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WO1999055805A1 - Procede pour marquer des liquides avec au moins deux substances de marquage et procede pour leur detection - Google Patents

Procede pour marquer des liquides avec au moins deux substances de marquage et procede pour leur detection Download PDF

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Publication number
WO1999055805A1
WO1999055805A1 PCT/EP1999/002452 EP9902452W WO9955805A1 WO 1999055805 A1 WO1999055805 A1 WO 1999055805A1 EP 9902452 W EP9902452 W EP 9902452W WO 9955805 A1 WO9955805 A1 WO 9955805A1
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WO
WIPO (PCT)
Prior art keywords
markers
radiation
marking
liquids
detection
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Application number
PCT/EP1999/002452
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German (de)
English (en)
Inventor
Frank Meyer
Gerhard Wagenblast
Karin Heidrun Beck
Christos Vamvakaris
Original Assignee
Basf Aktiengesellschaft
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Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU37073/99A priority Critical patent/AU3707399A/en
Publication of WO1999055805A1 publication Critical patent/WO1999055805A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/003—Marking, e.g. coloration by addition of pigments

Definitions

  • the present invention relates to a method for marking liquids with at least two marking substances, which is characterized in that the marking substances absorb in the spectral range from 600 to 1200 nm and as a result emit fluorescent radiation, have essentially non-overlapping absorption regions and at least one of the markers has a maximum absorption wavelength of more than 850 nm.
  • the present invention further relates to a method for the detection of such markers in liquids, which is characterized in that a radiation source is used which emits radiation in the absorption regions of the markers, and the fluorescent radiation emitted by the markers is detected or which is characterized in that a corresponding radiation source is used for each individual marking substance, which emits radiation in the absorption region of the marking substance, and the fluorescent radiation emitted by the marking substances is detected.
  • the present invention also relates to liquids which are labeled by the method of the present invention.
  • heating oil which is usually tax-privileged
  • diesel oil which is generally subject to higher taxes
  • liquid product streams in large-scale plants such as Oil refineries, mark and track them.
  • marking of the liquids is to be invisible to the human eye, one has to rely on marking substances which absorb outside the visible range of the spectrum and / or emit radiation. Because of the high sensitivity of the detection and the associated possibility of achieving reliable marking with small additions of the marking substance, marking substances which emit the absorbed radiation as fluorescent radiation are of particular importance here. As a rule, this emitted radiation is present 2 a lower frequency than the absorbed radiation (STOKES radiation), in rare cases the same (resonance fluorescence) or even a higher frequency (ATI-STOKES radiation).
  • hydrocarbons and hydrocarbon mixtures e.g. different qualities of diesel and petrol fuels and other mineral oils
  • marking substances which absorb and / or fluoresce above approximately 600 nm.
  • the emitted fluorescence radiation can also be found at (weight) concentrations of the markers in the relevant one
  • WO 94/02570 describes the use of markers from the class of metal-free or metal-containing phthalocyanines, metal-free or metal-containing naphthalocyanines, and nickel-dithiolene complexes for marking liquids
  • a inium compounds of aromatic amines, the methine dyes or the azulene square acid dyes are described which have their absorption maximum in the range from 600 to 1 200 nm and / or a fluorescence maximum in the range from 620 to 1 200 nm. Furthermore, a method is described which essentially consists in detecting the fluorescent radiation of the marking substance present in the liquid, which absorbs radiation in said spectral range. A detector is also described, which is used to detect the marking substance. However, the use of several marking substances at the same time is not explicitly mentioned.
  • the document US 5,525,516 also describes a method for marking mineral oils with compounds which have fluorescence in the NIR.
  • Substituted phthalocyanines, substituted naphthalocyanines and square or croconic acid derivatives are used as such markers.
  • one or more mineral oils can be marked not only with one but also with two or more compounds which fluoresce in the IR range.
  • these fluorescent compound (s) should preferably absorb below 850 nm, since above this wavelength the mineral oils showed strong absorption.
  • This document also claims a method for identifying mineral oils which have been labeled with one or more markers.
  • an excitation range for the marked mineral oil or the marking substances contained therein from 670 to 850 nm is specified. Beyond that, however, no further information is provided on how to proceed with more than one marker in the case of marking mineral oils.
  • a correspondingly marked gasoline sample is excited with radiation from a wavelength band of 600 to 2500 nm, which detects fluorescent light emitted by the dye in the wavelength band of approximately 600 to 2500 nm and uses the resulting detection signal to identify the marked sample.
  • This document also describes in detail the structure of a detector for detecting the fluorescent dyes in the marked gasoline samples. However, the use of several markers (dyes) is not discussed.
  • the object of the present invention was therefore to mark liquids by adding more than two marking substances, i.e. to be provided with a "fingerprint" that makes it difficult to readjust the marking.
  • This object was achieved by a method for marking liquids with at least two marking substances, which is characterized in that the marking substances
  • At least one of the marking substances has a wavelength of the absorption maximum of more than 850 nm. 5
  • At least one marking substance the absorption range of which is more than 850 nm, a larger wavelength range of absorption / fluorescence for marking liquids is opened up. This makes it possible to use a larger number of marking substances whose absorption areas do not essentially overlap.
  • Essentially non-overlapping absorption areas here means that the respective absorption spectra of any two markers in question, based on comparable conditions (such as the same liquid, the same molar concentration in the marked liquid and the same absorbing layer thickness of the marked ones) Liquid), should not overlap if possible. However, if there is overlap, the value of the extinction coefficient of one marker should not be more than about 5% of the value of the other marker at all wavelengths in the overlap range for each respective wavelength under consideration. This consideration is based on an absorption spectrum based on the blank value. This blank value corresponds to the absorption spectrum of the corresponding pure (unlabeled) liquid measured under comparable conditions.
  • marking substances whose respective wavelength of the absorption maximum lies in the spectral range from 600 to 1200 nm.
  • n marking substances are preferably used in the method according to the invention for marking liquids, where n denotes an integer from 2 to 10, that is to say values of 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • n marking substances is particularly preferably used in the method according to the invention for marking liquids, where n denotes an integer from 2 to 6, that is to say values of 2, 3, 4, 5 or 6.
  • n marking substances is very particularly preferably used in the method according to the invention for marking liquids, where n denotes an integer from 2 to 4, that is to say values of 2, 3 or 4.
  • the markers which absorb in the spectral range from 600 to 1200 nm and consequently emit fluorescent radiation are used in the process according to the invention and in the preferred ones 6
  • n equal to 2 to 10 n equal to 2 to 6 or n equal to 2 to 4 markers
  • compounds to which are selected from the group consisting of metal-free and metal-containing phthalocyanines, metal-free and metal-containing naphthalocyanines, nickel -Dithio - len- complexes, amino compounds of aromatic amines, methine dyes, squaric acid dyes and crocodic acid dyes.
  • n is 2 to 10
  • n is from 2 to 6
  • n is from 2 to 4 markers, preferably the same compounds used, which are selected from the group consisting of metal-free and metal-containing phthalocyanines, metal-free and metal-containing naphthalocyanines, nickel-dithiolene complexes, aminium compounds of aromatic amines, methine dyes , Square acid dyes and croconic acid dyes.
  • Markers which absorb at a wavelength of the absorption maximum of more than 850 nm and consequently emit fluorescent radiation are used in the process according to the invention and in the preferred embodiments in which a combination of n is 2 to 10, n is 2 up to 6 or n equals 2 to 4 markers, preferably at least one compound selected from the group consisting of metal-free and metal-containing naphthalocyanines, nickel-dithiolene complexes, aminium compounds of aromatic amines, methine dyes, squaric acid dyes and croconic acid dyes.
  • Suitable phthalocyanines obey, for example, the formula Ia
  • radicals R 1 to R 16 are hydrogen, halogen, hydroxysulfonyl or C ⁇ -C-dialkylsulfamoyl.
  • Suitable phthalocyanines also obey, for example, the formula Ib (Ib),
  • R 17 and R 18 or R 18 and R 19 or R 19 and R 20 together each represent a radical of the formula X 2 -C 2 HX 3 , wherein one of the two radicals X 2 and X 3 for oxygen and the other for imino or C ⁇ -C 4 alkylimino, and
  • R 19 and R 20 or R 17 and R 20 or R 17 and R 18 each independently represent hydrogen or halogen and
  • Me 1 has the meaning given above.
  • Suitable naphthalocyanines obey e.g. of formula II
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 each independently of one another are hydrogen, hydroxy, C 1 -C 2 -alkyl, C 3 -C 8 -cycloalkyl or C ⁇ -C 2 o Alkoxy, where the alkyl groups can each be interrupted by 1 to 4 oxygen atoms in ether function and are optionally substituted by phenyl, heterocyclic, saturated five-, six- or seven-membered rings, which also have one or two further nitrogen atoms and / or another May contain oxygen or sulfur atom in the ring, which are optionally mono- to trisubstituted with -C 4 alkyl, phenyl, benzyl or phenylethyl and which are bonded to the benzene ring via a (or the) ring nitrogen atom,
  • Y 9 , Y 10 , Y 11 and Y 12 independently of one another are each hydrogen, C 1 -C 8 -alkyl or C 1 -C 2 o -alkoxy, where the alkyl groups can each be interrupted by 1 to 4 oxygen atoms in ether function, halogen, hydroxysulfonyl or C ⁇ -C 4 -dialkylsulfamoyl and
  • Me 2 has the meaning of Me 1 or the rest
  • j is hydroxy, C ⁇ -C 2 o-alkoxy, C ⁇ -C 20 alkyl, C 2 -C 2 -alkenyl, C 3 -C 2 o-alkenyloxy or a radical of formula
  • Y 19 the importance of C ⁇ -C 2 -alkyl, C 2 -C 2 o ⁇ alkenyl or C 2 o-alkadienyl and Y 20 and Y 21 each independently represent the meaning of C ⁇ -C ⁇ alkyl, C 2 -C ⁇ alkenyl or the above radical OY 19 have.
  • naphthalocyanines of the formula II in which at least one of the radicals Y 1 to Y 8 are different from hydrogen. 10
  • naphthalocyanines are shown in US 5,526,516 under general formula II and, for example, in Table 4 and in US 5,703,229 under general formula III and, for example, in Table 4.
  • Suitable nickel-dithiolene complexes obey e.g. of formula III
  • L 1 , L 2 , L 3 and L 4 each independently of one another C 1 -C 2 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, phenyl, C 1 -C 2 o -alkylphenyl, C 1 -C o ⁇ alkoxyphenyl , where the alkyl groups can each be interrupted by 1 to 4 oxygen atoms in ether function, or L 1 and L 2 and / or L 3 and L 4 each together the rest of the formula
  • Z 1 , Z 2 , Z 3 and Z 4 are each independently of one another C 1 -C 2 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 2 o -alkanoyl or a radical of the formula 11
  • Z 7 for hydrogen or -C-C 20 alkyl, which is optionally by 1 to 4 oxygen atoms in ether function is interrupted
  • Z 8 is hydrogen, -CC 20 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, or halogen
  • a n ® mean the equivalent of an anion.
  • Suitable methine dyes obey e.g. Formula V
  • E 1 and E 2 each independently of one another oxygen, sulfur, imino or a radical of the formula
  • E 3 represents hydrogen, C 1 -C 6 -alkyl, chlorine or bromine and E 4 represents hydrogen or C 1 -C 6 -alkyl
  • Q 1 and Q 2 are each independently phenyl, C 5 -C 7 cycloalkyl, C 1 -C 2 alkyl which can be interrupted by 1 to 3 oxygen atoms in ether function and optionally by hydroxy, chlorine, 12
  • n 1, 2 or 3.
  • Suitable square acid dyes are e.g. those compounds which are shown in US Pat. No. 5,526,516 under general formula III and exemplarily in Table 2 and in US Pat. No. 5,703,229 under general formula IV and exemplarily in Table 2.
  • Suitable square acid dyes are also azulene square acid dyes, which e.g. obey Formula VI shown below
  • T 1 is hydrogen, halogen, amino, hydroxy, C 1 -C 2 alkoxy, phenyl, substituted phenyl, carboxyl, C 1 -C 2 alkoxycarbonyl, cyano or a radical of the formula -NT 7 -CO-T 6 , -CO-NT 6 T 7 or 0-CO-NT 6 T 7 , wherein T 6 and T 7 independently of one another each represent hydrogen, C 1 -C 2 alkyl, C 5 -C 7 cycloalkyl, phenyl, 2, 2, 6, 6- Tetramethyl-piperidin-4-yl or cyclohexylaminocarbonyl, and
  • T 2 , T 3 , T 4 and T 5 are each independently hydrogen or C_ .
  • -Ci 2 alkyl which is optionally substituted by halogen, amino, C ⁇ -C ⁇ 2 - alkoxy, phenyl, substituted phenyl, carboxyl, C ⁇ -C -alkoxy carbonyl or cyano, 13 with the proviso that when T 5 is hydrogen, the ring positions of the substituents JT 1 and T 4 can also be interchanged on one or both azulene rings within an azulene ring.
  • Suitable square acid dyes are e.g. also those compounds which obey the formula Via below,
  • each in the Ar independently of one another for an aromatic or heteroaromatic five- or six-membered ring which is optionally substituted by C 2 -C -alkoxy, C 1 -C 8 -alkylamino, C 1 -C 2 -dialkylamino or C ⁇ ⁇ Co ⁇ alkylthio, such as eg phenyl, naphthyl, thiophene, pyridine or thiazole.
  • the alkyl groups can each be interrupted by 1 to 4 oxygen atoms in ether function and optionally substituted by phenyl.
  • Ar is preferably phenyl which is mono-, di- or tri-substituted in the 2-, 2,4- or 2,4,6 position with the said radicals. If the phenyl is substituted several times, these radicals are preferably the same. In particular, those compounds are considered in which both Ar are the same.
  • Suitable croconic acid dyes are e.g. those compounds which are shown in US Pat. No. 5,526,516 under the general formula IV and are listed in Table 5 by way of example.
  • alkyl, alkylene or alkenyl radicals occurring in the above formulas can be either straight-chain or branched.
  • C 1 -C 2 -alkyl radicals which are optionally interrupted by 1 to 4 oxygen atoms in ether function, for example methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, Tridecyl, 3, 5, 5, 7-tetramethylnonyl, isotridecyl (the above terms isooctyl, isononyl, isodecyl and isotridecyl (the above terms isooctyl, is
  • C 3 -C ⁇ rj-cycloalkyl radicals branched or unbranched cycloalkyl radicals which are optionally interrupted by 1 to 4 oxygen atoms in ether function, for example cyclopropyl, cyclobutyl, cyclopentyl, tetrahydrofranyl, cyclohexyl, tetrahydropyranyl, cycloheptyl, oxepanyl, 1 Methyl - cyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclopropyl, 1, 2-dimethylcyclypropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclodecyl.
  • suitable N-Het in the A1N-Het groups of Me 1 or Me 2 are derived from, for example, pyrrole, pyrrolidine, pyrazole, pyrazolidine, imidazole, imidazoline, 1H-1, 2, 3- Triazole, 1, 2,3-triazolidine, 1H-1, 2, 4-triazole, 1, 2, 4-triazolidine, pyridine, piperidine, pyrazine, piperazine, pyridazine, morpholine, 1H-azepine, 2H-azepine, azepane, Oxazole, oxazolidine, thiazole, thiazolidine, 1,2,3-, 1,2,4- or 1,3,4-oxadiazole, 1,2,3-, 1,2,4- or
  • suitable heterocyclic, ring-shaped radicals for R 1 to R 16 or Y 1 to Y 8 are derived from heterocyclic, saturated five-, six- or seven-membered rings which also have one or two further nitrogen atoms and / or can contain another oxygen or sulfur atom in the ring, for example pyrrolidine, pyrazolidine, imidazoline, 1, 2, 3-triazolidine, 1, 2, 4-triazolidine, piperidine, piperazine, morpholine, azepane, oxazolidine, thiazolidine, 1 , 2,3-, 1,2,4- or 1, 3, 4-oxadiazolidine, or 1,2,3-, 1,2,4- or 1, 3, 4-thiadiazolidine, the heterocyclic rings optionally substituted one to three times with C 1 -C 4 alkyl, phenyl, benzyl or phenylethyl.
  • C 1 -C 8 -alkyl radicals which may be considered have already been mentioned above for
  • C 1 -C 2 -alkoxy radicals which are optionally interrupted by 1 to 4 oxygen atoms in ether function, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, hexyloxy, heptyloxy, Octyloxy, 2-ethylhexyloxy, isooctyloxy, nonyloxy, isononyloxy, decyloxy, isodecyloxy, undecyloxy, dodecyloxy, tridecyloxy, isotridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octa-decyloxy, methoxy-ethoxy-ethoxy-oxy-nonoxy 2-propoxyethoxy, 2-isopropoxyethoxy, 2-
  • suitable substituted phenyl is, for example, phenyl substituted by C 1 -C 6 -alkyl, C 1 -C 6 alkoxy, hydroxy or halogen.
  • 1 to 3 substituents can occur.
  • the phenyl is substituted with 1 or with 2 substituents Ci-C ⁇ -alkyl or -CC 6 alkoxy.
  • the substituent is preferably in para 16
  • the substituents are preferably in the 2,3-, 2,4-, 3,4- and 3,5-position.
  • Halogen in formula Ib, II, IV or VI is e.g. Fluorine, chlorine or bromine.
  • W radicals in formula Ia and X 2 or X 3 in formula Ib are, for example, methylimino, ethylimino, propylimino, isopropylimino or butylimino.
  • R 1 to R 16 in formula Ia and Y 9 to Y 12 in formula II are, for example, dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, di-butylsulfamoyl or N-methyl-N-ethylsulfamoyl.
  • C 3 -Co ⁇ alkenyloxy in formula II is, for example, allyloxy, methallyloxy but-3-en-l-yloxy, undec-10-en-l-yloxy, octadec-9-en-l-yloxy or EICOS-en-9, -l-yloxy.
  • Z 6 in formula IV means, for example, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl or 2-ethylhexanoyl.
  • the substituents can be, for example, -C 6 alkyl, phenyl -C 6 alkoxy, phenoxy, halogen, hydroxy, amino, Ci-Ce mono- or Dialkylamino or cyano come into consideration.
  • the rings are usually 1 to 3 times substituted.
  • Residues E 3 , E 4 , Q 1 and Q 2 in formula V are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl or hexyl.
  • Residues Q 1 and Q 2 are furthermore, for example, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, cyclopentyl, cyclohexyl, 2-methoxyethyl, 2-ethoxyethyl, 2 - or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2-chloroethyl, 2-bromoethyl, 2- or 3-chloropropyl, 2- or 3-bromopropyl, 2- Carboxyethyl, 2- or 3-carboxypropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or 3-methoxycarbonylpropy
  • Formula IV or V is derived, for example, from anions of organic or inorganic acids.
  • methanesulfonate, 4-methylbenzenesulfonate, acetate, trifluoroacetate, heptafluorobutyrate, chloride, bromide, iodide, perchlorate, tetrafluoroborate, nitrate, hexafluorophosphate or tetraphenylborate are particularly preferred.
  • Residues J in formula VI are e.g. Methylene, ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3-, 2,3- or 1,4-butylene, pentaethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene , Undecamethylene or dodecamethylene.
  • T 2 , T 3 , T 4 and T 5 in formula VI are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl , Hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, undecyl, dodecyl, fluoromethyl, chloromethyl, di-fluoroethyl, trifluoroethyl, trichloromethyl, 2-fluoroethyl, 2-chloroethyl, 2 -Bromethyl, 1, 1, 1-trifluoroethyl, heptafluoropropyl, 4-chloro
  • T 1 in formula VI is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, tert-pentyloxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbonyl, octyloxycarbon
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 independently of one another are each hydrogen, hydroxy, C 1 -C 4 -alkyl or C 1 -C 2 o-alkoxy and
  • Me 2 has the meaning of Me 1 or the rest
  • S i— (-0 - S i - 0 - Y 19 ) 2 ⁇ 21 19 corresponds to, in which R 19 is C ⁇ -C ⁇ 3 alkyl or C ⁇ o-C 2 o-alkadienyl and Y 20 and Y 21 are each independently of the other C ⁇ -C ⁇ 3 alkyl or C 2 -C alkenyl.
  • naphthalocyanines of the formula Ha in which Y 1 , Y 2 , Y 3 , Y, Y 5 , Y 6 , Y 7 and Y 8 each independently of one another are hydroxy, C 1 -C 8 -alkoxy, in particular C 1 -C 8 -alkoxy mean.
  • the alkoxy radicals can be the same or different.
  • naphthalocyanines of the formula Ha in which Me 2 is twice hydrogen.
  • markers are nickel-dithiolene complexes of the formula III in which L 1 , L 2 , L 3 and L 4 are each independently phenyl, C 1 -C 2 -alkylphenyl, C 1 -C 8 -alkoxyphenyl or by hydroxy and -C-C 20 alkyl substituted phenyl or L 1 and L 2 and L 3 and L 4 each together the rest of the formula
  • nickel-dithiolene complexes of the formula III in which L 1 and L 4 are each phenyl and L 2 and L 4 are each a radical of the formula 4- [CH 5 -C (CH 3 ) 2 ] -C 6 H mean.
  • the phthalocyanines of formula Ia are known per se and e.g. described in DE-B-1 073 739 or EP-A-155 780 or can be carried out according to methods known per se, such as are used in the production of phthalocyanines or naphthalocyanines and as described, for example, in F.H. Moser, A.L. Thomas "The Phthalocyanines", CRC Press, Boca Rota, Florida, 1983, or J. Am. Chem. Soc. Volume 106, pages 7404 to 7410, 1984.
  • the phthalocyanines of formula Ib are also known per se and e.g. in EP-A-155 780 or can be obtained according to the methods of the above-mentioned prior art (Moser, J.Am. Chem. Soc.).
  • naphthalocyanines of the formula II are likewise known per se and are described, for example, in EP-A-336 213, EP-A-358 080,
  • the nickel-dithiolene complexes of the formula III are also known per se and are described, for example, in EP-A-192 215.
  • aminium compounds of formula IV are also known per se and e.g. in US-A-3 484 467 or can be obtained according to the methods mentioned therein.
  • the methine dyes of formula V are also known per se and e.g. described in EP-A-464 543 or can be obtained according to the methods mentioned therein.
  • azulene square acid dyes of the formula VI are also known per se and are e.g. in EP-A-310 080 or US-A-4 990 649 or can be obtained according to the methods mentioned therein.
  • Liquids which can be labeled as markers with a combination of at least two of the compounds specified above are usually organic liquids, for example
  • Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, isopentanol, neopentanol or hexanol,
  • Glycols such as 1,2-ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 2,3- or 1,4-butylene glycol, di- or triethylene glycol or di- or tripropylene glycol,
  • Ethers such as methyl tert-butyl ether, 1,2-ethylene glycol mono- or dimethyl ether, 1,2-ethylene glycol mono- or diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran or dioxane,
  • Ketones such as acetone, methyl ethyl ketone or diacetone alcohol, 21
  • Esters such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate,
  • aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, white spirit,
  • natural oils such as olive oil, soybean oil or sunflower oil, or natural or synthetic motor, hydraulic or gear oils, e.g. Vehicle engine oil or sewing machine oil, or brake fluids
  • mineral oils such as gasoline, kerosene, diesel oil or heating oil.
  • the above-mentioned compounds are used particularly advantageously for marking mineral oils, for which marking is also required, e.g. for tax reasons.
  • marking is also required, e.g. for tax reasons.
  • the aim is to keep the amount of marking substances as low as possible.
  • Another reason for keeping the amount of marking substances as small as possible can be to prevent their possible damaging influences, for example on the fuel inlet and exhaust outlet area of internal combustion engines.
  • the (weight-based) total content of markers in the marked liquid is approximately 0.1 to 5000 ppb, preferably 1 to 2000 ppb and particularly preferably 1 to 1000 ppb.
  • the compounds mentioned above as markers are generally added in the form of solutions (stock solutions).
  • solutions in the case of mineral oils in particular, aromatic hydrocarbons such as toluene, xylene or higher-boiling aromatic mixtures are preferably suitable as solvents for preparing these stock solutions. 22
  • a total concentration of the marking substances of 0.5 to 50% by weight, based on the total weight of these stock solutions, is generally chosen.
  • Another object of the present invention is a method for the detection of marking substances in liquids which have been marked according to the method according to the invention and its preferred embodiments, which is characterized in that a radiation source is used which emits radiation in the absorption areas of all marking substances , and the fluorescent radiation emitted by the markers is detected.
  • Another object of the present invention is a method for the detection of marking substances in liquids which have been marked according to the method according to the invention and its preferred embodiments, which is characterized in that for each individual marking substance an appropriate radiation source is used, which radiation is emitted in the absorption region of the marking substance and the fluorescent radiation emitted by the marking substances is detected.
  • an excitation unit (A) which contains:
  • ⁇ i a radiation source, which is usually provided with collimator optics, and
  • ⁇ 2 usually a plane mirror, which is located opposite the radiation source on the side of the sample cell facing away from the radiation source and serves to increase the intensity radiated into the sample by reflection of the transmitted radiation,
  • a detection unit (D) which contains:
  • a photodetector (usually provided with collimator optics), in front of which there are usually optical filters (eg edge or interference filters) and possibly NIR polarizers, and which is arranged in such a way that its 23
  • ⁇ 2 usually a concave mirror, which is located opposite the photodetector on the side of the sample cell facing away from the photodetector and serves to reflect the fluorescence radiation emitted in the opposite direction (away from the photodetector) and thus to increase the detection sensitivity.
  • Excitation and detection units in the general sense are referred to as A and D (see above). Markers in the general sense are called M.
  • An excitation unit which is specially adapted to one of the marking substances M ⁇ by means of a corresponding radiation source i.e. the radiation source emits radiation in the absorption region of the marking substance M ⁇
  • a ⁇ An excitation unit which is specially adapted to one of the marking substances M ⁇ by means of a corresponding radiation source (i.e. the radiation source emits radiation in the absorption region of the marking substance M ⁇ ) is designated A ⁇ . Because e.g. the number n of markers in the preferred embodiments is 2 to 10 or 2 to 6 or 2 to 4, ⁇ can accordingly assume whole numerical values from 1 to 10 or 1 to 6 or 1 to 4.
  • a special detection unit which e.g. by means of appropriate optical filters (and possibly polarizers), specially adjusted to the emitted fluorescent radiation of one of the marking substances M ⁇ , is denoted by D ⁇ (or also as detection channel ⁇ ).
  • n marking substances with A (1, 2 ), A (l, 2,3), etc. 24 to A (l, 2,3, ..., 9,10) or A (l, 2), A (l, 2,3) etc. to A (l, 2,3, ..., 5,6) or A (1, 2), A (1, 2, 3), A (1, 2, 3, 4), where, for example, n is 2 to 10 or 2 to 6 or 2 to 4.
  • n marking substances for a detection unit D ⁇ , in which the adaptation to the emitted fluorescent radiation of the respective marking substance M ⁇ takes place through the use of appropriate photodetectors and / or optical filters (and possibly polarizers), in the case of n marking substances, the designations D (l, 2), D (l, 2,3), etc. to D (1, 2, 3, ..., 9, 10) or D (l, 2), D (l, 2,3) etc. to D (1, 2, ..., 5, 6) or D (1, 2), D (1, 2, 3), D (1, 2, 3, 4), where, for example, n is again the same 2 to 10 or 2 to 6 or 2 to 4.
  • n markers M ⁇ where n is again 2 to 10 or 2 to 6 or 2 to 4, respectively, are excited and detected one after the other with the units A ⁇ and D ⁇ respectively adapted to them, this is indicated by the notation "Al / Ml / Dl, A2 / M2 / D2, ... "etc. to” ... A9 / M9 / D9, A10 / M10 / D10 "or" Al / Ml / Dl, A2 / M2 / D2, .. . "etc. to” ...
  • n markers M ⁇ are excited simultaneously with n units A ⁇ and at the same time their emitted fluorescence radiation is detected with n units D ⁇ , this is done with
  • n markers are excited simultaneously with n units A ⁇ and at the same time their emitted fluorescence radiation with a unit D, e.g. a multi-wavelength detector (consisting of an optical, dispersive element, such as a prism or grating, and a line or area detector), this is detected with "A1 / A2 / ... / An / Ml / M2 / ... / Mn / D "or shorter with” A1 / A2 /.../ An / D ".
  • a unit D e.g. a multi-wavelength detector (consisting of an optical, dispersive element, such as a prism or grating, and a line or area detector)
  • the following methods and exemplary construction options of the detection devices can be used (n assumes, for example, the values from 2 to 10 or 2 to 6 or 2 to 4):
  • the structure corresponds essentially to the structure mentioned at the outset and shown in WO 94/02570.
  • appropriately adapted units A ⁇ or D ⁇ are used for each marker M ⁇ . This can be done radially around the sample cuvette by the spatially offset arrangement of several pairs of units A ⁇ and D ⁇ corresponding to the number of markers to be detected. The latter then preferably has a circular cross section.
  • the sample volumes (or sample paths) irradiated by the units A ⁇ are not - in the strict sense - identical.
  • the excitation beams (lying in one plane) intersect in a common piece of the sample volume.
  • the combination of excitation and detection of the n marking substances M ⁇ can be carried out either in succession or simultaneously.
  • Units A ⁇ and D ⁇ are located on the corresponding carousels (instead of individual plane mirrors ⁇ or concave mirrors ⁇ 2 ⁇ , it makes sense to use only one fixed plane or concave mirror in this case).
  • the corresponding radiation source ⁇ i ⁇ or the corresponding photodetector ⁇ i ⁇ is moved into the excitation or detection position by rotating the respective carousels.
  • the beam path through the marked sample and the irradiated sample volume are identical for each marking substance to be determined.
  • the combination of excitation and detection of the n markers M ⁇ can only be done one after the other.
  • a cylindrical sample cuvette which can be closed either at one or both ends with windows made of the same material as the cuvette or which is closed at both ends and preferably has side sample inlets and outlets, so a modified structure can be created.
  • the radiation sources ⁇ i ⁇ of the units A ⁇ can be located on a carousel (instead of individual plane mirrors ⁇ ⁇ , it makes sense to use only a fixed plane mirror).
  • the respective unit A ⁇ then radiates 26 parallel to the longitudinal axis of the cuvette.
  • the respective units D ⁇ blank (this time of course with 'their respective subunits ⁇ 2 ⁇ ) for detecting the fluorescence radiation emitted respectively placed around the sample cuvette.
  • the combination of excitation and detection of the n markers M ⁇ can only take place in succession (of course, the detection of the fluorescence radiation emitted simultaneously by several markers can be carried out simultaneously by the units D ⁇ ).
  • a) The structure can be similar to that described in b) under 1.1). Instead of a corresponding carousel for the subunits ⁇ i ⁇ , however, a polychromatic excitation unit A is used. The detection takes place according to the structure described under b) of I.l). The combination of excitation and detection of the n markers M ⁇ can only be done one after the other.
  • unit A irradiates parallel to the longitudinal axis of the cuvette. Radially (and thus perpendicular to the beam direction of the excitation radiation) the respective units D ⁇ can be placed around the sample cell.
  • the combination of excitation and detection of the n marking substances M ⁇ can be carried out either in succession or simultaneously.
  • the structure can be similar to that described in b) under II). Instead of a corresponding carousel for the photo detectors ⁇ x ⁇ , however, only one detection unit D, for example a multi-wavelength detector, is used.
  • the excitation takes place in accordance with the structure described under b) of II).
  • the combination of excitation and detection of the n markers M ⁇ can only be done one after the other. 27 b) If, based on the structure described in c) under II), for example a cylindrical sample cuvette is used, the unit D detects the fluorescence radiation emitted in each case parallel to the longitudinal axis of the cuvette.
  • the respective units A ⁇ (together with their corresponding plane mirrors ⁇ 2 ⁇ ) can be placed around the sample cuvette.
  • the combination of excitation and detection of the n marking substances M ⁇ can be carried out either in succession or simultaneously.
  • an excitation unit A which e.g. (Case ai) contains interchangeable radiation sources ⁇ i ⁇ .
  • A can also contain several radiation sources ⁇ i ⁇ , the respective radiation, e.g. (Case a) using optical fibers or optical fiber bundles or collinearly superimposing the individual beams of the radiation sources using optical elements, such as e.g. Beam splitter, dichroic beam splitter, grating, etc., is directed so that it enters the sample cell at the same location in each case.
  • the respective fluorescence radiation is detected in accordance with the structure described under a) of 1.2).
  • the combination of excitation and detection of the n markers M ⁇ can only be done one after the other.
  • a unit A as described under a) (case ai or case a 2 ), radiates parallel to the longitudinal axis of the cuvette. Radially (and thus perpendicular to the beam direction of the excitation radiation) the respective units D ⁇ can be placed around the sample cell.
  • the combination of excitation and detection of the n markers M ⁇ can only be carried out one after the other.
  • the combination of excitation and detection 28 tion of the n marking substances M ⁇ take place successively and potentially also simultaneously.
  • a detection unit D which, for example (case ai), contains interchangeable photodetectors and / or interchangeable optical filters (and possibly polarizers) ⁇ i ⁇ .
  • D can also contain a plurality of photodetectors ⁇ i ⁇ , to which the respective emitted fluorescent radiation, for example (case a 2 ), is fed by means of optical fibers or optical fiber bundles.
  • the excitation takes place in accordance with the structure described under b) of II).
  • the combination of excitation and detection of the n markers M ⁇ can only be done one after the other.
  • a cylindrical sample cuvette for example, a unit D, as described under a) (case ai or case a 2 ), detects the one emitted parallel to the longitudinal axis of the cuvette Fluorescence radiation. Radially to this (and thus perpendicular to the longitudinal axis of the cuvette), the respective units A ⁇ can be placed around the sample cuvette.
  • a unit D in accordance with case ai the combination of excitation and detection of the n marking substances M ⁇ can only take place in succession.
  • a unit D corresponding to case a 2 the combination of excitation and detection of the n marking substances M ⁇ can be carried out successively and potentially simultaneously.
  • the construction can be carried out using an excitation unit A, which, for example (case ai) contains exchangeable radiation sources ⁇ i ⁇ or radiation sources ⁇ i ⁇ , their respective radiation, for example (case a 2 ) by means of optical fibers or optical fiber bundles or collinear superimposition of the individual beams of the radiation sources by means of optical elements, such as beam price, dichroic beam splitters, gratings, etc., is guided so that it enters the sample cell at the same location in each case.
  • an excitation unit A which, for example (case ai) contains exchangeable radiation sources ⁇ i ⁇ or radiation sources ⁇ i ⁇ , their respective radiation, for example (case a 2 ) by means of optical fibers or optical fiber bundles or collinear superimposition of the individual beams of the radiation sources by means of optical elements, such as beam price, dichroic beam splitters, gratings, etc., is guided so that it enters the sample cell at the same location in each case.
  • a detection unit D can be used which, for example (case ai), has interchangeable photodetectors and / or interchangeable optical filters (and possibly polarizers) ⁇ i ⁇ 29 contains or several photodetectors ⁇ i ⁇ , to which the respective emitted fluorescent radiation, for example (case a) by means of optical fibers or optical fiber bundles, is fed.
  • ⁇ for the cases A (case a ⁇ ) / D (case a x), A (case a ⁇ ) / D (case a2) and A (case a) / D (case ai) the combination of excitation and detection of the n Markers M ⁇ only be made one after the other.
  • the combination of excitation and detection of the n marking substances M ⁇ can be carried out successively and potentially simultaneously.
  • the simultaneous excitation or detection of the n markers can in principle be carried out with the geometric conditions as described under point II) in a), point 1.2) in b), point 1.3) in b), point 1.4) in case a 2 of b), point 1.5) in case a 2 of b) and point 1.6) in case A (case a) / D (case a 2 ).
  • the arrangement of the respective pairs A ⁇ / D ⁇ essentially corresponds to the geometry explained in point II) in a) and to the geometry shown in WO 94/02570.
  • the optical axis of the unit A ⁇ (corresponding to the direction of the excitation beam) and the optical axis of the corresponding unit D ⁇ lie in a plane on which the longitudinal axis of the sample cell is perpendicular.
  • These two optical axes form an angle ⁇ , which is between 0 ° and 180 °, whereby the following should be defined: when looking from the unit A ⁇ in its beam direction, this angle should be + ⁇ or - ⁇ if the corresponding unit D ⁇ right or left of this 30th
  • a ⁇ (+) D ⁇ or A ⁇ (-) D ⁇ i.e. A1 (+) D1, A2 (+) D2, A3 (+) D3 etc. or A1 (-) D1, A2 (-) D2, A3 (-) D3 etc.
  • the excitation (and detection) of spatially different sample volumes takes place in such a way that the respective pairs Am / Dm are arranged in parallel planes.
  • the order of the levels can be in the form
  • the optical axes belonging to two adjacent units A ⁇ form an angle that is between 0 and 360 °.
  • n 2
  • corresponding angles between adjacent units A ⁇ of 180, 120, 90, 72 or 60 ° result.
  • complementary angles of 240, 270, 288 or 300 ° or -120, -90, -72 or -60 °
  • the levels do not only correspond to the sequence A1 (+) D1, A2 (+) D2, A3 (+) D3, ..., An (+) Dn (equivalent to this in the sequence A1 (-) D1, A2 (-) D2, A3 (-) D3, ..., An (-) Dn) but also, for example, in the sequence A1 (+) D1, A2 (-) D2, A3 (+) D3 , ..., An-l (- / +) Dn-l, An (+/-) Dn.
  • n 2 (180 °) or 4 (90 °) a cuvette with a rectangular cross-section is usually used; for n equal to 3 (120 °), 5 (72 °) or 6 (60 °) one is usually (for n a cuvette with a circular cross-section can of course also be used equal to 2 or 4.
  • the combination of excitation and detection of the n markers M ⁇ can be carried out both simultaneously and in succession using the arrangements mentioned. 31
  • the arrangement of the units A ⁇ can be designed in accordance with the explanations given under II.1). If the units A ⁇ are arranged in a row (case ai), the unit D can be installed in a fixed position in the corresponding ⁇ position if the radiation entrance window is of sufficient size or if appropriate imaging optics are used. Otherwise (case a 2 ), a (translational) tracking must take place in the corresponding position. In the case of the other arrangements of the units A ⁇ (case a 3 ), a (translational and rotary) adjustment of the unit D into the corresponding ⁇ positions must take place. Thus, in case ai, the combination of excitation and detection of the n markers M ⁇ can take place both simultaneously and in succession, in cases a 2 and a 3 only in succession.
  • a detection unit eg a multi-wavelength detector
  • a detection unit which, for example (case ai), contains exchangeable photodetectors and / or exchangeable optical filters (and possibly polarizers) ⁇ i ⁇ .
  • D can also contain several photodetectors ⁇ i ⁇ , which the respective emitted 32
  • Fluorescence radiation for example (case a 2 ) by means of optical fibers or optical fiber bundles, is supplied.
  • a unit D corresponding to case ai, the combination of excitation and detection 'of the n markers m.mu. only take place sequentially, as a change of the subunits must be ⁇ i ⁇ and possibly also a (translational or translational and rotational) readjustment of the unit D.
  • the combination of excitation and detection of the n marking substances M ⁇ can be carried out in succession and potentially (with a suitable arrangement of the units A ⁇ ), if, for example, by means of suitable optical devices, bundling (for example by optical lens) of the fluorescent radiation emitted by the marking substances M ⁇ onto the optical fibers or fiber bundles.
  • a detection unit for example a multi-wavelength detector
  • a detection unit which, for example (case ai), contains interchangeable photo detectors and / or interchangeable optical filters (and possibly polarizers) ⁇ i ⁇ .
  • D can also contain a plurality of photodetectors ⁇ i ⁇ , to which the respective emitted fluorescent radiation, for example (case a 2 ), is fed by means of optical fibers or optical fiber bundles.
  • the simultaneous excitation or detection of the n marking substances can in principle be carried out with the arrangements and geometric relationships as described in point II.1), point II.2) in case ai of a), point II.2) in b ), Point II.3) in case a 2 of a) and point II.3) in case a 2 of b). 33
  • the arrangements and exemplary construction options of detection devices in case II, i.e. with excitation in different sample volumes, are usually suitable for the simultaneous excitation of all n markers M ⁇ .
  • Such arrangements and exemplary construction options for detection devices are particularly suitable, in which the fluorescence radiation emitted in each case can also be detected simultaneously at spatially different locations.
  • the excitation radiation of the units A ⁇ can be pulsed or continuous, i.e. in continous wave (CW) mode.
  • the intensity of the excitation radiation of each unit A ⁇ can be modulated with a frequency f ⁇ , so that this unit A ⁇ excites fluorescence radiation of the marking substance M ⁇ which is also intensity-modulated with f ⁇ and which can be selectively measured by D ⁇ .
  • modulation frequencies are used which differ from the frequency of the power grid (usually 50 Hz) and the half and integer multiples of this frequency.
  • the different modulation frequencies f ⁇ allow the fluorescence radiation of the respective markers M ⁇ to be assigned and a better signal / noise ratio to be achieved.
  • the "lock-in method" is usually used to detect the intensity-modulated fluorescence signals.
  • a preferred embodiment of the method according to the invention for the detection of marking substances in liquids which have been marked according to the method according to the invention consists in the successive excitation of the n marking substances M ⁇ by their corresponding units A ⁇ in the same sample volume and the (temporally successive) Detection of the fluorescence radiation emitted by M ⁇ .
  • a further preferred embodiment of the method according to the invention for the detection of marking substances in liquids which have been marked according to the method according to the invention consists in the simultaneous excitation of the n marking substances M ⁇ by their corresponding units A ⁇ in the same sample volume and simultaneously or in succession 34 detection of the fluorescence radiation emitted by M ⁇ in each case by means of a multi-wavelength detector.
  • a further preferred embodiment of the method according to the invention for the detection of marking substances in liquids which have been marked according to the method according to the invention consists in the simultaneous excitation of the n marking substances M ⁇ by a polychromatic unit A in the same sample volume and the simultaneous or temporally successive one Detection of those emitted by M ⁇
  • Fluorescence radiation using a multi-wavelength detector Fluorescence radiation using a multi-wavelength detector.
  • a further preferred embodiment of the method according to the invention for the detection of marking substances in liquids which have been marked according to the method according to the invention consists in the simultaneous excitation of the n marking substances M ⁇ by respective units A ⁇ with the frequency f ⁇ intensity-modulated in the same sample volume and the simultaneous or sequential detection of the respective fluorescence radiation emitted by M ⁇ and intensity-modulated.
  • a further preferred embodiment of the method according to the invention for the detection of marking substances in liquids which have been marked according to the method according to the invention consists in the simultaneous excitation of the n marking substances M ⁇ by their corresponding units A ⁇ in different sample volumes and that in succession or at the same time detection of the fluorescence radiation emitted by M ⁇ by means of the respective unit D ⁇ .
  • ⁇ i ⁇ semiconductor lasers semiconductor diodes or solid-state lasers, which have a maximum emission in the spectral range from ⁇ ma ⁇ - 100 nm to ⁇ max + 20 nm, where ⁇ ma x denotes the wavelength of the absorption maximum of the respective marking substance M ⁇ .
  • Photodetectors ⁇ i ⁇ in the units D ⁇ are advantageously used as the photodetectors ⁇ i ⁇ in the units D ⁇ .
  • Interference filters and / or edge filters with a short-wave transmission edge in the range from m ax to ⁇ max + 80 nm are preferred as optical filters in the photo detectors ⁇ i ⁇ of the units D ⁇ , where ⁇ max denotes the wavelength of the absorption maximum of the respective marking substance M ⁇ . 35
  • NIR polarizers can also be used.
  • the absorption spectrum of the mixture of markers from A, B and C shows essentially no overlap of the absorption spectra of the individual markers.

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Abstract

L'invention concerne un procédé pour marquer des liquides avec au moins deux substances de marquage, caractérisé en ce que les substances de marquage sont absorbantes dans la gamme spectrale comprise entre 600 et 1200 nm, et par conséquent émettent un rayonnement fluorescent. Ledit procédé est en outre caractérisé en ce que lesdites substances de marquage présentent des plages d'absorption ne se chevauchant pratiquement pas, et au moins une des substances de marquage possède, à l'état maximal d'absorption, une longueur d'onde supérieure à 850 nm. L'invention concerne également un procédé pour détecter ces substances de marquage dans des liquides, caractérisé en ce que l'on utilise une source de rayonnement qui émet un rayonnement dans la plage d'absorption des substances de marquage, et l'on détecte le rayonnement fluorescent émis par les substances de marquage, ou caractérisé en ce que l'on utilise une source de rayonnement correspondante pour chaque substance de marquage individuelle, qui émet un rayonnement dans la plage d'absorption de la substance de marquage, et l'on détecte le rayonnement fluorescent émis par les substances de marquage. L'invention concerne en outre des liquides qui sont marqués selon ledit procédé.
PCT/EP1999/002452 1998-04-23 1999-04-12 Procede pour marquer des liquides avec au moins deux substances de marquage et procede pour leur detection WO1999055805A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37073/99A AU3707399A (en) 1998-04-23 1999-04-12 Method for marking liquids with at least two marker substances and method for detecting them

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19818177A DE19818177A1 (de) 1998-04-23 1998-04-23 Verfahren zur Markierung von Flüssigkeiten mit mindestens zwei Markierstoffen und Verfahren zu deren Detektion
DE19818177.9 1998-04-23

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WO1999055805A1 true WO1999055805A1 (fr) 1999-11-04

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AR (1) AR016218A1 (fr)
AU (1) AU3707399A (fr)
DE (1) DE19818177A1 (fr)
PE (1) PE20000464A1 (fr)
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WO (1) WO1999055805A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002050216A2 (fr) * 2000-12-20 2002-06-27 Basf Aktiengesellschaft Procede de marquage d'huile minerale
WO2007017602A2 (fr) * 2005-08-11 2007-02-15 Laboratoires Synth-Innove Marqueurs, leur procede de fabrication et leurs applications

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7208451B2 (en) * 2003-01-29 2007-04-24 Authentic Inc. IMS detection of chemical markers in petroleum products

Citations (3)

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Publication number Priority date Publication date Assignee Title
WO1994002570A1 (fr) * 1992-07-23 1994-02-03 Basf Aktiengesellschaft Utilisation de composes a absorption et/ou fluorescence dans le domaine ir, comme agents de marquage de substances liquides
US5525516A (en) * 1994-09-30 1996-06-11 Eastman Chemical Company Method for tagging petroleum products
US5710046A (en) * 1994-11-04 1998-01-20 Amoco Corporation Tagging hydrocarbons for subsequent identification

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994002570A1 (fr) * 1992-07-23 1994-02-03 Basf Aktiengesellschaft Utilisation de composes a absorption et/ou fluorescence dans le domaine ir, comme agents de marquage de substances liquides
US5525516A (en) * 1994-09-30 1996-06-11 Eastman Chemical Company Method for tagging petroleum products
US5525516B1 (en) * 1994-09-30 1999-11-09 Eastman Chem Co Method for tagging petroleum products
US5710046A (en) * 1994-11-04 1998-01-20 Amoco Corporation Tagging hydrocarbons for subsequent identification

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002050216A2 (fr) * 2000-12-20 2002-06-27 Basf Aktiengesellschaft Procede de marquage d'huile minerale
WO2002050216A3 (fr) * 2000-12-20 2003-05-22 Basf Ag Procede de marquage d'huile minerale
WO2007017602A2 (fr) * 2005-08-11 2007-02-15 Laboratoires Synth-Innove Marqueurs, leur procede de fabrication et leurs applications
WO2007017602A3 (fr) * 2005-08-11 2007-08-02 Synth Innove Lab Marqueurs, leur procede de fabrication et leurs applications
US8034626B2 (en) 2005-08-11 2011-10-11 Laboratoires Synth-Innove Labels, their production process and their uses

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PE20000464A1 (es) 2000-06-02
DE19818177A1 (de) 1999-10-28
AR016218A1 (es) 2001-06-20
AU3707399A (en) 1999-11-16

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