claim 1 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 at least the vinyl ester and of at least the α,β-unsaturated monocarboxylic acid ester:A1: 12; 2B: 12; 6C1: 10.5; 5D: 10.5; 8.5.
- Use, as additive which improves the resistance to cold and the filterability of fuels, of at least one copolymer according to either of Claims 1 and 2 in which the alpha-olefin is ethylene, and/or the vinyl ester is vinyl acetate, and/or the α,β-unsaturated monocarboxylic acid ester is 2-ethylhexyl acrylate.
- Use according to any one of Claims 1 to 3 of at least one terpolymer comprising units derived from ethylene, units derived from vinyl acetate and units derived from 2-ethylhexyl acrylate.
- Use according to any one of Claims 1 to 4 of at least one copolymer with a weight-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 any one of Claims 1 to 5 of at least one copolymer 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 6 of at least one copolymer 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 from 10 to 5000 ppm by weight of at least one copolymer comprising:- from 81 mol% to 87 mol% of at least one alpha-olefin,- from 10.5 mol% to less than 12 mol% of at least one vinyl ester,- from 1 mol% to 8.5 mol% of at least one α,β-unsaturated monocarboxylic acid ester, the said copolymer being included in a quadrilateral ABCD in which A, B, C and D represent the apexes of the said quadrilateral and correspond to the molar percentages of at least the vinyl ester and at least the α,β-unsaturated monocarboxylic acid ester:A: 12; 1B: 12; 6C: 10.5; 4D: 10.5; 8.5.
- Composition according to Claim 8, characterized in that it contains biodiesel of animal and/or vegetable origin.
- Composition according to Claim 8 or 9, 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 8 to 10, characterized in that it comprises from 100 to 1000 ppm by weight of the said copolymer, preferably from 150 to 500 ppm.
- Composition according to any one of Claims 8 to 11, characterized in that it comprises one or more other additives, different from the copolymers 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)
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EP2449063A1 EP2449063A1 (en) | 2012-05-09 |
EP2449063B1 true EP2449063B1 (en) | 2018-11-21 |
EP2449063B2 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 |
Country Status (19)
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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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FR2925916B1 (en) * | 2007-12-28 | 2010-11-12 | Total France | VINYL ETHYLENE / UNSATURATED TERPOLYMER / UNSATURATED ESTERS AS AN ADDITIVE TO ENHANCE COLD LIQUID HYDROCARBONS LIKE MEDIUM DISTILLATES AND FUELS OR COMBUSTIBLES |
BR112013021923A2 (en) * | 2011-03-25 | 2016-11-08 | Evonik Oil Additives Gmbh | 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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CA2765245A1 (en) | 2011-01-06 |
CA2765245C (en) | 2017-07-25 |
MX2012000172A (en) | 2012-02-28 |
BRPI1016080A2 (en) | 2016-05-10 |
FR2947558A1 (en) | 2011-01-07 |
ES2706903T5 (en) | 2021-12-14 |
PT2449063T (en) | 2019-02-04 |
CL2011003342A1 (en) | 2012-07-06 |
KR20120040161A (en) | 2012-04-26 |
EP2449063B2 (en) | 2021-07-28 |
ES2706903T3 (en) | 2019-04-01 |
EP2449063A1 (en) | 2012-05-09 |
EA201270129A1 (en) | 2012-05-30 |
JP2012532225A (en) | 2012-12-13 |
ZA201109307B (en) | 2012-09-26 |
MX363328B (en) | 2019-03-20 |
FR2947558B1 (en) | 2011-08-19 |
KR102002887B1 (en) | 2019-07-23 |
AR077631A1 (en) | 2011-09-14 |
SG177381A1 (en) | 2012-02-28 |
TW201116617A (en) | 2011-05-16 |
US20120102825A1 (en) | 2012-05-03 |
CN102549120A (en) | 2012-07-04 |
WO2011001352A1 (en) | 2011-01-06 |
AU2010267626B2 (en) | 2016-05-12 |
TWI496883B (en) | 2015-08-21 |
AU2010267626A1 (en) | 2012-02-02 |
BRPI1016080B1 (en) | 2018-10-16 |
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