EP1529093B1 - Odorisation du gaz avec des phenols et/ou des ethers de phenol - Google Patents

Odorisation du gaz avec des phenols et/ou des ethers de phenol Download PDF

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Publication number
EP1529093B1
EP1529093B1 EP03784163A EP03784163A EP1529093B1 EP 1529093 B1 EP1529093 B1 EP 1529093B1 EP 03784163 A EP03784163 A EP 03784163A EP 03784163 A EP03784163 A EP 03784163A EP 1529093 B1 EP1529093 B1 EP 1529093B1
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Prior art keywords
ester
carbon atoms
alkyl
acrylic acid
methyl
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EP03784163A
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German (de)
English (en)
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EP1529093A1 (fr
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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Symrise AG
Ruhrgas AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 containing alkyl acrylates and / or alkyl methacrylates and phenols and / or phenol ethers for the odorization of natural gas, a process for the odorization of natural gas and natural gas containing these mixtures.
  • the city and coke oven gas previously used for public gas supply contained intensely smelling components and therefore had a strong odor, so that escaping gas could be easily perceived.
  • Gas odorization means the addition of odor-intensive substances acting as warning or alarm substances (odorizing agents) to otherwise odorless gases.
  • Natural gas consists mainly of methane (typical methane contents are in the range 50 to 99 wt.%, Usually in the range 60 to 90 wt.%) And, depending on the origin, besides different proportions of ethane, propane and higher molecular weight hydrocarbons included.
  • gas is therefore odorized by the addition of odorous substances.
  • DVGW German Association of Gas and Water.
  • TFT tetrahydrothiophene
  • mercaptans or thioethers is also common.
  • shock odorization up to three times the amount of odorant is added to the gas as compared to conventional odorization.
  • the shock odorization is used, for example, when commissioning new networks or line sections for faster achievement of minimum odorant concentration or to detect small leaks in the gas installation.
  • THT and mercaptans are ideal for reliable odorization of gas.
  • combustion of such odorized gases produces sulfur oxides as combustion products - hundreds of tons per year across the country.
  • 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 are of practically no importance in this respect.
  • the document describes and claims allyl acrylate as an effective odorizing component.
  • JP-A-55-104393 discloses that odorants containing an alkyne and at least 2 compounds selected from a group consisting of methyl acrylate, ethyl acrylate, methymethacrylate, allyl methacrylate, ethyl propionate, methyl n-butyrate, Methyl iso-butyrate and prenyl acrylate is, 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.
  • Another object of the present invention is a method for the odorization of fuel gases with a methane content of at least 60 wt .-% with the mixtures according to the invention.
  • Another object of the present invention are fuel gases with a methane content of at least 60 wt .-% containing the mixtures of the invention.
  • mixtures according to the invention are excellent alternatives to known sulfur-free odorizing agents.
  • the alkyl or alkenyl groups of up to 5 carbon atoms may be methyl, ethyl, ethenyl, n-propyl, 1-propen-1-yl, 2-propen-1-yl, 2-propyl , 1-propen-2-yl, n-butyl, 1-butenyl, 2-butenyl, 3-butenyl, sec-butyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1,3-butadien-1-yl, 1,3-butadien-2-yl, 1-methylene-3-butenyl, 2 Methylpropyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1,1-dimethylethyl, n-pentyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4 Pentenyl, 1,3-pentadienyl, 2,4-pentadien
  • the alkoxy groups having 1 to 4 carbon atoms may be methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy or tert-butoxy groups.
  • Advantageous compounds of the formula (I) which contain at most 2 alkyl groups, at most 2 alkenyl groups, at most 2 acyl groups or at most 2 alkoxy groups.
  • inventively preferred compounds of formula (I) are liquid at 25 ° C and 1013 mbar. These liquids can also be highly viscous or oily.
  • ortho-phenols and 2,3-, 2,4-, 2,5- or 2,6-substituted phenols.
  • ortho-anisoles in particular ortho-anisoles, as well as 2,3-, 2,4-, 2,5- or 2,6-disubstituted anisoles are preferred.
  • 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, acrylic acid iso-pentyl ester 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.
  • C 1 -C 4 -alkyl methacrylates in particular methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, Methacrylic acid n-butyl ester and methacrylic acid iso-butyl ester.
  • Very particularly preferred methacrylic acid-C 1 -C 4 alkyl esters are methyl methacrylate and ethyl methacrylate.
  • Preferred odorants contain at least 2 or at least 3 acrylic acid alkyl esters, at least 2 or at least 3 alkyl methacrylates or at least one acrylic acid alkyl ester and at least one methacrylic acid alkyl ester.
  • Particularly preferred odorizing agents contain at least 2 or at least 3 acrylic acid alkyl esters.
  • the acrylate mixtures contain the low molecular weight alkyl acrylate and the higher molecular weight alkyl acrylate preferably in a weight ratio of 9: 1 to 1: 9, preferably from 7: 3 to 3: 7.
  • the odorant contains side by side at least two acrylic acid C 1 -C 4 alkyl esters, most preferably methyl acrylate and ethyl ester.
  • the compounds of the formula (I) can be used in the mixtures according to the invention in amounts of 1 to 100, preferably 10 to 100, in particular 20 to 50 parts by weight per 1000 parts by weight of acrylic acid C 1 -C 6 -alkyl ester and / or methacrylic acid-C 1 -C 6- alkyl esters are used.
  • 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 (BHT, Jonol), tert-butylhydroxyanisole, hydroquinone monomethyl ether and ⁇ -tocopherol.
  • the odorants can be added to an odorant also several antioxidants.
  • the odorants contain one, two or three antioxidants, preferably one or two antioxidants.
  • the antioxidants are preferably used in amounts of 0.01 to 5, in particular 0.05 to 2, especially 0.1 to 1 parts by weight per 1000 parts by weight of acrylic acid alkyl ester and / or methacrylic acid ester.
  • the total amount of antioxidants in the odorant is usually in the range 0.001-1% by weight, preferably in the range 0.01-0.5% by weight, particularly preferably in the range 0.05-0.25% by weight.
  • the amount of odorant with respect to the gas to be odorized is typically in the range 5 - 100 mg / m 3, preferably 5: - 50 mg / m 3, particularly preferably 10-40 mg / m 3 and most preferably 12-30 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 .-%) with regard to their odor odor 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 in 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. The industry standard THT was given the value 10.
  • Table 2 shows the ratings for phenols of the formula (Ia), the execution was carried out as described in Example 1.
  • Table 2 ⁇ / u> material material Me-Ac Et-Ac Bu-Ac rating 2-methoxyphenol 3 37 60 - 8.5 2-methoxyphenol 3 97 - - 8.5 3-methyl phenol 3 20 70 17 7.5 2-ethylphenol 3 37 60 - 8.5 2-ethylphenol 3 17 50 30 8th 2-isopropyl phenol 3 37 60 - 8.5 2-tert-butylphenol 3 37 60 - 8.5 2-methyl-5-isopropylphenol 3 37 60 - 8th 2-methyl-5-isopropylphenol 3 27 60 10 8th 2-methoxy-4-methylphenol 3 37 60 - 8.5 2-methoxy-4-methylphenol 3 - 97 - 8.5 2-tert-butyl-4-methylphenol 3 37 60 - 8th 2,6-diisopropylphenol 3 37 60 - 7.5
  • Table 3 shows the ratings for anisole of the formula (Ib), the procedure was carried out as described in Example 1.
  • Table 3 shows the ratings for anisole of the formula (Ib), the procedure was carried out as described in Example 1.
  • Table 3 ⁇ u> Table 3: ⁇ / u> material material Me-Ac Et-Ac Bu-Ac rating anisole 3 37 60 - 8.5 anisole 3 97 - - 8th 2-Methylanisole 3 37 60 - 8.5 4-allylanisole 3 37 60 - 8.5 4-methylanisole 3 37 60 - 8.5 2-Methylanisole 3 17 50 30 7.5 2-Methylanisole 3 - 97 - 8th 4-methylanisole 3 27 60 10 8th 4-allylanisole 3 10 60 27 7.5
  • Table 4 shows the evaluations for compounds of the formula (Ic), the procedure was carried out as described in Example 1.
  • Table 4 ⁇ / u> material material Me-Ac Et-Ac Bu-Ac rating 2-methyl benzoxazole 3 37 60 - 8.5 2-methyl benzoxazole 3 45 30 22 7.5 2-Ethylbenzoxazol 3 37 60 - 8th 2-Acetylbenzoxazol 3 37 60 - 7.5
  • Table 5 shows for comparison evaluations for phenols and phenol ethers, which are not in the context of the invention, the implementation was carried out as described in Example 1.
  • Table 5 ⁇ u> Table 5: ⁇ / u> material material Me-Ac Et-Ac rating 4-aminophenol 3 37 60 3 3-nitroanisole 3 37 60 4 5-amino-2-methoxyphenol 3 37 60 3 2-Cyclohexylphenol 3 37 60 5 2,6-dimethyl-4-nitrophenol 3 37 60 2 4-Phenoxyphenol 3 37 60 3
  • Table 6 shows odorants according to the invention with acrylates containing antioxidants. ⁇ u> Table 6: ⁇ / u> material material Me-Ac Et-Ac Bu-Ac BHT BHA Hydraulic 2-methoxyphenol 3 60 36.9 - 0.1.
  • Table 7 shows odorants according to the invention with methacrylates containing antioxidants.
  • Table 8 shows odorants according to the invention containing mixtures of compounds of the formula (I) according to the invention and antioxidants.
  • Table 9 shows odorants according to the invention with acrylates and methacrylates containing 0.1 parts by weight of antioxidants (BHT or BHA).
  • BHT 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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (15)

  1. Utilisation de mélanges contenant au moins un acrylate d'alkyle en C1-C6 ou au moins un méthacrylate d'alkyle en C1-C6, au moins un composé de formule (1)
    Figure imgb0017
     dans laquelle
    R1 représente l'hydrogène ou un groupe méthyle ou éthyle;
    R2 à R4 représentent, indépendamment les uns des autres, l'hydrogène, un groupe alcoxy de 1 à 4 atomes de carbone, un groupe acyle de 1 à 4 atomes de carbone, un groupe alkyle de 1 à 5 atomes de carbone ou un groupe alcényle de 2 à 5 atomes de carbone;
    ou R1 et R4 peuvent former ensemble un cycle ayant en tout 5 à 7 chaînons, qui est éventuellement substitué par des groupes alcoxy de 1 à 4 atomes de carbone ou des groupes alkyle de 1 à 4 atomes de carbone, et dont les chaînons sont constitués d'atomes de carbone et d'atomes d'azote, R1 et R4 ayant ensemble au moins un atome de carbone et au plus deux atomes d'azote en tant que chaînons cycliques; et éventuellement un antioxydant
    pour l'odorisation de gaz combustible ayant une teneur en méthane d'au moins 60 % en masse.
  2. Utilisation selon la revendication 1, caractérisée en ce que les composés de formule (I) sont choisis parmi des composés de formule (Ia)
    Figure imgb0018
     dans laquelle
    R2 à R4 représentent, indépendamment les uns des autres, l'hydrogène, un groupe alcoxy de 1 à 3 atomes de carbone, en particulier méthoxy, isopropoxy, un groupe alkyle de 1 à 3 atomes de carbone ou un groupe alcényle de 2 ou 3 atomes de carbone, en particulier méthyle, éthyle, isopropyle, vinyle, allyle.
  3. Utilisation selon la revendication 1, caractérisée en ce que les composés de formule (I) sont choisis parmi les composés de formule (Ib)
    Figure imgb0019
     dans laquelle
    R2 à R4 représentent, indépendamment les uns des autres, un groupe alcoxy de 1 à 3 atomes de carbone, en particulier méthoxy, isopropoxy, un groupe alkyle de 1 à 3 atomes de carbone ou un groupe alcényle de 2 ou 3 atomes de carbone, en particulier méthyle, éthyle, isopropyle, vinyle, allyle.
  4. Utilisation selon la revendication 1, caractérisée en ce que les composés de formule (I) sont choisis parmi les composés de formule (Ic) ou (Id)
    Figure imgb0020
     dans lesquelles
    R5 représente l'hydrogène, un groupe acétyle, propionyle, un groupe alkyle de 1 à 3 atomes de carbone, un groupe alcényle de 2 ou 3 atomes de carbone, en
    R6 particulier méthyle, éthyle, isopropyle, vinyle, allyle; représente l'hydrogène, un groupe alkyle de 1 à 3 atomes de carbone ou un groupe alcényle de 2 ou 3 atomes de carbone, en particulier l'hydrogène ou un groupe méthyle, éthyle, isopropyle, vinyle, allyle;
    A représente l'hydrogène, un groupe méthyle ou une paire d'électrons libres et le symbole "
    Figure imgb0021
    " désigne une simple liaison ou une double liaison.
  5. Utilisation selon au moins l'une des revendications 1 à 4, caractérisée en ce que les composés de formule (I) sont liquides à 25°C et sous 1013 mbar.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que les acrylates d'alkyle en C1-C6 sont choisis parmi l'acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-propyle, l'acrylate d'isopropyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de tert-butyle, l'acrylate de n-pentyle, l'acrylate d'isopentyle, l'acrylate de n-hexyle.
  7. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que les méthacrylates d'alkyle en C1-C6 sont choisis parmi le méthacrylate de méthyle, le méthacrylate d'éthyle, le méthacrylate de n-propyle, le méthacrylate d'isopropyle, le méthacrylate de n-butyle, le méthacrylate d'isobutyle, le méthacrylate de tert-butyle, le méthacrylate de n-pentyle, le méthacrylate d'isopentyle et le méthacrylate de n-hexyle.
  8. Utilisation selon au moins l'une des revendications 1 à 7, caractérisée en ce que les mélanges contiennent au moins deux acrylates d'alkyle en C1-C6.
  9. Utilisation selon au moins l'une des revendications 1 à 8, caractérisée en ce que les mélanges contiennent les composés de formule (I) en une proportion en masse de 1 à 100 pour 1000 parties en masse d'acrylates d'alkyle en C1-C6 et/ou de méthacrylates d'alkyle en C1-C6.
  10. Gaz combustible ayant une teneur en méthane d'au moins 60 % en masse, contenant au moins un acrylate d'alkyle en C1-C6 ou au moins un méthacrylate d'alkyle en C1-C6, au moins un composé de formule (I) et éventuellement un antioxydant.
  11. Gaz combustible selon la revendication 10, caractérisé en ce que le gaz combustible est du gaz naturel.
  12. Gaz naturel selon la revendication 10 ou 11, caractérisé en ce que l'antioxydant est choisi parmi un tert-butylhydroxytoluène, un tert-butylhydroxyanisole, l'éther monométhylique d'hydroquinone et l'α-tocophérol.
  13. Procédé d'odorisation de gaz combustible ayant une teneur en méthane d'au moins 60 % en masse, caractérisé en ce que l'on ajoute au gaz combustible un mélange contenant au moins un acrylate d'alkyle en C1-C6 ou au moins un méthacrylate d'alkyle en C1-C6, au moins un composé de formule (I), et éventuellement un antioxydant.
  14. Procédé selon la revendication 13, caractérisé en ce que la quantité totale d'antioxydants dans le mélange est de 0,001-1 % en masse.
  15. Procédé selon la revendication 13 ou 14, caractérisé en ce que l'on ajoute le mélange au gaz combustible en une quantité de 5-100 mg/m3 de gaz.
EP03784163A 2002-08-05 2003-08-02 Odorisation du gaz avec des phenols et/ou des ethers de phenol Expired - Lifetime EP1529093B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10235756A DE10235756A1 (de) 2002-08-05 2002-08-05 Gasodorierung mit Phenolen und/oder Phenolethern
DE10235756 2002-08-05
PCT/EP2003/008597 WO2004015040A1 (fr) 2002-08-05 2003-08-02 Odorisation du gaz avec des phenols et/ou des ethers de phenol

Publications (2)

Publication Number Publication Date
EP1529093A1 EP1529093A1 (fr) 2005-05-11
EP1529093B1 true EP1529093B1 (fr) 2007-05-16

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EP03784163A Expired - Lifetime EP1529093B1 (fr) 2002-08-05 2003-08-02 Odorisation du gaz avec des phenols et/ou des ethers de phenol

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EP (1) EP1529093B1 (fr)
AT (1) ATE362505T1 (fr)
AU (1) AU2003258565A1 (fr)
DE (2) DE10235756A1 (fr)
WO (1) WO2004015040A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE602005020843D1 (de) 2004-12-22 2010-06-02 Symrise Gmbh & Co Kg Auf acrylat und acetophenon basierendes odoriermittel für wasserstoff
WO2016019074A1 (fr) 2014-07-30 2016-02-04 Georgia-Pacific Consumer Products Lp Distributeurs d'assainisseur d'air, cartouches, systèmes et procédés associés

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3509054A (en) * 1958-05-05 1970-04-28 Ethyl Corp Liquid hydrocarbon compositions of boron esters
JPS55104393A (en) * 1979-02-02 1980-08-09 Nippon Zeon Co Ltd Fuel gas odorant
JPS55149391A (en) * 1979-05-10 1980-11-20 Riken Koryo Kogyo Kk Odorant for fuel gas
US4487613A (en) * 1983-09-26 1984-12-11 International Flavors & Fragrances Inc. Odorization of combustible hydrocarbon gases
DE19837066A1 (de) * 1998-08-17 2000-02-24 Haarmann & Reimer Gmbh Odorierung von Gas

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Publication number Publication date
DE10235756A1 (de) 2004-02-19
EP1529093A1 (fr) 2005-05-11
WO2004015040A1 (fr) 2004-02-19
DE50307299D1 (de) 2007-06-28
AU2003258565A1 (en) 2004-02-25
ATE362505T1 (de) 2007-06-15

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