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
• • 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
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • 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
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1608—Well defined compounds, e.g. hexane, benzene
• • 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
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids

Definitions

• 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.
• 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.
• 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) ,
• an aqueous, acidic fuchsinschwefeligen solution eg Schiff's reagent
• 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 ).
• 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.
• a semi-quantitative method using UV light is described, which is feasible only from a concentration of 100 ppm.
• (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.
• diazonium salts are not safe for safety and health reasons.
• 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.
• 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.
• 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.
• 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).
• an originally used hydrocarbon mixture e.g., a mineral oil such as diesel.
• 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.
• Schiff's reagent also: Schiff's reagent, fuchsin / sulfurous acid
• 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]
• 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.
• 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-derived fuels or lubricants which contain a plurality of hydrocarbons
• Additives selected from the group consisting of: flow improvers (
• 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.
• a total amount of the hydrocarbon or hydrocarbons eg in the form of a mineral oil, in particular a diesel fuel
• 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 pp
• 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.
• 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.
• 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.
• 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.
• 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.
• Example 1 Detection reaction of 1-ethoxyethyl acetate in diesel fuel
• 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.
• flow improvers flow improvers, anti-settling, here: WASA
• oxidation inhibitors metal deactivators
• corrosion inhibitors anti-foam
• Ignition accelerators Ignition accelerators
• biocides biocides
• 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.

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

Priority Applications (3)

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Publications (1)

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Citations (11)

• 2006
  • 2006-03-21 EP EP06111515A patent/EP1837389A1/fr not_active Withdrawn
• 2007
  • 2007-03-20 WO PCT/EP2007/052642 patent/WO2007107569A1/fr active Application Filing
  • 2007-03-20 EP EP07727119A patent/EP1999236A1/fr not_active Withdrawn

Patent Citations (11)

Non-Patent Citations (1)

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