EP2038382B1 - Melange odorisant pour combustible gazeux inodore - Google Patents

Melange odorisant pour combustible gazeux inodore Download PDF

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Publication number
EP2038382B1
EP2038382B1 EP07803935.1A EP07803935A EP2038382B1 EP 2038382 B1 EP2038382 B1 EP 2038382B1 EP 07803935 A EP07803935 A EP 07803935A EP 2038382 B1 EP2038382 B1 EP 2038382B1
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EP
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Prior art keywords
acrylate
composition
chosen
butyl
gaseous fuel
Prior art date
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Active
Application number
EP07803935.1A
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German (de)
English (en)
French (fr)
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EP2038382A2 (fr
Inventor
Patrick Charles
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Arkema France SA
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Arkema France SA
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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
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • 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
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • 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
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites

Definitions

  • the present invention relates to the field of odorants for gaseous fuels, in particular odorless, and more particularly to odorant compositions for the detection of gas leaks and the prevention of explosion risks resulting therefrom free of sulfur compound.
  • gaseous fuels used today whether natural gas, propane, butane, liquefied petroleum gas (or LPG), or even oxygen (for example for welds), are essentially odorless, either because of their origin or because of the purification treatment they received.
  • Natural gas is generally sent odorless to the consuming countries from the production sites, after an appropriate purification treatment, either by gas pipeline or (in a liquid state) in specialized vessels (LNG carriers).
  • LNG carriers specialized vessels
  • natural gas is thus received in a limited number of injection stations where the odorant is injected so that the natural gas that circulates both in the French pipeline network, and that stored in Underground tanks are odorised, allowing easy detection in the event of a leak, regardless of the portion of the network where it occurs.
  • natural gas can be distributed on the territory by a network of gas pipelines in which it circulates without odorant, which is then odorized at the entrance of the cities where it is consumed, which requires a number even higher injection stations.
  • the storage bins are most often maintained under nitrogen or natural gas in order to limit, at this stage, the risk of explosion.
  • alkyl sulphides and / or mercaptans used as odorants alone or as a mixture. Mention may be made, for example, of diethylsulfide, dimethylsulfide, methylethylsulfide or tetrahydrothiophene, tert-butyl mercaptan, isopropyl mercaptan which are widely used for their excellent properties, in particular those capable of triggering an alarming feeling in people in the event of leakage. accidental natural gas, and to initiate the necessary safeguarding operations as soon as possible.
  • odorant mixtures without sulfur compounds have been proposed: As examples, mention may be made of PL 72057 which describes odorant mixtures based on dicyclopentadiene, JP41-73895 specific ether and ester mixtures, WO 02/42396 mixtures based on norbornene or its derivatives, JP 80-060167 mixtures based on 5-ethylidene-2 norbornene and a 2-alkoxy-3-alkylpyrazine.
  • DE 19837066 describes a process for odorizing natural gas by adding a mixture comprising an alkyl acrylate, a nitrogen compound of the pyrazine type, and an antioxidant.
  • this mixture has the disadvantage of not having a characteristic odor of gas and is therefore likely to be confusing in the event of gas leakage. The risk is of course the non-detection of this leak and explosion, if the concentration of gas in the air reaches its lower explosive limit.
  • WO 2004/024852 discloses an odorant consisting of four components including an alkyl acrylate, an alkyl sulfide and an antioxidant stabilizing agent such as tert-butylhydroxytoluene, hydroquinone, etc .
  • WO 2005/103210 discloses an odorless gas odorant gas mixture consisting of an alkyl sulfide, an alkyl acrylate and a nitroxide alkyl acrylate polymer inhibiting compound.
  • acrylates are very reactive monomers which can polymerize spontaneously, especially on storage, to form polyacrylates.
  • uncontrolled polymerization is likely to endanger people in the vicinity of injection stations, such as residents or maintenance workers, because of a risk of explosion.
  • This polymerization occurring during storage, including for example in the bins or storage tanks of the injection stations, can also lead to fouling or even a quick clogging of the pipes between the storage tank and the injection point.
  • Such a phenomenon can lead to an uncontrolled decline in the concentration of odorant in natural gas, which increases the risk of undetected gas leakage.
  • hydroquinones are commonly added in acrylate-based odorant compositions to inhibit their polymerization, such as taught in US 3,816,267 which concerns the manufacture of acrylate.
  • the hydroquinone-based inhibitor system needs oxygen because the active form of the inhibitor is a molecule comprising a radical which is formed as a result of the reaction of the inhibitor with oxygen and traps the precursors of polymerization.
  • This inhibitor requires having a storage of the odorant mixture in air. This condition is not fulfilled when an odorant storage tank is pressurized with natural gas, which makes it possible to increase the efficiency of the odorant injection pumps in the gas. Storage under nitrogen also exists.
  • hydroquinone can not react with oxygen to form a radical and therefore does not play its role of inhibitor, which puts the user in danger of explosion risk uncontrolled polymerization but also can cause a fouling or even a quick clogging of the pipes between the storage tank and the injection point. This last point results in an uncontrolled decrease in the concentration of the odorant in the gas, which increases the risk of explosion due to undetected gas leaks.
  • the odorant mixture based on alkyl acrylate (s) according to the invention overcomes the disadvantages described above due not only to the absence of sulfur compound in the mixture (no release of SO 2 ) but also the absence of oxygen necessary for the activation of the non-nitroxylated polymerization inhibitors.
  • the odorant mixture according to the invention has a storage stability, regardless of the nature of the cover gas, whether or not containing oxygen.
  • the inhibitors do not require storage of the odoriferous compositon under air, while storage under air is made necessary for free radicals hydroquinone type.
  • This has the advantage, at the gas injection stations, of being able to store the odorizing composition in a suitable tank under pressure of natural gas and thus to be able to increase the efficiency of the injection pumps.
  • the odorant compositions according to the invention can also be stored under nitrogen in certain natural gas injection stations where the storage tanks are under nitrogen.
  • the compounds of formula (I) are preferably chosen from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl acrylates. , heptyl, octyl and / or dodecyl, and advantageously chosen from methyl acrylate, ethyl acrylate and / or n-butyl acrylate.
  • the composition according to the invention comprises, as inhibitor of formula (II), at least one compound derived from tetramethylpiperidine oxide (also known as TEMPO) of formula (IIa): wherein R 3 represents a hydroxy, amino, ester or amide group, preferably R 3 COO-, R 3 CON- where R 3 is a C 1 -C 4 alkyl radical.
  • TEMPO tetramethylpiperidine oxide
  • the polymerization inhibitor (s) (II) are used in an amount of 50 ppb to 1000 ppm by weight relative to the mass of acrylate (s) present in the mixture.
  • the odorizing composition according to the invention gives gaseous fuels, in particular natural gas after it has been injected into it, a high odor power, comparable to that obtained with odorants based on alkyl sulfides or mercaptans of the art. previous, allowing any person in the vicinity of a leak to recognize it, and to engage the appropriate security measures. This strong odor power is obtained at the same time as the disappearance of SO 2 released into the ecosphere after combustion of the gas thus odorized.
  • the present invention also relates to a process for odorizing an odorless gaseous fuel comprising the addition of an effective amount of a previously defined odorant composition consisting of at least one alkyl acrylate and at least one compound ( II) polymerization inhibitor of alkyl acrylates stable in the presence and in the absence of oxygen and optionally a solvent or a mixture of solvents inert to acrylates; said composition being characterized in that it comprises 50 ppb to 1000 ppm by weight of inhibitor (s) (II) relative to the mass of acrylate (s) present (s).
  • the amount of said composition can be determined by those skilled in the art through systematic tests, taking into account the particular characteristics of the gaseous fuel, and distribution networks.
  • this effective amount is in general between 1 and 500 mg / Nm 3 , preferably between 2 and 50 mg / Nm 3 .
  • composition according to the invention described above can be used as it is or be diluted in a solvent or a mixture of solvents inert with respect to the acrylates.
  • solvents mention may be made of cyclohexane and n-hexane.
  • the dilution of the composition can reach 85%, and 15 parts by weight of the composition according to the invention are diluted in 85 parts by weight of solvent.
  • the gaseous fuels to which the process according to the invention applies include: natural gas, propane, butane, liquefied petroleum gas (or LPG), or even oxygen or hydrogen, such as that generated by fuel cells.
  • natural gas propane, butane, liquefied petroleum gas (or LPG), or even oxygen or hydrogen, such as that generated by fuel cells.
  • LPG liquefied petroleum gas
  • oxygen or hydrogen such as that generated by fuel cells.
  • Natural gas is a preferred gaseous fuel according to the present invention because of its very wide diffusion and the importance of the distribution networks, making it particularly desirable to reduce any danger arising from a risk of leakage.
  • composition that can be used as odorant is added by injection into the specialized stations according to the usual techniques used in this field.
  • the sulfur dioxide content formed, after combustion of the gas thus odorized is equal to 7.3 mg / Nm 3 .
  • the gas thus odorized is subjected to an olfactory test from which it appears that it has a strong odor and therefore a good warning power.
  • Example 1 is then repeated by injecting into natural gas 10 mg per Nm 3 of the composition thus prepared in place of tetrahydrothiophene.
  • the content of sulfur dioxide formed, after combustion of the gas thus perfumed, is equal to 0 mg / Nm. 3 .
  • the gas thus odorized is subjected to an olfactory test, from which it emerges that the gas thus odorized has a good alerting power (strong odorous power similar (in intensity) to that of the composition of Example 1).
  • Example 1 is then repeated by injecting into natural gas 10 mg per Nm 3 of the composition thus prepared in place of the tetrahydrothiophene.
  • the sulfur dioxide content formed, after combustion of the gas thus odorized, is equal to 0 mg / Nm 3 .
  • the gas thus odorized is subjected to an olfactory test, from which it emerges that the gas thus odorized has a good alerting power (strong odorous power similar (in intensity) to that of the composition of Example 1)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
EP07803935.1A 2006-06-26 2007-06-25 Melange odorisant pour combustible gazeux inodore Active EP2038382B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0652636A FR2902798B1 (fr) 2006-06-26 2006-06-26 Melange odorisant pour combustible gazeux inodore
US85858706P 2006-11-13 2006-11-13
PCT/FR2007/051512 WO2008001000A2 (fr) 2006-06-26 2007-06-25 Melange odorisant pour combustible gazeux inodore

Publications (2)

Publication Number Publication Date
EP2038382A2 EP2038382A2 (fr) 2009-03-25
EP2038382B1 true EP2038382B1 (fr) 2019-04-03

Family

ID=37763994

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07803935.1A Active EP2038382B1 (fr) 2006-06-26 2007-06-25 Melange odorisant pour combustible gazeux inodore

Country Status (17)

Country Link
US (1) US8317887B2 (zh)
EP (1) EP2038382B1 (zh)
JP (1) JP5110662B2 (zh)
KR (2) KR101130599B1 (zh)
CN (3) CN101553557A (zh)
AU (1) AU2007264760B2 (zh)
BR (1) BRPI0713296B1 (zh)
CA (1) CA2655938C (zh)
DK (1) DK2038382T3 (zh)
EA (1) EA018470B1 (zh)
EG (1) EG26886A (zh)
FR (1) FR2902798B1 (zh)
MX (1) MX2009000180A (zh)
NZ (1) NZ574367A (zh)
TR (1) TR201907063T4 (zh)
WO (1) WO2008001000A2 (zh)
ZA (1) ZA200900266B (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101260331A (zh) * 2008-04-30 2008-09-10 西姆莱斯有限责任两合公司 具有改善的稳定性的气体加味剂
CA3002576A1 (en) * 2015-10-26 2017-05-04 Shell Internationale Research Maatschappij B.V. Odorized methane fluid and processes for producing odorized methane fluids and the use thereof
US10344237B2 (en) * 2017-04-13 2019-07-09 Welker, Inc. System and method for odorizing natural gas
FR3065375B1 (fr) 2017-04-25 2019-06-28 Arkema France Procede d'odorisation de fluide cryogenique
CN114561236B (zh) * 2022-01-24 2023-06-27 成都小号科技有限公司 一种适用于可燃气体泄露警示的环保添加剂

Citations (2)

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Publication number Priority date Publication date Assignee Title
DE19837066A1 (de) * 1998-08-17 2000-02-24 Haarmann & Reimer Gmbh Odorierung von Gas
WO2007042729A1 (fr) * 2005-10-11 2007-04-19 Arkema France Melange odorisant pour combustible gazeux inodore

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PL72057B1 (zh) 1971-02-16 1974-06-29
BE787750A (fr) 1971-08-20 1973-02-19 Union Carbide Corp Procede pour inhiber la polymerisation d'acrylates et methacrylates pendant leur distillation
JPS49131201A (zh) 1973-04-24 1974-12-16
JPS55137190A (en) 1979-04-11 1980-10-25 Tokyo Gas Co Ltd Addition of odor to fuel gas
JP2864164B2 (ja) 1990-11-05 1999-03-03 理研香料工業株式会社 燃料ガス用付臭剤
US5322960A (en) 1993-04-15 1994-06-21 Nippon Shokubai Co., Ltd. Method for inhibiting polymerization of (meth) acrylic acid and esters thereof
JP3378673B2 (ja) 1994-08-24 2003-02-17 東京瓦斯株式会社 燃料ガス用付臭剤
US5877344A (en) * 1997-06-13 1999-03-02 Ciba Specialty Chemicals Corporation Polymerization inhibition of acrylates using blends of nitroxides
US6300533B1 (en) * 1999-08-16 2001-10-09 Uniroyal Chemical Company, Inc. Inhibition of polymerization of ethylenically unsaturated monomers
DE10058805A1 (de) 2000-11-27 2002-06-06 Ticona Gmbh Odoriermittel für Gase
DE10240028A1 (de) * 2002-08-27 2004-03-11 Symrise Gmbh & Co. Kg Schwefelarme Odoriermittel für Flüssiggas
DE10359743A1 (de) * 2003-12-19 2005-07-14 Symrise Gmbh & Co. Kg Odorierung von Brenngas mit schwefelarmen Odoriermitteln
FR2868790B1 (fr) * 2004-04-08 2008-07-25 Arkema Sa Melange odorisant pour combustible gazeux inodore
US20060009732A1 (en) 2004-07-06 2006-01-12 Michael Hardy Method and apparatus for delivering a colonic lavage
JP4173895B2 (ja) 2006-03-31 2008-10-29 株式会社エヌ・ティ・ティ・ドコモ 広告配信システム

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Publication number Priority date Publication date Assignee Title
DE19837066A1 (de) * 1998-08-17 2000-02-24 Haarmann & Reimer Gmbh Odorierung von Gas
WO2007042729A1 (fr) * 2005-10-11 2007-04-19 Arkema France Melange odorisant pour combustible gazeux inodore

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KNIEBES D V: "PROPERTIES OF THE HUMAN OLFACTORY SYSTEM", IGT ODORIZATION SYMPOSIUM PROCEED, XX, XX, 1 January 1993 (1993-01-01), pages 59 - 72, XP008024485 *
MICHAEL K. GEORGES ET AL: "TEMPO-Mediated n -Butyl Acrylate Polymerizations", MACROMOLECULES, vol. 37, no. 4, 1 February 2004 (2004-02-01), US, pages 1297 - 1303, XP055294002, ISSN: 0024-9297, DOI: 10.1021/ma034409v *

Also Published As

Publication number Publication date
MX2009000180A (es) 2009-01-23
AU2007264760B2 (en) 2010-11-11
DK2038382T3 (da) 2019-05-20
EG26886A (en) 2014-11-19
CN104830390A (zh) 2015-08-12
WO2008001000A3 (fr) 2008-06-19
TR201907063T4 (tr) 2019-06-21
CN105779045A (zh) 2016-07-20
FR2902798A1 (fr) 2007-12-28
CA2655938C (fr) 2013-04-02
US8317887B2 (en) 2012-11-27
AU2007264760A1 (en) 2008-01-03
KR101130599B1 (ko) 2012-04-02
BRPI0713296B1 (pt) 2017-03-07
BRPI0713296A2 (pt) 2012-03-20
WO2008001000A2 (fr) 2008-01-03
EA200970057A1 (ru) 2009-06-30
FR2902798B1 (fr) 2009-04-24
JP5110662B2 (ja) 2012-12-26
KR20090024730A (ko) 2009-03-09
US20090300987A1 (en) 2009-12-10
CN104830390B (zh) 2020-08-21
NZ574367A (en) 2011-11-25
KR20110083758A (ko) 2011-07-20
JP2009541570A (ja) 2009-11-26
ZA200900266B (en) 2010-06-30
EP2038382A2 (fr) 2009-03-25
EA018470B1 (ru) 2013-08-30
CN101553557A (zh) 2009-10-07
CA2655938A1 (fr) 2008-01-03

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