EP1529091B1 - Esters for odorising combustible gases - Google Patents

Esters for odorising combustible gases Download PDF

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Publication number
EP1529091B1
EP1529091B1 EP03784159A EP03784159A EP1529091B1 EP 1529091 B1 EP1529091 B1 EP 1529091B1 EP 03784159 A EP03784159 A EP 03784159A EP 03784159 A EP03784159 A EP 03784159A EP 1529091 B1 EP1529091 B1 EP 1529091B1
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EP
European Patent Office
Prior art keywords
acrylic acid
esters
ester
methacrylic acid
alkyl esters
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EP03784159A
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German (de)
French (fr)
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EP1529091A1 (en
Inventor
Gerd Mansfeld
Jörg Eilers
Heinz-Jürgen BERTRAM
Florian Wolf
Heribert Kaesler
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EOn Ruhrgas AG
Symrise AG
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EOn Ruhrgas AG
Symrise AG
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    • 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/003—Additives for gaseous fuels
    • C10L3/006—Additives for gaseous fuels detectable by the senses

Definitions

  • the present invention relates to the use of mixtures of acrylic acid C 1 -C 6 alkyl esters and / or methacrylic acid C 1 -C 6 alkyl esters for the odorization of fuel gases, a process for the odorization of fuel gases and fuel gases containing these mixtures.
  • Fuel gases that do not have a sufficient inherent odor are usually mixed with intense-smelling compounds, i. Odoriert, so that in case of leaks or leaks they can be easily perceived. For safety reasons so-called odorants are added to the combustion gases, which are still perceptible even in high dilution and cause an alarm association in humans due to their exceptionally unpleasant odor.
  • sulfur compounds are used as odorants. Frequently used tetrahydrothiophene, tert-butyl mercaptan, dimethyl sulfide or ethylmercaptan.
  • JP-B-51-007481 mentions that acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and butyl acrylate are known to have weak odorant properties for fuel gases and have practically no significance in this respect.
  • The. Document describes and claims allyl acrylate as an effective odorizing component.
  • odorant containing an alkyne and at least 2 compounds selected from a group consisting of methyl acrylate, ethyl acrylate, Methyl methacrylate, allyl methacrylate, ethyl propionate, methyl n-butyrate, methyl isobutyrate and prenyl acrylate, and optionally tert-butylmercaptan, are suitable for the odorization of fuel gases.
  • JP-B-51-034841 "odor thresholds" of various substances were determined, with n-valeric acid, n-butyric acid, isobutyraldehyde and various methylamines having low odor odor thresholds. Nevertheless, it was found that ethyl acrylate or n-valeric acid used alone, because of their odor properties, not sufficiently odorizing act.
  • the optimized mixture comprised ethyl acrylate, n-valeric acid and triethylamine, this mixture containing equal parts by weight of n-valeric acid and triethylamine and 30 to 80% by weight of ethyl acrylate.
  • mixtures consisting of exactly two or containing at least 3 different acrylic acid C 1 -C 6 alkyl esters and / or methacrylic acid C 1 -C 6 alkyl esters, wherein the mixtures contain neither S nor N-containing compounds , are ideal for the odorization of fuel gases.
  • these mixtures exhibit synergistic effects in the odorization of fuel gases, ie that the mixtures of these compounds have a stronger effect than the sum of the individual constituents would suggest.
  • the present invention is the use of mixtures comprising acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters for the odorization of fuel gases, characterized in that these mixtures at least 3 and at most 6 different acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters, and optionally an antioxidant.
  • Another object of the present invention is a method for the odorization of fuel gases with the mixtures according to the invention and fuel gases containing the mixtures according to the invention.
  • the acrylic acid C 1 -C 6 -alkyl esters are advantageously selected from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate , N-pentyl acrylate, iso-pentyl acrylate and n-hexyl acrylate.
  • acrylic acid C 1 -C 4 -alkyl esters in particular methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate and iso-butyl acrylate.
  • Very particularly preferred acrylic acid C 1 -C 4 -alkyl esters are methyl acrylate, ethyl acrylate and n-butyl acrylate.
  • the methacrylic acid-C 1 -C 6 -alkyl esters are advantageously selected from the group comprising methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, methacrylic acid tert. butyl ester, n-pentyl methacrylate, iso-pentyl methacrylate and n-hexyl methacrylate.
  • methacrylic acid-C 1 -C 4 -alkyl esters in particular methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate
  • the present invention is the use of mixtures comprising acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters for the odorization of fuel gases, characterized in that these mixtures at least 3 and at most 6 different acrylic acid-C 1 -C 6 alkyl esters and / or methacrylic acid-C 1 -C 6 alkyl esters, and optionally an antioxidant.
  • Another object of the present invention is a method for the odorization of fuel gases with the mixtures according to the invention and fuel gases containing the mixtures according to the invention.
  • the acrylic acid C 1 -C 6 -alkyl esters are advantageously selected from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, acrylic acid tert. butyl ester, n-pentyl acrylate, iso-pentyl acrylate and n-hexyl acrylate.
  • acrylic acid C 1 -C 4 -alkyl esters in particular methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate and iso-butyl acrylate.
  • Very particularly preferred acrylic acid C 1 -C 4 -alkyl esters are methyl acrylate, ethyl acrylate and n-butyl acrylate.
  • the methacrylic acid-C 1 -C 6 -alkyl esters are advantageously selected from the group comprising methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, methacrylic acid tert. butyl ester, n-pentyl methacrylate, iso-pentyl methacrylate and n-hexyl methacrylate.
  • methacrylic acid-C 1 -C 4 -alkyl esters in particular methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and iso-butyl methacrylate.
  • Very particularly preferred C 1 -C 4 -alkyl methacrylates are methyl methacrylate and ethyl methacrylate.
  • Particularly suitable mixtures contain at least one ester from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, n-pentyl acrylate, isopropyl acrylate Methyl methacrylate and ethyl methacrylate, preferred mixtures at least one ester from the group comprising methyl acrylate, ethyl acrylate and n-butyl acrylate.
  • mixtures comprising at least two esters from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate and isopropyl acrylate preferably at least two esters from the group comprising methyl acrylate, ethyl acrylate and n-butyl acrylate.
  • mixtures comprising methyl acrylate and ethyl acrylate.
  • mixtures comprising methyl acrylate and n-butyl acrylate.
  • mixtures comprising ethyl acrylate and n-butyl acrylate.
  • a particularly preferred embodiment relates to mixtures comprising methyl acrylate, ethyl acrylate and an ester selected from n-butyl acrylate, methyl methacrylate and ethyl methacrylate.
  • the mixtures contain the compounds preferably in the weight ratio 1-4: 2-8: 1-4.
  • mixtures containing at least 4 and at most 6 different acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters are used, with mixtures being preferred which contain at least two compounds selected from methyl acrylate , Acrylic acid ethyl ester or n-butyl acrylate. Particularly preferred are mixtures containing methyl acrylate, ethyl acrylate and n-butyl acrylate.
  • Another object of the present invention relates to the use of mixtures for the odorization of fuel gases, characterized in that these mixtures consist of two different acrylic acid C 1 -C 6 -alkylestem and / or methacrylic acid-C 1 -C 6 -allcylestern and optionally one Antioxidant:
  • mixtures of methyl acrylate and ethyl acrylate advantageously contain the compounds in a ratio by weight of 2: 8-8: 2, preferably 3: 7-7: 3 and particularly preferably 6: 4-4: 6.
  • mixtures of methyl acrylate and n-butyl acrylate advantageously contain the compounds in a weight-related ratio of 8: 2-1: 9, preferably 6: 4-2: 8 and particularly preferably 6: 4-3: 7.
  • mixtures of ethyl acrylate and n-butyl acrylate are also preferred.
  • the mixtures advantageously contain the compounds in a weight-based ratio of 9: 1 to 1: 9, preferably 8: 2 to 4: 6 and particularly preferably 7: 3 to 6: 4.
  • the mixtures according to the invention with at least 3 and at most 6 different acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters may additionally contain further substances which are suitable for the odorization of fuel gases.
  • the odorization of natural or synthetic fuel gases or mixtures thereof can take place.
  • natural gas liquid natural gas (LNG), liquefied petroleum gas (LPG), city gas, heating gas, methane, ethane, ethene, propane, propene, Butane, isobutane, butene, pentane, or even fuel gases such as water gas, synthesis gas, generator gas or Kokereigas.
  • the odorants according to the invention are particularly suitable for the odorization of fuel gases containing methane, ethane, propane or butane, in particular for natural gas, town gas or liquefied petroleum gas.
  • the fuel gases may of course contain other compounds such as pentanes, hexanes or heptanes.
  • the odorant according to the invention can be added, for example, to increase the stability of common antioxidants.
  • examples include vitamin C and derivatives (eg ascorbyl palmitate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E, vitamin E acetate), vitamin A and derivatives (vitamin A - palmitate), phenolic benzylamines, formic acid, acetic acid, benzoic acid, sorbic acid, Hexamethylenetetramine, tert-butylhydroxytoluene, tert-butylhydroxyanisole, ⁇ -hydroxy acids (eg citric acid, lactic acid, malic acid), hydroquinone monomethyl ether.
  • Preferred antioxidants are tert-butylhydroxytoluene (Jonol, BHT), tert-butylhydroxyanisole, hydroquinone monomethyl ether and tocopherol.
  • the odorants contain one, two or three antioxidants, preferably one or two antioxidants.
  • the total amount of antioxidant based on the odorant is usually in the range 0.001-1 wt%, preferably in the range 0.01-0.5 wt%, particularly preferably in the range 0.05-0.25 wt%.
  • the weight-based amount of odorant based on the fuel gas to be odorized is typically in the range of 5-100 ppm (ppm: mg odorant per kg gas), preferably 5-50 ppm, more preferably 10-40 ppm and very particularly preferably 15-30 ppm or, in the case of gaseous combustion gases, typically in the range 5-100 mg / m 3 , preferably 5-50 mg / m 3 , more preferably 10 - 40 mg / m 3 and most preferably 15 - 30 mg / m 3 .
  • Me-Ac methyl acrylate; Et-Ac: ethyl acrylate; Bu-Ac: n-butyl acrylate; Me-Me: methyl methacrylate; Et-Me: ethyl methacrylate; Bu-Me: n-butyl methacrylate; BHT: tert-butylhydroxytoluene; BHA: tert-butylhydroxyanisole; Hydr: hydroquinone monomethyl ether
  • the odorants according to the invention were evaluated in concentrations of 10, 25 and 50 mg / m 3 natural gas (methane content: 85 wt.%) Odorally with respect to their warning smell and their warning intensity against unodorated natural gas (blank). These concentrations correspond to the typical concentrations of odorant in natural gas under normal conditions or shock odorization.
  • the experiment was carried out at room temperature (about 20 ° C) such that in a gas stream in a tube, the odorant is metered. At the end of this 2 m long tube (within the tube is the homogenization), the exiting odorized gas is evaluated by a group of trained examiners (8 to 12 people) odor. The rating was on a scale from 1 (very weak / very little warning) to 10 (very strong / very warning), the values given are mean values.
  • Table 1 shows the evaluation of pure esters. ⁇ b> ⁇ u> Table 1: ⁇ / u> ⁇ /b> Me-Ac Et-Ac Bu-Ac Me-Me Et-Me rating 100 - - - - 6 - 100 - - - 6.5 - - 100 - - 7 - - - 100 - 6.5 - - - - 100 6.5
  • Table 2 shows the evaluations for mixtures according to the invention, the procedure was carried out as described in Example 1.
  • Table 3 shows odorants according to the invention containing antioxidants.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

Odorizing fuel gases with a methane content of at least 60 wt.% comprises adding a mixture of two to six C1-C6 alkyl (meth)acrylate esters and optionally an antioxidant. An Independent claim is also included for a fuel gas with a methane content of at least 60 wt.% containing such a mixture.

Description

Die vorliegende Erfindung betrifft die Verwendung von Mischungen von Acrylsäure-C1-C6-alkylestem und/oder Methacrylsäure-C1-C6-alkylestern zur Odorierung von Brenngasen, ein Verfahren zur Odorierung von Brenngasen und Brenngase enthaltend diese Mischungen.The present invention relates to the use of mixtures of acrylic acid C 1 -C 6 alkyl esters and / or methacrylic acid C 1 -C 6 alkyl esters for the odorization of fuel gases, a process for the odorization of fuel gases and fuel gases containing these mixtures.

Brenngase, die keinen ausreichenden Eigengeruch aufweisen, werden üblicherweise mit intensiv riechenden Verbindungen versetzt, d.h. odoriert, damit im Falle von Undichtigkeiten oder Leckagen diese leicht wahrgenommen werden können. Aus Sicherheitsgründen werden den Brenngasen sogenannte Odoriermittel zugesetzt, die auch in hoher Verdünnung noch wahrnehmbar sind und auf Grund ihres außergewöhnlich unangenehmen Geruchs eine Alarmassoziation beim Menschen hervorrufen.Fuel gases that do not have a sufficient inherent odor are usually mixed with intense-smelling compounds, i. Odoriert, so that in case of leaks or leaks they can be easily perceived. For safety reasons so-called odorants are added to the combustion gases, which are still perceptible even in high dilution and cause an alarm association in humans due to their exceptionally unpleasant odor.

Typischerweise werden als Odoriermittel Schwefelverbindungen eingesetzt. Häufige Verwendung finden Tetrahydrothiophen, tert.-Butylmercaptan, Dimethylsulfid oder auch Ethylmercaptan.Typically, sulfur compounds are used as odorants. Frequently used tetrahydrothiophene, tert-butyl mercaptan, dimethyl sulfide or ethylmercaptan.

Da eine Reduzierung oder Vermeidung von Schwefelverbindungen in Brenngasen, unter anderem aus ökologischen Gründen, angestrebt wird, wurden bereits Versuche unternommen, schwefelfreie Odoriermittel zu entwickeln.Since a reduction or avoidance of sulfur compounds in fuel gases, among other things for ecological reasons, is sought, attempts have already been made to develop sulfur-free odorants.

JP-B-51-007481 erwähnt, dass Acrylsäurealkylester wie Methylacrylat, Ethylacrylat und Butylacrylat bekanntermaßen schwache Odoriereigenschaften für Brenngase aufweisen und diesbezüglich praktisch keine Bedeutung haben. Das. Dokument beschreibt und beansprucht Allylacrylat als wirksame Odorierkomponente. JP-B-51-007481 mentions that acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and butyl acrylate are known to have weak odorant properties for fuel gases and have practically no significance in this respect. The. Document describes and claims allyl acrylate as an effective odorizing component.

In JP-A-55-104393 ist beschrieben, dass Odoriermittel enthaltend ein Alkin und mindestens 2 Verbindungen gewählt aus einer Gruppe, welche aus Methylacrylat, Ethylacrylat, Methylmethacrylat, Allylmethacrylat, Ethylpropionat, Methyl-n-butyrat, Methyl-iso-butyrat und Prenylacrylat besteht, sowie gegebenenfalls tert-Butylmercaptan, zur Odorierung von Brenngasen geeignet sind.In JP-A-55-104393 It is described that odorant containing an alkyne and at least 2 compounds selected from a group consisting of methyl acrylate, ethyl acrylate, Methyl methacrylate, allyl methacrylate, ethyl propionate, methyl n-butyrate, methyl isobutyrate and prenyl acrylate, and optionally tert-butylmercaptan, are suitable for the odorization of fuel gases.

In JP-B-51-034841 wurden "Odor-Schwellenwerte" diverser Stoffe ermittelt, wobei n-Valeriansäure, n-Buttersäure, Isobutyraldehyd und verschiedene Methylamine niedrige geruchliche "Odor-Schwellenwerte" aufwiesen. Trotzdem zeigte sich, dass Ethylacrylat oder n-Valeriansäure alleine eingesetzt, auf Grund ihrer geruchlichen Eigenschaften, nicht ausreichend odorierend wirken. Die optimierte Mischung umfasste Ethylacrylat, n-Valeriansäure und Triethylamin, wobei diese Mischung gleiche Gewichtsteile an n-Valeriansäure und Triethylamin sowie 30 bis 80 Gew.% Ethylacrylat enthielt.In JP-B-51-034841 "odor thresholds" of various substances were determined, with n-valeric acid, n-butyric acid, isobutyraldehyde and various methylamines having low odor odor thresholds. Nevertheless, it was found that ethyl acrylate or n-valeric acid used alone, because of their odor properties, not sufficiently odorizing act. The optimized mixture comprised ethyl acrylate, n-valeric acid and triethylamine, this mixture containing equal parts by weight of n-valeric acid and triethylamine and 30 to 80% by weight of ethyl acrylate.

In DE-A 19837066 wurde das Problem der schwefelfreien Gasodorierung mittels Mischungen enthaltend mindestens einen Acrylsäure-C1-C12-alkylester und eine Stickstoffverbindung mit einem Siedepunkt im Bereich 90 bis 210°C und einem Molekulargewicht von 80 bis 160 gelöst, wobei Mischungen enthaltend mindestens zwei verschiedene Acrylsäurealkylester, bevorzugt sind. Als besonders geeignete Stickstoffverbindungen werden alkylsubstituierte 1,4-Pyrazine beschrieben.In DE-A 19837066 the problem of sulfur-free gas odorization has been solved by means of mixtures containing at least one acrylic acid C 1 -C 12 -alkyl ester and a nitrogen compound having a boiling point in the range 90 to 210 ° C and a molecular weight of 80 to 160, mixtures containing at least two different alkyl acrylates, are preferred. Particularly suitable nitrogen compounds are described as being alkyl-substituted 1,4-pyrazines.

Es wurden alternative Odoriermittel zur Odorierung von Brenngasen gesucht, insbesondere solche, die weder S- noch N-haltige Verbindungen enthalten.Alternative odorants have been sought for the odorization of fuel gases, especially those containing neither S nor N-containing compounds.

Es wurde nun gefunden, dass Mischungen bestehend aus genau zwei oder enthaltend mindestens 3 verschiedenen Acrylsäure-C1-C6-alkylester und/oder Methacrytsäure-C1-C6-alkylester, wobei die Mischungen weder S- noch N-haltige Verbindungen enthalten, sich hervorragend zur Odorierung von Brenngasen eignen. Überraschenderweise wurde gefunden, dass diese Mischungen bei der Odorierung von Brenngasen synergistische Effekte zeigen, d.h. dass die Mischungen dieser Verbindungen eine stärkere Wirkung aufweisen, als die Summe der einzelnen Bestandteile erwarten lässt.It has now been found that mixtures consisting of exactly two or containing at least 3 different acrylic acid C 1 -C 6 alkyl esters and / or methacrylic acid C 1 -C 6 alkyl esters, wherein the mixtures contain neither S nor N-containing compounds , are ideal for the odorization of fuel gases. Surprisingly, it has been found that these mixtures exhibit synergistic effects in the odorization of fuel gases, ie that the mixtures of these compounds have a stronger effect than the sum of the individual constituents would suggest.

Gegenstand der vorliegenden Erfindung ist die Verwendung von Mischungen enthaltend Acrylsäure-C1-C6-alkylester und/oder Methacrylsäure-C1-C6-allcylester zur Odorierung von Brenngasen, dadurch gekennzeichnet, dass diese Mischungen mindestens 3 und höchstens 6 verschiede Acrylsaure-C1-C6-alkylester und/oder Methacrylsäure-C1-C6-allcylester enthalten, sowie gegebenenfalls ein Antioxidans.The present invention is the use of mixtures comprising acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters for the odorization of fuel gases, characterized in that these mixtures at least 3 and at most 6 different acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters, and optionally an antioxidant.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Odorierung von Brenngasen mit den erfindungsgemäßen Mischungen sowie Brenngase enthaltend die erfindungsgemäßen Mischungen.Another object of the present invention is a method for the odorization of fuel gases with the mixtures according to the invention and fuel gases containing the mixtures according to the invention.

Die Acrylsäure-C1-C6-alkylester werden vorteilhaft gewählt aus der Gruppe umfassend Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-propylester, Acrylsäure-iso-propylester, Acrylsäure-n-butylester, Acrylsäure-iso-butylester, Acrylsäure-tert-butylester, Acrylsäure-n-pentylester, Acrylsäure-iso-pentylester und Acrylsäure-n-hexylester.The acrylic acid C 1 -C 6 -alkyl esters are advantageously selected from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate , N-pentyl acrylate, iso-pentyl acrylate and n-hexyl acrylate.

Bevorzugt sind Acrylsäure-C1-C4-alkylester, insbesondere Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-propylester, Acrylsäure-iso-propylester, Acrylsäure-n-butylester und Acrylsäure-iso-butylester. Ganz besonders bevorzugte Acrylsäure-C1-C4-alkylester sind Acrylsäuremethylester, Acrylsäureethylester und Acrylsäure-n-butylester.Preference is given to acrylic acid C 1 -C 4 -alkyl esters, in particular methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate and iso-butyl acrylate. Very particularly preferred acrylic acid C 1 -C 4 -alkyl esters are methyl acrylate, ethyl acrylate and n-butyl acrylate.

Die Methacrylsäure-C1-C6-alkylester werden vorteilhaft gewählt aus der Gruppe umfassend Methacrylsäuremethylester, Methacrylsäureethylester, Methacrylsäure-n-propylester, Methacrylsäure-iso-propylester, Methacrylsäure-n-butylester, Methacrylsäure-iso-butylester, Methacrylsäure-tert.-butylester, Methacrylsäure-n-pentylester, Methacrylsäure-iso-pentylester und Methacrylsäure-n-hexylester.The methacrylic acid-C 1 -C 6 -alkyl esters are advantageously selected from the group comprising methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, methacrylic acid tert. butyl ester, n-pentyl methacrylate, iso-pentyl methacrylate and n-hexyl methacrylate.

Bevorzugt sind Methacrylsäure-C1-C4-alkylester, insbesondere Methacrylsäuremethylester, Methacrylsäureethylester, Methacrylsäure-n-propylester, Methacrylsäure-iso-propylester, Methacrylsäure-n-butylester und Methacrylsäure-iso-butyl-Gegenstand der vorliegenden Erfindung ist die Verwendung von Mischungen enthaltend Acrylsäure-C1-C6-alkylester und/oder Methacrylsäure-C1-C6-alkylester zur Odorierung von Brenngasen, dadurch gekennzeichnet, dass diese Mischungen mindestens 3 und höchstens 6 verschiedenen Acrylsäure-C1-C6-alkylester und/oder Methacrylsäure-C1-C6-alkylester enthalten, sowie gegebenenfalls ein Antioxidans.Preference is given to methacrylic acid-C 1 -C 4 -alkyl esters, in particular methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate The present invention is the use of mixtures comprising acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters for the odorization of fuel gases, characterized in that these mixtures at least 3 and at most 6 different acrylic acid-C 1 -C 6 alkyl esters and / or methacrylic acid-C 1 -C 6 alkyl esters, and optionally an antioxidant.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Odorierung von Brenngasen mit den erfindungsgemäßen Mischungen sowie Brenngase enthaltend die erfindungsgemäßen Mischungen.Another object of the present invention is a method for the odorization of fuel gases with the mixtures according to the invention and fuel gases containing the mixtures according to the invention.

Die Acrylsäure-C1-C6-alkylester werden vorteilhaft gewählt aus der Gruppe umfassend Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-propylester, Acrylsäure-iso-propylester, Acrylsäure-n-butylester, Acrylsäure-iso-butylester, Acrylsäure-tert.-butylester, Acrylsäure-n-pentylester, Acrylsäure-iso-pentylester und Acrylsäure-n-hexylester.The acrylic acid C 1 -C 6 -alkyl esters are advantageously selected from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, acrylic acid tert. butyl ester, n-pentyl acrylate, iso-pentyl acrylate and n-hexyl acrylate.

Bevorzugt sind Acrylsäure-C1-C4-alkylester, insbesondere Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-propylester, Acrylsäure-iso-propylester, Acrylsäure-n-butylester und Acrylsäure-iso-butylester. Ganz besonders bevorzugte Acrylsäure-C1-C4-alkylester sind Acrylsäuremethylester, Acrylsäureethylester und Acrylsäure-n-butylester.Preference is given to acrylic acid C 1 -C 4 -alkyl esters, in particular methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate and iso-butyl acrylate. Very particularly preferred acrylic acid C 1 -C 4 -alkyl esters are methyl acrylate, ethyl acrylate and n-butyl acrylate.

Die Methacrylsäure-C1-C6-alkylester werden vorteilhaft gewählt aus der Gruppe umfassend Methacrylsäuremethylester, Methacrylsäureethylester, Methacrylsäure-n-propylester, Methacrylsäure-iso-propylester, Methacrylsäure-n-butylester, Methacrylsäure-iso-butylester, Methacrylsäure-tert.-butylester, Methacrylsäure-n-pentylester, Methacrylsäure-iso-pentylester und Methacrylsäure-n-hexylester.The methacrylic acid-C 1 -C 6 -alkyl esters are advantageously selected from the group comprising methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, methacrylic acid tert. butyl ester, n-pentyl methacrylate, iso-pentyl methacrylate and n-hexyl methacrylate.

Bevorzugt sind Methacrylsäure-C1-C4-alkylester, insbesondere Methacrylsäuremethylester, Methacrylsäureethylester, Methacrylsäure-n-propylester, Methacrylsäure-iso-propylester, Methacrylsäure-n-butylester und Methacrylsäure-iso-butylester. Ganz besonders bevorzugte Methacrylsäure-C1-C4-allcylester sind Methacrylsäuremethylester und Methacrylsäureethylester.Preference is given to methacrylic acid-C 1 -C 4 -alkyl esters, in particular methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and iso-butyl methacrylate. Very particularly preferred C 1 -C 4 -alkyl methacrylates are methyl methacrylate and ethyl methacrylate.

Besonders geeignete Mischungen enthalten mindestens einen Ester aus der Gruppe umfassend Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-propylester, Acrylsäure-iso-propylester, Acrylsäure-n-butylester, Acrylsäure-iso-butylester, Acrylsäure-n-pentylester, Acrylsäure-iso-pentylester, Methacrylsäuremethylester und Methacrylsäureethylester, bevorzugte Mischungen mindestens einen Ester aus der Gruppe umfassend Acrylsäuremethylester, Acrylsäureethylester und Acrylsäure-n-butylester.Particularly suitable mixtures contain at least one ester from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, n-pentyl acrylate, isopropyl acrylate Methyl methacrylate and ethyl methacrylate, preferred mixtures at least one ester from the group comprising methyl acrylate, ethyl acrylate and n-butyl acrylate.

Bevorzugt sind Mischungen enthaltend mindestens zwei Ester aus der Gruppe umfassend Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-propylester, Acrylsäure-iso-propylester, Acrylsäure-n-butylester, Acrylsäure-iso-butylester, Acrylsäure-n-pentylester und Acrylsäure-iso-pentylester, bevorzugt mindestens zwei Ester aus der Gruppe umfassend Acrylsäuremethylester, Acrylsäureethylester und Acrylsäure-n-butylester.Preference is given to mixtures comprising at least two esters from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate and isopropyl acrylate preferably at least two esters from the group comprising methyl acrylate, ethyl acrylate and n-butyl acrylate.

Besonders bevorzugt sind Mischungen enthaltend Acrylsäuremethylester und Acrylsäureethylester.Particular preference is given to mixtures comprising methyl acrylate and ethyl acrylate.

Ebenfalls besonders bevorzugt sind Mischungen enthaltend Acrylsäuremethylester und Acrylsäure-n-butylester.Likewise particularly preferred are mixtures comprising methyl acrylate and n-butyl acrylate.

Weiterhin besonders bevorzugt sind Mischungen enthaltend Acrylsäureethylester und Acrylsäure-n-butylester.Also particularly preferred are mixtures comprising ethyl acrylate and n-butyl acrylate.

Eine besonders bevorzugte Ausführungsform betrifft Mischungen enthaltend Acrylsäuremethylester, Acrylsäureethylester und einen Ester gewählt aus Acrylsäure-n-butylester, Methacrylsäuremethylester und Methacrylsäureethylester.A particularly preferred embodiment relates to mixtures comprising methyl acrylate, ethyl acrylate and an ester selected from n-butyl acrylate, methyl methacrylate and ethyl methacrylate.

Die Mischungen enthalten die Verbindungen bevorzugt im gewichtsbezogenen Verhältnis 1-4 : 2-8 : 1-4.The mixtures contain the compounds preferably in the weight ratio 1-4: 2-8: 1-4.

Weiterhin bevorzugt sind Mischungen, die die genannten Ester im gewichtsbezogenen Verhältnis 1-2 : 1-2 : 6-8 enthalten.Preference is furthermore given to mixtures which contain the stated esters in the weight-based ratio 1-2: 1-2: 6-8.

In einer weiteren bevorzugten Ausführungsform werden Mischungen enthaltend mindestens 4 und höchstens 6 verschiedene Acrylsäure-C1-C6-alkylester und/oder Methacrylsäure-C1-C6-alkylester eingesetzt, wobei Mischungen bevorzugt sind, die mindestens zwei Verbindungen enthalten gewählt aus Acrylsäuremethylester, Acrylsäureethylester oder Acrylsäure-n-butylester. Besonders bevorzugt sind Mischungen, die Acrylsäuremethylester, Acrylsäureethylester und Acrylsäure-n-butylester enthalten.In a further preferred embodiment, mixtures containing at least 4 and at most 6 different acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters are used, with mixtures being preferred which contain at least two compounds selected from methyl acrylate , Acrylic acid ethyl ester or n-butyl acrylate. Particularly preferred are mixtures containing methyl acrylate, ethyl acrylate and n-butyl acrylate.

Ein weiterer Gegenstand der vorliegenden Erfindung betrifft die Verwendung von Mischungen zur Odorierung von Brenngasen, dadurch gekennzeichnet, dass diese Mischungen bestehen aus zwei verschiedenen Acrylsäure-C1-C6-alkylestem und/oder Methacrylsäure-C1-C6-allcylestern sowie gegebenenfalls einem Antioxidans:Another object of the present invention relates to the use of mixtures for the odorization of fuel gases, characterized in that these mixtures consist of two different acrylic acid C 1 -C 6 -alkylestem and / or methacrylic acid-C 1 -C 6 -allcylestern and optionally one Antioxidant:

Bevorzugt sind Mischungen bestehend aus Acrylsäuremethylester, Acrylsäureethylester oder Acrylsäure-n-butylester und einem anderen Acrylsäure-C1-C6-alkylester und/oder Methacrylsäure-C1-C6-alkylester sowie gegebenenfalls einem Antioxidans.Preference is given to mixtures consisting of methyl acrylate, ethyl acrylate or n-butyl acrylate and another C 1 -C 6 -alkyl acrylate and / or C 1 -C 6 -alkyl methacrylate and optionally an antioxidant.

Bevorzugt sind Mischungen bestehend aus Acrylsäuremethylester, Acrylsäureethylester oder Acrylsäure-n-butylester und einem anderen Acrylsäure-C1-C6-alkylester und/oder Methacrylsäure-C1-C6-alkylester aus der Gruppe umfassend Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-propylester, Acrylsäure-iso-propylester, Acrylsäure-n-butylester, Acrylsäure-iso-butylester, Acrylsäure-tert.-butylester, Acrylsäure-n-pentylester, Acrylsäure-iso-pentylester, Acrylsäure-n-hexylester, Methacrylsäuremethylester, Methacrylsäureethylester, Methacrylsäure-n-propylester, Methacrylsäure-iso-propylester, Methacrylsäure-n-butylester und Methacrylsäure-iso-butylester.Preference is given to mixtures consisting of methyl acrylate, ethyl acrylate or n-butyl acrylate and another C 1 -C 6 -alkyl acrylate and / or C 1 -C 6 -alkyl methacrylate from the group comprising methyl acrylate, ethyl acrylate, acrylic acid n-butyl propyl ester, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, iso-pentyl acrylate, n-hexyl acrylate, methyl methacrylate, methacrylic acid, methacrylic acid -n-propyl Methacrylic acid iso-propyl ester, methacrylic acid n-butyl ester and methacrylic acid iso-butyl ester.

Bevorzugt sind Mischungen aus Acrylsäuremethylester und Acrylsäureethylester. Die Mischungen enthalten die Verbindungen vorteilhafterweise im gewichtsbezogenen Verhältnis 2:8-8:2, bevorzugt 3:7-7:3 und besonders bevorzugt 6:4-4:6.Preference is given to mixtures of methyl acrylate and ethyl acrylate. The mixtures advantageously contain the compounds in a ratio by weight of 2: 8-8: 2, preferably 3: 7-7: 3 and particularly preferably 6: 4-4: 6.

Weiterhin bevorzugt sind Mischungen aus Acrylsäuremethylester und Acrylsäure-n-butylester. Die Mischungen enthalten die Verbindungen vorteilhafterweise im gewichtsbezogenen Verhältnis 8:2-1:9, bevorzugt 6 : 4 - 2 : 8 und besonders bevorzugt 6:4-3:7.Further preferred are mixtures of methyl acrylate and n-butyl acrylate. The mixtures advantageously contain the compounds in a weight-related ratio of 8: 2-1: 9, preferably 6: 4-2: 8 and particularly preferably 6: 4-3: 7.

Ebenfalls bevorzugt sind Mischungen aus Acrylsäureethylester und Acrylsäure-n-butylester. Die Mischungen enthalten die Verbindungen vorteilhafterweise im gewichtsbezogenen Verhältnis 9 : 1 - 1 : 9, bevorzugt 8 : 2 - 4 : 6 und besonders bevorzugt 7 : 3 - 6 : 4.Also preferred are mixtures of ethyl acrylate and n-butyl acrylate. The mixtures advantageously contain the compounds in a weight-based ratio of 9: 1 to 1: 9, preferably 8: 2 to 4: 6 and particularly preferably 7: 3 to 6: 4.

Es ist insbesondere überraschend, dass Mischungen bestehend aus den oben genannten Acrylsäure-C1-C6-alkylestern, d.h. Mischungen von verschiedenen Acrylsäurealkylestern ohne den Zusatz weiterer Odoriennittel, eine gute Alarmwirkung aufweisen.It is particularly surprising that mixtures consisting of the above-mentioned acrylic acid C 1 -C 6 -alkyl esters, ie mixtures of different alkyl acrylates without the addition of further Odoriennittel, have a good alarm effect.

Selbstverständlich können die erfindungsgemäßen Mischungen mit mindestens 3 und höchstens 6 verschiedenen Acrylsäure-C1-C6-alkylestern und/oder Methacrylsäure-C1-C6-alkylestern zusätzlich weitere Stoffe enthalten, die zur Odorierung von Brenngasen geeignet sind.Of course, the mixtures according to the invention with at least 3 and at most 6 different acrylic acid C 1 -C 6 -alkyl esters and / or methacrylic acid-C 1 -C 6 -alkyl esters may additionally contain further substances which are suitable for the odorization of fuel gases.

Mit den erfindungsgemäßen Mischungen kann die Odorierung von natürlichen oder synthetischen Brenngasen oder von Gemischen davon erfolgen. Es seien beispielsweise genannt: Erdgas, LNG (Liquid Natural Gas), Flüssiggas (LPG: Liquefied Petroleum Gas), Stadtgas, Heizgas, Methan, Ethan, Ethen, Propan, Propen, Butan, Isobutan, Buten, Pentan, oder auch Brenngase wie Wassergas, Synthesegas, Generatorgas oder Kokereigas.With the mixtures according to the invention the odorization of natural or synthetic fuel gases or mixtures thereof can take place. Examples include: natural gas, liquid natural gas (LNG), liquefied petroleum gas (LPG), city gas, heating gas, methane, ethane, ethene, propane, propene, Butane, isobutane, butene, pentane, or even fuel gases such as water gas, synthesis gas, generator gas or Kokereigas.

Die erfindungsgemäßen Odoriermittel eignen sich besonders für die Odorierung von Brenngasen, die Methan, Ethan, Propan oder Butan enthalten, insbesondere für Erdgas, Stadtgas oder Flüssiggas.The odorants according to the invention are particularly suitable for the odorization of fuel gases containing methane, ethane, propane or butane, in particular for natural gas, town gas or liquefied petroleum gas.

Die Brenngase können selbstverständlich weitere Verbindungen wie beispielsweise Pentane, Hexane oder Heptane enthalten.The fuel gases may of course contain other compounds such as pentanes, hexanes or heptanes.

Dem erfindungsgemäßen Odoriermittel können beispielsweise zur Stabilitätserhöhung gängige Antioxidantien zugesetzt werden. Beispielhaft sollen genannt werden Vitamin C und Derivate (z.B. Ascorbylpalmitat, Ascorbylacetat), Tocopherole und Derivate (z.B. Vitamin E, Vitamin E - acetat), Vitamin A und Derivate (Vitamin A - palmitat) phenolische Benzylamine, Ameisensäure, Essigsäure, Benzoesäure, Sorbinsäure, Hexamethylentetramin, tert.-Butylhydroxytoluol, tert.-Butylhydroxyanisol, α-Hydroxysäuren (z.B. Zitronensäure, Milchsäure, Apfelsäure), Hydrochinonmonomethylether. Bevorzugte Antioxidantien sind tert.-Butylhydroxytoluol (Jonol, BHT), tert.-Butylhydroxyanisol, Hydrochinonmonomethylether und Tocopherol.The odorant according to the invention can be added, for example, to increase the stability of common antioxidants. Examples include vitamin C and derivatives (eg ascorbyl palmitate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E, vitamin E acetate), vitamin A and derivatives (vitamin A - palmitate), phenolic benzylamines, formic acid, acetic acid, benzoic acid, sorbic acid, Hexamethylenetetramine, tert-butylhydroxytoluene, tert-butylhydroxyanisole, α-hydroxy acids (eg citric acid, lactic acid, malic acid), hydroquinone monomethyl ether. Preferred antioxidants are tert-butylhydroxytoluene (Jonol, BHT), tert-butylhydroxyanisole, hydroquinone monomethyl ether and tocopherol.

Es können dem erfindungsgemäßen Odoriermittel auch mehrere Antioxidantien zugesetzt werden. Vorteilhafterweise enthalten die Odoriermittel ein, zwei oder drei Antioxidantien, bevorzugt sind ein oder zwei Antioxidantien. Die Gesamtmenge an Antioxidans bezogen auf das Odoriermittel liegt üblicherweise im Bereich 0,001 - 1 Gew.%, bevorzugt im Bereich 0,01 - 0,5 Gew.%, besonders bevorzugt im Bereich 0,05 - 0,25 Gew.%.It is also possible to add a plurality of antioxidants to the odorant according to the invention. Advantageously, the odorants contain one, two or three antioxidants, preferably one or two antioxidants. The total amount of antioxidant based on the odorant is usually in the range 0.001-1 wt%, preferably in the range 0.01-0.5 wt%, particularly preferably in the range 0.05-0.25 wt%.

Die gewichtsbezogene Menge an Odoriermittel bezogen auf das zu odorierende Brenngas liegt bei flüssig vorliegenden Gasen typischerweise im Bereich 5 - 100 ppm (ppm: mg Odoriermittel pro kg Gas), bevorzugt 5 - 50 ppm, besonders bevorzugt 10-40 ppm und ganz besonders bevorzugt 15-30 ppm bzw. bei gasförmig vorliegenden Brenngasen typischerweise im Bereich 5-100 mg/m3, bevorzugt 5-50 mg/m3, besonders bevorzugt 10 - 40 mg/m3 und ganz besonders bevorzugt 15 - 30 mg/m3.The weight-based amount of odorant based on the fuel gas to be odorized is typically in the range of 5-100 ppm (ppm: mg odorant per kg gas), preferably 5-50 ppm, more preferably 10-40 ppm and very particularly preferably 15-30 ppm or, in the case of gaseous combustion gases, typically in the range 5-100 mg / m 3 , preferably 5-50 mg / m 3 , more preferably 10 - 40 mg / m 3 and most preferably 15 - 30 mg / m 3 .

Die folgenden Beispiele erläutern die Erfindung:The following examples illustrate the invention:

Sofern nicht anders angegeben beziehen sich alle Angaben auf Gewichtsanteile.Unless otherwise indicated, all figures are by weight.

Verwendete Abkürzungen:Used abbreviations:

Me-Ac: Methylacrylat; Et-Ac: Ethylacrylat; Bu-Ac: n-Butylacrylat; Me-Me: Methylmethacrylat; Et-Me: Ethylmethacrylat; Bu-Me: n-Butylmethacrylat; BHT: tert.-Butylhydroxytoluol; BHA: tert.-Butylhydroxyanisol; Hydr: HydrochinonmonomethyletherMe-Ac: methyl acrylate; Et-Ac: ethyl acrylate; Bu-Ac: n-butyl acrylate; Me-Me: methyl methacrylate; Et-Me: ethyl methacrylate; Bu-Me: n-butyl methacrylate; BHT: tert-butylhydroxytoluene; BHA: tert-butylhydroxyanisole; Hydr: hydroquinone monomethyl ether

Beispiel 1example 1

Die erfindungsgemäßen Odoriermittel wurden in Konzentrationen von 10, 25 und 50 mg/m3 Erdgas (Methan-Gehalt: 85 Gew.%) geruchlich bezüglich ihres Warngeruchs und ihrer Warnintensität gegen unodoriertes Erdgas (Blindwert) bewertet. Diese Konzentrationen entsprechen den typischen Konzentrationen an Odoriermittel im Erdgas bei üblichen Bedingungen bzw. bei Stoßodorierung.The odorants according to the invention were evaluated in concentrations of 10, 25 and 50 mg / m 3 natural gas (methane content: 85 wt.%) Odorally with respect to their warning smell and their warning intensity against unodorated natural gas (blank). These concentrations correspond to the typical concentrations of odorant in natural gas under normal conditions or shock odorization.

Die Versuchsdurchführung erfolgte bei Raumtemperatur (etwa 20°C) derart, dass in einen Gasstrom in einem Rohr das Odoriermittel eindosiert wird. Am Ende dieses 2 m langen Rohres (innerhalb des Rohres erfolgt die Homogenisierung) wird das austretende odorierte Gas von einer Gruppe geschulter Prüfer (8 bis 12 Personen) geruchlich bewertet. Die Bewertung erfolgte auf einer Skala von 1 (sehr schwach / sehr wenig warnend) bis 10 (sehr stark / sehr warnend), die angegebenen Werte sind Mittelwerte.The experiment was carried out at room temperature (about 20 ° C) such that in a gas stream in a tube, the odorant is metered. At the end of this 2 m long tube (within the tube is the homogenization), the exiting odorized gas is evaluated by a group of trained examiners (8 to 12 people) odor. The rating was on a scale from 1 (very weak / very little warning) to 10 (very strong / very warning), the values given are mean values.

Die Ergebnisse waren für die 3 untersuchten Konzentrationen (10, 25 und 50 mg / m3 Gas) weitgehend gleich. Tabelle 1 zeigt die Bewertung der reinen Ester. Tabelle 1: Me-Ac Et-Ac Bu-Ac Me-Me Et-Me Bewertung 100 - - - - 6 - 100 - - - 6,5 - - 100 - - 7 - - - 100 - 6,5 - - - - 100 6,5 The results were largely the same for the 3 concentrations tested (10, 25 and 50 mg / m 3 gas). Table 1 shows the evaluation of pure esters. <b><u> Table 1: </ u></b> Me-Ac Et-Ac Bu-Ac Me-Me Et-Me rating 100 - - - - 6 - 100 - - - 6.5 - - 100 - - 7 - - - 100 - 6.5 - - - - 100 6.5

Beispiel 2Example 2

Tabelle 2 zeigt die Bewertungen für Mischungen im Sinne der Erfindung, die Durchführung erfolgte wie in Beispiel 1 beschrieben. Tabelle 2: Me-Ac Et-Ac Bu-Ac Me-Me Et-Me Bewertung 40 60 - - - 8,5 60 40 - - - 8 50 - 50 - - 8,5 30 - 70 - - 8,5 - 60 40 - - 8,5 - 80 20 - - 8 30 40 30 - - 8 10 10 80 - - 8 10 80 10 - - 8 40 20 40 - - 8 40 40 - 20 - 8,5 30 - 20 50 - 8 - 30 - 30 40 7,5 - - 25 50 25 7,5 20 20 10 30 20 7,5 40 50 - 10 - 8,5 Table 2 shows the evaluations for mixtures according to the invention, the procedure was carried out as described in Example 1. <b><u> Table 2: </ u></b> Me-Ac Et-Ac Bu-Ac Me-Me Et-Me rating 40 60 - - - 8.5 60 40 - - - 8th 50 - 50 - - 8.5 30 - 70 - - 8.5 - 60 40 - - 8.5 - 80 20 - - 8th 30 40 30 - - 8th 10 10 80 - - 8th 10 80 10 - - 8th 40 20 40 - - 8th 40 40 - 20 - 8.5 30 - 20 50 - 8th - 30 - 30 40 7.5 - - 25 50 25 7.5 20 20 10 30 20 7.5 40 50 - 10 - 8.5

Beispiel 3Example 3

Tabelle 3 zeigt erfindungsgemäße Odoriermittel enthaltend Antioxidantien. Tabelle 3: Me-Ac Et-Ac Bu-Ac Me-Me Me-Et BHT BHA Hydr 40 59,9 - - - 0,1 - - 49,9 - 50 - - - - 0,1 - 59,9 40 - - - 0,1 - 30 39,8 30 - - - 0,1 0,1 10 10 79,9 - - - 0,1 - 39,9 40 - 20 - 0,1 - - 30 - 20 49,9 - - 0,1 - - 30 - 30 39,9 0,1 - - - - 25 49,8 25 - - 0,2 20 20 10 29,9 20 0,1 - - 40 49,8 - 10 - 0,1 0,1 - 30 - 39,9 20 10 0,1 - - 10 79,9 10 - - 0,1 - - - - 25 49,9 25 - 0,1 - 20 20 10 29,9 20 - - 0,1 Table 3 shows odorants according to the invention containing antioxidants. <b><u> Table 3: </ u></b> Me-Ac Et-Ac Bu-Ac Me-Me Me Et BHT BHA Hydraulic 40 59.9 - - - 0.1 - - 49.9 - 50 - - - - 0.1 - 59.9 40 - - - 0.1 - 30 39.8 30 - - - 0.1 0.1 10 10 79.9 - - - 0.1 - 39.9 40 - 20 - 0.1 - - 30 - 20 49.9 - - 0.1 - - 30 - 30 39.9 0.1 - - - - 25 49.8 25 - - 0.2 20 20 10 29.9 20 0.1 - - 40 49.8 - 10 - 0.1 0.1 - 30 - 39.9 20 10 0.1 - - 10 79.9 10 - - 0.1 - - - - 25 49.9 25 - 0.1 - 20 20 10 29.9 20 - - 0.1

Claims (18)

  1. Use of mixtures for odorising fuel gases, characterised in that these mixtures consist of two different acrylic acid C1-C6 alkyl esters and/or methacrylic acid C1-C6 alkyl esters and optionally an antioxidant.
  2. Use of mixtures containing acrylic acid C1-C6 alkyl esters and/or methacrylic acid C1-C6 alkyl esters for odorising fuel gases, characterised in that these mixtures contain at least three and at most six different acrylic acid C1-C6 alkyl esters and/or methacrylic acid C1-C6 alkyl esters and optionally an antioxidant, and in that they contain neither S-containing compounds nor N-containing compounds.
  3. Use according to either claim 1 or claim 2, characterised in that the methacrylic acid C1-C6 alkyl esters are selected from the group comprising methacrylic acid methyl esters, methacrylic acid ethyl esters, methacrylic acid-n-propyl esters, methacrylic acid-iso-propyl esters, methacrylic acid-n-butyl esters, methacrylic acid-iso-butyl esters, methacrylic acid-tert-butyl esters, methacrylic acid-n-pentyl esters, methacrylic acid-iso-pentyl esters and methacrylic acid-n-hexyl esters.
  4. Use according to at least one of claims 1 to 3, characterised in that the acrylic acid C1-C6 alkyl esters are selected from the group comprising acrylic acid methyl esters, acrylic acid ethyl esters, acrylic acid-n-propyl esters, acrylic acid-iso-propyl esters, acrylic acid-n-butyl esters, acrylic acid-iso-butyl esters, acrylic acid-tert-butyl esters, acrylic acid-n-pentyl esters, acrylic acid-iso-pentyl esters and acrylic acid-n-hexyl esters.
  5. Use according to at least one of claims 1 to 4, characterised in that the mixtures contain at least one ester from the group of acrylic acid methyl ester, acrylic acid ethyl ester and acrylic acid-n-butyl ester.
  6. Use according to at least one of claims 2 to 5, characterised in that the mixtures contain at least two esters from the group of acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid-n-propyl ester, acrylic acid-iso-propyl ester, acrylic acid-n-butyl ester, acrylic acid-iso-butyl ester, acrylic acid-n-pentyl ester and acrylic acid-iso-pentyl ester.
  7. Use according to at least one of claims 2 to 6, characterised in that the mixtures contain acrylic acid methyl ester, acrylic acid ethyl ester and an ester selected from acrylic acid-n-butyl ester, methacrylic acid methyl ester and methacrylic acid ethyl ester.
  8. Use according to claim 7, characterised in that the mixtures contain the esters in the ratio by weight of 1-4 : 2-8 : 1-4.
  9. Use according to claim 7, characterised in that the mixtures contain the esters in the ratio by weight of 1-2 : 1-2 : 6-8.
  10. Use according to claim 1, characterised in that the mixture contains acrylic acid methyl ester and acrylic acid ethyl ester in the ratio by weight of 2:8 - 8:2.
  11. Use according to claim 1, characterised in that the mixture contains acrylic acid methyl ester and acrylic acid-n-butyl ester in the ratio by weight of 8 : 2 - 1 : 9.
  12. Use according to claim 1, characterised in that the mixture contains acrylic acid ethyl ester and acrylic acid-n-butyl ester in the ratio by weight of 9 : 1 - 1 : 9.
  13. Use according to at least one of claims 1 to 12, characterised in that the mixtures are added to the fuel gas in a quantity by weight of from 5 to 100 mg/kg in the case of liquid fuel gases and mg/m3 in the case of gaseous fuel gases.
  14. Fuel gas containing a mixture for odorising, as defined in claim 2, and at least three and at most six different acrylic acid C1-C6 alkyl esters and/or methacrylic acid C1-C6 alkyl esters and optionally an antioxidant.
  15. Fuel gas containing as an odorising means a mixture, which consists of two different acrylic acid C1-C6 alkyl esters and/or methacrylic acid C1-C6 alkyl esters and optionally an antioxidant.
  16. Fuel gas according to either claim 14 or claim 15, characterised in that the fuel gas is natural gas, town gas or liquid gas.
  17. Process for odorising fuel gas, characterised in that a mixture consisting of two different acrylic acid C1-C6 alkyl esters and/or methacrylic acid C1-C6 alkyl esters and optionally an antioxidant is added to the fuel gas.
  18. Process for odorising fuel gas, characterised in that a mixture containing neither S-containing compounds nor N-containing compounds and at least three and at most six different acrylic acid C1-C6 alkyl esters and/or methacrylic acid C1-C6 alkyl esters and optionally an antioxidant is added to the fuel gas.
EP03784159A 2002-08-05 2003-08-02 Esters for odorising combustible gases Expired - Lifetime EP1529091B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10235753A DE10235753A1 (en) 2002-08-05 2002-08-05 Odorizing methane-rich fuel gases, especially natural gas, comprises adding a mixture of two to six alkyl (meth)acrylate esters
DE10235753 2002-08-05
PCT/EP2003/008592 WO2004015036A1 (en) 2002-08-05 2003-08-02 Esters for odorising combustible gases

Publications (2)

Publication Number Publication Date
EP1529091A1 EP1529091A1 (en) 2005-05-11
EP1529091B1 true EP1529091B1 (en) 2008-02-20

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Publication number Priority date Publication date Assignee Title
CN113956904A (en) * 2021-11-25 2022-01-21 沈阳光正工业有限公司 Sulfur-free odor additive for combustible gas and preparation method thereof

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US9717815B2 (en) 2014-07-30 2017-08-01 Georgia-Pacific Consumer Products Lp Air freshener dispensers, cartridges therefor, systems, and methods

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JPS55104393A (en) * 1979-02-02 1980-08-09 Nippon Zeon Co Ltd Fuel gas odorant
US4487613A (en) * 1983-09-26 1984-12-11 International Flavors & Fragrances Inc. Odorization of combustible hydrocarbon gases
DE19837066A1 (en) * 1998-08-17 2000-02-24 Haarmann & Reimer Gmbh Odorizing a gas, e.g. city gas comprises adding an acrylic acid, nitrogen compound and antioxidant to the gas

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113956904A (en) * 2021-11-25 2022-01-21 沈阳光正工业有限公司 Sulfur-free odor additive for combustible gas and preparation method thereof

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WO2004015036A1 (en) 2004-02-19
EP1529091A1 (en) 2005-05-11
AU2003253377A1 (en) 2004-02-25
ATE386791T1 (en) 2008-03-15
DE50309212D1 (en) 2008-04-03
DE10235753A1 (en) 2004-02-19

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