EP1837389A1 - Markers for hydrocarbons - Google Patents

Abstract

Mixture (A) comprises one or more hydrocarbons, a marking agent for the respective hydrocarbon and preferably one or more further additives; where the marking agent comprises one or more ether compound (I). Mixture (A) comprises one or more hydrocarbons, a marking agent for the respective hydrocarbon and preferably one or more further additives; where the marking agent comprises one or more ether compound (I) of formula (-CH(-O-R 1>)-O-Y 1>-R 2>). R 1>1-6C (preferably 1-3C) alkyl, preferably ethyl; R 2>H or 1-6C (preferably 1-3C) alkyl, preferably methyl; and Y 1>C=O (preferred), CH 2 or =CH-CH 3. An independent claim is included for a procedure for marking a hydrocarbon or its mixture, preferably crude oil from petroleum or lubricant comprising adding (I) to the hydrocarbon or its mixture, where the presence of sufficient quantity of (I) in (A) is confirmed using Schiffs reagent.

Description

The present invention relates to the use of compounds of the formula (I) given below as (pH-dependent) marking agents for hydrocarbons, in particular for petroleum-derived fuels or lubricants (mineral oils). The invention further relates to corresponding mixtures comprising one or more hydrocarbons and the said marking agents. Moreover, the present invention relates to methods of labeling a hydrocarbon or a hydrocarbon mixture in which one or more compounds of formula (1) are added as a labeling agent to the hydrocarbon or hydrocarbon mixture. Finally, the invention also relates to a method for detecting compounds of the formula (1) in a mixture according to the invention under the action of an aqueous, acidic fuchsinschwefeligen solution (eg Schiff's reagent), wherein a visible color reaction occurs (identification of a labeled hydrocarbon or a labeled hydrocarbon mixture) ,

For various reasons, there is a need for marking hydrocarbons or hydrocarbon mixtures and especially mineral oil products. For example, in Germany taxed diesel for agricultural use lower than for normal cars, so a corresponding marking is required. But also e.g. Markers are added to distinguish high quality diesel from lower quality grades. There is often a desire to use a marking agent whose presence is not readily apparent to the labeled hydrocarbon or hydrocarbon mixture (e.g., a mineral oil product such as diesel); only after carrying out a preferably simple detection test should the mark become clearly recognizable.

1-Alkoxyester have been described variously in the patent literature, they are used eg in the olfactory and flavor industry as depot preparations for the release of aldehydes (see US 4,296,137 . US 4,386,063 and EP 1 285 906 ).

In EP 0 385 441 describes the use of 1,4-dimethyl-2-nitrobenzene as a marker for mineral oil products, especially diesel. The lower detection limit is in the range of 20 to 100 ppm. The presence of the 1,4-dimethyl-2-nitrobenzene used as a marker can be detected by thin-layer chromatography and comprises several steps; he is thus consuming and feasible only in the laboratory. Furthermore, a semi-quantitative method using UV light is described, which is feasible only from a concentration of 100 ppm.

The use of (C ₁ -C ₄ ) -alkyl phenyl ketones such as acetophenone as marker substances for mineral oil products and organic solvents is described in EP 0 310 319 described. The use concentration of the marker substance should therefore be in the range of 100 to 10,000 ppm and in particular 1000 ppm. The presence of the (C ₁ -C ₄ ) -alkylphenyl ketones used as markers is achieved by a multistage process, wherein Key component 2,4-dinitrophenylhydrazine is added, which leads to a clearly visible color reaction.

Aniline derivatives as marking agents for mineral oils are used in DE 42 38 994 described. The minimum detection concentration is 10 ppm or below. Proof of the presence of the aniline derivatives used as markers is achieved by treating the labeled mineral oil with an aqueous acid diazonium salt solution, so that the aniline derivative couples with the diazonium salt to form an azo dye and ultimately results in a clearly visible color reaction. However, diazonium salts are not safe for safety and health reasons.

In EP 0 736 080 For example, azo dyes are described as pH-dependent markers for labeling hydrocarbons. The minimum detection concentration is 10 ppm or below. The presence of the azo dyes used as markers can be detected by treating the labeled hydrocarbon with an acidic aqueous-alcoholic or acidic alcoholic solution which optionally also contains a metal halide. This results in a clearly visible color reaction.

The above acknowledged prior art discloses (a) readily available, but only consuming detectable markers and on the other hand (b) marking agents, although easy to detect, whose product properties, however, make their handling expensive (such as crystalline state of matter, cf. EP 0 736 080 and health concern, compare DE 42 38 994 ).

• leichte Zugänglichkeit
• Einsetzbarkeit auch in konzentrierter Form
• Farblosigkeit
• gute Löslichkeit in dem zu markierenden Kohlenwasserstoff(gemisch)
• hohe Stabilität in dem zu markierenden Kohlenwasserstoff(gemisch)
• inertes Verhalten gegenüber den zu markierenden Kohlenwasserstoffen und gegenüber gegebenenfalls zugesetzten Additiven
• vorzugsweise kein Vorkommen in aus natürlichen Quellen erhaltenen Kohlenwasserstoffen, insbesondere Mineralölen
• einfache Nachweisbarkeit in Mischungen mit den zu markierenden Kohlenwasserstoffen bzw. Kohlenwasserstoffgemischen
• Nachweis selbst geringer Mengen an Markierungsmitteln durch ausgeprägte Farbreaktion
• rascher Verlauf der Nachweisreaktion
• schlechte Entfernbarkeit aus dem Kohlenwasserstoff-Gemisch.

In view of the above-referenced prior art, it has been the primary object of the present invention to provide alternative or improved means for marking hydrocarbons (especially hydrocarbon mixtures such as mineral oils, eg diesel). The marking agents should fulfill a number of requirements, in particular:

• easy accessibility
• Usability even in concentrated form
• colorlessness
• good solubility in the hydrocarbon to be marked (mixture)
• high stability in the hydrocarbon to be marked (mixture)
• inert behavior towards the hydrocarbons to be marked and to any additives added
• preferably no occurrence in hydrocarbons obtained from natural sources, in particular mineral oils
• easy detectability in mixtures with the hydrocarbons or hydrocarbon mixtures to be marked
• Detection of even small amounts of labeling agents by pronounced color reaction
• rapid course of the detection reaction
• poor removability from the hydrocarbon mixture.

• einen oder mehrere Kohlenwasserstoffe,
• ein Markierungsmittel für den bzw. die Kohlenwasserstoffe sowie
• vorzugsweise ein oder mehrere weitere Additive,

wobei das Markierungsmittel eine oder mehrere Verbindungen der Formel (1) umfasst oder aus einer oder mehreren Verbindungen der Formel (1) besteht

wobei

R¹

eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 6 C-Atomen ist, bevorzugt eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 5 C-Atomen, besonders bevorzugt eine unverzweigte Alkylgruppe mit 1 bis 3 C-Atomen und insbesondere bevorzugt Ethyl,

R²

H oder eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 6 C-Atomen ist, bevorzugt H oder eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 5 C-Atomen, besonders bevorzugt eine unverzweigte Alkylgruppe mit 1 bis 3 C-Atomen, und insbesondere bevorzugt Methyl, und

Y

CH₂, CH-CH₃ oder C=O bedeutet, bevorzugt CH₂ oder C=O, besonders bevorzugt C=O.

According to a first aspect, the stated object is achieved by a mixture comprising

• one or more hydrocarbons,
• a marking agent for the hydrocarbon (s) as well as
• preferably one or more further additives,

wherein the labeling agent comprises one or more compounds of the formula (1) or consists of one or more compounds of the formula (1)

in which

R ¹

is a branched or unbranched alkyl group having 1 to 6 C atoms, preferably a branched or unbranched alkyl group having 1 to 5 C atoms, particularly preferably an unbranched alkyl group having 1 to 3 C atoms and especially preferably ethyl,

R ²

Is H or a branched or unbranched alkyl group having 1 to 6 C atoms, preferably H or a branched or unbranched alkyl group having 1 to 5 C atoms, particularly preferably an unbranched alkyl group having 1 to 3 C atoms, and particularly preferably methyl, and

Y

CH ₂ , CH-CH ₃ or C = O, preferably CH ₂ or C = O, particularly preferably C = O.

In this case, any combination of a preferred meaning of one of the groups R ¹ , R ² or Y with one of the meanings of the other groups given is itself a preferred combination. Thus, for example, it is preferable to provide as R ^{1 group} an unbranched alkyl group having 1 to 2 C atoms, irrespective of whether R ² and / or Y themselves have a preferred meaning or not.

R¹

eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 5 C-Atomen ist,

R²

H oder eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 5 C-Atomen ist und

Y

CH₂ oder C=O bedeutet.

However, particular preference is given to mixtures according to the invention in which the marking agent comprises one or more compounds of the formula (I) or consists of one or more compounds of the formula (I)

R ¹

is a branched or unbranched alkyl group having 1 to 5 C atoms,

R ²

H or is a branched or unbranched alkyl group having 1 to 5 carbon atoms and

Y

CH ₂ or C = O means.

R¹

eine unverzweigte Alkylgruppe mit 1 bis 3 C-Atomen ist,

R²

eine unverzweigte Alkylgruppe mit 1 bis 3 C-Atomen ist und

Y

C=O bedeutet.

More preferred is a mixture according to the invention, wherein the marking agent comprises one or more compounds of formula (I) or consists of one or more compounds of formula (1), wherein

R ¹

is an unbranched alkyl group having 1 to 3 carbon atoms,

R ²

is an unbranched alkyl group having 1 to 3 carbon atoms and

Y

C = O means.

The marking agents to be used according to the invention, which comprise one or more compounds of the formula (I), meet all the requirements indicated above. They are very stable, especially in mineral oils, and the detection reaction with Schiff's reagent is very rapid and reliable. Due to the color reaction occurring in the detection with Schiff's reagent, photometric quantification of the compounds of the formula (1) is also possible. This allows, for example, to detect an undesirable dilution of an originally used hydrocarbon mixture (e.g., a mineral oil such as diesel).

R¹

Ethyl ist,

R²

Methyl ist und

Y

C=O bedeutet.

Most preferred are mixtures according to the invention in which the labeling agent comprises one or more compounds of formula (1) or consists of one or more compounds of formula (1), wherein in the compound of formula (I) or in one of the compounds of Formula 1)

R ¹

Ethyl is,

R ²

Methyl is and

Y

C = O means.

Most preferred is thus the use of 1-ethoxyethyl acetate having the following structural formula (Ia) (formula (1) where R ¹ = ethyl; R ² = methyl; Y = C = O; CAS No .: 1608-72-6, eg producible as in US 4,387,036 described and commercially available):

Particularly good results were obtained with 1-ethoxyethyl acetate as a marking agent, it shows excellent stability in hydrocarbons, in particular mineral oils, and the detection reaction with Schiff's reagent proceeds very rapidly and reliably.

The marking agents of the formula (1) to be used according to the invention react under the hydrolyzing action of an aqueous acidic fuchsin sulfuric acid solution (Schiff's reagent) to give acetaldehyde, which in turn reacts with the fuchsin-sulphurous acid in a color reaction, i. it comes to a color change, along with a clearly visible color deepening.

The so-called Schiff's reagent (also: Schiff's reagent, fuchsin / sulfurous acid) is a detection agent for aldehydes introduced by H. Schiff. General Preparation Procedure for Schiff's Reagent: dissolve fuchsin in distilled water and decolorize after addition of hydrochloric acid with sodium sulfite (formation of sulfur dioxide). This colorless solution turns red with aldehyde addition; For the reaction mechanism, see literature (eg Anal. Chem. 32, 1307-1311 (1960) ).

Fuchsin (empirical formula: C ₂₀ H ₁₉ N ₃ , M _R 301.39) has the following structural formula [(methyl fuchsin, 3-methyl parafuchsin, 4 - [(4-aminophenyl) - (4-imino-2,5-cyclohexadiene-1 -ylidene) -methyl] -2-methylaniline, Basic Violet 14, CI 42510]

By aqueous acid fuchsinschwefeliger acid solution is a well-known in the art commercially available fuchsinschwefelige acid (Schiff's reagent) for the detection of aldehydes to understand. (e.g., Merck KGaA, 64271 Darmstadt, article number: 109034).

The mixtures according to the invention are present under normal conditions (1013 mbar, 25 ° C.) in the liquid state. They include one or more hydrocarbons, which are preferably straight or branched chain aliphatic or aromatic hydrocarbons, especially hydrocarbons derived from petroleum. Usually, several different hydrocarbons are present in a mixture according to the invention, i. there is a hydrocarbon mixture. Preferred hydrocarbon mixtures present in a mixture according to the invention are mineral oils, i. energy sources (fuels, fuels) or lubricants (oils and fats) produced from petroleum (crude oil).

Hydrocarbon mixtures (comprising a plurality of hydrocarbons) which can be particularly preferably marked by the marking agents to be used according to the invention are, in particular, mineral oils (see above), in the context of the present invention under mineral oils fuels, in particular gasoline (in particular gasoline according to DIN EN 228), kerosene ( For example, aviation fuel in accordance with ASTM D910 grade 100 LL or jet fuel, jet fuel such as Jet A-1 or Jet B) or diesel (in particular according to DIN EN 590) and oils, especially fuel oil (in particular according to DIN 51603) or Motor oil. Particular preference is again given to the so-called middle distillates, which have a boiling range of from 180 to 360 ° C. under atmospheric pressure (1013 mbar); diesel fuel according to DIN EN 590 is particularly preferred.

Commercially available fuels or oils, such as diesel fuels or heating oils, which are to be characterized in accordance with the invention using a marking agent, regularly contain additives. A mixture according to the invention therefore comprises (in particular if it comprises petroleum-derived fuels or lubricants which contain a plurality of hydrocarbons), preferably in a total concentration in the range from 0.0001 to 2% by volume, based on the total volume of the mixture, of one or more Additives selected from the group consisting of: flow improvers (anti-settling agents, eg in the case of diesel fuel wax anti-settling additives, WASA), oxidation inhibitors (antioxidants), metal deactivators, corrosion inhibitors, antifoam agents, ignition accelerators, detergents, particle-reducing agents Substances, anti-knock agents, anti-carburetor additives, anti-repellency agents, anti-smoke agents, biocides, conductivity improvers, burn-off aids, fragrances, anti-wear agents and viscosity improvers. A petroleum-based lubricant may also be added to a mixture according to the invention comprising a petroleum-derived fuel.

• (L1) Isopropylmyristat, Benzylbenzoat, Diethylphthalat und deren Mischungen,
• (L2) Isododecan, n-Paraffine mit 9 bis 14 C-Atomen, iso-Paraffine mit 9 bis 14 C-Atomen, Naphthalin, Alkylnaphthaline (insbesondere Methylnaphthaline) und deren Mischungen.

For the preparation of a mixture according to the invention, it may be helpful for ease of dosing or handling, the marking agent one or more hydrocarbons (eg, a mineral oil such as a middle distillate (eg diesel)) in the form of a mixture with one or more solution or Add diluents. The solvent or diluent must be compatible with the marking agent (s) and the hydrocarbons to be marked. Preferred solvents or diluents are substances from one of the following groups L1 and L2 or a mixture of substances from both groups L1 and L2, consisting of:

• (L1) isopropyl myristate, benzyl benzoate, diethyl phthalate and mixtures thereof,
• (L2) isododecane, n-paraffins having 9 to 14 carbon atoms, iso-paraffins having 9 to 14 carbon atoms, naphthalene, alkylnaphthalenes (especially methylnaphthalenes) and mixtures thereof.

• bezogen auf das Gesamtgewicht der Mischung 40 bis 95 Gew.-%, vorzugsweise 50 bis 90 Gew.-% einer oder mehrerer Verbindungen der Formel (I)
  
  wobei R¹, R² und Y die in den Ansprüchen 1 bis 4 angegebene Bedeutung besitzen,
  sowie
• eine Substanz aus einer der folgenden Gruppen L1 und L2 oder eine Mischung von Substanzen aus beiden Gruppen L1 und L2, bestehend aus:
  • (L1) Isopropylmyristat, Benzylbenzoat, Diethylphthalat und deren Mischungen,
  • (L2) Isododecan, n-Paraffine mit 9 bis 14 C-Atomen, iso-Paraffine mit 9 bis 14 C-Atomen, Naphthalin, Alkylnaphthaline (insbesondere Methylnaphthaline) und deren Mischungen.

The invention also relates to a corresponding mixture comprising marking agents and a solvent or diluent compatible therewith (and preferably with the hydrocarbons to be marked). Such a mixture according to the invention preferably comprises

• based on the total weight of the mixture 40 to 95 wt .-%, preferably 50 to 90 wt .-% of one or more compounds of formula (I)
  
  wherein R ¹ , R ² and Y have the meaning given in claims 1 to 4,
  such as
• a substance from one of the following groups L1 and L2 or a mixture of substances from both groups L1 and L2, consisting of:
  • (L1) isopropyl myristate, benzyl benzoate, diethyl phthalate and mixtures thereof,
  • (L2) isododecane, n-paraffins having 9 to 14 carbon atoms, iso-paraffins having 9 to 14 carbon atoms, naphthalene, alkylnaphthalenes (especially methylnaphthalenes) and mixtures thereof.

Solvents of the group L2 are e.g. under the name Shellsol D60 or Shellsol D100 (mixtures of n- and iso-paraffins) or Shellsol T (mixture of iso-paraffins) commercially available.

Particularly preferred mixtures according to the invention which comprise one or more hydrocarbons preferably comprise (a) a total amount of the hydrocarbon or hydrocarbons (eg in the form of a mineral oil, in particular a diesel fuel) of at least 80% by weight, preferably at least 90% by weight. , preferably at least 95% by weight, more preferably at least 98% by weight, and preferably, (b) a total amount of marking agents of formula (I) in the range of 10 ppm to 1000 ppm, preferably in the range of 25 ppm to 250 ppm, and more preferably in the range 30 ppm to 100 ppm, each based on the total weight of the mixture.

wobei R¹, R² und Y die oben angegebene Bedeutung besitzen, vorzugsweise eine der oben als bevorzugt angegebenen Bedeutungen, als Markierungsmittel für Kohlenwasserstoffe, insbesondere für aus Erdöl gewonnene Kraft- oder Schmierstoffe. Hinsichtlich der bevorzugten Kohlenwasserstoffe bzw. der bevorzugten (vorzugsweise aus Erdöl gewonnenen) Kohlenwasserstoffmischungen wird auf die obigen Ausführungen verwiesen, die hier entsprechend gelten.The invention also relates to the use of one or more compounds of the formula (I)

where R ¹ , R ² and Y have the abovementioned meaning, preferably one of the meanings given above as preferred, as a marking agent for hydrocarbons, in particular for petroleum-derived fuels or lubricants. With regard to the preferred hydrocarbons or the preferred (Preferably derived from petroleum) hydrocarbon mixtures reference is made to the above statements, which apply here accordingly.

• Zugeben einer Menge einer oder mehrerer Verbindungen der Formel (I)
  

wobei R¹, R² und Y die oben angebebene Bedeutung besitzen, zu dem Kohlenwasserstoff oder der Kohlenwasserstoffmischung, wobei die insgesamt zugegebene Menge der Verbindung oder Verbindungen der Formel (1) ausreicht, um die Verbindung oder Verbindungen der Formel (1) in der Mischung durch Schiffs Reagenz nachzuweisen. Hinsichtlich der bevorzugten Kohlenwasserstoffe bzw. der bevorzugten (vorzugsweise aus Erdöl gewonnenen) Kohlenwasserstoffmischungen wird erneut auf die obigen Ausführungen verwiesen, die hier entsprechend gelten.The invention further relates to a method for labeling a hydrocarbon or a hydrocarbon mixture (and optionally identifying the labeled hydrocarbon or the marked mixture), in particular for marking a petroleum-derived fuel or lubricant, comprising the following step:

• Adding an amount of one or more compounds of the formula (I)
  

wherein R ¹ , R ² and Y are as defined above, to the hydrocarbon or the hydrocarbon mixture, wherein the total added amount of the compound or compounds of formula (1) is sufficient to the compound or compounds of formula (1) in the mixture by Schiff's reagent. With regard to the preferred hydrocarbons or the preferred (preferably derived from petroleum) hydrocarbon mixtures, reference is again made to the above statements, which apply here accordingly.

In a method according to the invention for labeling a hydrocarbon or a hydrocarbon compound, the amount of one or more compounds of formula (I) is preferably in the form of a mixture according to the invention, which in addition to the marking agent still one of the preferred solvents or diluents to the hydrocarbon or added to the hydrocarbon mixture.

A hydrocarbon marked according to the invention or a hydrocarbon mixture marked according to the invention is preferably identified by reaction with Schiff's reagent.

• Zugeben von 0,01 bis 1,0 Gewichtsteilen, bevorzugt 0,05 bis 0,5 Gewichtsteilen und besonders bevorzugt 0,1 bis 0,25 Gewichtsteilen fuchsinschwefeliger Säure (Schiffs Reagenz) (insbesondere in handelsüblicher Form) zu 1,0 Gewichtsteilen einer erfindungsgemäßen, nach dem erfindungsgemäßen Verfahren markierten, Mischung, die neben dem oder den Kohlenwasserstoffen ein oder mehrere Markierungsmittel der Formel (I) umfasst,
• Schütteln der so erhaltenen Nachweismischung, vorzugsweise für einen Zeitraum im Bereich von 15 Sekunden bis 3 Minuten, bevorzugt für einen Zeitraum im Bereich von 30 Sekunden bis 2 Minuten,
• nach Beenden des Schüttelvorgangs Erlauben einer Phasentrennung in der Reaktionsmischung und Überprüfen der wässrigen (unteren) Phase hinsichtlich eines Farbumschlags (der üblicherweise mit einer Farbvertiefung einhergeht).

A preferred method according to the invention for labeling a hydrocarbon or a hydrocarbon mixture and identifying the labeled hydrocarbon or the marked hydrocarbon mixture comprises the following identification steps:

• Adding from 0.01 to 1.0 parts by weight, preferably from 0.05 to 0.5 parts by weight, and more preferably from 0.1 to 0.25 parts by weight of fuchsinschwefeliger acid (Schiff's reagent) (in particular in commercial form) to 1.0 parts by weight of an inventive , mixture marked according to the process of the invention, which comprises one or more marking agents of the formula (I) in addition to the hydrocarbon or hydrocarbons,
• Shaking the detection mixture thus obtained, preferably for a period in the range of 15 seconds to 3 minutes, preferably for a period in the range of 30 seconds to 2 minutes,
• after completion of the agitation, allow a phase separation in the reaction mixture and check the aqueous (lower) phase for a color change (usually associated with a color well).

• photometrische Messung der wässrigen Phase gegen eine Lösung bekannter Konzentration.

In a preferred method of the invention for identifying a labeled hydrocarbon or a labeled hydrocarbon mixture, the level of label in the mixture is quantified. A corresponding method comprises the following additional step (after reaction with Schiff's reagent):

• photometric measurement of the aqueous phase against a solution of known concentration.

The compounds of the formula (I) to be used according to the invention can be prepared in a simple manner and thus represent inexpensive and readily accessible compounds. In contrast to the aldehydes resulting therefrom by hydrolysis, they behave in mixtures with hydrocarbons to be marked (in particular in the above specified hydrocarbon mixtures such as mineral oils such as diesel or the like) extremely compatible, stable and unobtrusive.

Further aspects of the present invention will become apparent from the appended claims.

The following examples are intended to explain the invention in more detail. Unless otherwise indicated, all data are by weight.

Example 1: Detection reaction of 1-ethoxyethyl acetate in diesel fuel

1-Ethoxyethylacetat the formula (la) was detected in diesel fuel according to DIN EN 590 with fuchsinschwefeliger acid (Schiff reagent).

It was used diesel fuel, namely commercial, ready-to-use diesel fuel, which contained a total of about 500 ppm of conventional additives: flow improvers (flow improvers, anti-settling, here: WASA), oxidation inhibitors, metal deactivators, corrosion inhibitors, anti-foam, Ignition accelerators, detergents, biocides.

1. (a) 0 ppm (ohne Zusatz; Referenzprobe),
2. (b) 100 ppm,
3. (c) 50 ppm,
4. (d) 30 ppm

Each 10.0 g of this diesel fuel were with

1. (a) 0 ppm (without additive, reference sample),
2. (b) 100 ppm,
3. (c) 50 ppm,
4. (d) 30 ppm

1-Ethoxyethylacetat the formula (la) is added to produce a mixture according to the invention, which in addition to a hydrocarbon mixture also contains a compound of formula (I) (here: compound of formula (Ia)).

To the mixture according to the invention 2.0 g fuchsinschwefelige acid (Schiff's reagent) was added and shaken for 1 minute. Thereafter, the phases separated and the color change of the lower aqueous phase was evaluated. The results are shown in the following table: Without addition 30 ppm 50 ppm 100 ppm Color change aqueous phase none Visible dark pink discoloration Intense violet discoloration Very intense, dark purple discoloration

As can be seen from the table, a dosage of 30 ppm of 1-ethoxyethyl acetate in diesel fuel, after carrying out the detection reaction, already showed a clear color change with a corresponding color deepening.

The aqueous phase was photometrically measured against a solution of known concentration of product dye and quantified here by the amount of 1-ethoxyethyl acetate.

Example 2 Stability Study of 1-Ethoxyethyl Acetate (Formula (Ia) in Diesel Fuel According to DIN EN 590)

1. (a) 6°C / dunkel
2. (b) Raumtemperatur (RT, ca. 20°C) / Fenster (d.h. am Fenster stehend, dabei wetterabhängig zeitweilig dem direkten Sonnlicht ausgesetzt), und
3. (c) 40°C / dunkel

gelagert. Anschließend wurde der Gehalt an 1-Ethoxyethylacetat der Formel (la) jeweils gegen einen internen Standard per Gaschromatographie jeweils nach 1, 2 und 4 Wochen bestimmt. Die Ergebnisse sind in der folgenden Tabelle dargestellt. Dauer Lagerbedingungen 1-Ethoxyethylacetat [%] 1,0% Dosierung 1-Ethoxyethylacetat [%] 0,1% Dosierung 7 Tage 6°C/dunkel 100% 100% RT/Fenster 100% 100% 40°C/dunkel 100% 100% 14 Tage 6°C/dunkel 99% 100% RT/Fenster 96% 98% 40°C/dunkel 97% 100% 30 Tage 6°C/dunkel 97% 95% RT/Fenster 96% 98% 40°C/dunkel 97% 93% Diesel fuel (see Example 1) was admixed with 0.1% by weight or 1.0% by weight of 1-ethoxyethyl acetate of the formula (Ia) and then added

1. (a) 6 ° C / dark
2. (b) room temperature (RT, approx. 20 ° C) / window (ie standing at the window, depending on the weather, temporarily exposed to direct sunlight), and
3. (c) 40 ° C / dark

stored. Subsequently, the content of 1-ethoxyethyl acetate of the formula (Ia) was determined in each case against an internal standard by gas chromatography in each case after 1, 2 and 4 weeks. The results are shown in the following table. duration storage conditions 1-ethoxyethyl acetate [%] 1.0% dosage 1-ethoxyethyl acetate [%] 0.1% dosage 7 days 6 ° C / dark 100% 100% RT / Windows 100% 100% 40 ° C / dark 100% 100% 14 days 6 ° C / dark 99% 100% RT / Windows 96% 98% 40 ° C / dark 97% 100% 30 days 6 ° C / dark 97% 95% RT / Windows 96% 98% 40 ° C / dark 97% 93%

As can be seen from the table, 1-ethoxyethyl acetate in the dosages 0.1% by weight and 1.0% by weight in diesel fuel, over a period of 4 weeks, shows a very good stability.

Claims (14)

Comprising mixture one or more hydrocarbons, a marking agent for the hydrocarbon (s) and preferably one or more further additives, wherein the labeling agent comprises one or more compounds of the formula (I) or consists of one or more compounds of the formula (I)

in which R ^{1 is} a branched or unbranched alkyl group having 1 to 6 C atoms, preferably a branched or unbranched alkyl group having 1 to 5 C atoms, particularly preferably an unbranched alkyl group having 1 to 3 C atoms and particularly preferably ethyl, R ^{2 is} H or a branched or unbranched alkyl group having 1 to 6 C atoms, preferably H or a branched or unbranched alkyl group having 1 to 5 C atoms, more preferably an unbranched alkyl group having 1 to 3 C atoms, and particularly preferred Methyl, and Y is CH ₂ , CH-CH ₃ or C = O, preferably CH ₂ or C = O, more preferably C = O. A mixture according to claim 1, wherein the labeling agent comprises one or more compounds of formula (I) or consists of one or more compounds of formula (I), wherein R ^{1 is} a branched or unbranched alkyl group having 1 to 5 C atoms, R ^{2 is} H or a branched or unbranched alkyl group having 1 to 5 C atoms and Y is CH ₂ or C = O. Mixture according to one of the preceding claims, wherein the marking agent comprises one or more compounds of formula (I) or consists of one or more compounds of formula (I), wherein R ^{1 is} an unbranched alkyl group having 1 to 3 C atoms, R ^{2 is} an unbranched alkyl group having 1 to 3 C atoms and YC = O means. Mixture according to one of the preceding claims, wherein the marking agent comprises one or more compounds of formula (I) or consists of one or more compounds of formula (I), wherein in the compound of formula (I) or in one of the compounds of formula (I) R ^{1 is} ethyl, R ^{2 is} methyl and YC = O means. Mixture according to one of the preceding claims, further comprising a substance from one of the following groups L1 and L2 or a mixture of substances from both groups L1 and L2, consisting of: (L1) isopropyl myristate, benzyl benzoate, diethyl phthalate and mixtures thereof, (L2) isododecane, n-paraffins having 9 to 14 carbon atoms, iso-paraffins having 9 to 14 carbon atoms, naphthalene, alkylnaphthalenes (especially methylnaphthalenes) and mixtures thereof. Mixture according to one of the preceding claims, comprising a petroleum-derived fuel or lubricant containing a plurality of hydrocarbons. Mixture according to one of the preceding claims, comprising a petroleum-derived fuel or lubricant selected from the group consisting of gasoline, kerosene, diesel, fuel oil and motor oil. Mixture according to one of the preceding claims, comprising in a total concentration in the range of 0.0001 to 2 vol.%, Based on the total volume of the mixture, one or more additives selected from the group consisting of: flow improvers, oxidation inhibitors (antioxidants), metal deactivators, Corrosion inhibitors, antifoaming agents, ignition accelerators, detergents, particulate reducing agents, anti-knock agents, anti-carburetor additives, anti-repellence agents, smoke reducing agents, biocides, conductivity improvers, burn-off aids, fragrances, anti-wear agents and viscosity improvers. Mixture according to one of the preceding claims, comprising (a) a total amount of the hydrocarbon or hydrocarbons of at least 80% by weight, preferably at least 90% by weight, preferably at least 95% by weight, particularly preferably at least 98% by weight, and preferably (B) a total amount of marking agent or agents of the formula (I) in the range of 10 ppm to 1000 ppm, preferably in the range of 25 ppm to 250 ppm, and more preferably in the range from 30 ppm to 100 ppm, based in each case Total weight of the mixture. Comprising mixture based on the total weight of the mixture, from 40 to 95% by weight, preferably from 50 to 90% by weight, of one or more compounds of the formula (I)

wherein R ¹ , R ² and Y have the meaning given in claims 1 to 4,
such as a substance from one of the following groups L1 and L2 or a mixture of substances from both groups L1 and L2, consisting of: (L1) isopropyl myristate, benzyl benzoate, diethyl phthalate and mixtures thereof, (L2) isododecane, n-paraffins having 9 to 14 carbon atoms, iso-paraffins having 9 to 14 carbon atoms, naphthalene, alkylnaphthalenes (especially methylnaphthalenes) and mixtures thereof. Use of one or more compounds of the formula (1)

wherein R ¹ , R ² and Y have the meaning given in claims 1 to 4,
as a marking agent for hydrocarbons, in particular for petroleum-derived fuels or lubricants. Process for the marking of a hydrocarbon or a hydrocarbon mixture, in particular for petroleum-derived fuels or lubricants, comprising the following step: Adding an amount of one or more compounds of the formula (I)

wherein R ¹ , R ² and Y have the meaning given in claims 1 to 4, to the hydrocarbon or the hydrocarbon mixture, wherein the total added amount of the compound or compounds is sufficient to detect the compound or compounds of formula (I) in the mixture by Schiff's reagent. The process of claim 12, wherein the amount of one or more compounds of formula (1) in the form of a mixture of claim 10 is added to the hydrocarbon or hydrocarbon mixture. The process of claim 12 or 13 further comprising the following step of identifying the labeled hydrocarbon or hydrocarbon mixture: - Reacting the labeled hydrocarbon or the marked hydrocarbon mixture with Schiff's reagent.