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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/20—Organic compounds containing halogen
  • C10L1/202—Organic compounds containing halogen aromatic bond
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/20—Organic compounds containing halogen
  • C10L1/203—Organic compounds containing halogen hydroxyl compounds; ethers, acetals, ketals
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/04—Specifically adapted fuels for turbines, planes, power generation

Definitions

• the present invention relates to the use of triarylbenzene derivatives as marking tracers for liquid fuels and fuels; liquid fuels and fuels containing such derivatives; a method of marking fuels and liquid fuels with such derivatives; and a method for determining whether liquid fuels initially containing these tracers have been tampered with, used illegally or stolen.
• Marking fuels and liquid fuels with different types of chemical markers is well known in the art.
• Various compounds have been used for this purpose, as well as numerous analytical techniques for the detection of markers (for example, gas chromatography coupled with mass spectrometry).
• An important application is to mark combustible fuels according to their level of taxation.
• the deliberate removal of the tracer for illegal purposes is an important issue. Since tracers were dyes so far, "disposal methods" have been called “bleaching methods”. These methods are physical (for example: adsorption on charcoal or on silica gel) or chemical (for example: acid or basic treatment). Therefore, these markers must be resistant to such disposal methods, be fully compatible with fuels liquids, and be identifiable by an appropriate analytical method.
• Fraud involving fuels or liquid fuels covers various acts: falsification by bleaching or cutting, illegal use, contraband and theft.
• Laundering forgery concerns the conversion of low-tax fuel or liquid fuel into higher-taxed fuel or liquid fuel, for example - in France - the conversion of heating oil into diesel fuel.
• Falsification by cutting concerns the dilution of a high-rate fuel or liquid fuel by a low-tax fuel or liquid fuel.
• Illegal use refers to the illegal use of low-tax fuel or liquid fuel instead of higher-rate fuel or liquid fuel. Smuggling involves the purchase of low-tax fuel or liquid fuel in one country to resell it in another country where taxes are higher.
• WO2012 / 153132 A1 discloses aromatic organic labels substituted with at least one bromine and / or one fluorine atom, and / or one or more fluoroalkyl groups.
• the combustion of fuels labeled with such compounds can produce hydrogen bromide and / or hydrogen fluoride in the flue gases.
• Bromide and hydrogen fluoride are known to be particularly corrosive to the engine.
• Hydrogen fluoride is well known to be highly toxic to people and the environment.
• WO2014 / 008164 discloses aryl and tritylated alkyl ethers as tracers for the labeling of hydrocarbons. Such tracers appear as not having good resistance to the abovementioned methods of elimination.
• No. 7,858,373 describes the use of a variety of organic compounds for use in the labeling of liquid fuels such as hydrocarbons and oils.
• Combinations of markers can be used as digital marking systems, the ratio of the concentration of each marker forming a code of the labeled product.
• triarylbenzenes are particularly effective for the marking of liquid fuels and fuels.
• these triarylbenzenes are particularly resistant to bleaching attempts chemical and physical.
• most of these triarylbenzenes contain only carbon and hydrogen, and the burning of these compounds used as markers produces only carbon dioxide and water.
• the present invention therefore firstly relates to the use as marker tracer of fuels and liquid fuels of at least one compound of Formula I:
• the benzene ring A is optionally substituted in at least one of the 2, 4 or 6 positions by:
• a linear, branched or cyclic C1-C18 alkyl radical optionally substituted with at least one halogen and / or optionally interrupted by at least one oxygen;
• the benzene rings B, C and D are substituted, independently of one another, in at least one ortho, meta or para position relative to the benzene ring A by:
• Ci - Cis optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or
• At least one benzene ring B, C and D may also comprise a 5-7 membered aliphatic ring attached to it, for example a 6-membered ring,
• any atom can be replaced by one of its isotopes.
• the benzene ring A is unsubstituted or substituted by alkoxy - Ci 8.
• the benzene rings B, C and D are substituted with:
• Ci-Cis an alkyl radical, linear, branched or cyclic, Ci-Cis, especially C 1 -C 12 , in particular Ci-C 6 , optionally substituted by at least one halogen; or at least one halogen.
• Halogen falling within the definition of Formula I may be F, Cl, Br and I, and especially F, Cl and Br.
• the compound of formula I may especially be chosen from:
• the invention also relates to a fuel or liquid fuel containing as tracer label at least one compound of Formula I.
• liquid fuels or fuels obtained from petroleum among which mention may be made of gasoline, diesel fuel, domestic fuel oil, kerosene, kerosene;
• liquid fuels or fuels obtained from plants such as biofuels, among which mention may be made of vegetable oils, ethanol, butanol, ethyl tert-butyl ether (ETBE), methyl esters of fatty acid.
• vegetable oils ethanol, butanol, ethyl tert-butyl ether (ETBE), methyl esters of fatty acid.
• ETBE ethyl tert-butyl ether
• the compounds of Formula I can be prepared by palladium-catalyzed Suzuki coupling between a 1,3,5-trihalogenoarene optionally substituted at the 2, 4 or 6 positions and three equivalents of an arylboronic acid in the presence of a mineral base:
• the compounds of Formula I not being substituted on the benzene ring A can also be prepared by cyclotrimerization of aryl methyl ketones according to:
• the reaction takes place at 80 to 150 ° C in the presence of catalysts or desiccants.
• the catalysts are Bronsted or Lewis acids.
• the use of arenesulphonic acids is well described in the literature.
• the use of a catalytic amount of 4-toluenesulfonic acid monohydrate is described in Zhao, Y .; Li, J.; Li, C.; Yin, K.; Ye, D.; Jia, X. Green Chem. 2010, 12, 1370.
• the compound of formula I can be added to the fuel or liquid fuel at a rate of 0.01 to 500 mg / l, in particular at a rate of 0.02 to 20 mg / l, and more particularly at a level of 0.1 to 5 mg / L.
• the subject of the invention is also a process for marking liquid fuels or fuels, characterized in that a 0.1 to 40% by weight solution of the compound of Formula I is prepared in a solvent or a mixture of solvents. and that said solution is injected into the fuel or liquid fuel for example in line in a pipeline or the loading arm of a tanker truck, or in a tank to obtain the target concentration of the marker in the fuel or liquid fuel.
• a 0.2 to 20% by weight solution of the compound of Formula I is prepared in the solvent or solvent mixture.
• the solvent or solvents may be chosen from aromatic solvents such as toluene, ethylbenzene, xylenes, mesitylene, 1,2,4-trimethylbenzene, cumene, p-cymene and aromatic hydrocarbons (for example Shellsol).
• aromatic solvents such as toluene, ethylbenzene, xylenes, mesitylene, 1,2,4-trimethylbenzene, cumene, p-cymene and aromatic hydrocarbons (for example Shellsol).
• aliphatic solvents such as pentane, hexanes, cyclohexane, heptanes, 2,2,4-trimethylpentane, white spirits, kerosene, isoparaffins, paraffins; among oxygenated and / or nitrogenous solvents such as ketones, ethers, esters, lactones, phenols, amides, lactams; or from halogenated solvents such as chlorobenzene, 1,2-dichlorobenzene, 1 ', ⁇ , ⁇ , ⁇ -trifluorotoluene.
• aliphatic solvents such as pentane, hexanes, cyclohexane, heptanes, 2,2,4-trimethylpentane, white spirits, kerosene, isoparaffins, paraffins
• oxygenated and / or nitrogenous solvents such as ketones, ethers, esters, lactones, phenols, amides, lact
• the invention also relates to a method for determining whether liquid fuels have been falsified by bleaching, characterized in that a sample of the fuel or liquid fuel suspected to have been tampered with and it is analyzed to determine if the concentration of the compound of Formula I in said sample is lower than the initial concentration, and if so, it is deduced that the sample has been falsified by bleaching.
• the invention also relates to a method for determining whether liquid fuels have been falsified by cutting, or have been used illegally or have been smuggled or stolen, characterized by the fact that take a sample of fuel or liquid fuel suspected to have been falsified or illegally used or smuggled or stolen, and analyzed for the presence of the compound of Formula I in the sample, and, if so, it can be concluded that the sample was falsified or used illegally or is smuggled or stolen.
• the marker (s) according to the invention can be used individually or in combination with other markers.
• liquid fuels or fuels labeled with one or more compounds of Formula I can be analyzed qualitatively or quantitatively, for example by the following methods: gas chromatography coupled to a flame ionization detector or a mass spectrometer; high performance liquid chromatography coupled to a diode array detector or mass spectrometer.
• the tube was stirred using a linear stirrer at 300 motions / min for 10 min.
• the liquid was then filtered through a 0.2 ⁇ polytetrafluoroethylene (PTFE) membrane and analyzed by GC / FID.
• PTFE polytetrafluoroethylene
• the tube was stirred using a linear stirrer at 300 motions / min for 10 min. After a few minutes of rest, the liquid constituting the phase
• a mixture of 134.2 g of 4'-methylacetophenone and 19 g of 4-toluenesulphonic acid monohydrate was heated to 140 ° C with stirring. The water was distilled off to reach the temperature and then during the course of the reaction. The temperature of 140 ° C was maintained for 24 hours.
• the title compound was prepared according to the procedure of Example 1 except that the starting mixture was a mixture of 176.3 g of 4'-isobutylacetophenone and 19 g of 4-toluenesulfonic acid monohydrate.
• the title compound was prepared according to the procedure of Example 1 except that the starting mixture was a mixture of 10 g of 4'-butylacetophenone and 1.1 g of 4-toluenesulfonic acid monohydrate.
• the title compound was prepared according to the procedure of Example 1 except that the starting mixture was a mixture of 10 g of 4'-ethylacetophenone and 1.3 g of 4-toluenesulphonic acid monohydrate.
• Example 6 1, 3, 5-Tris (4-fluorophenyl) benzene
• 1,3,5-Tri (4-chlorophenyl) enzene was prepared according to the procedure of Example 1, replacing 4'-methylacetophenone with 4'-chloroacetophenone.
• the crude product was recrystallized from ethanol. 36.8 g of yellowish-white crystals were obtained.
• 1,3,5-Tri (4-bromophenyl) benzene was prepared according to the procedure of Example 1, replacing 4'-methylacetophenone with 4'-bromoacetophenone. The crude product was recrystallized from toluene. 54.3 g of yellowish-white crystals were obtained. Table 8
• Example 9 1-Dodecyloxy-2,4,6-tris (4-fluorophenyl) benzene
• Example 10 1-O-oxyoxy-2,4,6-tris (4-fluorophenyl) benzene
• Example 11 1-Butoxy-2,4,6-tris (4-fluorophenyl) benzene
• 1-Butoxy-2,4,6-tribromobenzene was prepared according to the procedure of Example 9 substituting 1-bromobutane for 1-bromododecane. Under an argon atmosphere, a mixture of 774 mg of 1-butoxy-2,4,6-tribromobenzene, 1.007 g of 4-fluorophenylboronic acid, 15 mg of palladium acetate and 52 mg of triphenylphosphine in 4 mL of an aqueous solution of 2M sodium carbonate and 13 mL of 1-propanol was refluxed with stirring for 2 h.
• Example 12 1-Dodecyloxy-2,4,6-tris (3,4-difluorophenyl) benzene
• Example 13 (of the invention): 1 -Octyloxy-2,4,6-tris (3,4-difluorophenyl) benzene
• Example 14 1-Dodecyloxy-2,4,6-tris (4-methylphenyl) benzene
• Example 15 1-Oxytyloxy-2,4,6-tris (4-methylphenyl) benzene
• Example 16 1-Butoxy-2,4,6-tris (4-methylphenyl) benzene
• the product is marketed by Sigma-Aldrich (ref 764671.
• Patent application WO2014 / 008164 describes in particular the ((3- (sec-butyl) -4- (decyloxy) phenyl) formulationthanetriyl) tribenzène, sold under the name ® Accutrace S10.
• the compound of Example 2 is significantly more resistant to silica treatment than the compound of Comparative Example 19. Moreover, the marker of Comparative Example 19 is completely removed by nitric acid while the compound of Example 2 shows very good resistance to this chemical agent.
• the product is marketed by Sigma-Aldrich (ref.
• Example 2 is significantly more resistant to treatment with activated carbon than TPB. In addition, the compound of Example 2 is superior to TPB for resistance to treatment with silica.
• the average percentage reduction of the airflow in the injector at 0.1 mm needle lift is 70.8 for the unlabeled fuel and 69.5 for the marker fuel.
• the addition of the marker therefore has no significant influence on the fouling of the injection nozzles.

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• Chemical Kinetics & Catalysis (AREA)
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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

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• 2016
  • 2016-03-30 FR FR1652729A patent/FR3049614B1/fr active Active
• 2017
  • 2017-03-09 WO PCT/FR2017/050517 patent/WO2017168066A1/fr not_active Ceased
  • 2017-03-09 EP EP17717209.5A patent/EP3436552B1/de active Active
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