EP1109881A1 - Gas odorization method - Google Patents

Gas odorization method

Info

Publication number
EP1109881A1
EP1109881A1 EP99944331A EP99944331A EP1109881A1 EP 1109881 A1 EP1109881 A1 EP 1109881A1 EP 99944331 A EP99944331 A EP 99944331A EP 99944331 A EP99944331 A EP 99944331A EP 1109881 A1 EP1109881 A1 EP 1109881A1
Authority
EP
European Patent Office
Prior art keywords
gas
acrylic acid
weight
jonol
parts
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.)
Granted
Application number
EP99944331A
Other languages
German (de)
French (fr)
Other versions
EP1109881B1 (en
Inventor
Gerd Mansfeld
Ute Rohde
Fritz Henke
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.)
Dragoco Gerberding and Co GmbH
EOn Ruhrgas AG
Symrise AG
Original Assignee
Haarmann and Reimer GmbH
Ruhrgas AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Haarmann and Reimer GmbH, Ruhrgas AG filed Critical Haarmann and Reimer GmbH
Priority to SI9930239T priority Critical patent/SI1109881T1/en
Priority to EP03004711A priority patent/EP1329495B1/en
Publication of EP1109881A1 publication Critical patent/EP1109881A1/en
Application granted granted Critical
Publication of EP1109881B1 publication Critical patent/EP1109881B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 odorization of gas.
  • City and coke oven gases obtained by thermal processes contained intensely smelling components and therefore had a strong intrinsic odor, so that escaping gas could easily be perceived.
  • THT and Mercaptane are ideal for reliable gas odorization.
  • sulfur dioxide is produced as a combustion product - only a little at each individual burning point, but a few hundred tons per year nationwide.
  • the smell should be unpleasant and distinctive (from kitchen and
  • Household odorous substances are excluded). It is said to cause an alarm association in people who smell leaking gas.
  • the odorant should be as non-toxic as possible and must not form toxic combustion products.
  • the odorant should have a high volatility and evaporate as residue-free as possible.
  • a suitable odorant must neither condense at winter temperatures nor segregate nor adhere to metallic lines.
  • the odorant should be stable in storage and chemically resistant to the gas and to the systems. It must neither promote corrosion nor attack conventional seals.
  • Alkyl acrylates, vinyl or alkyl ethers and mixtures thereof JP 76-7481
  • n-valeric acid optionally in combination with ethyl acrylate and / or triethylamine (JP 76-34 841)
  • the new odorant can be added to the gas in the same order of magnitude as sulfur-containing compounds and does not produce any corrosion-promoting products during combustion.
  • the acrylic acid esters A include acrylic acid methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl , octyl and dodecyl esters.
  • mixtures of acrylic acid-C 1 -C 4 -alkyl esters are used as component A; a particularly preferred combination contains methyl and ethyl acrylates side by side.
  • the acrylate Mixtures can each contain the lower and the higher esters in a weight ratio of 9: 1 to 1: 9, preferably 7: 3 to 3: 7.
  • Preferred nitrogen compounds B primarily include compounds
  • the nitrogen compounds B include, for example
  • Lactones such as caprolactone
  • Nitriles such as 2-nonenenitrile and compounds of the formula
  • R 1 to R 4 independently of one another are hydrogen or C 1 -C 4 -alkyl, preferably methyl or ethyl.
  • Preferred compounds (I) are e.g. 2-methylpyrazine, 2,3-dimethylpyrazine, 2,6-
  • the nitrogen compounds B can be used in amounts of 1 to 100, preferably 30 to 100, in particular 10 to 50 parts by weight per 1,000 parts by weight A.
  • the odorants can contain antioxidants, as described, for example, in Römpp-Lexikon Chemie Version 1.3.
  • the antioxidants C are preferably used in amounts of 0.01 to 5, in particular 0.05 to 2, especially 0.1 to 1 part by weight per 1,000 parts by weight A.
  • Preferred gas odorants can have, for example, the following compositions:

Landscapes

  • 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)
  • Treating Waste Gases (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Detergent Compositions (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerisation Methods In General (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A mixture of acrylic acid and nitrogen compounds is particularly adapted to achieve a sulphur-free odorization of a gas.

Description

Odorierung von GasOdorization of gas
Die vorliegende Erfindung betrifft die Odorierung von Gas.The present invention relates to the odorization of gas.
Durch thermische Verfahren gewonnene Stadt- und Kokereigase enthielten intensiv riechende Komponenten und besaßen deshalb einen starken Eigengeruch, so daß austretendes Gas leicht wahrgenommen werden konnte.City and coke oven gases obtained by thermal processes contained intensely smelling components and therefore had a strong intrinsic odor, so that escaping gas could easily be perceived.
Aufgrund seiner Herkunft (Erdgas) und eines höheren Reinheitsgrades ist das heute im öffentlichen Netz verwendete Gas an sich nahezu geruchslos; wenn Leckagen nicht rechtzeitig bemerkt werden, bauen sich schnell explosionsfähige Gas/Luft- Gemische mit hohem Gefahrenpotential auf. Aus Sicherheitsgründen wird Gas deswegen durch Zusatz von Riechstoffen odoriert. So ist in Deutschland vorgeschrieben, daß alle Gase, welche keinen genügenden Eigengeruch besitzen und in der öffentlichen Gasversorgung verteilt werden (DVGW-Arbeitsblatt G 260), nach dem DVGW-Arbeitsblatt G 280 odoriert werden; DVGW = Deutscher Verein des Gas- und Wasserfaches e.V., Eschborn. Diese Odoriermittel sind auch noch in großer Verdünnung wahrnehmbar und rufen aufgrund ihres außergewöhnlich unange- nehmen Geruchs wunschgemäß eine Alarmassoziation beim Menschen hervor. InDue to its origin (natural gas) and a higher degree of purity, the gas used in the public network today is almost odorless; if leaks are not noticed in time, explosive gas / air mixtures with a high risk potential build up quickly. For safety reasons, gas is therefore odorized by adding fragrances. In Germany, for example, it is mandatory that all gases that do not have a sufficient odor and are distributed in the public gas supply (DVGW worksheet G 260) are odorized according to DVGW worksheet G 280; DVGW = German Gas and Water Association, Eschborn. These odorants can also be perceived in great dilution and, due to their unusually unpleasant smell, can cause an alarm association in humans. In
Deutschland werden zur Zeit etwa 90 % des Brauchgases mit Tetrahydrothiophen (THT) odoriert (12 - 25 mg/m3); daneben ist auch noch die Odorierung mit Mercaptanen oder Thioethern üblich.Germany is currently about 90% of the process gas is odorized with tetrahydrothiophene (THT) (12 - 25 mg / m 3 ); in addition, odorization with mercaptans or thioethers is also common.
THT und Mercaptane sind für eine zuverlässige Odorierung von Gas hervorragend geeignet. Im Zuge eines sensibleren Umgangs mit der Umwelt ist jedoch zu beachten, daß bei der Verbrennung derart odorierter Gase Schwefeldioxid als Verbrennungsprodukt anfällt - an jeder einzelnen Brennstelle nur wenig, landesweit gesehen aber einige hundert Tonnen pro Jahr. Man würde diesen Nachteil gerne überwinden, hat dabei aber eine Reihe von Forderungen zu erfüllen: 1. Der Geruch soll unangenehm und unverwechselbar sein (aus Küche undTHT and Mercaptane are ideal for reliable gas odorization. In the course of a more sensitive handling of the environment, however, it should be noted that when such gases are odorized, sulfur dioxide is produced as a combustion product - only a little at each individual burning point, but a few hundred tons per year nationwide. One would like to overcome this disadvantage, but there are a number of requirements to be met: 1. The smell should be unpleasant and distinctive (from kitchen and
Haushalte geläufige Riechstoffe scheiden aus). Er soll bei Menschen, die ausgetretenes Gas riechen, eine Alarmassoziation hervorrufen.Household odorous substances are excluded). It is said to cause an alarm association in people who smell leaking gas.
2. Jede Person mit durchschnittlichem Riechvermögen und durchschnittlicher physiologischer Kondition muß den Geruch wahrnehmen können.2. Every person with average smell and average physiological condition must be able to perceive the smell.
3. Die Warngeruchsstufe (= mittlere Geruchsintensivität) muß erreicht werden, bevor die Zündgrenze oder ein kinetischer Kohlenmonoxid-Gehalt erreicht ist.3. The warning odor level (= average odor intensity) must be reached before the ignition limit or a kinetic carbon monoxide content is reached.
4. Das Odoriermittel soll möglichst ungiftig sein und darf keine toxischen Verbrennungsprodukte bilden.4. The odorant should be as non-toxic as possible and must not form toxic combustion products.
5. Das Odoriermittel soll eine hohe Flüchtigkeit aufweisen und möglichst rückstandsfrei verdampfen.5. The odorant should have a high volatility and evaporate as residue-free as possible.
6. Ein geeignetes Odoriermittel darf weder bei winterlichen Temperaturen kondensieren noch sich entmischen noch an metallischen Leitungen haften.6. A suitable odorant must neither condense at winter temperatures nor segregate nor adhere to metallic lines.
7. Das Odoriermittel soll rückstandsfrei verbrennen.7. The odorant should burn without residue.
8. Das Odoriermittel soll lagerstabil und gegenüber dem Gas sowie gegenüber den Anlagen chemisch beständig sein. Es darf weder die Korrosion fördern noch übliche Dichtungen angreifen.8. The odorant should be stable in storage and chemically resistant to the gas and to the systems. It must neither promote corrosion nor attack conventional seals.
Man hat bereits Anstrengungen unternommen, neue Gasodoriermittel bereitzustellen. So wurden beispielsweise vorgeschlagenEfforts have been made to provide new gas odorants. For example, have been suggested
- Alkylacrylate, Vinyl- bzw. Alkylether und deren Mischungen (JP 76-7481), n-Valeriansäure, gegebenenfalls in Kombination mit Ethylacrylat und/oder Triethylamin (JP 76-34 841),Alkyl acrylates, vinyl or alkyl ethers and mixtures thereof (JP 76-7481), n-valeric acid, optionally in combination with ethyl acrylate and / or triethylamine (JP 76-34 841),
Mischungen aus Schwefelverbindungen und aliphatischem Aldehyd (JP 78-35 562),Mixtures of sulfur compounds and aliphatic aldehyde (JP 78-35 562),
Cycohexen (JP 83-42 235),Cycohexene (JP 83-42 235),
Norbornenderivate (JP 87- 1998) undNorbornene derivatives (JP 87-1998) and
gesättigte Ether, gesättigte Ester sowie deren Mischungen mit Mercaptanen.saturated ethers, saturated esters and their mixtures with mercaptans.
Es wurde nun gefunden, daß man durch Zusätze vonIt has now been found that by adding
A. Acrylsäure-C j-C 12-, vorzugsweise -C]-C8-alkylestern,A. acrylic acid-C j -C 12 -, preferably -C ] -C 8 -alkyl esters,
B. Stickstoffverbindungen und gegebenenfallsB. nitrogen compounds and optionally
C. AntioxidantienC. Antioxidants
fortschrittlich odoriertes Gas erhält, das die wünschenswerten Eigenschaften weitgehend in sich vereinigt. Das neue Odoriermittel kann dem Gas in gleicher Größenordnung wie schwefelhaltige Verbindungen zugesetzt werden und erzeugt bei der Verbrennung keine korrosionsfördernden Produkte.receives progressively odorized gas that largely combines the desirable properties. The new odorant can be added to the gas in the same order of magnitude as sulfur-containing compounds and does not produce any corrosion-promoting products during combustion.
Die Acryl säureester A umfassen Acrylsäuremethyl-, -ethyl-, -n-propyl-, -isopropyl-, -n-butyl-, -isobutyl-, -tert.-butyl-, -pentyl-, -hexyl-, -heptyl-, -octyl- und -dodecylester. In einer bevorzugten Ausführungsform werden als Komponente A Mischungen aus Acrylsäure-C C^-alkylestern eingesetzt; eine besonders bevorzugte Kombination enthält nebeneinander Acrylsäuremethyl- und -ethylester. Die Acrylat- mischungen können die niederen und die höheren Ester jeweils im Gewichtsverhältnis von 9: 1 bis 1 :9, vorzugsweise 7:3 bis 3:7 enthalten.The acrylic acid esters A include acrylic acid methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl , octyl and dodecyl esters. In a preferred embodiment, mixtures of acrylic acid-C 1 -C 4 -alkyl esters are used as component A; a particularly preferred combination contains methyl and ethyl acrylates side by side. The acrylate Mixtures can each contain the lower and the higher esters in a weight ratio of 9: 1 to 1: 9, preferably 7: 3 to 3: 7.
Bevorzugte Stickstoffverbindungen B umfassen vor allem VerbindungenPreferred nitrogen compounds B primarily include compounds
mit einem Flammpunkt über 20°C, vorzugsweise über 40°C (gemessen nach ISO 2719),with a flash point above 20 ° C, preferably above 40 ° C (measured according to ISO 2719),
mit einem Molekulargewicht von 80 bis 160, vorzugsweise 1 10 bis 145,with a molecular weight of 80 to 160, preferably 1 10 to 145,
mit einem Siedepunkt von 90 bis 210, vorzugsweise 1 10 bis 165°C.with a boiling point of 90 to 210, preferably 1 10 to 165 ° C.
Die Stickstoffverbindungen B umfassen beispielsweiseThe nitrogen compounds B include, for example
Lactone wie CaprolactonLactones such as caprolactone
Nitrile wie 2-Nonennitril und Verbindungen der FormelNitriles such as 2-nonenenitrile and compounds of the formula
wobeiin which
R1 bis R4 unabhängig voneinander für Wasserstoff oder Cι-C4-Alkyl, bevorzugt Methyl oder Ethyl stehen.R 1 to R 4 independently of one another are hydrogen or C 1 -C 4 -alkyl, preferably methyl or ethyl.
Bevorzugte Verbindungen (I) sind z.B. 2-Methylpyrazin, 2,3-Dimethylpyrazin, 2,6-Preferred compounds (I) are e.g. 2-methylpyrazine, 2,3-dimethylpyrazine, 2,6-
Dimethylpyrazin, 2,3,5-Trimethylpyrazin, Tetramethylpyrazin, 2-Ethylpyrazin, 2,3- Diethylpyrazin, 5,2-Methylethylpyrazin, 2,3-Methylethylpyrazin. 5,2,3-Methyl- diethylpyrazin und 3,5.2- sowie 3,6,2-Dimethylethylpyrazin, 2,3-Methylethylpyrazin und Tetramethylpyrazin sind bevorzugt. Die Stickstoffverbindungen B können in Mengen von 1 bis 100, vorzugsweise 30 bis 100, insbesondere 10 bis 50 Gewichtsteilen pro 1 000 Gewichtsteile A eingesetzt werden.Dimethylpyrazine, 2,3,5-trimethylpyrazine, tetramethylpyrazine, 2-ethylpyrazine, 2,3-diethylpyrazine, 5,2-methylethylpyrazine, 2,3-methylethylpyrazine. 5,2,3-methyl-diethylpyrazine and 3,5,2- and 3,6,2-dimethylethylpyrazine, 2,3-methylethylpyrazine and tetramethylpyrazine are preferred. The nitrogen compounds B can be used in amounts of 1 to 100, preferably 30 to 100, in particular 10 to 50 parts by weight per 1,000 parts by weight A.
Die Odoriermittel können zum Schutz vor unerwünschter Oxidation Antioxidantien enthalten, wie sie beispielsweise bei Römpp-Lexikon Chemie Version 1.3 beschrieben sind. Bevorzugte Antioxidantien umfassen Butylhydroxyanisol, Jonol = tert.-Butylhydroxytoluol, Hydrochinonmonomethylether und α-Tocopherol.To protect against unwanted oxidation, the odorants can contain antioxidants, as described, for example, in Römpp-Lexikon Chemie Version 1.3. Preferred antioxidants include butylated hydroxyanisole, Jonol = tert-butylated hydroxytoluene, hydroquinone monomethyl ether and α-tocopherol.
Die Antioxidantien C werden bevorzugt in Mengen von 0,01 bis 5, insbesondere 0,05 bis 2, speziell 0,1 bis 1 Gewichtsteilen pro 1 000 Gewichsteile A eingesetzt.The antioxidants C are preferably used in amounts of 0.01 to 5, in particular 0.05 to 2, especially 0.1 to 1 part by weight per 1,000 parts by weight A.
Bevorzugte Gasodorierungsmittel können beispielsweise folgende Zusammen- Setzungen besitzen: Preferred gas odorants can have, for example, the following compositions:
Beispiel 1example 1
Ethylacrylat 600 gEthyl acrylate 600 g
Methylacrylat 360 gMethyl acrylate 360 g
5,2,3-Methyldiethylpyrazin 39 g5,2,3-methyldiethylpyrazine 39 g
Jonol l gJonol l g
Beispiel 2Example 2
Ethylacrylat 535 gEthyl acrylate 535 g
Methylacrylat 400 gMethyl acrylate 400 g
2-Methylpyrazin 64 g2-methylpyrazine 64 g
Jonol i gJonol i g
Beispiel 3Example 3
Ethylacrylat 320 gEthyl acrylate 320 g
Methylacrylat 637 gMethyl acrylate 637 g
3,5(6),2-Dimethylethylpyrazin 42 g3.5 (6), 2-dimethylethylpyrazine 42 g
Jonol i gJonol i g
Beispiel 4Example 4
Ethylacrylat 460 gEthyl acrylate 460 g
Methylacrylat 460 gMethyl acrylate 460 g
2,6-Dimethylpyrazin 79 g2,6-dimethylpyrazine 79 g
Jonol l g Beispiel 5Jonol lg Example 5
Ethylacrylat 520 gEthyl acrylate 520 g
Methylacrylat 459 gMethyl acrylate 459 g
2,3,5-Trimethylpyrazin 20 g2,3,5-trimethylpyrazine 20 g
Jonol i gJonol i g
Beispiel 6Example 6
Ethylacrylat 885 gEthyl acrylate 885 g
Methylacrylat 100 gMethyl acrylate 100 g
2,3-Methylethylpyrazin H g2,3-methylethylpyrazine H g
Jonol i gJonol i g
Beispiel 7Example 7
Ethylacrylat 700 gEthyl acrylate 700 g
Methylacrylat 274 gMethyl acrylate 274 g
2,3-Dimethylpyrazin 25 g2,3-dimethylpyrazine 25 g
Jonol i gJonol i g
Beispiel 8Example 8
Ethylacrylat 350 gEthyl acrylate 350 g
Methylacrylat 600 gMethyl acrylate 600 g
Tetramethylpyrazin 49 gTetramethylpyrazine 49 g
Jonol i g Beispiel 9Jonol ig Example 9
Ethylacrylat 144 gEthyl acrylate 144 g
Methylacrylat 800 gMethyl acrylate 800 g
2-Ethylpyrazin 56 g2-ethyl pyrazine 56 g
Beispiel 10Example 10
Ethylacrylat 615 gEthyl acrylate 615 g
Methylacrylat 300 gMethyl acrylate 300 g
5,2-Methylethylpyrazin 85 g5,2-methylethylpyrazine 85 g
Beispiel 11Example 11
Ethylacrylat 320 gEthyl acrylate 320 g
Methylacrylat 649 gMethyl acrylate 649 g
3,5(6),2-Dimethylethylpyrazin 15 g3.5 (6), 2-dimethylethylpyrazine 15 g
2,3-Dimethylethylpyrazin 15 g2,3-dimethylethylpyrazine 15 g
Jonol i gJonol i g
Beispiel 12Example 12
Ethylacrylat 120 gEthyl acrylate 120 g
Methylacrylat 807 gMethyl acrylate 807 g
2-Ethylpyrazin 30 g2-ethyl pyrazine 30 g
5,2-Methylethylpyrazin 42 g5,2-methylethylpyrazine 42 g
Jonol i g Beispiel 13Jonol ig Example 13
Ethylacrylat 520 gEthyl acrylate 520 g
Methylacrylat 434 gMethyl acrylate 434 g
2,6-Dimethylpyrazin 20 g2,6-dimethylpyrazine 20 g
2,3-Methylethylpyrazin 25 g2,3-methylethylpyrazine 25 g
Jonol i gJonol i g
Beispiel 14Example 14
Ethylacrylat 320 gEthyl acrylate 320 g
Methylacrylat 633 gMethyl acrylate 633 g
2,3-Diethylpyrazin 34 g2,3-diethylpyrazine 34 g
2,3-Methylethylpyrazin 12 g2,3-methylethylpyrazine 12 g
Jonol l gJonol l g
Beispiel 15Example 15
Ethylacrylat 759 gEthyl acrylate 759 g
Methylacrylat 200 gMethyl acrylate 200 g
2-Methylpyrazin 30 g2-methylpyrazine 30 g
Tetramethylpyrazin 10 gTetramethylpyrazine 10 g
Jonol l g Jonol l g

Claims

Patentansprüche claims
1. Verfahren zum Odorieren von Gas durch Zusatz1. Method for odorizing gas by addition
A. mindestens eines Acrylsäure-C ι -C j 2-alky lesters,A. at least one acrylic acid C 1 -C 2 alkyl reader,
B. mindestens einer N- Verbindung mit einem Siedpunkt von 90 bis 210°C und einem Molekulargewicht von 80 bis 160 und gegebenenfallsB. at least one N compound with a boiling point of 90 to 210 ° C and a molecular weight of 80 to 160 and optionally
C. eines Antioxidans.C. an antioxidant.
2. Verfahren nach Anspruch 1, wonach man mindestens 2 verschiedene Acryl- säureester A zusetzt.2. The method according to claim 1, after which at least 2 different acrylic acid esters A are added.
3. Verfahren nach Anspruch 1, wonach man als Komponente A eine Mischung aus zwei unterschiedlichen Acrylsäure-C j-C6-alkylestern zusetzt.3. The method according to claim 1, according to which a mixture of two different acrylic acid-C jC 6 alkyl esters is added as component A.
4. Verfahren nach Anspruch 3, wonach das Gewichtsverhältnis der beiden Acrylsäureester-Klassen 9:l bis 1 :9 beträgt.4. The method according to claim 3, wherein the weight ratio of the two classes of acrylic acid ester is 9: 1 to 1: 9.
5. Verfahren nach Ansprüchen 1 bis 4, wonach man als Komponente B eine Verbindung der Formel5. The method according to claims 1 to 4, after which as component B a compound of the formula
einsetzt, wobeiuses, whereby
R1 bis R4 unabhängig voneinander für Wasserstoff oder C C^Alkyl stehen. R 1 to R 4 are independently hydrogen or CC ^ alkyl.
6. Verfahren nach Ansprüchen 1 bis 5, wonach die Komponente B in einer Menge von 1 bis 100 Gewichtsteilen pro 1 000 Gewichtsteile A eingesetzt wird.6. The method according to claims 1 to 5, wherein component B is used in an amount of 1 to 100 parts by weight per 1,000 parts by weight A.
7. Verfahren nach Ansprüchen 1 bis 6, wonach die Komponente C in einer Menge von 0,01 bis 5 Gewichtsteilen pro 1 000 Gewichtsteile A eingesetzt wird.7. The method according to claims 1 to 6, wherein component C is used in an amount of 0.01 to 5 parts by weight per 1,000 parts by weight A.
8. Nach Verfahren gemäß Ansprüchen 1 bis 6 odoriertes Gas. 8. Process odorized according to claims 1 to 6.
EP99944331A 1998-08-17 1999-08-04 Gas odorization method Expired - Lifetime EP1109881B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
SI9930239T SI1109881T1 (en) 1998-08-17 1999-08-04 Gas odorization method
EP03004711A EP1329495B1 (en) 1998-08-17 1999-08-04 Composition for gas odorization

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19837066A DE19837066A1 (en) 1998-08-17 1998-08-17 Odorizing a gas, e.g. city gas comprises adding an acrylic acid, nitrogen compound and antioxidant to the gas
DE19837066 1998-08-17
PCT/EP1999/005639 WO2000011120A1 (en) 1998-08-17 1999-08-04 Gas odorization method

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EP1109881A1 true EP1109881A1 (en) 2001-06-27
EP1109881B1 EP1109881B1 (en) 2003-03-05

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US (1) US7108803B1 (en)
EP (2) EP1329495B1 (en)
JP (1) JP3818060B2 (en)
AT (2) ATE233802T1 (en)
AU (1) AU750863B2 (en)
BR (1) BR9913053A (en)
CA (1) CA2340729C (en)
CZ (1) CZ296172B6 (en)
DE (3) DE19837066A1 (en)
DK (2) DK1109881T3 (en)
EE (1) EE200100095A (en)
ES (2) ES2292868T3 (en)
HU (1) HU227576B1 (en)
IL (1) IL141169A (en)
MX (1) MXPA01001769A (en)
NO (1) NO330898B1 (en)
PL (1) PL190984B1 (en)
PT (1) PT1109881E (en)
RU (1) RU2226207C2 (en)
SK (1) SK286720B6 (en)
TR (1) TR200100463T2 (en)
WO (1) WO2000011120A1 (en)
YU (1) YU49389B (en)

Cited By (2)

* 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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CN115057764A (en) * 2022-06-30 2022-09-16 辽宁厚安科技有限公司 Polymerization inhibitor for sulfur-free odorizing agent

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