EP2038382B1 - Melange odorisant pour combustible gazeux inodore - Google Patents
Melange odorisant pour combustible gazeux inodore Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- acrylate
- composition
- chosen
- butyl
- gaseous fuel
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 61
- 239000003205 fragrance Substances 0.000 title description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 64
- 239000003345 natural gas Substances 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000446 fuel Substances 0.000 claims description 20
- 239000003112 inhibitor Substances 0.000 claims description 19
- -1 N-(tert-butyl)-N-(1-[ethoxy(ethyl)phosphino]propyl) nitroxide Chemical class 0.000 claims description 18
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical class CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims 2
- 239000011877 solvent mixture Substances 0.000 claims 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000007789 gas Substances 0.000 description 29
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 238000003860 storage Methods 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 7
- 238000004880 explosion Methods 0.000 description 6
- 150000003464 sulfur compounds Chemical class 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 230000009965 odorless effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YBVRFTBNIZWMSK-UHFFFAOYSA-N 2,2-dimethyl-1-phenylpropan-1-ol Chemical compound CC(C)(C)C(O)C1=CC=CC=C1 YBVRFTBNIZWMSK-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(CC(*)CC1(C)C)N1[O+] Chemical compound CC(C)(CC(*)CC1(C)C)N1[O+] 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- XYWDPYKBIRQXQS-UHFFFAOYSA-N di-isopropyl sulphide Natural products CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical class CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical class CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
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)
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- 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)
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 |
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EP2038382A2 EP2038382A2 (fr) | 2009-03-25 |
EP2038382B1 true EP2038382B1 (fr) | 2019-04-03 |
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Application Number | Title | Priority Date | Filing Date |
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EP07803935.1A Active EP2038382B1 (fr) | 2006-06-26 | 2007-06-25 | Melange odorisant pour combustible gazeux inodore |
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US (1) | US8317887B2 (ru) |
EP (1) | EP2038382B1 (ru) |
JP (1) | JP5110662B2 (ru) |
KR (2) | KR20110083758A (ru) |
CN (3) | CN105779045A (ru) |
AU (1) | AU2007264760B2 (ru) |
BR (1) | BRPI0713296B1 (ru) |
CA (1) | CA2655938C (ru) |
DK (1) | DK2038382T3 (ru) |
EA (1) | EA018470B1 (ru) |
EG (1) | EG26886A (ru) |
FR (1) | FR2902798B1 (ru) |
MX (1) | MX2009000180A (ru) |
NZ (1) | NZ574367A (ru) |
TR (1) | TR201907063T4 (ru) |
WO (1) | WO2008001000A2 (ru) |
ZA (1) | ZA200900266B (ru) |
Families Citing this family (5)
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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 |
ES2827274T3 (es) * | 2015-10-26 | 2021-05-20 | Shell Int Research | Fluidos de metano odorizados y procesos para la producción de fluidos de metano odorizados y su uso |
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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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 |
Family Cites Families (15)
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PL72057B1 (ru) | 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 (ru) | 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 |
-
2006
- 2006-06-26 FR FR0652636A patent/FR2902798B1/fr active Active
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2007
- 2007-06-25 KR KR1020117015323A patent/KR20110083758A/ko not_active Application Discontinuation
- 2007-06-25 BR BRPI0713296A patent/BRPI0713296B1/pt active IP Right Grant
- 2007-06-25 KR KR1020087031544A patent/KR101130599B1/ko active IP Right Grant
- 2007-06-25 MX MX2009000180A patent/MX2009000180A/es active IP Right Grant
- 2007-06-25 EA EA200970057A patent/EA018470B1/ru unknown
- 2007-06-25 EP EP07803935.1A patent/EP2038382B1/fr active Active
- 2007-06-25 TR TR2019/07063T patent/TR201907063T4/tr unknown
- 2007-06-25 ZA ZA200900266A patent/ZA200900266B/xx unknown
- 2007-06-25 AU AU2007264760A patent/AU2007264760B2/en active Active
- 2007-06-25 JP JP2009517347A patent/JP5110662B2/ja active Active
- 2007-06-25 CN CN201610089879.0A patent/CN105779045A/zh active Pending
- 2007-06-25 CN CNA2007800240535A patent/CN101553557A/zh active Pending
- 2007-06-25 CA CA2655938A patent/CA2655938C/fr active Active
- 2007-06-25 CN CN201510113754.2A patent/CN104830390B/zh active Active
- 2007-06-25 NZ NZ574367A patent/NZ574367A/en unknown
- 2007-06-25 DK DK07803935.1T patent/DK2038382T3/da active
- 2007-06-25 WO PCT/FR2007/051512 patent/WO2008001000A2/fr active Application Filing
- 2007-06-25 US US12/306,007 patent/US8317887B2/en active Active
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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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Also Published As
Publication number | Publication date |
---|---|
TR201907063T4 (tr) | 2019-06-21 |
CA2655938C (fr) | 2013-04-02 |
KR20110083758A (ko) | 2011-07-20 |
JP2009541570A (ja) | 2009-11-26 |
CN104830390A (zh) | 2015-08-12 |
JP5110662B2 (ja) | 2012-12-26 |
FR2902798B1 (fr) | 2009-04-24 |
US20090300987A1 (en) | 2009-12-10 |
NZ574367A (en) | 2011-11-25 |
WO2008001000A2 (fr) | 2008-01-03 |
AU2007264760A1 (en) | 2008-01-03 |
EP2038382A2 (fr) | 2009-03-25 |
BRPI0713296A2 (pt) | 2012-03-20 |
ZA200900266B (en) | 2010-06-30 |
EA200970057A1 (ru) | 2009-06-30 |
CA2655938A1 (fr) | 2008-01-03 |
CN104830390B (zh) | 2020-08-21 |
BRPI0713296B1 (pt) | 2017-03-07 |
US8317887B2 (en) | 2012-11-27 |
KR101130599B1 (ko) | 2012-04-02 |
FR2902798A1 (fr) | 2007-12-28 |
MX2009000180A (es) | 2009-01-23 |
KR20090024730A (ko) | 2009-03-09 |
AU2007264760B2 (en) | 2010-11-11 |
CN105779045A (zh) | 2016-07-20 |
CN101553557A (zh) | 2009-10-07 |
EA018470B1 (ru) | 2013-08-30 |
WO2008001000A3 (fr) | 2008-06-19 |
DK2038382T3 (da) | 2019-05-20 |
EG26886A (en) | 2014-11-19 |
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