EP1529092B1 - Odorisation de gaz par des cetones - Google Patents

Odorisation de gaz par des cetones Download PDF

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Publication number
EP1529092B1
EP1529092B1 EP03784160A EP03784160A EP1529092B1 EP 1529092 B1 EP1529092 B1 EP 1529092B1 EP 03784160 A EP03784160 A EP 03784160A EP 03784160 A EP03784160 A EP 03784160A EP 1529092 B1 EP1529092 B1 EP 1529092B1
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EP
European Patent Office
Prior art keywords
acrylate
alkyl
methacrylate
methyl
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03784160A
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German (de)
English (en)
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EP1529092A1 (fr
Inventor
Gerd Mansfeld
Jörg Eilers
Heinz-Jürgen BERTRAM
Florian Wolf
Heribert Kaesler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EOn Ruhrgas AG
Symrise AG
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EOn Ruhrgas AG
Symrise AG
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Publication of EP1529092A1 publication Critical patent/EP1529092A1/fr
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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, 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 containing alkyl acrylates and / or alkyl methacrylates and acyclic or cyclic ketones 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.
  • 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 have practically no significance in this respect.
  • the document describes and claims allyl acrylate as an effective odorizing component.
  • JP-A-55-104393 it is described 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.
  • alkyl or alkenyl groups mentioned 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-pentadienyl, 1-methylbutyl, 1-methyl
  • the compounds of the formula (I) may be present in the respective (E) or (Z) form or as a mixture of the double bond isomers.
  • inventively preferred compounds of formula (I) are liquid at 25 ° C and 1013 mbar. These liquids can also be highly viscous or oily.
  • 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 in particular methyl acrylate, ethyl acrylate, n-propyl ester, acrylic acid iso-propyl ester, acrylic acid-n-butyl acrylate and iso-butyl are preferred.
  • 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, Tert-butyl methacrylate, 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 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 at least two acrylic acid C 1 -C 4 alkyl esters side by side; most preferably methyl acrylate and ethyl acrylate.
  • 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-butylated hydroxyanisole, ⁇ -hydroxyacids (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 wt%, preferably in the range 0.01-0.5 wt%, particularly preferably in the range 0.05-0.25 wt%.
  • 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 .
  • the odorants according to the invention were evaluated in concentrations of 10, 25 and 50 mg / m 3 natural gas (methane content: 85 wt .-%) by smell 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 in shock odorization.
  • concentrations of odorant in natural gas under normal conditions or in shock odorization correspond to the typical concentrations of odorant in natural gas under normal conditions or in shock odorization.
  • THT or a mixture according to JP-B-51-034841 contained (60 wt .-% ethyl acrylate, 20 wt .-% n-valeric acid and 20 wt .-% triethylamine).
  • 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 1 shows references and mixtures according to the invention in comparison.
  • Table 2 shows the evaluations for cyclic ketones of the formula (Ia), which was carried out as described in Example 1.
  • Table 3 shows the evaluations for acyclic ketones of the formula (Ib), the procedure was carried out as described in Example 1.
  • Table 4 shows odorants according to the invention with acrylates containing antioxidants.
  • Table 5 shows odorants according to the invention with methacrylates containing antioxidants.
  • Table 6 shows odorants according to the invention containing mixtures of compounds of the formula (I) according to the invention and antioxidants.
  • Table 7 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)
  • Liquid Carbonaceous Fuels (AREA)

Claims (13)

  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 imgb0018
     dans laquelle
    X représente un groupe alkyle de 1 à 3 atomes de carbone ou un groupe alcényle de 2 à 4 atomes de carbone;
    Y représente l'hydrogène, un groupe alkyle de 1 à 5 atomes de carbone ou un groupe alcényle de 2 à 5 atomes de carbone;
    A représente l'hydrogène, ou un groupe méthyle, éthyle, méthoxy, acétoxy;
    Z représente l'hydrogène, un groupe alkyle de 1 à 5 atomes de carbone ou un groupe alcényle de 2 à 5 atomes de carbone;
    le symbole "
    Figure imgb0019
    " désigne une simple liaison ou une double liaison;
    ou X et Z peuvent former ensemble un cycle carboné ayant en tout 5 à 8 chaînons qui présente éventuellement une autre double liaison et/ou au plus 2 autres substituants du groupe constitué par méthoxy, méthyle ou éthyle;
    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 imgb0020
     dans laquelle
    A et Y ont la signification indiquée dans la revendication 1;
    m est 0 ou 1.
  3. Utilisation selon la revendication 1, caractérisée en ce que les composés de formule (I) sont choisis parmi les composés de formule (Ib)
    Figure imgb0021
     dans laquelle
    X représente un groupe méthyle ou éthyle;
    Y représente l'hydrogène, un groupe alkyle de 1 à 3 atomes de carbone ou un groupe alcényle de 2 ou 3 atomes de carbone;
    Z représente l'hydrogène, un groupe alkyle de 1 à 4 atomes de carbone ou un groupe alcényle de 2 à 4 atomes de carbone;
    le symbole "
    Figure imgb0022
    " désigne une simple liaison ou une double liaison.
  4. Utilisation selon au moins l'une des revendications 1 à 3, 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.
  5. Utilisation selon au moins l'une des revendications 1 à 3, 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.
  6. Utilisation selon au moins l'une des revendications 1 à 5, caractérisée en ce que les mélanges contiennent au moins deux acrylates d'alkyle en C1-C6.
  7. Utilisation selon au moins l'une des revendications 1 à 6, 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.
  8. 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.
  9. Gaz combustible selon la revendication 8, caractérisé en ce que le gaz combustible est du gaz naturel.
  10. Gaz naturel selon la revendication 8 ou 9, caractérisé en ce que l'antioxydant est choisi parmi un tert-butylhydroxytoluène, un tert-butylhydroxyanisole, l'éther monométhylique d'hydroquinone et l'α-tocophérol.
  11. 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.
  12. Procédé selon la revendication 11, caractérisé en ce que la quantité totale d'antioxydants dans le mélange est de 0,001-1 % en masse.
  13. Procédé selon la revendication 11 ou 12, caractérisé en ce que l'on ajoute le mélange au gaz combustible en une quantité de 5-100 mg/m3 de gaz.
EP03784160A 2002-08-05 2003-08-02 Odorisation de gaz par des cetones Expired - Lifetime EP1529092B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10235750A DE10235750A1 (de) 2002-08-05 2002-08-05 Gasodorierung mit Ketonen
DE10235750 2002-08-05
PCT/EP2003/008594 WO2004015037A1 (fr) 2002-08-05 2003-08-02 Odorisation de gaz par des cetones

Publications (2)

Publication Number Publication Date
EP1529092A1 EP1529092A1 (fr) 2005-05-11
EP1529092B1 true EP1529092B1 (fr) 2007-07-04

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EP (1) EP1529092B1 (fr)
AT (1) ATE366297T1 (fr)
AU (1) AU2003255361A1 (fr)
DE (2) DE10235750A1 (fr)
WO (1) WO2004015037A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006067112A1 (fr) * 2004-12-22 2006-06-29 Symrise Gmbh & Co. Kg Agent odorisant pour hydrogene a base d'acrylate et d'acetophenone
US9717815B2 (en) 2014-07-30 2017-08-01 Georgia-Pacific Consumer Products Lp Air freshener dispensers, cartridges therefor, systems, and methods

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL36219C (fr) * 1932-05-17
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

Also Published As

Publication number Publication date
DE50307624D1 (de) 2007-08-16
AU2003255361A1 (en) 2004-02-25
WO2004015037A1 (fr) 2004-02-19
DE10235750A1 (de) 2004-02-19
ATE366297T1 (de) 2007-07-15
EP1529092A1 (fr) 2005-05-11

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