EP4077602B1 - Marking composition - Google Patents
Marking composition Download PDFInfo
- Publication number
- EP4077602B1 EP4077602B1 EP20830182.0A EP20830182A EP4077602B1 EP 4077602 B1 EP4077602 B1 EP 4077602B1 EP 20830182 A EP20830182 A EP 20830182A EP 4077602 B1 EP4077602 B1 EP 4077602B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- hydrocarbon
- les
- radical compound
- additives
- 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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- 239000000203 mixture Substances 0.000 title claims description 130
- -1 radical compound Chemical class 0.000 claims description 64
- 239000000654 additive Substances 0.000 claims description 59
- 150000002430 hydrocarbons Chemical class 0.000 claims description 43
- 229930195733 hydrocarbon Natural products 0.000 claims description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims description 38
- 230000000996 additive effect Effects 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003599 detergent Substances 0.000 claims description 9
- 238000004435 EPR spectroscopy Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 239000007866 anti-wear additive Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000005069 Extreme pressure additive Substances 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- HQQKMOJOCZFMSV-UHFFFAOYSA-N dilithium phthalocyanine Chemical compound [Li+].[Li+].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HQQKMOJOCZFMSV-UHFFFAOYSA-N 0.000 claims description 2
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical class C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 13
- 239000011701 zinc Substances 0.000 description 12
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 239000002199 base oil Substances 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 229920002367 Polyisobutene Polymers 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001362 electron spin resonance spectrum Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BTHAQRDGBHUQMR-UHFFFAOYSA-N [S]P(=O)=O Chemical compound [S]P(=O)=O BTHAQRDGBHUQMR-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 241000209504 Poaceae Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 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
- 229930195712 glutamate Natural products 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229940070721 polyacrylate Drugs 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003873 salicylate salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/40—Six-membered ring containing nitrogen and carbon only
-
- 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
- C10L1/003—Marking, e.g. coloration by addition of pigments
-
- 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
- C10L1/16—Hydrocarbons
- C10L1/1608—Well defined compounds, e.g. hexane, benzene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2493—Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing 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
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/30—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a nitrogen-to-oxygen bond
- C10M133/34—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a nitrogen-to-oxygen bond containing a nitroso group
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- 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
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/16—Tracers which serve to track or identify the fuel component or fuel composition
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/20—Containing nitrogen-to-oxygen bonds
- C10M2215/204—Containing nitrogen-to-oxygen bonds containing nitroso groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
- C10M2215/227—Phthalocyanines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/42—Flashing oils or marking oils
Definitions
- the present invention relates to the marking of compositions comprising at least one hydrocarbon and of additive composition intended to be added to compositions comprising at least one hydrocarbon.
- compositions which can be detected by analyzes and therefore allow the determination of the origin of the compositions.
- compositions comprising at least one hydrocarbon or additive compositions intended to be added to compositions comprising at least one hydrocarbon or compositions comprising water and urea used in the automotive field, particularly in exhaust gas post-treatment devices.
- An objective of the present invention is to provide marking making it possible to detect the origin of a composition comprising at least one hydrocarbon or of a composition comprising water and urea and used in the automotive field.
- Another objective of the present invention is to provide marking making it possible to trace the manufacturing process of a composition comprising at least one hydrocarbon and to ensure the quality of the process.
- An objective of the invention is to provide such marking which is simple to use and which can be carried out on site without the need for imposing equipment.
- the present invention which relates to the use of a radical compound in a composition comprising at least one hydrocarbon or in an additive composition intended to be added to a composition comprising at least one hydrocarbon, or in a composition comprising water and urea and intended to be used in the automotive field to mark said compositions, the marking being followed by Electronic Paramagnetic Resonance (EPR) (by detection of the radical compound).
- EPR Electronic Paramagnetic Resonance
- Radical compounds are compounds detectable in small quantities by Electron Paramagnetic Resonance (EPR). Portable RPE devices are available.
- EPR Electron Paramagnetic Resonance
- the invention makes it possible, by adding a small quantity, in particular of the order of ppm, of radical compound in a composition comprising at least one hydrocarbon, to mark said composition, the analysis of this composition being able to be carried out quickly and in the field in particular by Electronic Paramagnetic Resonance (EPR) (by detection of the radical compound).
- EPR Electronic Paramagnetic Resonance
- the present invention therefore advantageously makes it possible to quickly obtain knowledge of the origin of the composition comprising at least one hydrocarbon and for example to detect possible counterfeits.
- the present invention also advantageously allows rapid knowledge of the origin of a composition comprising water and urea and intended for use in the automotive field, for example in post-processing devices. treatment of vehicle exhaust gases to reduce polluting emissions.
- the invention makes it possible, by adding a known quantity of radical compound in an additive composition intended to be added to a composition comprising at least one hydrocarbon, to be able to determine the quantity of additive composition added to the composition comprising at least one hydrocarbon and thus verify if this quantity corresponds to the usual quantities and meets the quality criteria of the manufacturing process, the analysis to determine the quantity of composition of additives added to the composition comprising at least one hydrocarbon and thus verifying whether this quantity corresponds to the usual quantities and meets the quality criteria of the manufacturing process is carried out by RPE (by detection of the radical compound).
- the present invention allows the marking of a composition comprising at least one hydrocarbon and of a composition comprising water and urea and intended to be used in the automotive field and the tracing of the process for preparing a composition comprising at least one hydrocarbon.
- the marking being followed by RPE (by detection of the radical compound) and the tracing carried out by RPE (by detection of the radical compound).
- the radical compound can be chosen from all the radical compounds known to those skilled in the art.
- the radical compound must not react with the constituents of the composition comprising at least one hydrocarbon or with the additive composition.
- the radical product is preferably colorless.
- the radical compound has no influence on the properties of the composition comprising at least one hydrocarbon or the composition of additives.
- the radical compound should preferably be stable, preferably stable for at least 3 months, preferably at least 6 months, preferably at least 12 months.
- the term "stable" means a radical compound whose RPE intensity of a composition comprising this compound after aging varies at most 10% relative to the RPE intensity of a composition. comprising this compound without aging (fresh composition).
- the aging conditions for compositions comprising at least one hydrocarbon are storage for at least 3 months, preferably at least 6 months, preferably at least 12 months, at room temperature.
- the aging conditions for the additive compositions correspond to storage at a temperature between 30 and 50°C for at least 3 months, preferably at least 6 months, preferably at least 12 months.
- radical compounds are for example nitroxides (nitroxide radicals), trityl radicals, radicals stabilized by a polycyclic aromatic structure (asphaltenes for example) or conjugated systems (dilithium phthalocyanine), sterically hindered phenyl and isoindoline radicals. .
- the radical compound is added in an amount of between 0.1 and 100 ⁇ M, preferably between 5 and 50 ⁇ M.
- the radical compound can only be detected by EPR and by no other analysis (EPR being a very sensitive analysis).
- hydrocarbon or “hydrocarbons” means aromatic compounds from the benzene family, alkenes, alkanes and cycloalkanes.
- compositions comprising at least one hydrocarbon means compositions such as for example base oils, lubricants, fuels (gasoline, diesel, biofuel), bitumens, etc.
- composition comprising water and urea and intended for use in the automotive field
- compositions which can be used in particular in post-treatment devices. exhaust gases, more particularly SCR devices to limit polluting emissions. These compositions may also include additives as defined in the patent EP2129452 . As an example, we can cite AdBlue ® marketed by the company Total or Clearnox ® marketed by the company Total.
- base oil means oils of mineral, synthetic or vegetable origin as well as their mixtures.
- Mineral or synthetic oils typically used in the application belong to one of the classes defined in the API classification as summarized in the table below. Saturates content Sulfur content Viscosity index Group 1 Mineral oils ⁇ 90% > 0.03% 80 ⁇ VI ⁇ 120 Group 2 Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120 Group 3 Hydroisomerized oils ⁇ 90% ⁇ 0.03% ⁇ 120 Group 4 DTP Group 5 Other bases not included in bases groups 1 to 4
- Group 1 mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes and then purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
- Group 2 and 3 oils are obtained by more severe purification processes, for example a combination of hydrotreating, hydrocracking, hydrogenation and catalytic dewaxing.
- Synthetic Group 4 and 5 base oils can be chosen from esters, silicones, glycols, polybutene, polyalphaolefins (PAO), alkylbenzene or alkylnaphthalene.
- the polyalphaolefins used as base oils are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and whose viscosity at 100°C is between 1.5 and 15 mm 2 .s -1 according to ASTM D445. Their average molecular mass is generally between 250 and 3000 according to the ASTM D5296 standard.
- the base oils can also be oils of natural origin, for example esters of alcohols and carboxylic acids, which can be obtained from natural resources such as sunflower oil, rapeseed oil, palm oil, soy etc.
- base oils can be used alone or in a mixture.
- Mineral oil can be combined with synthetic oil.
- the present invention also relates to a method of marking and/or tracing, in particular marking and/or tracing detectable by EPR, of a composition comprising at least one hydrocarbon comprising the addition of a radical compound to said composition comprising at least one hydrocarbon or an additive composition intended to be added to the composition comprising at least one hydrocarbon, said method also comprises a step of detecting the marking and/or tracing (and therefore the radical compound) by EPR.
- the present invention also relates to a marking method, in particular marking detectable by EPR, of a composition comprising at least one hydrocarbon comprising the addition to said composition of a radical compound, said method also comprises a step of detecting the marking (and therefore the radical compound) by RPE.
- the present invention also relates to a method of traceability of the process for preparing a composition comprising at least one hydrocarbon and an additive composition comprising the addition of a radical compound to the additive composition intended to be added to the composition comprising at least one hydrocarbon, said method also comprising a step of detecting said radical compound by EPR.
- knowing the quantity of radical compound in the additive composition and the dilution of the additive composition in the composition comprising at least one hydrocarbon it is possible, by analyzing the RPE spectrum, to know the quantity of radical compound in the composition comprising at least one hydrocarbon and (since the radical compound is stable) determine whether the correct quantity of additive composition has been added to meet the quality standards.
- the present application also relates to a method of marking, in particular marking detectable by EPR, of a composition comprising water and urea intended to be used in the automotive field comprising the addition of a radical compound to said composition, said method also comprises a step of detecting the marking by RPE.
- the present invention also relates to a composition
- a composition comprising water, urea, an additive chosen from thickeners, viscosity index (VI) improving additives, anti-wear and extreme pressure additives, dispersants, anti-foam additives. , antioxidant additives, anti-rust additives, pour point improvers and detergents, said composition being intended for use in the automotive field, said composition comprising a radical compound.
- VI viscosity index
- compositions, the radical compound and the quantity of radical compound are as defined above.
- An additive composition for a B7 diesel composition comprising 8.3 mM nitroxide is prepared.
- the nitroxide content is chosen so as to have, after dilution of the additive composition (1200 ppm) in the diesel composition B7, the nitroxide is present in a content of 10 ⁇ M (1.9 ppm).
- the formulation for RPE analysis is as follows: The additive composition comprising nitroxide is diluted in a B7 diesel composition at the nominal nitroxide concentration of 10 ⁇ M. Samples are prepared for EPR measurement then the spectra are performed at room temperature on a continuous X-band spectrometer with a field center with a g factor of 2.005 and a magnetic field window of 100 G. Spectra acquisition takes 15s. The signal intensity is measured as the height of the nitroxide peak and is compared to the value at t0 (fresh sample).
- a nitroxide solution (10 ⁇ M) is added to a base oil.
- the composition obtained is added to a 5 mm tube for RPE.
- An EPR spectrum is carried out at room temperature under the same conditions as in Example 1. The spectrum is carried out at t0 (just after preparation of the composition) then at t0 + 4 months and t0 + 6 months.
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
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- Lubricants (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
La présente invention concerne le marquage de compositions comprenant au moins un hydrocarbure et de composition d'additif destinée à être additionnée dans des compositions comprenant au moins un hydrocarbure.The present invention relates to the marking of compositions comprising at least one hydrocarbon and of additive composition intended to be added to compositions comprising at least one hydrocarbon.
Pour lutter contre les produits de contrefaçon et protéger le savoir-faire d'une entreprise, il est de plus en plus important de pouvoir déterminer rapidement si un produit appartient ou non à cette entreprise.To combat counterfeit products and protect a company's know-how, it is increasingly important to be able to quickly determine whether or not a product belongs to that company.
En cas d'accident, par exemple fuite d'une composition et éventuelle contamination de l'environnement, il est impératif de pouvoir déterminer l'origine des compositions.In the event of an accident, for example leak of a composition and possible contamination of the environment, it is imperative to be able to determine the origin of the compositions.
Enfin, il présente un intérêt de pouvoir avoir un indicateur, dans une composition finale, permettant de tracer le procédé de préparation et donc garantir la qualité de ladite composition. Dans le domaine des carburants, il est important de garantir une homogénéité des compositions, notamment lors de l'additivation des carburants, et ainsi de pouvoir tracer le procédé de préparation.Finally, it is of interest to be able to have an indicator, in a final composition, making it possible to trace the preparation process and therefore guarantee the quality of said composition. In the field of fuels, it is important to guarantee homogeneity of compositions, particularly when adding fuels, and thus to be able to trace the preparation process.
Il existe actuellement des composés ajoutés aux compositions qui peuvent être détectés par des analyses et donc permettre la détermination de l'origine des compositions.There are currently compounds added to compositions which can be detected by analyzes and therefore allow the determination of the origin of the compositions.
Le document
Cependant, les composés actuellement mis en oeuvre pour un tel marquage nécessitent une analyse en laboratoire sur des appareils sophistiqués. Il n'est donc pas possible d'avoir rapidement et simplement, sur site, les analyses nécessaires.However, the compounds currently used for such marking require laboratory analysis on sophisticated devices. It is therefore not possible to have the necessary analyzes quickly and simply, on site.
Il existe un intérêt à fournir un procédé de marquage de compositions comprenant au moins un hydrocarbure ou de compositions d'additifs destinées à être ajoutées aux compositions comprenant au moins un hydrocarbure ou de compositions comprenant de l'eau et de l'urée utilisées dans le domaine automobile, notamment dans les dispositifs de post-traitement des gaz d'échappement.There is an interest in providing a process for marking compositions comprising at least one hydrocarbon or additive compositions intended to be added to compositions comprising at least one hydrocarbon or compositions comprising water and urea used in the automotive field, particularly in exhaust gas post-treatment devices.
Un objectif de la présente invention est de fournir un marquage permettant de détecter l'origine d'une composition comprenant au moins un hydrocarbure ou d'une composition comprenant de l'eau et de l'urée et utilisée dans le domaine automobile.An objective of the present invention is to provide marking making it possible to detect the origin of a composition comprising at least one hydrocarbon or of a composition comprising water and urea and used in the automotive field.
Un autre objectif de la présente invention est de fournir un marquage permettant de tracer le procédé de fabrication d'une composition comprenant au moins un hydrocarbure et de s'assurer de la qualité du procédé.Another objective of the present invention is to provide marking making it possible to trace the manufacturing process of a composition comprising at least one hydrocarbon and to ensure the quality of the process.
Un objectif de l'invention est de fournir un tel marquage qui soit d'utilisation simple et qui puisse être effectuée sur place sans nécessité d'appareillage imposant.An objective of the invention is to provide such marking which is simple to use and which can be carried out on site without the need for imposing equipment.
D'autres objectifs apparaîtront à la lecture de la description de l'invention qui suit.Other objectives will appear on reading the description of the invention which follows.
Ces objectifs sont remplis par la présente invention qui concerne l'utilisation d'un composé radicalaire dans une composition comprenant au moins un hydrocarbure ou dans une composition d'additif destinée à être additionné à une composition comprenant au moins un hydrocarbure, ou dans une composition comprenant de l'eau et de l'urée et destinée à être utilisée dans le domaine automobile pour marquer lesdites compositions, le marquage étant suivi par Résonance Paramagnétique Electronique (RPE) (par détection du composé radicalaire).These objectives are fulfilled by the present invention which relates to the use of a radical compound in a composition comprising at least one hydrocarbon or in an additive composition intended to be added to a composition comprising at least one hydrocarbon, or in a composition comprising water and urea and intended to be used in the automotive field to mark said compositions, the marking being followed by Electronic Paramagnetic Resonance (EPR) (by detection of the radical compound).
Les composés radicalaires sont des composés détectables en faible quantité par Résonance Paramagnétique Electronique (RPE). Il existe des appareils de RPE portatifs.Radical compounds are compounds detectable in small quantities by Electron Paramagnetic Resonance (EPR). Portable RPE devices are available.
Ainsi, de manière particulièrement avantageuse, l'invention permet, en ajoutant une quantité faible, notamment de l'ordre du ppm, de composé radicalaire dans une composition comprenant au moins un hydrocarbure, de marquer ladite composition, l'analyse de cette composition pouvant être effectuée de manière rapide et sur le terrain notamment par Résonance Paramagnétique Electronique (RPE) (par détection du composé radicalaire).Thus, in a particularly advantageous manner, the invention makes it possible, by adding a small quantity, in particular of the order of ppm, of radical compound in a composition comprising at least one hydrocarbon, to mark said composition, the analysis of this composition being able to be carried out quickly and in the field in particular by Electronic Paramagnetic Resonance (EPR) (by detection of the radical compound).
La présente invention permet donc de manière avantageuse d'avoir rapidement des connaissances sur l'origine de la composition comprenant au moins un hydrocarbure et par exemple de détecter les éventuelles contrefaçons.The present invention therefore advantageously makes it possible to quickly obtain knowledge of the origin of the composition comprising at least one hydrocarbon and for example to detect possible counterfeits.
La présente invention permet également de manière avantageuse d'avoir rapidement des connaissances sur l'origine d'une composition comprenant de l'eau et de l'urée et destinée à être utilisée dans le domaine automobile, par exemple dans les dispositifs de post-traitement des gaz d'échappement de véhicules pour réduire les émissions polluantes.The present invention also advantageously allows rapid knowledge of the origin of a composition comprising water and urea and intended for use in the automotive field, for example in post-processing devices. treatment of vehicle exhaust gases to reduce polluting emissions.
De manière particulièrement avantageuse, l'invention permet, en ajoutant une quantité connue de composé radicalaire dans une composition d'additif destinée à être additionné à une composition comprenant au moins un hydrocarbure, de pouvoir déterminer la quantité de composition d'additifs additionnée à la composition comprenant au moins un hydrocarbure et ainsi vérifier si cette quantité correspond aux quantités usuelles et répond aux critères de qualité du procédé de fabrication, l'analyse pour déterminer la quantité de composition d'additifs additionnée à la composition comprenant au moins un hydrocarbure et ainsi vérifier si cette quantité correspond aux quantités usuelles et répond aux critères de qualité du procédé de fabrication est effectuée par RPE (par détection du composé radicalaire).In a particularly advantageous manner, the invention makes it possible, by adding a known quantity of radical compound in an additive composition intended to be added to a composition comprising at least one hydrocarbon, to be able to determine the quantity of additive composition added to the composition comprising at least one hydrocarbon and thus verify if this quantity corresponds to the usual quantities and meets the quality criteria of the manufacturing process, the analysis to determine the quantity of composition of additives added to the composition comprising at least one hydrocarbon and thus verifying whether this quantity corresponds to the usual quantities and meets the quality criteria of the manufacturing process is carried out by RPE (by detection of the radical compound).
Ainsi, la présente invention permet le marquage de composition comprenant au moins un hydrocarbure et de composition comprenant de l'eau et de l'urée et destinée à être utilisée dans le domaine automobile et le traçage du procédé de préparation d'une composition comprenant au moins un hydrocarbure, le marquage étant suivi par RPE (par détection du composé radicalaire) et le traçage réalisé par RPE (par détection du composé radicalaire).Thus, the present invention allows the marking of a composition comprising at least one hydrocarbon and of a composition comprising water and urea and intended to be used in the automotive field and the tracing of the process for preparing a composition comprising at least one hydrocarbon. least one hydrocarbon, the marking being followed by RPE (by detection of the radical compound) and the tracing carried out by RPE (by detection of the radical compound).
Le composé radicalaire peut être choisi parmi tous les composés radicalaires connus de l'homme du métier. Notamment, le composé radicalaire ne doit pas réagir avec les constituants de la composition comprenant au moins un hydrocarbure ou avec la composition d'additifs.The radical compound can be chosen from all the radical compounds known to those skilled in the art. In particular, the radical compound must not react with the constituents of the composition comprising at least one hydrocarbon or with the additive composition.
Le produit radicalaire est de préférence incolore.The radical product is preferably colorless.
De préférence, le composé radicalaire n'a pas d'influence sur les propriétés de la composition comprenant au moins un hydrocarbure ou la composition d'additifs.Preferably, the radical compound has no influence on the properties of the composition comprising at least one hydrocarbon or the composition of additives.
Le composé radicalaire doit de préférence être stable, de préférence stable pendant au moins 3 mois, de préférence au moins 6 mois, de préférence au moins 12 mois.The radical compound should preferably be stable, preferably stable for at least 3 months, preferably at least 6 months, preferably at least 12 months.
Dans le cadre de la présente invention, on entend par « stable » un composé radicalaire dont l'intensité en RPE d'une composition comprenant ce composé après vieillissement varie au plus de 10% par rapport à l'intensité en RPE d'une composition comprenant ce composé sans vieillissement (composition fraiche). Les conditions de vieillissement pour les compositions comprenant au moins un hydrocarbure est un stockage pendant au moins 3 mois, de préférence au moins 6 mois, de préférence au moins 12 mois, à température ambiante. Les conditions de vieillissement pour les compositions d'additifs correspondent à un stockage à une température comprise entre 30 et 50°C pendant au moins 3 mois, de préférence au moins 6 mois, de préférence au moins 12 mois.In the context of the present invention, the term "stable" means a radical compound whose RPE intensity of a composition comprising this compound after aging varies at most 10% relative to the RPE intensity of a composition. comprising this compound without aging (fresh composition). The aging conditions for compositions comprising at least one hydrocarbon are storage for at least 3 months, preferably at least 6 months, preferably at least 12 months, at room temperature. The aging conditions for the additive compositions correspond to storage at a temperature between 30 and 50°C for at least 3 months, preferably at least 6 months, preferably at least 12 months.
Des exemples de composés radicalaires sont par exemple les nitroxydes (radicaux nitroxyde), les radicaux trityle, les radicaux stabilisés par une structure aromatique polycyclique (les asphaltènes par exemple) ou les systèmes conjugués (phtalocyanine de dilithium), les radicaux phényles et isoindolines stériquement encombrés.Examples of radical compounds are for example nitroxides (nitroxide radicals), trityl radicals, radicals stabilized by a polycyclic aromatic structure (asphaltenes for example) or conjugated systems (dilithium phthalocyanine), sterically hindered phenyl and isoindoline radicals. .
De préférence, le composé radicalaire est ajouté dans une quantité comprise entre 0,1 et 100 µM, de préférence entre 5 et 50 µM.Preferably, the radical compound is added in an amount of between 0.1 and 100 µM, preferably between 5 and 50 µM.
A ces faibles concentrations, le composé radicalaire ne peut être détecté que par RPE et par aucune autre analyse (la RPE étant une analyse très sensible).At these low concentrations, the radical compound can only be detected by EPR and by no other analysis (EPR being a very sensitive analysis).
Dans le cadre de la présente invention, on entend par « hydrocarbure » ou « hydrocarbures » des composés aromatiques de la famille du benzène, des alcènes, des alcanes et des cycloalcanesIn the context of the present invention, the term “hydrocarbon” or “hydrocarbons” means aromatic compounds from the benzene family, alkenes, alkanes and cycloalkanes.
Dans le cadre de la présente invention, on entend par « compositions comprenant au moins un hydrocarbure » des compositions telles que par exemple des huiles de base, des lubrifiants, des carburants (essence, diesel, biocarburant), des bitumes, etc.In the context of the present invention, the term “compositions comprising at least one hydrocarbon” means compositions such as for example base oils, lubricants, fuels (gasoline, diesel, biofuel), bitumens, etc.
Dans le cadre de la présente invention, on entend par « composition comprenant de l'eau et de l'urée et destinée à une utilisation dans le domaine de l'automobile » des compositions qui peuvent être utilisées notamment dans les dispositifs de post-traitement des gaz d'échappement, plus particulièrement des dispositifs SCR pour limiter les émissions polluantes. Ces compositions peuvent également comprendre des additifs tels que définis dans le brevet
Dans le cadre de la présente invention, on entend par « composition d'additif destinée à être ajouté aux compositions comprenant au moins un hydrocarbure » des compositions comprenant des additifs généralement utilisé dans le domaine pétrolier, notamment dans les lubrifiants, les huiles de base, les carburants, les bitumes, etc. A titre d'exemple les compositions d'additifs peuvent comprendre au moins l'un des additifs suivants :
- Les épaississants dont le rôle est d'augmenter la viscosité de la composition, à chaud comme à froid, ou des additifs améliorants d'indice de viscosité (VI). De préférence, ces additifs sont le plus souvent des polymères de faible poids moléculaire, de l'ordre de 2000 à 50 000 Dalton (Mn). Ils pourront être choisis parmi les PIB (de l'ordre de 2000 dalton), poly-Acrylate ou Poly Méthacrylates (de l'ordre de 30000 dalton), Oléfine-copolymères, Copolymères d'oléfine et d'Alpha Oléfines, EPDM, Polybutènes, Poly-Alphaoléfines à haut poids moléculaire (viscosité 100°C > 150), copolymères Styrène-Oléfine, hydrogénés ou non ;
- Les additifs anti-usure et extrême pression. Les additifs anti-usure et les additifs extrême pression protègent les surfaces en frottement par formation d'un film protecteur adsorbé sur ces surfaces. Il existe une grande variété d'additifs anti-usure. De manière préférée pour la composition lubrifiante selon l'invention, les additifs anti-usure sont choisis parmi des additifs phospho-soufrés comme les alkylthiophosphates métalliques, en particulier les alkylthiophosphates de zinc, et plus spécifiquement les dialkyldithiophosphates de zinc ou ZnDTP. Les composés préférés sont de formule Zn((SP(S)(OR3)(OR4))2, dans laquelle R3 et R4, identiques ou différents, représentent indépendamment un groupement alkyle, préférentiellement un groupement alkyle comportant de 1 à 18 atomes de carbone. Les phosphates d'amines sont également des additifs anti-usure qui peuvent être employés dans la composition lubrifiante selon l'invention. Toutefois, le phosphore apporté par ces additifs peut agir comme poison des systèmes catalytiques des automobiles car ces additifs sont générateurs de cendres. On peut minimiser ces effets en substituant partiellement les phosphates d'amines par des additifs n'apportant pas de phosphore, tels que, par exemple, les polysulfures, notamment les oléfines soufrées;
- Les dispersants. Les dispersants sont des additifs bien connus employés dans la formulation de composition lubrifiante, notamment pour application dans le domaine marin. Leur rôle premier est de maintenir en suspension les particules présentes initialement ou apparaissant dans la composition lubrifiante au cours de son utilisation dans le moteur. Ils préviennent leur agglomération en jouant sur l'encombrement stérique. Ils peuvent présenter également un effet synergique sur la neutralisation. Les dispersants utilisés comme additifs pour lubrifiant contiennent typiquement un groupement polaire, associé à une chaîne hydrocarbonée relativement longue, contenant généralement de 50 à 400 atomes de carbone. Le groupement polaire contient typiquement au moins un élément azote, oxygène ou phosphore. Les composés dérivés de l'acide succinique sont des dispersants particulièrement utilisés comme additifs de lubrification. On utilise en particulier les succinimides, obtenues par condensation d'anhydrides succiniques et d'amines, les esters succiniques obtenus par condensation d'anhydrides succiniques et d'alcools ou polyols. Ces composés peuvent être ensuite traités par divers composés notamment soufre, oxygène, formaldéhyde, acides carboxyliques et composés contenant du bore ou du zinc pour produire par exemple des succinimides boratées ou des succinimides bloqués au zinc. Les bases de Mannich, obtenues par polycondensation de phénols substitués par des groupements alkyls, de formaldéhyde et d'amines primaires ou secondaires, sont également des composés utilisés comme dispersants dans les lubrifiants. Par exemple, on peut citer les PIB succinimides par exemple boratés ou bloqués au zinc ;
- Les additifs anti-mousse, par exemple des polymères polaires tels que polyméthylsiloxanes, polyacrylates,
- Les additifs anti-oxydants en/ou anti-rouille. L'additif antioxydant permet généralement de retarder la dégradation de la composition lubrifiante en service. Cette dégradation peut notamment se traduire par la formation de dépôts, par la présence de boues ou par une augmentation de la viscosité de la composition lubrifiante. Parmi les additifs antioxydants couramment employés, on peut citer les additifs antioxydants de type phénolique, les additifs antioxydants de type aminé, les additifs antioxydants phosphosoufrés. Certains de ces additifs antioxydants, par exemple les additifs antioxydants phosphosoufrés, peuvent être générateurs de cendres. Les additifs antioxydants phénoliques peuvent être exempt de cendres ou bien être sous forme de sels métalliques neutres ou basiques. Les additifs antioxydants peuvent notamment être choisis parmi les phénols stériquement encombrés, les esters de phénol stériquement encombrés et les phénols stériquement encombrés comprenant un pont thioéther, les diphénylamines, les diphénylamines substituées par au moins un groupement alkyle en C1-C12, les N,N'-dialkyle-aryle-diamines et leurs mélanges. De préférence selon l'invention, les phénols stériquement encombrés sont choisis parmi les composés comprenant un groupement phénol dont au moins un carbone vicinal du carbone portant la fonction alcool est substitué par au moins un groupement alkyle en C1- C10, de préférence un groupement alkyle en C1-C6, de préférence un groupement alkyle en C4, de préférence par le groupement ter-butyle. Les composés aminés sont une autre classe d'additifs antioxydants pouvant être utilisés, éventuellement en combinaison avec les additifs antioxydants phénoliques. Des exemples de composés aminés sont les amines aromatiques, par exemple les amines aromatiques de formule NR5R6R7 dans laquelle R5 représente un groupement aliphatique ou un groupement aromatique, éventuellement substitué, R6 représente un groupement aromatique, éventuellement substitué, R7 représente un atome d'hydrogène, un groupement alkyle, un groupement aryle ou un groupement de formule R8S(O)zR9 dans laquelle R8 représente un groupement alkylène ou un groupement alkenylène, R9 représente un groupement alkyle, un groupement alcényle ou un groupement aryle et
z représente 0, 1ou 2. Des alkyl phénols sulfurisés ou leurs sels de métaux alcalins et alcalino-terreux peuvent également être utilisés comme additifs antioxydants. Une autre classe d'additifs antioxydants est celle des composés cuivrés, par exemples les thio- ou dithio-phosphates de cuivre, les sels de cuivre et d'acides carboxyliques, les dithiocarbamates, les sulphonates, les phénates, les acétylacétonates de cuivre. Les sels de cuivre I et II, les sels d'acide ou d'anhydride succiniques peuvent également être utilisés. Les additifs modificateur de frottement. L'additif modificateur de frottement peut être choisi parmi un composé apportant des éléments métalliques et un composé exempt de cendres. Parmi les composés apportant des éléments métalliques, on peut citer les complexes de métaux de transition tels que Mo, Sb, Sn, Fe, Cu, Zn dont les ligands peuvent être des composés hydrocarbonés comprenant des atomes d'oxygène, d'azote, de soufre ou de phosphore. Les additifs modificateurs de frottement exempt de cendres sont généralement d'origine organique et peuvent être choisis parmi les monoesters d'acides gras et de polyols, les amines alcoxylées, les amines grasses alcoxylées, les époxydes gras, les époxydes gras de borate; les amines grasses ou les esters de glycérol d'acide gras. Selon l'invention, les composés gras comprennent au moins un groupement hydrocarboné comprenant de 10 à 24 atomes de carbone. - Les améliorants du point d'écoulement. En ralentissant la formation de cristaux de paraffine, les additifs abaisseurs de point d'écoulement améliorent généralement le comportement à froid de la composition lubrifiante selon l'invention. Comme exemple d'additifs abaisseurs de point d'écoulement, on peut citer les polyméthacrylates d'alkyle, les polyacrylates, les polyarylamides, les polyalkylphénols, les polyalkylnaphtalènes, les polystyrènes alkylés. ;
- Les détergents. Les additifs détergents permettent généralement de réduire la formation de dépôts à la surface des pièces métalliques par dissolution des produits secondaires d'oxydation et de combustion. Les additifs détergents utilisables sont généralement connus de l'homme de métier. Les additifs détergents peuvent être des composés anioniques comprenant une longue chaîne hydrocarbonée lipophile et une tête hydrophile. Le cation associé peut être un cation métallique d'un métal alcalin ou alcalino-terreux. Les additifs détergents sont préférentiellement choisis parmi les sels de métaux alcalins ou de métaux alcalino-terreux d'acides carboxyliques, les sulfonates, les salicylates, les naphténates, ainsi que les sels de phénates. Les métaux alcalins et alcalino-terreux sont préférentiellement le calcium, le magnésium, le sodium ou le baryum. Ces sels métalliques comprennent généralement le métal en quantité stoechiométrique ou bien en excès, donc en quantité supérieure à la quantité stoechiométrique. Il s'agit alors d'additifs détergents surbasés ; le métal en excès apportant le caractère surbasé à l'additif détergent est alors généralement sous la forme d'un sel métallique insoluble dans l'huile, par exemple un carbonate, un hydroxyde, un oxalate, un acétate, un glutamate, préférentiellement un carbonate.
- Thickeners whose role is to increase the viscosity of the composition, both hot and cold, or viscosity index (VI) improving additives. Preferably, these additives are most often polymers of low molecular weight, of the order of 2000 to 50,000 Dalton (Mn). They can be chosen from PIB (around 2000 dalton), poly-Acrylate or Poly Methacrylates (around 30000 dalton), Olefin-copolymers, Olefin and Alpha Olefin copolymers, EPDM, Polybutenes , High molecular weight poly-Alphaolefins (viscosity 100°C > 150), Styrene-Olefin copolymers, hydrogenated or not;
- Anti-wear and extreme pressure additives. Anti-wear additives and extreme pressure additives protect friction surfaces by forming a film protector adsorbed on these surfaces. There is a wide variety of anti-wear additives. Preferably for the lubricating composition according to the invention, the anti-wear additives are chosen from phospho-sulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTP. The preferred compounds are of formula Zn((SP(S)(OR3)(OR4))2, in which R3 and R4, identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms Amine phosphates are also anti-wear additives which can be used in the lubricating composition according to the invention. However, the phosphorus provided by these additives can act as a poison in the catalytic systems of automobiles because these additives generate ash. These effects can be minimized by partially substituting the amine phosphates with additives which do not provide phosphorus, such as, for example, polysulphides, in particular sulfur-containing olefins;
- Dispersants. Dispersants are well-known additives used in the formulation of lubricating compositions, particularly for application in the marine sector. Their primary role is to maintain in suspension the particles initially present or appearing in the lubricating composition during its use in the engine. They prevent their agglomeration by playing on steric hindrance. They may also have a synergistic effect on neutralization. Dispersants used as lubricant additives typically contain a polar group, associated with a relatively long hydrocarbon chain, generally containing 50 to 400 carbon atoms. The polar group typically contains at least one nitrogen, oxygen or phosphorus element. Compounds derived from succinic acid are dispersants particularly used as lubrication additives. In particular, succinimides are used, obtained by condensation of succinic anhydrides and amines, succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols. These compounds can then be treated with various compounds including sulfur, oxygen, formaldehyde, carboxylic acids and compounds containing boron or zinc to produce, for example, borated succinimides or zinc-blocked succinimides. Mannich bases, obtained by polycondensation of phenols substituted with alkyl groups, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants. For example, we can cite succinimide PIBs, for example borated or zinc-blocked;
- Anti-foam additives, for example polar polymers such as polymethylsiloxanes, polyacrylates,
- Anti-oxidant and/or anti-rust additives. The antioxidant additive generally makes it possible to delay the degradation of the lubricating composition in service. This degradation can in particular result in the formation of deposits, the presence of sludge or an increase in the viscosity of the lubricating composition. Among the commonly used antioxidant additives, mention may be made of phenolic-type antioxidant additives, amine-type antioxidant additives and phosphosulfur-containing antioxidant additives. Some of these antioxidant additives, for example phosphosulfur antioxidant additives, can generate ash. Phenolic antioxidant additives can be ash-free or in the form of neutral or basic metal salts. The antioxidant additives may in particular be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted by at least one C1-C12 alkyl group, N,N '-dialkyl-aryl-diamines and mixtures thereof. Preferably according to the invention, the sterically hindered phenols are chosen from compounds comprising a phenol group of which at least one vicinal carbon of the carbon carrying the alcohol function is substituted by at least one C1-C10 alkyl group, preferably an alkyl group. C1-C6, preferably a C4 alkyl group, preferably the tert-butyl group. Amino compounds are another class of antioxidant additives that can be used, possibly in combination with phenolic antioxidant additives. Examples of amino compounds are aromatic amines, for example aromatic amines of formula NR5R6R7 in which R5 represents an aliphatic group or an aromatic group, optionally substituted, R6 represents an aromatic group, optionally substituted, R7 represents a hydrogen atom, an alkyl group, an aryl group or a group of formula R8S(O)zR9 in which R8 represents an alkylene group or an alkenylene group, R9 represents an alkyl group, an alkenyl group or an aryl group and z represents 0, 1 or 2 Sulfurized alkyl phenols or their alkali and alkaline earth metal salts can also be used. be used as antioxidant additives. Another class of antioxidant additives is that of copper compounds, for example copper thio- or dithio-phosphates, copper salts and carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper I and II salts, succinic acid or anhydride salts can also be used. Friction modifier additives. The friction modifier additive can be chosen from a compound providing metallic elements and an ash-free compound. Among the compounds providing metallic elements, mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn whose ligands can be hydrocarbon compounds comprising atoms of oxygen, nitrogen, sulfur or phosphorus. The ash-free friction modifier additives are generally of organic origin and can be chosen from monoesters of fatty acids and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, fatty borate epoxides; fatty amines or glycerol esters of fatty acids. According to the invention, the fatty compounds comprise at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
- Pour point improvers. By slowing down the formation of paraffin crystals, the pour point depressant additives generally improve the cold behavior of the lubricating composition according to the invention. As an example of pour point depressant additives, mention may be made of polyalkyl methacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes. ;
- Detergents. Detergent additives generally help reduce the formation of deposits on the surface of metal parts by dissolving secondary oxidation and combustion products. The detergent additives which can be used are generally known to those skilled in the art. The detergent additives may be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation may be a metal cation of an alkali or alkaline earth metal. The detergent additives are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, as well as phenate salts. The alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts generally include the metal in stoichiometric quantity or in excess, therefore in quantity greater than the stoichiometric quantity. These are then overbased detergent additives; the excess metal providing the overbased character to the detergent additive is then generally in the form of a metal salt insoluble in the oil, for example a carbonate, a hydroxide, an oxalate, an acetate, a glutamate, preferably a carbonate .
Dans le cadre de la présente invention, on entend par « huile de base » des huiles d'origine minérales, synthétiques ou végétales ainsi que leurs mélanges.In the context of the present invention, the term “base oil” means oils of mineral, synthetic or vegetable origin as well as their mixtures.
Les huiles minérales ou synthétiques généralement utilisées dans l'application appartiennent à l'une des classes définies dans la classification API telle que résumée dans le tableau ci-dessous.
Les huiles minérales de Groupe 1 peuvent être obtenues par distillation de bruts naphténiques ou paraffiniques sélectionnés puis purification de ces distillats par des procédés tels l'extraction au solvant, le déparaffinage au solvant ou catalytique, l'hydrotraitement ou l'hydrogénation.Group 1 mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes and then purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
Les huiles des Groupes 2 et 3 sont obtenues par des procédés de purification plus sévères, par exemple une combinaison parmi l'hydrotraitement, l'hydrocraquage, l'hydrogénation et le déparaffinage catalytique.
Les huiles de base synthétiques de Groupe 4 et 5 peuvent être choisies parmi les esters, les silicones, les glycols, le polybutène, les polyalphaoléfines (PAO), l'alkylbenzène ou l'alkylnaphtalène. Les polyalphaoléfines utilisées comme huiles de base sont par exemple obtenues à partir de monomères comprenant de 4 à 32 atomes de carbone, par exemple à partir d'octène ou de décène, et dont la viscosité à 100 °C est comprise entre 1,5 et 15 mm2.s-1 selon la norme ASTM D445. Leur masse moléculaire moyenne est généralement comprise entre 250 et 3000 selon la norme ASTM D5296.
Les huiles de base peuvent également être des huiles d'origine naturelle, par exemple des esters d'alcools et d'acides carboxyliques, pouvant être obtenus à partir de ressources naturelles telles que l'huile de tournesol, de colza, de palme, de soja etc.The base oils can also be oils of natural origin, for example esters of alcohols and carboxylic acids, which can be obtained from natural resources such as sunflower oil, rapeseed oil, palm oil, soy etc.
Ces huiles de base peuvent être utilisées seules ou en mélange. Une huile minérale peut être combinée avec une huile synthétique.These base oils can be used alone or in a mixture. Mineral oil can be combined with synthetic oil.
La présente invention concerne également une méthode de marquage et/ou traçage, notamment marquage et/ou traçage détectable par RPE, de composition comprenant au moins un hydrocarbure comprenant l'addition d'un composé radicalaire à ladite composition comprenant au moins un hydrocarbure ou à une composition d'additif destinée à être ajoutée à la composition comprenant au moins un hydrocarbure, ladite méthode comprend également une étape de détection du marquage et/ou traçage (et donc du composé radicalaire) par RPE.The present invention also relates to a method of marking and/or tracing, in particular marking and/or tracing detectable by EPR, of a composition comprising at least one hydrocarbon comprising the addition of a radical compound to said composition comprising at least one hydrocarbon or an additive composition intended to be added to the composition comprising at least one hydrocarbon, said method also comprises a step of detecting the marking and/or tracing (and therefore the radical compound) by EPR.
La présente invention concerne également une méthode de marquage, notamment marquage détectable par RPE, de composition comprenant au moins un hydrocarbure comprenant l'addition à ladite composition d'un composé radicalaire, ladite méthode comprend également une étape de détection du marquage (et donc du composé radicalaire) par RPE.The present invention also relates to a marking method, in particular marking detectable by EPR, of a composition comprising at least one hydrocarbon comprising the addition to said composition of a radical compound, said method also comprises a step of detecting the marking (and therefore the radical compound) by RPE.
La présente invention concerne également une méthode de traçabilité du procédé de préparation d'une composition comprenant au moins un hydrocarbure et une composition d'additif comprenant l'addition d'un composé radicalaire à la composition d'additif destinée à être ajoutée à la composition comprenant au moins un hydrocarbure, ledit procédé comprenant également une étape de détection dudit composé radicalaire par RPE.The present invention also relates to a method of traceability of the process for preparing a composition comprising at least one hydrocarbon and an additive composition comprising the addition of a radical compound to the additive composition intended to be added to the composition comprising at least one hydrocarbon, said method also comprising a step of detecting said radical compound by EPR.
En effet, connaissant la quantité de composé radicalaire dans la composition d'additifs et la dilution de la composition d'additifs dans la composition comprenant au moins un hydrocarbure, il est possible, en analysant le spectre RPE, de connaître la quantité de composé radicalaire dans la composition comprenant au moins un hydrocarbure et (puisque le composé radicalaire est stable) déterminer si la bonne quantité de composition d'additif a été ajoutée pour remplir les standards de qualité.Indeed, knowing the quantity of radical compound in the additive composition and the dilution of the additive composition in the composition comprising at least one hydrocarbon, it is possible, by analyzing the RPE spectrum, to know the quantity of radical compound in the composition comprising at least one hydrocarbon and (since the radical compound is stable) determine whether the correct quantity of additive composition has been added to meet the quality standards.
La présente demande concerne également une méthode de marquage, notamment marquage détectable par RPE, d'une composition comprenant de l'eau et de l'urée destinée à être utilisée dans le domaine automobile comprenant l'addition d'un composé radicalaire à ladite composition, ladite méthode comprend également une étape de détection du marquage par RPE.The present application also relates to a method of marking, in particular marking detectable by EPR, of a composition comprising water and urea intended to be used in the automotive field comprising the addition of a radical compound to said composition, said method also comprises a step of detecting the marking by RPE.
La présente invention concerne également une composition comprenant de l'eau, de l'urée, un additif choisi parmi les épaississants, additifs améliorants d'indice de viscosité (VI), additifs anti-usure et extrême pression, dispersants, additifs anti-mousse, additifs anti-oxydant, additifs anti-rouille, améliorants du point d'écoulement et détergents, ladite composition étant destinée à être utilisée dans le domaine automobile, ladite composition comprenant un composé radicalaire.The present invention also relates to a composition comprising water, urea, an additive chosen from thickeners, viscosity index (VI) improving additives, anti-wear and extreme pressure additives, dispersants, anti-foam additives. , antioxidant additives, anti-rust additives, pour point improvers and detergents, said composition being intended for use in the automotive field, said composition comprising a radical compound.
Les définitions des compositions, du composé radicalaire et de la quantité de composé radicalaire sont tels que définis ci-dessus.The definitions of the compositions, the radical compound and the quantity of radical compound are as defined above.
La présente demande va maintenant être décrite à l'aide des exemples suivants non limitatifs.
- La
figure 1 montre l'intensité du signal RPE en fonction du temps pour des compositions de diesel B7 additionnée de 10µM de nitroxide. - La
figure 2 montre les spectres RPE d'un échantillon d'huile de base comprenant 10µM de nitroxide à T0, T0+4 mois et T0+6 mois.
- There
figure 1 shows the intensity of the RPE signal as a function of time for compositions of B7 diesel added with 10µM of nitroxide. - There
figure 2 shows the EPR spectra of a base oil sample comprising 10µM of nitroxide at T0, T0+4 months and T0+6 months.
Une composition d'additif pour une composition diesel B7 comprenant 8,3 mM de nitroxide est préparée. La teneur en nitroxide est choisie de façon à avoir après dilution de la composition d'additifs (1200 ppm) dans la composition diesel B7, le nitroxide est présent dans une teneur de 10 µM (1,9 ppm).An additive composition for a B7 diesel composition comprising 8.3 mM nitroxide is prepared. The nitroxide content is chosen so as to have, after dilution of the additive composition (1200 ppm) in the diesel composition B7, the nitroxide is present in a content of 10 µM (1.9 ppm).
La composition d'addiftif est séparée en plusieurs échantillons:
- Un échantillon est laissé à température ambiante puis à différents temps est formulé pour analyse RPE, chaque spectre RPE est répété trois fois (A, B et C)
- Un échantillon est laissé à 50°C puis à différents temps est formulé pour analyse RPE, chaque spectre RPE est répété trois fois (A 50, B 50 et C 50)
- A sample is left at room temperature then at different times is formulated for EPR analysis, each EPR spectrum is repeated three times (A, B and C)
- A sample is left at 50°C then at different times is formulated for EPR analysis, each EPR spectrum is repeated three times (A 50, B 50 and C 50)
La formulation pour analyse RPE est la suivante : La composition d'additif comprenant le nitroxide est diluée dans une composition diesel B7 à la concentration nominale en nitroxide de 10 µM. Des échantillons sont préparés pour mesure RPE puis les spectres sont réalisés à température ambiante sur un spectromètre X-bande continu avec un centre de champ au facteur g de 2.005 et une fenêtre de champ magnétique de 100 G. L'acquisition des spectres prend 15s. L'intensité du signal est mesurée comme la hauteur du pic du nitroxide et est comparée à la valeur à t0 (échantillon frais).The formulation for RPE analysis is as follows: The additive composition comprising nitroxide is diluted in a B7 diesel composition at the nominal nitroxide concentration of 10 µM. Samples are prepared for EPR measurement then the spectra are performed at room temperature on a continuous X-band spectrometer with a field center with a g factor of 2.005 and a magnetic field window of 100 G. Spectra acquisition takes 15s. The signal intensity is measured as the height of the nitroxide peak and is compared to the value at t0 (fresh sample).
Les résultats des spectres sont donnés à la
Ces résultats montrent la possibilité d'utiliser des marqueurs radicalaires dans des compositions comprenant au moins un composé radicalaire.These results show the possibility of using radical markers in compositions comprising at least one radical compound.
Une solution de nitroxide (10µM) est ajoutée à une huile de base. La composition obtenue est ajoutée dans un tube 5 mm pour RPE. Un spectre RPE est réalisé à température ambiante dans les mêmes conditions qu'à l'exemple 1. Le spectre est réalisé à t0 (juste après la préparation de la composition) puis à t0 + 4 mois et t0 + 6 mois.A nitroxide solution (10µM) is added to a base oil. The composition obtained is added to a 5 mm tube for RPE. An EPR spectrum is carried out at room temperature under the same conditions as in Example 1. The spectrum is carried out at t0 (just after preparation of the composition) then at t0 + 4 months and t0 + 6 months.
Les résultats des spectres sont donnés à la
Ces résultats montrent des spectres totalement superposables prouvant que le composé radicalaire est stable dans l'huile de base et peut donc être utilisé comme marqueur ou traceur du procédé de préparation de composition comprenant au moins un hydrocarbure.These results show completely superimposable spectra proving that the radical compound is stable in the base oil and can therefore be used as a marker or tracer of the process for preparing a composition comprising at least one hydrocarbon.
Claims (8)
- Use of a radical compound in a composition comprising at least one hydrocarbon or in a composition comprising water and urea and intended for use in the automotive field or in an additive composition intended for addition to a composition comprising at least one hydrocarbon, for marking said compositions, said marking being monitored by electron paramagnetic resonance (EPR).
- Use according to claim 1, in which the composition comprising the radical compound has an EPR intensity, after ageing for at least 3 months, which varies by at most 10%, relative to the EPR intensity of a composition comprising this radical compound without ageing, the ageing corresponding to storage at a temperature of between 30°C and 50°C.
- Use according to claim 1 or 2, in which the radical compound is chosen from nitroxides (nitroxyl radicals), trityl radicals, radicals stabilised by a polycyclic aromatic structure (asphaltenes, for example) or conjugated systems (dilithium phthalocyanine), phenyl radicals and sterically encumbered isoindolines.
- Use according to any one of claims 1 to 3, wherein the radical compound is added in a content of 0.1 and 100 µM, preferably between 5 and 50 µM.
- A method of marking and/or tracing a composition comprising at least one hydrocarbon comprising adding a radical compound to said composition comprising at least one hydrocarbon or to an additive composition intended to be added to the composition comprising at least one hydrocarbon, the said method using electron paramagnetic resonance (EPR).
- A method of traceability of the process for preparing a composition comprising at least one hydrocarbon and an additive composition comprising the addition of a radical compound to the additive composition intended to be added to the composition comprising at least one hydrocarbon, said method using electron paramagnetic resonance (EPR).
- A method of marking a composition comprising water and urea intended for use in the automotive field, comprising the addition of a radical compound to the said composition, the said method using electron paramagnetic resonance (EPR).
- Composition comprising water, urea and an additive chosen from thickeners, viscosity index (VI) improver additives, anti-wear and extreme pressure additives, dispersants, anti-foam additives, anti-oxidant additives, anti-rust additives, flow point improvers and detergents, the said composition being intended for use in the automotive field, and comprising a radical compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1914669A FR3104607B1 (en) | 2019-12-17 | 2019-12-17 | Composition marking |
| PCT/EP2020/086684 WO2021122929A1 (en) | 2019-12-17 | 2020-12-17 | Composition marking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP4077602A1 EP4077602A1 (en) | 2022-10-26 |
| EP4077602B1 true EP4077602B1 (en) | 2024-05-15 |
Family
ID=69903468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20830182.0A Active EP4077602B1 (en) | 2019-12-17 | 2020-12-17 | Marking composition |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP4077602B1 (en) |
| FR (1) | FR3104607B1 (en) |
| WO (1) | WO2021122929A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804447A (en) * | 1992-07-23 | 1998-09-08 | Basf Aktiengesellschaft | Use of compounds which absorb and/or fluoresce in the IR region as markers for liquids |
| DE4320456A1 (en) * | 1993-06-21 | 1994-12-22 | Basf Ag | Use of aminotriarylmethanes for marking hydrocarbons and new aminotriarylmethanes |
| US5711767A (en) * | 1996-07-11 | 1998-01-27 | Ciba Specialty Chemicals Corporation | Stabilizers for the prevention of gum formation in gasoline |
| FR2912932B1 (en) | 2007-02-23 | 2011-06-10 | Total France | AQUEOUS SOLUTION FOR THE TREATMENT OF EXHAUST GASES FROM DIESEL ENGINES |
-
2019
- 2019-12-17 FR FR1914669A patent/FR3104607B1/en active Active
-
2020
- 2020-12-17 EP EP20830182.0A patent/EP4077602B1/en active Active
- 2020-12-17 WO PCT/EP2020/086684 patent/WO2021122929A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021122929A1 (en) | 2021-06-24 |
| EP4077602A1 (en) | 2022-10-26 |
| FR3104607A1 (en) | 2021-06-18 |
| FR3104607B1 (en) | 2022-10-21 |
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