EP2066766B1 - Agent odorant pauvre en soufre à stabilité améliorée - Google Patents

Agent odorant pauvre en soufre à stabilité améliorée Download PDF

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Publication number
EP2066766B1
EP2066766B1 EP07820469.0A EP07820469A EP2066766B1 EP 2066766 B1 EP2066766 B1 EP 2066766B1 EP 07820469 A EP07820469 A EP 07820469A EP 2066766 B1 EP2066766 B1 EP 2066766B1
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EP
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Prior art keywords
weight
ppm
odorant
compounds
acrylic acid
Prior art date
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Revoked
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EP07820469.0A
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German (de)
English (en)
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EP2066766A1 (fr
Inventor
Marcus Eh
Jörg Eilers
Ingo Wöhrle
Norbert Andreas Braun
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Th Geyer Ingredients & Co Kg GmbH
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Symrise 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, 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 low-sulfur odorants comprising or consisting of A) methyl acrylate and / or ethyl ester, B) tetrahydrothiophene (THT) and C) hydroquinone monomethyl ether in specific concentrations.
  • the proportion of hydroquinone monomethyl ether is very low.
  • an odorizing agent according to the invention may comprise one, two or more stabilizing components, compare in this regard the information on the components D) and E) below.
  • the invention also relates to a corresponding fuel gas (preferably natural gas) having a methane content of at least 60% by weight, which comprises a proportion of the odorant according to the invention.
  • the town and coke oven gas previously used for public gas supply contained intensely smelling components and therefore had one strong odor, so that escaping gas could be easily perceived.
  • gas odorization is meant the addition of odorous, acting as warning or alarm substances (odorants) to gases that have no significant odor, i. to otherwise substantially or completely 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 99 wt .-% and usually 80 to 99 wt .-%) and may, depending on the origin, besides different shares Containing ethane, propane and higher molecular weight hydrocarbons.
  • Natural gas H (H high) has a methane content of 87 to 99.1% by volume
  • gas is therefore odorized by the addition of odorous substances.
  • DVGW German Association of Gas and Water
  • These odorants are also perceptible in high dilution and call due to their exceptionally unpleasant odor as desired, an alarm association in humans.
  • the odorant must not only smell unpleasant and unmistakable, but above all clearly represent a warning smell. Therefore, the odor of the odorized gas must not escape from everyday life, eg from the kitchen and man Household, be familiar.
  • THT tetrahydrothiophene
  • the odorization with mercaptans 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 alone is ideal for reliable odorization of gas.
  • sulfur oxides as combustion products.
  • 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 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, to Odoration of fuel gases are suitable.
  • the amount of odorant is 50 ppm by weight (mg / kg gas), preferably greater than or equal to 100 ppm.
  • LPG LPG
  • TBM tert-butylmercaptan
  • 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.
  • Ethyl acrylate or n-valeric acid used alone did not have sufficient odorizing.
  • An optimized mixture comprised 50-90% by weight of ethyl acrylate, 10-50% by weight of n-valeric acid and optionally triethylamine.
  • the most effective mixture included 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; a corresponding mixture consisting of 60% by weight of ethyl acrylate and 20% by weight of n-valeric acid and triethylamine was added to a gaseous fuel gas at 10 mg / m 3 .
  • Odorants for fuel gases consisting of ethyl acrylate (70 wt .-%) and tert-butyl mercaptan (30 wt .-%) are made JP-B 51-021402 known. This mixture was added to a gaseous fuel gas in an amount of 5 mg / m 3 .
  • Odorants for the odorization of hot gases consisting of a) 30-70 wt .-% C 1 -C 4 -Alkylmercaptanen, b) 10-30 wt .-% n-valeraldehyde and / or isovaleraldehyde, n-butyric acid and / or isobutyric acid and optionally c) up to 60% by weight of tetrahydrothiophene (THT) are in DE-A 31 51 215 described. These odorants were added to heating gas in amounts of 5-40 mg / m 3 .
  • Mixtures comprising a) 1 part by weight of dimethyl sulfide, b) 0.8-3 parts by weight of tert-butyl mercaptan and c) 0.1-0.2 parts by weight of tert-heptyl mercaptan or 0.05-0.3 parts by weight of tert-hexyl mercaptan for O. -Dor suits of fuel gases are out JP-A 61-223094 known. These mixtures had a smell of tertiary butyl mercaptan associated with the smell of city gas.
  • norbornene derivatives for fuel gas odorization is out JP-A 55056190 known.
  • LPG was mixed at 40 mg / kg with a mixture of equal parts of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene and 50 mg / kg with a mixture of 80% by weight of 5-ethylidene-2 norbornene and 20 wt .-% ethyl acrylate.
  • US 4,487,613 proposes odorants for fuel gases with a high proportion of sulfur-containing compounds, which additionally contain the smoke-odor enhancing compounds 2-methoxy-3-isobutylpyrazine and / or 4-methyl-4-mercapto-2-pentanone contain.
  • the according to US 4,487,613 Odorating agents disclosed may also contain small amounts of methyl acrylate.
  • WO 2005/061680 describes the use of a mixture containing (a) at least two different acrylic acid C 1 -C 6 -alkyl esters, (b) at least one compound selected from the group consisting of C 1 -C 6 -mercaptans, C 4 -C 12 -thiophenes , the C 2 -C 8 sulphides or the C 2 -C 6 disulphides and (c) at least one compound from the group of the norbornenes, the C 1 -C 6 carboxylic acids, the C 1 -C 6 aldehydes, the C 8 -C 14 -phenols, C 7 -C 14 -anoles or C 4 -C 14 -pyrazines and optionally (d) an antioxidant for odorizing fuel gas with a methane content of at least 60% by weight.
  • WO 2005/103210 proposed mixtures allegedly represent improved odorants.
  • WO 2005/103210 leads among other things, that the N-oxides proposed there, effectively prevent odorants to be avoided, free radical polymerization of the acrylic acid esters contained therein. Particularly preferred are in WO 2005/103210 Mixtures comprising ethyl acrylate and THT.
  • N-oxides alone do not cause completely sufficient stabilization of the odorant concerned.
  • Interactions between the N-oxides and the thioethers may occur, in particular in the presence of metals and metal surfaces, for example in the containers for storing the odorants, so that the warning odor of the odorants proposed there change and worsen.
  • Interactions between the N-oxides with metals and metal surfaces can also lead to consumption due to the reaction of the N-oxides, so that comprehensive stabilization of the acrylic esters is no longer ensured in every case.
  • N-oxides can be oxidized in the presence of copper ions (to the corresponding nitrones) or reduced in the presence of iron ions (to the corresponding N-hydroxy compounds).
  • Another object of the present invention is a fuel gas with a methane content of at least 60 wt .-% comprising an inventive odorant.
  • an inventive odorant for use in fuel gases according to the invention, reference is made to the following statements on preferred odorants.
  • the fuel gas to be odorized or the fuel gas according to the invention has a methane content of at least 60% by weight, preferably of at least 70% by weight and more preferably of at least 75% by weight
  • the total amount of methyl acrylate and ethyl acrylate (component (A)) in the odorants according to the invention is at least 75 wt .-%, preferably at least 84 wt .-%.
  • the preferred weight ratio of methyl acrylate to ethyl acrylate is in the range 9: 1-1: 9, preferably in the range 7: 3-3: 7, in particular in the range 3: 1-1: 4
  • the weight ratio of methyl acrylate to ethyl acrylate is particularly preferably in the range from 1: 1 to 1: 3.
  • the compound tetrahydrothiophene (component (B)) is contained in the odorants according to the invention at 2 to 19.5% by weight, preferably at 5 to 15% by weight.
  • component (C) The compound hydroquinone monomethyl ether (4-methoxyphenol, MeHQ) (component (C)) is contained in the odorizing agents according to the invention in very small amounts, which are in the range from 5 to 50 ppm, preferably 10 to 20 ppm.
  • component (C) is surprisingly not required to achieve a high stability of the odorant; the use of the inventively provided small amount of component (C) is particularly in the presence of component (E) for stability reasons advantageous (see also the examples).
  • Odorants according to the invention preferably comprise
  • component (D) 0.025-0.2% by weight of butylhydroxytoluene and / or butylated hydroxyanisole and or as component (E) 5 - 500 ppm of one or more compounds of the formula (I) in which R is selected from the group consisting of H, -OH, -NH 2 and -O 2 CR 1 , where R 1 is an alkyl radical having 1 to 4 carbon atoms.
  • the total amount of the compounds of component (D) butylhydroxytoluene (BHT, ionol, 2,6-di-tert-butyl-p-cresol, E 321) and / or butylated hydroxyanisole (BHA, E 320) in the odorants according to the invention in the range of 0.025-0.2% by weight, preferably in the range of 0.05-0.15% by weight.
  • component (C) Due to the presence of component (C), in particular in combination with one or both other components (D) and / or (E), in particular a high storage stability of the odorant according to the invention and an odorized fuel gas according to the invention is achieved.
  • Storage stability tests have shown that the warning odor odorant according to the invention in a fuel gas over a period of more than 8 months at 40 ° C (incubator) remains largely the same, see also the examples below.
  • component (C) and one of components (D) and / or (E) a particularly high storage stability is achieved.
  • the total amount of component (E) in preferred odorants according to the invention is in the range of 5 to 500 ppm, preferably in the range of 10 to 200 ppm.
  • the compounds of formula (I) are stable N-oxides.
  • the amount of odorant based on the fuel gas to be odorized is typically in the range 2 to 100 mg / m 3 , preferably 3 to 50 mg / m 3 , more preferably 5 to 40 mg / m 3, and most preferably 8 to 35 mg / m 3 .
  • the odorants according to the invention and the fuel gases containing these mixtures preferably contain neither tert-butylmercaptan (TBM) nor ethylmercaptan in addition to THT (component (B)).
  • the odorant does not comprise any mercaptan at all.
  • TBM tert-butylmercaptan
  • component (B) ethylmercaptan
  • particular preference is given to containing no further sulfur-containing compound in the odorant according to the invention.
  • R is selected from the group consisting of H and -OH.
  • the particularly preferred mixtures are distinguished by a particularly high storage stability.
  • combinations of hydroquinone monomethyl ether (component (C)) and at least a further component (D) and / or (E) partially observed synergistic stability improvements.
  • component (E) one or more compounds of the formula (I) are contained in an odorizing agent according to the invention, these do not show the disadvantages of the invention discussed above WO 2005/103210 proposed odorant, which is probably due to the presence of component (C), that is, the presence of the small amount of hydroquinone monomethyl ether.
  • particularly relevant methods for the odorization of fuel gas with a methane content of at least 60 wt .-% correspond in their preferred embodiments, the particularly preferred odorants according to the invention.
  • an odorant according to the invention is added to a fuel gas to be odorized in an amount which causes a warning odor.
  • Preferably used amounts of odorant based on the amount of fuel gas to be odorized are given above.
  • the odorants according to the invention of the following Table 1 were evaluated in concentrations of 10 and 25 mg / Nm 3 natural gas (natural gas L, methane content: about 85 vol .-%) by smell with respect to their warning smell and their warning intensity against un-natural gas (blank). These concentrations correspond to the typical concentrations of odorant in natural gas under normal conditions.
  • 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.

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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)
  • Cosmetics (AREA)

Claims (11)

  1. Agent odorant comprenant ou constitué par
    (A) au moins 75 % en poids d'ester méthylique de l'acide acrylique et/ou d'ester éthylique de l'acide acrylique,
    (B) 2 à 19,5 % en poids de tétrahydrothiophène (THT),
    (C) 5 à 50 ppm d'éther monométhylique d'hydroquinone, ainsi qu'aucun, un ou deux composants choisis dans le groupe constitué par
    (D) 0,025 à 0,2 % en poids de butylhydroxytoluène et/ou de butylhydroxyanisol
    et
    (E) 5 à 500 ppm d'un ou de plusieurs composés de formule (I)
    Figure imgb0013
     dans laquelle
    R est choisi dans le groupe constitué par H, -OH, -NH2 et -O2CR1, R1 signifiant un radical alkyle de 1 à 4 atomes C,
    par rapport au poids total de l'agent odorant.
  2. Agent odorant selon la revendication 1, comprenant
    (D) 0,025 à 0,2 % en poids de butylhydroxytoluène et/ou de butylhydroxyanisol
    et/ou
    (E) 5 à 500 ppm d'un ou de plusieurs composés de formule (I)
    Figure imgb0014
     dans laquelle
    R est choisi dans le groupe constitué par H, -OH, -NH2 et -O2CR1, R1 signifiant un radical alkyle de 1 à 4 atomes C.
  3. Agent odorant selon l'une quelconque des revendications précédentes, comprenant ou constitué par
    (A) au moins 84 % en poids d'ester méthylique de l'acide acrylique et/ou d'ester éthylique de l'acide acrylique,
    et/ou
    (B) 5 à 15 % en poids de tétrahydrothiophène (THT),
    et/ou
    (C) 10 à 20 ppm d'éther monométhylique d'hydroquinone,
    et/ou
    (D) 0,05 à 0,15 % en poids de butylhydroxytoluène et/ou de butylhydroxyanisol
    et/ou
    (E) 10 à 200 ppm d'un ou de plusieurs composés de formule (I).
  4. Agent odorant selon l'une quelconque des revendications précédentes, comprenant
    (A) au moins 84 % en poids d'ester méthylique de l'acide acrylique et/ou d'ester éthylique de l'acide acrylique,
    (B) 5 à 15 % en poids de tétrahydrothiophène (THT),
    et
    (C) 10 à 20 ppm d'éther monométhylique d'hydroquinone, ainsi qu'aucun, un ou deux composants choisis dans le groupe constitué par
    (D) 0,05 à 0,15 % en poids de butylhydroxytoluène et/ou de butylhydroxyanisol
    et
    (E) 10 à 200 ppm d'un ou de plusieurs composés de formule (I).
  5. Agent odorant selon l'une quelconque des revendications précédentes, comprenant dans le composant (E) un ou plusieurs composés de formule (I)
    Figure imgb0015
     dans laquelle
    R est choisi dans le groupe constitué par H et -OH.
  6. Agent odorant selon l'une quelconque des revendications précédentes, comprenant
    (A) au moins 84 % en poids d'ester méthylique de l'acide acrylique et/ou d'ester éthylique de l'acide acrylique,
    (B) 5 à 15 % en poids de tétrahydrothiophène (THT),
    et
    (C) 10 à 20 ppm d'éther monométhylique d'hydroquinone, ainsi qu'un ou deux composants choisis dans le groupe constitué par
    (D) 0,05 à 0,15 % en poids de butylhydroxytoluène
    et
    (E) 10 à 200 ppm d'un ou de plusieurs composés de formule (I)
    Figure imgb0016
     dans laquelle
    R est choisi dans le groupe constitué par H et -OH.
  7. Agent odorant selon l'une quelconque des revendications précédentes, ne comprenant ni tert.-butylmercaptan (TBM), ni éthylmercaptan.
  8. Agent odorant selon l'une quelconque des revendications précédentes, dans lequel l'agent odorant ne comprend pas de mercaptan.
  9. Agent odorant selon l'une quelconque des revendications précédentes, dans lequel l'agent odorant ne comprend pas de composé contenant du soufre outre le tétrahydrothiophène (THT).
  10. Gaz de combustion ayant une proportion de méthane d'au moins 60 % en poids, comprenant un agent odorant tel que défini dans l'une quelconque des revendications précédentes.
  11. Gaz de combustion selon la revendication 10, caractérisé en ce que le gaz de combustion est du gaz naturel.
EP07820469.0A 2006-09-22 2007-09-21 Agent odorant pauvre en soufre à stabilité améliorée Revoked EP2066766B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL07820469T PL2066766T3 (pl) 2006-09-22 2007-09-21 Środki nawaniające o niskiej zawartości siarki i o polepszonej trwałości

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE202006014741U DE202006014741U1 (de) 2006-09-22 2006-09-22 Schwefelarme Odoriermittel mit verbesserter Stabilität
PCT/EP2007/060057 WO2008034901A1 (fr) 2006-09-22 2007-09-21 Agent odorant pauvre en soufre à stabilité améliorée

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EP2066766A1 EP2066766A1 (fr) 2009-06-10
EP2066766B1 true EP2066766B1 (fr) 2015-07-01

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EP07820469.0A Revoked EP2066766B1 (fr) 2006-09-22 2007-09-21 Agent odorant pauvre en soufre à stabilité améliorée

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US (1) US20110155616A1 (fr)
EP (1) EP2066766B1 (fr)
CN (1) CN101517045A (fr)
DE (1) DE202006014741U1 (fr)
DK (1) DK2066766T3 (fr)
ES (1) ES2548521T3 (fr)
PL (1) PL2066766T3 (fr)
WO (1) WO2008034901A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202006018157U1 (de) * 2006-11-28 2007-03-22 Symrise Gmbh & Co. Kg Odoriermittel mit verbesserter Stabilität
CA2924342C (fr) * 2013-10-01 2016-10-18 Aygaz Anonim Sirketi Odorizant gazeux sans soufre
CA2956623C (fr) 2014-07-30 2020-10-27 Georgia-Pacific Consumer Products Lp Distributeurs d'assainisseur d'air, cartouches, systemes et procedes associes
EP3368641B1 (fr) * 2015-10-26 2020-09-16 Shell Internationale Research Maatschappij B.V. Fluide de méthane odorisé et procédés de production de fluides de méthane odorisés et leur utilisation
CN108138063B (zh) * 2015-10-26 2020-08-11 国际壳牌研究有限公司 包含甲烷和示踪剂的流体和制造其的方法以及其用途
CN113956904A (zh) * 2021-11-25 2022-01-21 沈阳光正工业有限公司 一种可燃气体用无硫含量的气味添加剂及其制备方法

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US4608240A (en) 1983-11-04 1986-08-26 Hylsa, S.A. Method for the desulfurization of hydrocarbon gas
WO2005061680A1 (fr) 2003-12-19 2005-07-07 Symrise Gmbh & Co. Kg Odorisation de gaz combustible a l'aide d'odorisants pauvres en soufre
WO2005103210A1 (fr) 2004-04-08 2005-11-03 Arkema France Melange odorisant pour combustible gazeux inodore
US20060009372A1 (en) 2002-08-27 2006-01-12 Symrise Gmbh & Co. Kg Low-sulphur odorants for liquid gas

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US4608240A (en) 1983-11-04 1986-08-26 Hylsa, S.A. Method for the desulfurization of hydrocarbon gas
US20060009372A1 (en) 2002-08-27 2006-01-12 Symrise Gmbh & Co. Kg Low-sulphur odorants for liquid gas
WO2005061680A1 (fr) 2003-12-19 2005-07-07 Symrise Gmbh & Co. Kg Odorisation de gaz combustible a l'aide d'odorisants pauvres en soufre
WO2005103210A1 (fr) 2004-04-08 2005-11-03 Arkema France Melange odorisant pour combustible gazeux inodore

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ACRYLATE ESTERS, A SUMMARY OF SAFETY AND HANDLING, 2002
CARCINOGENESIS STUDIES OF ETHYL ACRYLATE IN F344/N RATS AND B6C3F1 MICE, 1986, pages 20
CHEMICAL SAFETY DATA SHEETS: CORROSIVES AND IRRITANTS, vol. 3, 1990, XP055289411, ISBN: 0-85186-923-8
CUTIE ET AL.: "« The effects of MEHQ on the polymerization of acrylic acid in the preparation of superabsorbent gels »", J. APPL. POLYM. SCI., vol. 64, 1997, pages 577 - 589
HAZARDOUS SUBSTANCE FACT SHEET: ETHYL ACRYLATE, 2002, New Jersey
KIRK-OTHMER, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, vol. 1, 1991, pages 308 - 309 , 320-322
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SIGMA ALDRICH, 2003
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TECHNICAL INFORMATION : ETHYL ACRYLATE - BASF, 2004
ULLMANN'S ENCYCLOPEDIA OF INDUST. CHEM., 1985, pages 169 - 170, ISBN: 3-527-20101-7

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WO2008034901A1 (fr) 2008-03-27
US20110155616A1 (en) 2011-06-30
PL2066766T3 (pl) 2016-04-29
CN101517045A (zh) 2009-08-26
ES2548521T3 (es) 2015-10-19
DE202006014741U1 (de) 2006-11-23
DK2066766T3 (en) 2015-10-05
EP2066766A1 (fr) 2009-06-10

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