EP1109881B1 - Gas odorization method - Google Patents

Gas odorization method Download PDF

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Publication number
EP1109881B1
EP1109881B1 EP99944331A EP99944331A EP1109881B1 EP 1109881 B1 EP1109881 B1 EP 1109881B1 EP 99944331 A EP99944331 A EP 99944331A EP 99944331 A EP99944331 A EP 99944331A EP 1109881 B1 EP1109881 B1 EP 1109881B1
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Prior art keywords
gas
acrylate
process according
jonol
weight
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German (de)
French (fr)
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EP1109881A1 (en
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Gerd Mansfeld
Ute Rohde
Fritz Henke
Heribert Kaesler
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Dragoco Gerberding and Co GmbH
EOn Ruhrgas AG
Symrise AG
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Haarmann and Reimer GmbH
Ruhrgas 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 gas odorization.
  • City and coke oven gases obtained by thermal processes contained intense smelling components and therefore had a strong inherent smell, so that escaping Gas could be perceived easily.
  • 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 6 -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 compounds (I) are e.g. 2-methylpyrazine, 2,3-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyrazine, tetramethylpyrazine, 2-ethylpyrazine, 2,3-diethylpyrazine, 5,2-methylethylpyrazine, 2,3-methylethylpyrazine, 5,2,3-methyldiethylpyrazine 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 of A are used become.
  • the odorants can be used to protect against unwanted oxidation antioxidants included, as for example in Römpp-Lexikon Chemie Version 1.3 are described.
  • the antioxidants C are preferred in amounts of 0.01 to 5, in particular 0.05 up to 2, especially 0.1 to 1 part by weight per 1,000 parts by weight A.
  • Preferred gas odorants can, for example, have the following compositions have:

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

Abstract

Odorizing a gas comprises adding a 1-12C acrylic acid, a nitrogen compound having a boiling point of 90-210 degrees C and a molecular weight of 80-160, and an antioxidant.

Description

Die vorliegende Erfindung betrifft die Odorierung von Gas.The present invention relates to gas odorization.

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 intense smelling components and therefore had a strong inherent smell, so that escaping Gas could be perceived easily.

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 unangenehmen Geruchs wunschgemäß eine Alarmassoziation beim Menschen hervor. 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.Due 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 own smell 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 exceptionally unpleasant smell, can cause an alarm association in humans as desired. In Germany about 90% of the process gas is currently 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 und Haushalte geläufige Riechstoffe scheiden aus). Er soll bei Menschen, die ausgetretenes Gas riechen, eine Alarmassoziation hervorrufen.
  • 2. Jede Person mit durchschnittlichem Riechvermögen und durchschnittlicher physiologischer Kondition muß den Geruch wahrnehmen können.
  • 3. Die Warngeruchsstufe (= mittlere Geruchsintensivität) muß erreicht werden, bevor die Zündgrenze oder ein kinetischer Kohlenmonoxid-Gehalt erreicht ist.
  • 4. Das Odoriermittel soll möglichst ungiftig sein und darf keine toxischen Verbrennungsprodukte bilden.
  • 5. Das Odoriermittel soll eine hohe Flüchtigkeit aufweisen und möglichst rückstandsfrei verdampfen.
  • 6. Ein geeignetes Odoriermittel darf weder bei winterlichen Temperaturen kondensieren noch sich entmischen noch an metallischen Leitungen haften.
  • 7. Das Odoriermittel soll rückstandsfrei verbrennen.
  • 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.
    • THT and mercaptans 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 (fragrances common in the kitchen and households are eliminated). It is said to cause an alarm association in people who smell leaking gas.
  • 2. Every person with average smell and average physiological condition must be able to perceive the smell.
  • 3. The warning odor level (= average odor intensity) must be reached before the ignition limit or a kinetic carbon monoxide content is reached.
  • 4. The odorant should be as non-toxic as possible and must not form toxic combustion products.
  • 5. The odorant should be highly volatile and evaporate as residue-free as possible.
  • 6. A suitable odorant must neither condense at winter temperatures nor segregate nor adhere to metallic lines.
  • 7. The odorant should burn without residue.
  • 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 common seals.

    • Man hat bereits Anstrengungen unternommen, neue Gasodoriermittel bereitzustellen. So wurden beispielsweise vorgeschlagen

    • Alkylacrylate, Vinyl- bzw. Alkylether und deren Mischungen (JP 51-7481),
    • n-Valeriansäure, in Kombination mit Ethylacrylat und/gegebenenfalls Triethylamin (JP 51-34 841),
    • Mischungen aus Schwefelverbindungen und aliphatischem Aldehyd (JP 53-35 562),
    • Cycohexen (JP 58-42 235),
    • Norbornenderivate (JP 62-1998) und
    • gesättigte Ether, gesättigte Ester sowie deren Mischungen mit Mercaptanen.
    Efforts have been made to provide new gas odorants. For example, have been suggested
    • Alkyl acrylates, vinyl or alkyl ethers and mixtures thereof (JP 51-7481),
    • n-valeric acid, in combination with ethyl acrylate and / or triethylamine (JP 51-34 841),
    • Mixtures of sulfur compounds and aliphatic aldehyde (JP 53-35 562),
    • Cycohexene (JP 58-42 235),
    • Norbornene derivatives (JP 62-1998) and
    • saturated ethers, saturated esters and their mixtures with mercaptans.

    Es wurde nun gefunden, daß man durch Zusätze von

  • A. Acrylsäure-C1-C12-, vorzugsweise-C1-C8-alkylestem,
  • B. Bestimmten Stickstoffverbindungen und gegebenenfalls
  • C. Antioxidantien
    • 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.It has now been found that additions of
  • A. acrylic acid-C 1 -C 12 -, preferably-C 1 -C 8 -alkyl esters,
  • B. Certain nitrogen compounds and optionally
  • C. Antioxidants
    • 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 Acrylsäureester 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-C1-C6-alkylestem eingesetzt; eine besonders bevorzugte Kombination enthält nebeneinander Acrylsäuremethyl- und -ethylester. Die Acrylatmischungen 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 6 -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.

    Die Stickstoffverbindungen B umfassen vor allem Verbindungen

    • mit einem Flammpunkt über 20°C, vorzugsweise über 40°C (gemessen nach ISO 2719),
    • mit einem Molekulargewicht von 80 bis 160, vorzugsweise 110 bis 145,
    • mit einem Siedepunkt von 90 bis 210, vorzugsweise 110 bis 165°C.
    The nitrogen compounds B mainly comprise compounds
    • with a flash point above 20 ° C, preferably above 40 ° C (measured according to ISO 2719),
    • with a molecular weight of 80 to 160, preferably 110 to 145,
    • with a boiling point of 90 to 210, preferably 110 to 165 ° C.

    und sind Verbindungen der Formel

    Figure 00040001
    wobei

    R1 bis R4
    unabhängig voneinander für Wasserstoff oder C1-C4-Alkyl, bevorzugt Methyl oder Ethyl stehen.
    and are compounds of the formula
    Figure 00040001
    in which
    R 1 to R 4
    are independently hydrogen or C 1 -C 4 alkyl, preferably methyl or ethyl.

    Bevorzugte Verbindungen (I) sind z.B. 2-Methylpyrazin, 2,3-Dimethylpyrazin, 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. Preferred compounds (I) are e.g. 2-methylpyrazine, 2,3-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethylpyrazine, tetramethylpyrazine, 2-ethylpyrazine, 2,3-diethylpyrazine, 5,2-methylethylpyrazine, 2,3-methylethylpyrazine, 5,2,3-methyldiethylpyrazine and 3,5,2- and 3,6,2-dimethylethylpyrazine, 2,3-methylethylpyrazine and tetramethylpyrazine are preferred.

    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.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 of A are used become.

    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.The odorants can be used to protect against unwanted oxidation antioxidants included, as for example in Römpp-Lexikon Chemie Version 1.3 are described. 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 preferred in amounts of 0.01 to 5, in particular 0.05 up to 2, especially 0.1 to 1 part by weight per 1,000 parts by weight A.

    Bevorzugte Gasodorierungsmittel können beispielsweise folgende Zusammensetzungen besitzen: Preferred gas odorants can, for example, have the following compositions have:

    Beispiel 1example 1

    Ethylacrylatethyl acrylate 600 g600 g Methylacrylatmethyl acrylate 360 g360 g 5,2,3-Methyldiethylpyrazin5,2,3-Methyldiethylpyrazin 39 g39 g JonolJonol 1 g1 g

    Beispiel 2Example 2

    Ethylacrylatethyl acrylate 535 g535 g Methylacrylatmethyl acrylate 400 g400 g 2-Methylpyrazin2-methylpyrazine 64 g64 g JonolJonol 1 g1 g

    Beispiel 3Example 3

    Ethylacrylatethyl acrylate 320 g320 g Methylacrylatmethyl acrylate 637 g637 g 3,5(6),2-Dimethylethylpyrazin3.5 (6), 2-Dimethylethylpyrazin 42 g42 g JonolJonol 1 g1 g

    Beispiel 4Example 4

    Ethylacrylatethyl acrylate 460 g460 g Methylacrylatmethyl acrylate 460 g460 g 2,6-Dimethylpyrazin2,6-dimethyl pyrazine 79 g79 g JonolJonol 1 g1 g

    Beispiel 5Example 5

    Ethylacrylatethyl acrylate 520 g520 g Methylacrylatmethyl acrylate 459 g459 g 2,3,5-Trimethylpyrazin2,3,5-trimethyl pyrazine 20 g20 g JonolJonol 1 g1 g

    Beispiel 6Example 6

    Ethylacrylatethyl acrylate 885 g885 g Methylacrylatmethyl acrylate 100 g100 g 2,3-Methylethylpyrazin2,3-methylethylpyrazine 14 g14 g JonolJonol 1 g1 g

    Beispiel 7Example 7

    Ethylacrylatethyl acrylate 700 g700 g Methylacrylatmethyl acrylate 274 g274 g 2,3-Dimethylpyrazin2,3-dimethylpyrazine 25 g25 g JonolJonol 1 g1 g

    Beispiel 8Example 8

    Ethylacrylatethyl acrylate 350 g350 g Methylacrylatmethyl acrylate 600 g600 g Tetramethylpyrazintetramethylpyrazine 49 g49 g JonolJonol 1 g1 g

    Beispiel 9Example 9

    Ethylacrylatethyl acrylate 144 g144 g Methylacrylatmethyl acrylate 800 g800 g 2-Ethylpyrazin2-ethyl pyrazine 56 g56 g

    Beispiel 10Example 10

    Ethylacrylatethyl acrylate 615 g615 g Methylacrylatmethyl acrylate 300 g300 g 5,2-Methylethylpyrazin5,2-methylethylpyrazine 85 g85 g

    Beispiel 11Example 11

    Ethylacrylatethyl acrylate 320 g320 g Methylacrylatmethyl acrylate 649 g649 g 3,5(6),2-Dimethylethylpyrazin3.5 (6), 2-Dimethylethylpyrazin 15 g15 g 2,3-Dimethylethylpyrazin2,3-Dimethylethylpyrazin 15 g15 g JonolJonol 1 g1 g

    Beispiel 12Example 12

    Ethylacrylatethyl acrylate 120 g120 g Methylacrylatmethyl acrylate 807 g807 g 2-Ethylpyrazin2-ethyl pyrazine 30 g30 g 5,2-Methylethylpyrazin5,2-methylethylpyrazine 42 g42 g JonolJonol 1 g1 g

    Beispiel 13Example 13

    Ethylacrylatethyl acrylate 520 g520 g Methylacrylatmethyl acrylate 434 g434 g 2,6-Dimethylpyrazin2,6-dimethyl pyrazine 20 g20 g 2,3-Methylethylpyrazin2,3-methylethylpyrazine 25 g25 g JonolJonol 1 g1 g

    Beispiel 14Example 14

    Ethylacrylatethyl acrylate 320 g320 g Methylacrylatmethyl acrylate 633 g633 g 2,3-Diethylpyrazin2,3-diethylpyrazine 34 g34 g 2,3-Methylethylpyrazin2,3-methylethylpyrazine 12 g12 g JonolJonol 1 g1 g

    Beispiel 15Example 15

    Ethylacrylatethyl acrylate 759 g759 g Methylacrylatmethyl acrylate 200 g200 g 2-Methylpyrazin2-methylpyrazine 30 g30 g Tetramethylpyrazintetramethylpyrazine 10 g10 g JonolJonol 1 g1 g

    Claims (7)

    1. A process for odorising a gas by adding
      A at least one C1-C12-alkyl acrylate,
      B at least one compound of the formula (I)
      Figure 00120001
         wherein
         R1 to R4, independently, represent hydrogen or a C1-C4-alkyl group and optionally
      C an antioxidant.
    2. A process according to Claim 1, wherein at least 2 different acrylates A are added.
    3. A process according to Claim 1, wherein a mixture of two different C1-C6-alkyl acrylates is added as component A.
    4. A process according to Claim 3, wherein the ratio by weight of the two kinds of acrylate is 9:1 to 1:9.
    5. A process according to Claims 1 to 4, wherein component B is used in an amount of 1 to 100 parts by weight per 1 000 parts by weight of A.
    6. A process according to Claims 1 to 5, wherein component C is used in an amount of 0.01 to 5 parts by weight per 1 000 parts by weight of A.
    7. An odorised gas, characterised in that it is obtainable by a process according to one of Claims 1 to 6.
    EP99944331A 1998-08-17 1999-08-04 Gas odorization method Expired - Lifetime EP1109881B1 (en)

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    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
    DE19837066 1998-08-17
    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
    PCT/EP1999/005639 WO2000011120A1 (en) 1998-08-17 1999-08-04 Gas odorization method

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    EP1109881B1 true EP1109881B1 (en) 2003-03-05

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    EP1109881A1 (en) 2001-06-27
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    AU5730899A (en) 2000-03-14
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    EP1329495A3 (en) 2006-04-05
    CA2340729A1 (en) 2000-03-02
    WO2000011120A1 (en) 2000-03-02
    HU227576B1 (en) 2011-08-29
    NO330898B1 (en) 2011-08-08
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    HUP0103084A3 (en) 2003-01-28
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    SK286720B6 (en) 2009-04-06
    PT1109881E (en) 2003-07-31

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