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WO2022161960A1 - Procédé de marquage de carburants - Google Patents

Procédé de marquage de carburants Download PDF

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Publication number
WO2022161960A1
WO2022161960A1 PCT/EP2022/051657 EP2022051657W WO2022161960A1 WO 2022161960 A1 WO2022161960 A1 WO 2022161960A1 EP 2022051657 W EP2022051657 W EP 2022051657W WO 2022161960 A1 WO2022161960 A1 WO 2022161960A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel
compound
formula
marker
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2022/051657
Other languages
English (en)
Inventor
Hans Reichert
Leonhard Feiler
Rene Fischer
Oliver Seeger
Korinna Dormann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2022161960A1 publication Critical patent/WO2022161960A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0083—Solutions of dyes

Definitions

  • the present invention relates to a method for marking fuels, and to compounds of formula (I) for use in the method.
  • Fuel samples are generally required to be labelled for a variety of purposes such as to distinguish between taxed and untaxed fuel oils or as brand identification for organic based liquids.
  • fuels have been differentiated by means of colour, for example by including an appropriate dyestuff in the fuel, since colour is the simplest way of identifying fuel either by eye or quantitatively using a spectrophotometer.
  • the fuel is ideally marked with trace amounts of material ( ⁇ 50ppm) such that the properties conferred by the marker chemical do not affect the bulk liquid. It should also be possible to detect concentrations as low as 5% of the marker in fuel in cases were the fuel has been diluted with unmarked fuel.
  • GB2344599A relates to a method of marking liquids comprising the steps of adding a photochromic compound, such as, for example, spirooxazines (particularly but not exclusively spiro (indolino) oxazines) and heterocyclochromenes, in particular benzopyrans or napthopyrans, to the liquid and exposing the liquid to ultraviolet light to increase the visibility of the photochromic compound whereby the colour or intensity of the compound after exposure to ultraviolet light acts as an identification marker for the liquid.
  • a photochromic compound such as, for example, spirooxazines (particularly but not exclusively spiro (indolino) oxazines) and heterocyclochromenes, in particular benzopyrans or napthopyrans
  • the dichromophoric compounds of formula (I) used according to the invention differ fundamentally from the monochromophoric compounds disclosed in GB2344599A. They exhibit a higher colour strength and their discoloration process is more pronounced and
  • WO2010/039152A1 relates to a method comprising: testing a fuel for a presence of a first marker in the fuel in a predetermined concentration range; and testing the fuel for a presence of a second marker in the fuel, wherein: the presence of the first marker in the fuel in the predetermined concentration range and an absence of the second marker in the fuel is indicative that the fuel is unaltered, the presence of the first marker in the fuel in a concentration less than the predetermined concentration range is indicative that the fuel is altered, and the presence of the second marker in the fuel is indicative of an altered fuel.
  • EP2524812A2 relates to a remote marking system comprising at least one marker unit and at least one target, wherein: said marker unit comprises at least one emitter configured to emit at least one tracer signal; and said target comprises at least one receiving medium configured to change its state upon reception of said tracer signal thereby recording the position at which said tracer signal is received.
  • EP2524812A2 relates to a photochromic solution comprising a photochromic material selected from the consisting of a spiro-oxazine compound, a naphthopyran compound, a spiropyrans compound, a triarylmethane compound, a stilbene compound, an azastilbene compound, a nitrone compound, a fulgide compound, a diarylethylene compound, a quinine compound and any combination thereof; and a solvent.
  • a photochromic material selected from the consisting of a spiro-oxazine compound, a naphthopyran compound, a spiropyrans compound, a triarylmethane compound, a stilbene compound, an azastilbene compound, a nitrone compound, a fulgide compound, a diarylethylene compound, a quinine compound and any combination thereof; and a solvent.
  • TTIs time temperature indicators
  • the compound of formula (I) can undergo photo- induced coloration by irradiation with photons of a specific energy range, the coloration being followed by a time- and temperature-dependent decoloration; i.e. offers two detection possibilities which can be observed with the naked eye, or detected with a simple spectrometer. Due to the photochromic properties a high protection against counterfeit is possible, making the element ideally suitable for fuel marking.
  • the present invention provides a method of marking liquids, in particular fuels, comprising the steps of a) adding at least one photochromic compound of the formula the liquid, wherein R 1 to R 4 are independently of each other hydrogen, C 1 -C 6 alkoxy, halogen, CF 3 , -C 1 -C 6 alkyl, or -NO 2 , R 5 is hydrogen, halogen, -C 1 -C 6 alkoxy, -COOH, -COO-C 1 -C 8 alkyl, -CF 3 , or phenyl; R 11 is hydrogen, or R 11 and R 5 form together a phenyl ring; R a is -C 1 -C 6 alkyl, R b is -C 1 -C 6 alkyl, or together with R a form a 5-6 membered ring; and L is a divalent linker; and b) converting the compound of formula (I) from an original stable state into a metastable state by photo
  • the compound of formula (I) is added to the liquid, in particular the fuel, to be marked at a concentration that imparts no visible colour to the liquid.
  • the photochromic compound becomes visible upon exposure to light, preferably blue light, or UV light.
  • the liquid is preferably a fuel.
  • fuel refers to products having a predominantly hydrocarbon composition, although they may contain minor amounts of oxygen, nitrogen, sulfur or phosphorus.
  • fuel includes crude oils, as well as products derived from petroleum refining processes.
  • a “fuel” includes without limitation crude oil, lubricating oil, hydraulic fluid, brake fluid, gasoline, diesel fuel, kerosene, jet fuel, heating oil and heavy fuel oil.
  • the petroleum hydrocarbon is selected from the group consisting of gasoline, diesel fuel, kerosene, and jet fuel, and even more preferably from the group consisting of gasoline and diesel fuel.
  • the present invention is particularly suitable for marking fuels as the compounds recommended show stability therein and may be detected at ppm, or sub-ppm levels.
  • the absorbance of the photochromic compound used in the present invention is such that the absorbance on exposure to UV light under the appropriate temperature conditions is greater than 0.1 , more preferably greater than 0.2.
  • the marked liquid in particular fuel, is preferably illuminated by an ultraviolet source or a flash lamp, such as a photographic flash lamp.
  • the marked liquid is illuminated at a constant distance for a constant length of time at a specified temperature to ensure reproducibility of the colour formation thereby ensuring the correct identification of the liquid from the detected marker.
  • the sample of liquid, in particular fuel, to be identified is stored in a light free environment prior to exposure to ultraviolet light to ensure that any change in colour that has occurred in the marker during its exposure to ambient light is reversed prior to testing.
  • the sample may be heated in a sealed vial to reverse the colour change prior to illumination.
  • the increased visibility of the compound by exposure to the UV light may be reversed by the removal of the UV light source.
  • the method may comprise taking a sample of the liquid from the bulk liquid in a vial, if necessary cooling to a specified temperature, exposing the sample to UV light to enable the detection of the compound and thereby identify the liquid and returning the sample back to the bulk liquid.
  • the change to the colourless state will then occur in the bulk liquid especially if it is in a light free environment.
  • the photochromic compound is preferably provided as a liquid, in particular fuel, concentrate for addition to the liquid to be marked.
  • a concentrate of between 1% to 10% of the marker in an organic solvent is used.
  • Organic solvents suitable for this purpose are, for example, alkyl benzenes, alkylnaphthalenes or a proprietary blend of such compounds.
  • Polar organic solvents may be included to increase the solubility of the marker compound in the concentrate, such as formamide, N,N-dimethylformamide and N- methylpyrrolidone.
  • the solvents are a mixture of aromatic and aprotic solvents.
  • solvents may be used singly or in blends but must be miscible with the liquid, in particular the fuel, being marked.
  • the final concentration of the marker in the liquid, in particular in the fuel is between 1 ppm and 30 ppm (w/vol) but the level will be dependent upon the inherent colour of the solvent used.
  • the method and compounds of the present invention may be provided in combination with other markers.
  • the photochromic compounds may be used in conjunction with existing solvent dyes, such as mono- and bis-azo dyes, quinoline, methine, xanthene, perylene and anthraquinone based dyes.
  • the photochromic compounds may be used in combination with colourless marker chemicals often found in fuels which require alkaline conditions for the formation of colour in an extracted aqueous layer, such as quinizarin, coumarin and those covered by WO96/32462 with both types of compound being detectable independently of one other.
  • the photochromic compounds may also be used in combination with, or added as a mixture with, colourless marker chemicals which require acidic conditions for the formation of colour, such as basic azo dyes.
  • the present invention also provides a number of compounds for use in the method.
  • the compounds of formula (I) used in the method possess the ability to change colour or shade reversibly in light of a particular frequency or intensity.
  • R1 is hydrogen, C 1 -C 6 alkoxy, halogen, C 1 -C 6 alkyl, or -NO 2 ;
  • R 2 is hydrogen or C 1 -C 6 alkoxy;
  • R 3 is NO2, or halogen;
  • R 4 is hydrogen, C 1 -C 6 alkoxy, or halogen;
  • R 5 is hydrogen, halogen, methoxy or –COOH
  • R 11 is hydrogen, R a is methyl or ethyl, R b is methyl or ethyl, L is a divalent linker.
  • divalent linker refers to any divalent capable of linking two spiropyran moieties together.
  • Examples of divalent linker groups are selected from C 1 -C 12 alkylene, C 1 -C 12 alkenylene, C 1 -C 12 alkynylene, , , , wherein R 6 is hydrogen, halogen, C 1 -C 6 alkoxy, CF 3 , NO 2 , preferably methoxy, or hydrogen. s is 1 to 4, preferably 1 or 2. C 1 -C 6 alkoxy is preferably methoxy.
  • halogen refers to fluoro, chloro, bromo or iodo. More preferred: R 1 is hydrogen or methoxy. R 2 is hydrogen or methoxy. R 3 is nitro. R 4 is hydrogen. R 5 is hydrogen, halogen, methoxy or -COOH, R a is methyl. R b is methyl. Examples of compounds of the formula (I), wherein R 3 is NO 2 , R 4 is H, are presented in Table 1. Table 1.
  • the indicator compound can undergo photo-induced coloration by irradiation with photons of a specific energy range (conversion of the second isomeric form, thermodynamically more stable) into the first isomeric form (open form) the coloration being followed by a time- and temperature-dependent decoloration (conversion of the first isomeric form into the second isomeric form).
  • the system has at least one thermal process leading from one metastable state to one stable state, where the two states of the spiroaromatic compounds are characterized by a distinctly different color and/or any other measurable physical parameter such as luminescence, refraction index, conductivity and the like.
  • the stable state may be converted into the metastable state using one or any combination of stimuli, among others the following processes: a) photonic induction, or b) thermal induction, and
  • the metastable state is substantially not affected by anyone or any combination of stimuli such as a) photo induction, b) piezo induction, c) electro induction, d) chemo induction.
  • stimuli such as a) photo induction, b) piezo induction, c) electro induction, d) chemo induction.
  • Photoinduction means that the initially colourless compound of formula (I) is irradiated with light, preferably in the UV or near-UV range, as a result a reversible internal valence isomerisation from a colourless inactivated state to a coloured activated one is induced. A reverse discolouration process then proceeds at a rate that is time and temperature dependent.
  • the decoloration can be followed by eye, or by the use a photospectrometer. Under ambient conditions the decoloration is nearly completed after 60 seconds.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

La présente invention concerne un procédé de marquage de carburants comprenant les étapes consistant à : a) ajouter au moins un composé photochromique de formule (I) au carburant, et b) convertir le composé de formule (I) d'un état stable d'origine à un état métastable par induction photonique, i) un changement dans une propriété optique et/ou ii) la détection de la re-conversion dépendant de la température dans le temps de l'état métastable à l'état stable d'origine agissant en tant que marqueur d'identification pour le carburant.
PCT/EP2022/051657 2021-01-29 2022-01-25 Procédé de marquage de carburants Ceased WO2022161960A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21154334.3 2021-01-29
EP21154334 2021-01-29

Publications (1)

Publication Number Publication Date
WO2022161960A1 true WO2022161960A1 (fr) 2022-08-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2022/051657 Ceased WO2022161960A1 (fr) 2021-01-29 2022-01-25 Procédé de marquage de carburants

Country Status (1)

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WO (1) WO2022161960A1 (fr)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0438734A1 (fr) 1990-01-22 1991-07-31 BASF Aktiengesellschaft Huiles minérales marquées, ainsi que procédé de marquage d'huiles minérales au moyen de colorants basiques
US5205840A (en) 1991-09-30 1993-04-27 Morton International, Inc. Markers for petroleum, method of tagging, and method of detection
WO1995000606A1 (fr) 1993-06-21 1995-01-05 Basf Aktiengesellschaft Utilisation d'aminotriarylmethanes pour le marquage d'hydrocarbures, et nouveaux aminotriarylmethanes
WO1995007460A1 (fr) 1993-09-04 1995-03-16 Basf Aktiengesellschaft Procede permettant de detecter la presence de naphthylamines dans des huiles minerales
WO1995010581A1 (fr) 1993-10-12 1995-04-20 Basf Aktiengesellschaft Procede de detection d'huiles minerales marquees et nouveaux colorants azoiques
WO1996002613A1 (fr) 1994-07-13 1996-02-01 Basf Aktiengesellschaft Utilisation de benzaldehydes pour marquer des hydrocarbures
US5498808A (en) 1995-01-20 1996-03-12 United Color Manufacturing, Inc. Fluorescent petroleum markers
WO1996032462A1 (fr) 1995-04-13 1996-10-17 United Color Manufacturing, Inc. Marqueurs de petrole incolores
GB2344599A (en) 1998-12-10 2000-06-14 John Hogg Technical Solutions Method for marking liquids and compounds for use in said method
WO2010039152A1 (fr) 2008-10-03 2010-04-08 Authentix, Inc. Marquage de carburant pour authentification
US20110059545A1 (en) 2007-01-22 2011-03-10 Freshpoint Holdings Sa Time-temperature indicator based on oligomeric spiroaromatics
EP2524812A2 (fr) 2011-05-18 2012-11-21 Bloomfield Science Museum Jerusalem Marquage à distance et solution photochromique

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0438734A1 (fr) 1990-01-22 1991-07-31 BASF Aktiengesellschaft Huiles minérales marquées, ainsi que procédé de marquage d'huiles minérales au moyen de colorants basiques
US5205840A (en) 1991-09-30 1993-04-27 Morton International, Inc. Markers for petroleum, method of tagging, and method of detection
WO1995000606A1 (fr) 1993-06-21 1995-01-05 Basf Aktiengesellschaft Utilisation d'aminotriarylmethanes pour le marquage d'hydrocarbures, et nouveaux aminotriarylmethanes
WO1995007460A1 (fr) 1993-09-04 1995-03-16 Basf Aktiengesellschaft Procede permettant de detecter la presence de naphthylamines dans des huiles minerales
WO1995010581A1 (fr) 1993-10-12 1995-04-20 Basf Aktiengesellschaft Procede de detection d'huiles minerales marquees et nouveaux colorants azoiques
WO1996002613A1 (fr) 1994-07-13 1996-02-01 Basf Aktiengesellschaft Utilisation de benzaldehydes pour marquer des hydrocarbures
US5498808A (en) 1995-01-20 1996-03-12 United Color Manufacturing, Inc. Fluorescent petroleum markers
WO1996032462A1 (fr) 1995-04-13 1996-10-17 United Color Manufacturing, Inc. Marqueurs de petrole incolores
GB2344599A (en) 1998-12-10 2000-06-14 John Hogg Technical Solutions Method for marking liquids and compounds for use in said method
US20110059545A1 (en) 2007-01-22 2011-03-10 Freshpoint Holdings Sa Time-temperature indicator based on oligomeric spiroaromatics
WO2010039152A1 (fr) 2008-10-03 2010-04-08 Authentix, Inc. Marquage de carburant pour authentification
EP2524812A2 (fr) 2011-05-18 2012-11-21 Bloomfield Science Museum Jerusalem Marquage à distance et solution photochromique

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