EP1346012A2

EP1346012A2 - Method for the marking of mineral oil

Info

Publication number: EP1346012A2
Application number: EP01986904A
Authority: EP
Inventors: Christos Vamvakaris; Patrik Schneider; Gerhard Wagenblast; Roland Merger; Claudia Kräh
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2000-12-20
Filing date: 2001-12-19
Publication date: 2003-09-24
Also published as: CZ20031728A3; DE10063955A1; RU2298580C2; PL366143A1; AU3845602A; CA2431120A1; HUP0302162A2; CN1271177C; UA73630C2; KR20030065555A; JP2004524388A; CA2431120C; JP3854227B2; CN1529746A; BR0116374A; KR100849641B1; IL156307A0; US20040110302A1; WO2002050216A3; WO2002050216A2

Abstract

The invention relates to a method for the marking of hydrocarbons, by addition of at least one first marking agent( subsequently referred to as first marking agent), characterised in that, in addition, at least one further second marking agent is added to the hydrocarbon, which, under conditions for removal of the first marking agent, is not completely removable from the hydrocarbon. The invention further relates to hydrocarbons which are to be marked by said method, solutions for marking hydrocarbons, containing at least one first marking agent and at least one second marking agent as defined by the method according to the invention and optionally containing further additives.

Description

Mineral oil marking process

description

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.

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.

A wide variety of marking methods, as well as marking substances and their mixtures, are proposed for marking hydrocarbons, in particular mineral oils.

Thus, for example, suitable 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.

In the documents WO 94/02570, WO 99/56125, WO 99/558051, US

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.

A serious disadvantage with those marking methods in which the detection of the marking substance is connected with an extraction step is that such an extraction method also permits the illegal removal of the marking substance by third parties.

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.

We have found that this object is achieved by the method described above for marking hydrocarbons.

In particular, 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. In particular, these are mineral oils, for example fuels, such as gasoline, kerosene or diesel fuel, or oils, such as heating oil or motor oil. Furthermore, 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".

Under normal conditions, the 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.

It should be noted here that such hydrocarbons are often additionally colored with (solvent) dyes. In the mineral oil sector, for example, 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. However, such a color marking should not be understood as a marking in the sense of the invention. On the other hand, substances that are not directly visually recognizable but are only detected by the specific detection method are usually used as markers. Such 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.

Accordingly, according to the physical and / or chemical processes for removing the first marker, the secondary marker must still be present in an amount sufficient for its detection.

The phrase "complete or almost complete disposal" is to be understood such that the primary marker is no longer recognizable, for example, visually in the hydrocarbon, but this was the case before its removal that the primary marker was removed using optical detection methods, e.g. Fluorescence detectors, can no longer be recognized, but this was the case previously, or that the detection of this marker is no longer possible within the framework of the extraction and possibly derivatization process intended for it, whereas this was the case previously.

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.

If, in the context of this preferred embodiment, the first marking substance can be removed under acidic conditions, the second marking substance can accordingly not be completely removed under acidic conditions or under both acidic and basic conditions. In the latter case, 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. s 3 P Cn 3 td td M? ti cn og cn td er 03 c! P ¹ <PNS ≤ 3 ≤ tA ω F <P- 3 cn HP ¹ er α J o φ P- P ⁾ X b ⁾ P- Φ Φ Φ = J b O ι-i φ o rr b φ Φ P- Φ P> P- P- o = Ω o = P ⁾ b P- Φ b φ N ⁾ bmo li nb rr cn P b P- 03 P- tr φ cn rr? Rs; P bb Φ rr b er b rr 03 <£ t Φ tr 03 cn ιQ ii b £ cn rr

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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.

In the following list of the acid extractable marking substances, the name of the respective variable was taken from the correspondingly cited font in order to maintain clarity. For the specific meaning of the variables and their preferences, reference is expressly made to the disclosure of the respective script.

The following are explicitly considered as acid extractable markers:

from the document EP 0 519 270 azo compounds of the formula

where n is 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 ⁷ -CC ₄ alkyl,

R ^{8 is} hydrogen or -CC ₄ alkyl,

R ⁹ Ci-Cia-alkyl or cyclohexyl and

L is C ₁ -C ₃ -alkylene,

from the document EP 0 679 710 azo compounds of the formula

wherein 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

from the document EP 0 803 563 azo compounds of the formula

in which R ^{1 is} C ¹ -C ₃ -alkyl, R ² C ¹ -C ₃ -alkylene and 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

where X and Y have the meaning given above,

from the document EP 0 989 164 azo compounds 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,

from the document WO 94/11466 anilines of the formula

in which R ¹ and R ² are each independently hydrogen,

Ci —Cι 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,

C ₂ -C ₁₈ alkenyl, nitro or a radical of the formula OL ¹ , NL- ^T -L ² , COOL ¹ or S0 ₂ NL ¹ L ² , in which L ¹ and L ² each have the abovementioned meaning, and

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-Ciβ-alkyl, C ₃ -Cι ₈ alkenyl or optionally substituted phenyl,

with the proviso that at least one of the radicals R ³ , R ⁵ or R ^{7 is} hydrogen, from the document WO 95/07460 naphthylamines of the formula

in which 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,

from WO 95/17483 azo dyes of the formula

in which ring A can be fused to benzo

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-Cβ-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,

from US 4,209,302 the naphthylamine derivatives selected from the group consisting of

wherein R 1 and R _{2 can} each be hydrogen or alkyl having one to 20 carbon atoms,

and from German laid-open specification 2 129 590 azo compounds of the formula

where m 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

(CH ₂ ) _m -CH-0-CH-OR ₃ ,

R ₂ CH ₃

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,

the aromatic nuclei A, B and C can carry further water-insoluble substituents.

Basically 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.

In the following list of the basic extractable marking substances, the name of the respective variable was taken from the correspondingly cited font in order to maintain clarity. For the specific meaning of the variables and their preferences, reference is expressly made to the disclosure of the respective script.

Explicitly extractable markers are explicitly considered:

from US 3,764,273 the compounds selected from the group consisting of

Quinizarines of the formula in which R denotes an alkyl radical with 1 to 20 carbon atoms or a furfuryl radical,

the azo dye of the formula

and the azo arbstof f of the formula

from US 5, 252, 106 azo compounds of the formula

in which the 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, and the 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,

from the document EP 0 509 818 azo compounds of the formula

wherein the groups Ri and R ₂ are identical or different and are each hydrogen or Cι-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,

from the document WO 94/21752 anthraquinones of the formula

in the 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, Cι-C ₄ alkoxy, (Cι-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,

and from WO 95/10581 azo dyes of the formula

in which the ring A can be fused to benzo and

1 or 2,

m 1 to 4,

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.

If, within the scope of this preferred embodiment, the first marker can be removed with aqueous acidic extractants, the second marker is accordingly not completely removable with aqueous acidic extractants or with both aqueous acidic and aqueous basic extractants. In the latter case, 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.

An "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.

In accordance with what has already been said, this means that the hydrocarbons marked in this way are neither by a combination of acidic and subsequent basic nor by a combination of basic and subsequent acidic treatment or by a combination of aqueous-acidic and subsequent aqueous-basic or by one Combination of aqueous-basic and subsequent aqueous-acidic extraction can be freed from the secondary marker. Secondary markers, which are selected from the group consisting of the compounds of the formula Ia, are preferably used in the process according to the invention and its preferred and particularly preferred embodiments

of the formula Ib

and formula Ic

where the variables mean

u, v and w are integers 1, 2 or 3,

R ¹ , R ² and R ³ 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,

and 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.

In particular, 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

If u and w are 2, the 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 and

KC ₃ - or C ₄ -alkylene, in which up to two non-adjacent CH ₂ groups can be replaced by carbonyl groups.

As 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,

2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1 -dimethylbutyl, 1,2 -dimethylbutyl, 1, 3 -dimethylbutyl, 2, 2 -dimethylbutyl, 2,3-dimethylbutyl, 3, 3 -dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,2- Trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, l-ethyl-2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n- Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl. For 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.

For 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.

The latter formulas include, for example, the radicals -CH ₂ -0-C (0) -CH ₃ and -CH ₂ -C (0) -0-CH ₃ (each s = 1) and -CH ₂ -0-C ( 0) -C ₂ H ₅ and -CH ₂ -C (0) -0-C ₂ H ₅ (s = 2 in each case).

15

The 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.

20 For K, the following are 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 ) ₄ -, -C (0) - (CH ₂ ) ₃ -,

25 -C (0) - (CH ₂ ) ₂ - _/ -C (0) - (CH ₂ ) ₃ -C (0) -, -0- (CH) ₂ -, -C ~ (CH ₂ ) ₃ - , -0- (CH ₂ ) ₄ -, -CH ₂ -O-CH ₂ -, -CH ₂ -0- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -0- (CH ₂ ) ₂ -, -CH ₂ -0- (CH ₂ ) ₃ -, -C (0) -0-CH ₂ -C (0) -, -C (0) -CH ₂ -0-CH ₂ -C (0) - or -C (0) -0- (CH ₂ ) ₂ -C (0) -.

_Q The C ₃ or C ₄ alkylene radicals that are particularly suitable for K are already included in the previous list.

For marking the hydrocarbons of the at least one first and the at least one Zweitmarkierstoffe be applied either in _sub-oc substance or in the form of solutions. In general, 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

40 th "packages", ie concentrated solutions of the dyes and / or markers used for coloring and / or marking, are present. For the purposes of the present invention is accordingly in such a package in addition to the taggant, the Erstmarkierstoff, 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.

The 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.

Organic solvents are suitable as solvents. 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.

Other cosolvents, e.g. 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 γ-butyrolactone, carbonates, such as ethylene carbonate or propylene carbonate, phenols, such as t-butylphenol or nonylphenol, esters, such as methyl phthalate, ethyl phthalate, 2-ethylhexyl phthalate, ethyl acetate, butyl acetate or amide cyclohexyl, hexyl acetate N, N-dimethylformamide, N, N-diethylacetamide or N-methylpyrrolidinone, or mixtures thereof.

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.

In the context of the present invention, hydrocarbons are also claimed which have been marked in accordance with the method according to the invention and its preferred and particularly preferred embodiments. Furthermore, 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.

Such solutions, in particular for marking hydrocarbons, have already been described above, with no further additives being mentioned here.

Furthermore, such solutions are also to be understood as the “packages” which have also already been mentioned above, further additives being understood to mean the (solvent) dyes usually still present in these packages.

In contrast, the cosolvents given above as examples are not to be understood as additional additives but rather as additional solvents.

On the other hand, other additives in such solutions include denaturing agents, fuel additives, special stabilizers, such as dispersing aids against cold flocculation, etc.

Examples:

A) Investigation of potential secondary markers

Substances corresponding to formulas Ia, Ib or Ic shown above have been investigated as possible secondary markers (e) for hydrocarbons.

For this purpose, solutions of the substances in a concentration of 10 mg per kg, that is prepared in a concentration of 10 ppm, in Shellsol ^® AB (Fa. Shell) and analyzed by HPLC and UV-De- tektion ( "blank sample"). On the one hand, this served to answer the question whether the determination of the respective substance by means of a UV detector was disturbed by components made from the hydrocarbon and, on the other hand, the substance in question would provide sufficient UV absorption.

In addition, measurements were carried out on samples of the labeled hydrocarbon which had previously been treated with 50% aqueous sulfuric acid (“acid extract.”) Or 10% aqueous sodium hydroxide solution (“basic extract.”). This was intended to determine whether the respective secondary marking substance would be extracted from the hydrocarbon under aqueous acidic or aqueous basic conditions. was traced and, if necessary, how much marking substance was left in it.

The UV absorption or signal area (“SF”) obtained in millivolt seconds for the respective substance at the corresponding wavelength λ (in nm) is given in Table 1 below.

Table 1

In principle, all substances listed in Table 1 are suitable as secondary markers under the corresponding conditions, ie after acidic or basic or after acidic combined with basic extraction, since components of diesel fuel can be clearly recognized.

In the case of the 1,3-indandion, due to its very low retention and unfavorable peak shape, it was not possible to determine the exact concentration. This could explain why the signal area of the acid extracted sample is higher than that of the blank sample.

For the hydrocarbon samples marked with anisole, benzyl acetate and ethylbenzoylacetate, it must be assumed that - due to the higher hydrophobicity of these substances - Koelu-. tion with components occurs.

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.

Claims

claims

1. A method for marking hydrocarbons by adding at least one first marker (first marker), characterized in that at least one second marker (second marker) is additionally added to the hydrocarbons, which under the conditions of removing the at least one first marker from the carbon. hydrogen is not completely removable.

2. The method according to claim 1, characterized in that the absorption maximum of the at least one secondary marker is below a wavelength of 500 nm.

3. The method according to claim 1 or 2, 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 neither under acidic nor under basic conditions Conditions can be completely removed from the hydrocarbons.

4. The method according to claim 1 or 2, characterized in that the at least one primary marker can be removed with aqueous acidic or aqueous basic extraction agents and the at least one secondary marker cannot be completely removed with aqueous acidic or basic aqueous extraction agents or the at least one secondary marker is not completely removable from the hydrocarbons with aqueous acidic or basic aqueous extractants.

5. The method according to claim 3 or 4, characterized 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 extraction agents.

Method according to one or more of claims 3 to 5, characterized in that the at least one secondary marker is selected from the group consisting of the compounds of formula Ia of the formula Ib

and formula Ic

where the variables mean

u, v and w are integers 1, 2 or 3,

R ¹ , R ² and R ³ L, LO-, 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 in the case that 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

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 between such oxygen atoms which may be present and between those oxygen atoms which may be present and heteroatoms optionally 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 ₂ group between such carbonyl groups which may be present and carbonyl groups which are bonded to L,

R 'is hydrogen or L,

and 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 ₃ -C ₅ alkylene, in which one CH ₂ 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.

7. The method according to claim 6, characterized in that in formula Ia, Ib and Ic mean

u, v and w are integers 1 or 2,

R ¹ , R ² and R ³ L, LO-, LOC (O) - or R'-C (O) -, where in the event that u and w are 2, the radicals R ¹ and R ^{3 are in} each case one another may be the same or different

L Ci -Cio-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 ₂ groups can be replaced by carbonyl groups, with the proviso that at least one CH or CH ₂ group is located between such carbonyl groups which may be present and carbonyl groups which are bonded to L,

R 'is hydrogen or L and

KC ₃ - or C4-alkylene, in which up to two non-adjacent CH ₂ ~ groups can be replaced by carbonyl groups.

8. Hydrocarbons which have been labeled according to a method according to claims 1 to 7.

9. Solutions containing as components

at least one solvent,

at least one first marker and at least one second marker as defined by the method according to one or more of claims 1 to 7 and

if necessary, other additives.