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
• • 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
• • 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
  • C10L1/1857—Aldehydes; Ketones
• • 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
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • 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
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
  • C10L1/2286—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen triple bonds, e.g. nitriles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T436/00—Chemistry: analytical and immunological testing
  • Y10T436/13—Tracers or tags

Definitions

• the invention relates to a method for marking hydrocarbons by adding at least one first marker (hereinafter referred to as first marker), which is characterized in that at least one second marker (second marker) is added to the hydrocarbons, which under the conditions of Removal of the at least one primary marker from the hydrocarbons is not completely removable.
• first marker hereinafter referred to as first marker
• second marker at least one second marker
• the invention further relates to hydrocarbons which have been labeled according to such a method, and to solutions for marking hydrocarbons which contain at least one first marker and at least one second marker as defined by the method according to the invention and, if appropriate, further additives.
• the labeling of hydrocarbons e.g. of products from the refining of petroleum is usually carried out for tax reasons, since the same product can be taxed differently depending on the application.
• Heating oil is usually marked as it is subject to less taxation than diesel oil that is identical in composition. To the extent that the prices for heating oil and diesel fuel differ, the incentive to illegally blend diesel fuel with heating oil or to use heating oil as a diesel fuel by removing the marking material increases.
• marking methods as well as marking substances and their mixtures, are proposed for marking hydrocarbons, in particular mineral oils.
• acid-extractable markers for hydrocarbons or mineral oils are described in EP 0 519 270, EP 0 679 710, EP 0 803 563, EP 0 989 164, WO 94/11466, WO 95/07460, WO 95/17483 and US 4,209,302, and acid-extractable dyes, which can also be used as marking substances, in German Offenlegungsschrift 2 129 590.
• Basic extractable markers are described in the documents US Pat. No. 3,764,273, US Pat. No. 5,252,106, EP 0 509 818, WO 94/21752 and WO 95/10581.
• the marking substances are usually detected visually by their concentration in the extract and / or by their reaction with suitable reagents to form colored reaction products.
• 5,525,516 and US Pat. No. 5,710,046 describe methods for marking hydrocarbons or mineral oils with marking substances which absorb or fluoresce in the infrared region of the spectrum and can thereby be detected.
• the object of the present invention was therefore to provide a method for marking hydrocarbons which, even after removal of the first marker substance or substances, enables the detection of the existing marker and / or makes the removal of the marker economically uninteresting.
• At least one secondary marker is used in the method according to the invention, the absorption maximum of which is below a wavelength of 500 nm. Secondary markers with such absorption behavior are therefore hardly or not at all perceptible in most hydrocarbons, especially in mineral oils, especially when they are added in the usual amounts.
• Hydrocarbons in the sense of the invention are generally understood to mean products such as are obtained in the refining of petroleum. These are, for example, propane, butane, pentane, hexane, heptane, octane, isooctane, benzene, toluene, xylene, ethylbenzene, tetralin, decalin or wench hylnaphthalene.
• mineral oils for example fuels, such as gasoline, kerosene or diesel fuel, or oils, such as heating oil or motor oil.
• this also includes products as they arise when processing certain types of plants, such as rapeseed or sunflowers. Such products are also known under the term "bio-diesel”.
• hydrocarbons are generally in a liquid or gaseous state.
• Gaseous hydrocarbons e.g. Propane or butane can be converted into the liquid form, for example by compression.
• hydrocarbons are often additionally colored with (solvent) dyes.
• solvent dyes
• this is used for direct visual recognition of the manufacturer of the mineral oil product in question or the fiscal classification it is subject to.
• a color marking should not be understood as a marking in the sense of the invention.
• markers can also be colored, but are then, due to their usually low concentration in the hydrocarbon, either covered by the intrinsic color of the hydrocarbon or its coloring using (solvent) dye (s).
• the property of the secondary marker "not being completely removable under the conditions of removal of the at least one primary marker from the hydrocarbons" means that after the primary marker has been removed there is still a detectable residual concentration of the secondary marker in the hydrocarbon.
• This residual concentration is usually assumed to be at least 25% of the initial concentration, so that if the concentration of the secondary marker is correspondingly low, reliable detection can still be carried out after removal of the primary marker. In individual cases, however, this minimum concentration can also be fallen below. This is the case, for example, if a particularly sensitive detection method is available for the secondary marker in question.
• Removal of the primary marker is to be understood as any chemical and / or physical process that leads to a complete or almost complete removal of the primary marker.
• Such processes can be the separation of the first marker by means of chromatographic processes, extraction processes with a wide variety of solvents or solvent mixtures, distillation processes, filtration processes Use of materials which adsorb such primary markers, oxidative or reductive destruction and photolytic decomposition of the primary marker, possibly with the participation of oxidizing agents such as (air) oxygen.
• the primary marker can also have been converted into a derivative beforehand, which is then removed from the hydrocarbon by physical or chemical processes.
• the secondary marker must still be present in an amount sufficient for its detection.
• a preferred embodiment of the method according to the invention is characterized in that the at least one primary marker is removable under acidic or basic conditions and the at least one secondary marker is accordingly not completely removable under acidic or basic conditions or the at least one secondary marker is neither under acidic nor under basic conditions is completely removable from the hydrocarbons.
• the second marking substance can accordingly not be completely removed under acidic conditions or under both acidic and basic conditions.
• the hydrocarbons marked according to the invention cannot be freed from the secondary marking substance even by a combination of acidic and subsequent basic treatment.
• An analogous approach applies if the primary marking substance can be removed under basic conditions.
• ⁇ P- 0) ⁇ er b> Q b P- rr ⁇ b er H? V bb t ⁇ ⁇ - ⁇ ⁇ 3 ⁇ li b cn cn cn ⁇ ⁇ P- b ⁇ Q b cn P- ) cn ⁇ er cn ⁇ P- rr P ) rr P ) • li H- bb
• Acid extractable markers which can be used as possible first markers in the context of this embodiment of the invention are described in the documents EP 0 519 270, EP 0 679 710, EP 0 803 563, EP 0 989 164, WO 94/11466, WO already cited above 95/07460, WO 95/17483, US 4,209,302 and in German Offenlegungsschrift 2 129 590.
• n zero or 1
• R 1 , R 2 , R 3 and R 5 are the same or different and are each independently hydrogen, C 1 -C 4 -alkyl, C,-C 4 -alkoxy, halogen or nitro,
• R 4 and R 6 are identical or different and independently of each other are hydrogen, C 4 alkyl, Ci -C4 alkoxy, halogen, nitro or Ci -C 4 alkanoylamino,
• R 8 is hydrogen or -CC 4 alkyl
• L is C 1 -C 3 -alkylene
• R 1 and R 2 are selected from hydrogen, methyl, ethyl, methoxy, halogen, cyano and nitro and
• R 3 is selected from methyl, methoxy, methoxyethoxy and morpholino, i
• R 1 is C 1 -C 3 -alkyl
• R 2 C 1 -C 3 -alkylene
• R 3 is C 1 -C 2 -alkyl
• X and Y are the same or different and are selected from What serstoff, -CC 3 alkyl, Ci -C 3 alkoxy, halogen and nitro and
• Z is hydrogen or a group of the formula
• N NX - (C 2 -C 6 alkyl) 2 wherein X and Y are the same or different and are each selected from hydrogen, methyl, ethyl, isopropyl, butyl, methoxy, halogen and nitro, and
• Z is hydrogen or amino
• R 1 and R 2 are each independently hydrogen
• Ci —C ⁇ 8 alkyl which is all substituted and can be interrupted by 1 to 3 oxygen atoms in ether function or 1 to 3 C 1 -C 4 alkylimino groups, C 3 -C 8 8 alkenyl, optionally substituted phenyl or R 1 and R 2 together with the nitrogen atom connecting them is a 5- or 6-membered saturated heterocyclic radical which may have a further hetero atom, or R 1 also a radical of the formula OL 1 or NL ⁇ -L 2 , in which L 1 and L 2 independently of one another each represent hydrogen, optionally substituted C 1 -C 8 -alkyl, C 3 -C 1 -a alkenyl or optionally substituted phenyl,
• R 3 and R 7 each independently of one another hydrogen, optionally substituted C 1 -C 18 -alkyl, C 2 -C 18 alkenyl, cyano, nitro, formyl, optionally substituted C -C 4 alkanoyl, formylamino, optionally substituted C 2 -C 4 -alkanoylamino, benzoylamino or a radical of the formula OL 1 , CH 2 COOL 1 , NL- T -L 2 , SL 1 or S0 2 NL 1 L 2 , in which L 1 and L 2 each have the abovementioned meaning , or together with R 2 C 2 -C 3 -alkylene, which is optionally substituted one to three times by methyl, or optionally substituted by phenyl-substituted C 2 -C 3 -alkenylene,
• R 4 is hydrogen, optionally substituted C 1 -C 8 alkyl
• R 5 and R 6 each independently of one another hydrogen, optionally substituted C 1 -C 18 -alkyl, C 2 -C 8 alkenyl, optionally substituted phenyl, nitro, formylamino, optionally substituted C 2 -C 4 alkanoyl, formylamino, optionally substituted C 2 -C 4 -alkanoylamino, benzoylamino or a radical of the formula OL 1 , NL- T -L 2 , S0 2 NL 1 L 2 , S0 2 L 3 , COL 1 or COOL 1 , wherein L 1 and L 2 each have the abovementioned meaning and L 3 represents optionally substituted Ci-Ci ⁇ -alkyl, C 3 -C ⁇ 8 alkenyl or optionally substituted phenyl,
• R 1 and R 2 each independently of one another are hydrogen, Ci-Cia-alkyl, which is optionally substituted and can be interrupted by 1 to 3 oxygen atoms in ether function or 1 to 3 C 1 -C 4 alkylimino groups, C 5 -C 7- cycloalkyl, C 3 -Ci 8 -alkenyl, optionally substituted phenyl or R 1 and R 2 together with the nitrogen atom connecting them a 5- or 6-membered saturated heterocyclic radical, which may have a further hetero atom, and
• R 3 , R 4 , R 5 and R 6 each independently of one another are hydrogen, -CC 8 alkyl, benzyl, cyano, nitro, -C 4 -alkanoyl, C 1 -C 4 -alkanoylamino, benzoylamino, hydroxysulfonyl or a radical of the formula OL 1 , COOL 1 , NL- T -L 2 or CONL- T -L 2 , wherein L 1 and L 2 each represent hydrogen, optionally substituted Ci-Ce-alkyl, C 5 -C 7 cycloalkyl or optionally substituted phenyl, or R 3 together with R 2 C 3 alkylene, which is optionally substituted by hydroxy, mean, where, when the radicals NR i -R 2 and NL 1 L 2 are peri-permanent, R 1 and L 1 together can also mean isopropylidene,
• n zero or 1
• R 1 is hydrogen or Ci-Cis-alkyl, which can be interrupted by 1 to 4 oxygen atoms in ether function,
• R 2 Ci-Cis-alkyl which can be interrupted by 1 to 4 oxygen atoms in ether function, or a radical of the formula L-NX- T -X 2 , wherein L is C 2 -C 8 alkylene and X 1 and X 2 independently of one another each for Ci-C ⁇ -alkyl or together with the nitrogen atom connecting them for a 5- or 6-membered saturated heterocyclic radical, which may still contain an oxygen atom in the ring,
• R 3 , R 4 , R 5 , R 6 and R 7 independently of one another are each hydrogen, C1-C1 5 -alkyl or Ci-Cis-alkoxy and
• R 8 is hydrogen, C1-C1 5 -alkyl, -CC 5 -alkoxy, cyano, nitro or a radical of the formula COOX 3 , wherein X 3 is hydrogen, C 1 -C 15 -alkyl, which has 1 to 4 oxygen atoms in ether function may be interrupted, or represents a radical of the formula L-NX 1 X 2 , in which L, X 1 and X 2 each have the abovementioned meaning,
• R 1 and R 2 can each be hydrogen or alkyl having one to 20 carbon atoms
• n is an integer from 1 to 3
• n is the number 1 or 2
• X represents a hydrogen atom or the nitro group
• Y is a hydrogen or chlorine atom, a nitro, lower alkyl or lower alkoxy group with 1 to 3 carbon atoms,
• Z and Z 'each represent a hydrogen or chlorine atom, a lower alkyl or lower alkoxy group having 1 to 3 carbon atoms or a lower acylamino group,
• Ri is an alkyl group or the group
• R 2 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms and
• R 3 represents an alkyl group with 1 to 18 carbon atoms or a cycloalkyl group
• aromatic nuclei A, B and C can carry further water-insoluble substituents.
• extractable markers which can be used as possible first markers in this embodiment of the invention are described in the publications US Pat. No. 3,764,273, US Pat. No. 5,252,106, EP 0 509 818, WO 94/21752 and WO 95/10581 already cited above.
• radicals W are selected from the group consisting of C 1 -C 3 alkoxy and hydrogen, with the proviso that at least one radical W is C 1 -C 3 alkoxy
• radicals X and Y are the same or different and selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, condensed aryl, substituted condensed aryl, halogen, nitro, cyano and alkoxy
• the groups Ri and R 2 are identical or different and are each hydrogen or C ⁇ -C mean-C7 alkyl groups, at least one radical R is a C 3 -C 7 alkyl group, and wherein the group- R 3 are the same or different and each represents hydrogen, nitro, chlorine, bromine, fluorine, cyano, ethyl or methyl, at least one R 3 being selected from nitro, chlorine, bromine, fluorine and cyano,
• R 1 is hydrogen, Ci-Cis-alkyl, which is optionally substituted by cyano, or optionally by C1-C 4 -alkyl, hydroxy or -CC 4 -alkoxy-substituted phenyl and
• R 2 is hydrogen or a radical of the formula XR 3 , in which X is oxygen or sulfur and R 3 is Ci-Cia-alkyl, which is optionally substituted by hydroxy, cyano or phenyl and by 1 to 3 oxygen atoms in ether function or 1 to 3 N- (Ci- C4 alkyl) imino groups may be interrupted, or phenyl optionally substituted by C1-C4 alkyl, hydroxy, C ⁇ -C 4 alkoxy, (C ⁇ -C 4 -mono- or dialkylcarbamoyl) - C 1 -C 4 -alkoxy or Ci-Ca-mono- or dialkyl-sulfamoyl, where the alkyl groups can be interrupted by 1 to 3 oxygen atoms in ether function, are substituted,
• X 1 is hydrogen, C1-C 4 -alkyl, cyano, nitro or phenylazo, which is optionally substituted once or twice by C1-C 4 -alkyl
• X 2 is hydrogen, C1-C 4 -alkyl, cyano, nitro, -C-C 4 -alkoxy or i -Ci 6 -alkoxycarbonyl
• X 3 is hydrogen, C 1 -C 4 alkyl, cyano or -CC 6 alkoxycarbonyl and
• X 4 hydrogen, hydroxy, CI-C B alkyl, which is optionally substituted by phenyl, -CC 4 alkoxy, amino, Ci -C dialkylamino or Ci -Cig monoalkylamino, the alkyl chain optionally by 1 to 3 Oxygen atoms interrupted in ether function mean.
• the second marker is accordingly not completely removable with aqueous acidic extractants or with both aqueous acidic and aqueous basic extractants.
• the hydrocarbons marked according to the invention cannot be freed from the second marking substance even by a combination of aqueous-acidic and subsequent aqueous-basic extraction.
• An analogous approach arises in the event that the primary marker can be removed with aqueous basic extractants.
• aqueous acidic or basic extractant is to be understood here as an extractant which has a higher water content than the sum of the usual (residual) water contents of its components.
• a particularly preferred embodiment of the method according to the invention consists in that the at least one secondary marker can be completely removed from the hydrocarbons neither under acidic nor under basic conditions or neither with aqueous acidic nor with aqueous basic extracting agents.
• u, v and w are integers 1, 2 or 3,
• R 1 , R 2 and R 3 L L, L-0-, LOC (O) -, R ' 2 NC (0) -, R'-C (O) -, LC (0) -0-, LC (0 ) -NR'-, (LC (0) -) 2 N-, R ' 2 NC (0) -NR' - or CN, where if u and w are greater than 1 and v is 3, the radicals R 1 and R 3 or R 2 can each be the same or different from one another
• L C1-C 20 alkyl in which CH 2 groups can be replaced by oxygen atoms, with the proviso that there are at least two carbon atoms between such oxygen atoms which may be present and between those oxygen atoms which may be present and hetero atoms which are bonded to L, and / or in which non-adjacent CH groups can be replaced by carbonyl groups with the proviso that there is at least one CH or CH group between such carbonyl groups which may be present and carbonyl groups which are bonded to L,
• R ' is hydrogen or L
• R 'and L if they are present in the radicals R 1 , R 2 and / or R 3 more than once, can in each case be the same or different from one another, and KC -C 5 alkylene in which one CH group can be replaced by an oxygen atom and / or in which up to two non-adjacent CH 2 groups can be replaced by carbonyl groups.
• secondary markers are used which are selected from the group consisting of the compounds of the formulas Ia, Ib and Ic shown above in which
• u, v and w are integers 1 or 2
• R 1 , R 2 and R 3 L, LO-, LOC (0) - or R'-C (O) -, for which
• radicals R 1 and R 3 can each be the same or different from one another
• L C 1 -C 0 -alkyl, in which CH 2 groups can be replaced by oxygen atoms, with the proviso that there are at least two carbon atoms in each case between such oxygen atoms which may be present and between those oxygen atoms which may be present and hetero atoms which are bonded to L, and / or in which non-adjacent CH 2 groups can be replaced by carbonyl groups, with the proviso that at least one CH or CH 2 group is present between such carbonyl groups which may be present and carbonyl groups which may be bonded to L,
• R ' is hydrogen or L
• KC 3 - or C 4 -alkylene in which up to two non-adjacent CH 2 groups can be replaced by carbonyl groups.
• C1-C 20 alkyl for L are branched or unbranched alkyl chains, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n -Pentyl, 1-methylbutyl,
• L come as -CC 20 alkyl, in which CH 2 groups can be replaced by oxygen atoms, for example - (CH 2 -CH 2 -O-) p H, - (CH 2 -CH 2 -0-) p CH 3 , - (CH 2 -CH (CH 3 ) -0-) q H or - (CH 2 -CH (CH 3 ) -0-) r CH 3 in question, where p values of 1, 2, 3, 4, 5 or 6, q assumes values of 1, 2, 5 3, 4 or 5 and r assumes values of 1, 2, 3 or 4.
• L come as -C ⁇ C 2 o-alkyl radicals in which CH 2 groups can be replaced by oxygen atoms and carbonyl groups, -CH 2 -0-C (0) - [(CH 2 ) s ] H and -CH 2 - C (0) -0- [(CH 2 ) a ] H, in which s 1 Q takes integer values from 1 to 17.
• Ci-Cio-alkyl radicals which are particularly suitable for L have already been listed in the exemplary lists for the -C-C o-alkyl radicals.
• C -C 5 alkylene radicals in which one CH 2 group can be replaced by an oxygen atom and / or up to two non-adjacent CH 2 groups can be replaced by carbonyl groups - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, -C (0) -0-C (0) -, -C (0) -CH 2 -C (0) -, -C (0) - (CH 2 ) 2 -C (0) -, -C (0) - (CH 2 ) 2 -C (0) -, -C ⁇ 0) - (CH 2 ) 4 -, -C (0) - (CH 2 ) 3 -,
• a total concentration of the marking substances of 20 to 80% by weight, based on the solution, is chosen for the latter form.
• the marking substances can also be used as components in so-called
• the present invention is accordingly in such a package in addition to the taggant, the Clearmarkierstoff, one (Solvent) dye and a solvent-5 that is at least a tel Zweitmarkierstoff as an additional component.
• the packages usually contain 10 to 20% by weight of first marker, 5 to 25% by weight of second marker, 10 up to 20% by weight of (solvent) dye and, in addition to 100% by weight, solvent.
• concentration details given for the solutions and packages are generally correct. Depending on the chemical nature of the specific components, however, the upper and lower limit values for the dyes and markers can also be exceeded or undershot. Furthermore, it can of course also happen that lower values have to be set for some of the components or higher values can be set for the other components. The exact setting of the composition can normally be easily determined by the specialist in the course of routine preliminary tests.
• Aromatic hydrocarbons such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatics, which is commercially available under the name Shellsol AB (Shell), are preferably used.
• Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol or cyclohexanol
• glycols such as butylethylene glycol or methylpropylene glycol
• amines such as triethylamine, diisooctylamine, dicyclohexylamine , Aniline, N-methylaniline, N, N-dimethylaniline, toluidine or xylidine, alkanolamines, such as 3- (2-methoxyethoxy) ropylamine, o-cresol, m-cresol, p-cresol, ketones, such as diethyl ketone or cyclohexanone, lactones, such as ⁇ -butyl
• the labeled hydrocarbons preferably have a content of 5 to 1000 ppm, in particular 10 to 1000 ppm, based on the total amount of first and second marker substance (s). Particularly noteworthy is a content of 10 to 500 ppm, in particular 50 to 100 ppm.
• hydrocarbons are also claimed which have been marked in accordance with the method according to the invention and its preferred and particularly preferred embodiments.
• solutions for marking hydrocarbons are claimed which contain at least one primary marker and at least one secondary marker as defined by the method according to the invention and, if appropriate, further additives.
• additives in such solutions include denaturing agents, fuel additives, special stabilizers, such as dispersing aids against cold flocculation, etc.
• the UV absorption or signal area (“SF”) obtained in millivolt seconds for the respective substance at the corresponding wavelength ⁇ (in nm) is given in Table 1 below.
• the other substances are not only characterized by their suitable chromatographic behavior, but are also very sensitive to detect. This applies in particular to acetophenone, 4-methoxyacetophenone, benzonitrile and methyl benzoate, which is why these compounds are particularly suitable as secondary markers under the corresponding conditions.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Paints Or Removers (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

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