EP3615638B1 - Process for cryogenic fluid odorisation - Google Patents
Process for cryogenic fluid odorisation Download PDFInfo
- Publication number
- EP3615638B1 EP3615638B1 EP18722690.7A EP18722690A EP3615638B1 EP 3615638 B1 EP3615638 B1 EP 3615638B1 EP 18722690 A EP18722690 A EP 18722690A EP 3615638 B1 EP3615638 B1 EP 3615638B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cryogenic fluid
- odorizing agent
- odorizing
- agent
- temperature
- 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
- 239000012530 fluid Substances 0.000 title claims description 108
- 238000000034 method Methods 0.000 title claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 127
- 239000007788 liquid Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 26
- -1 cyclic sulfides Chemical class 0.000 claims description 17
- 238000009472 formulation Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003949 liquefied natural gas Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- LOCHFZBWPCLPAN-UHFFFAOYSA-N butane-2-thiol Chemical compound CCC(C)S LOCHFZBWPCLPAN-UHFFFAOYSA-N 0.000 claims description 6
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Chemical compound C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 claims description 6
- RVIXKDRPFPUUOO-UHFFFAOYSA-N dimethylselenide Chemical compound C[Se]C RVIXKDRPFPUUOO-UHFFFAOYSA-N 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 claims description 6
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- LNIMMWYNSBZESE-UHFFFAOYSA-N 2-Ethyl-3-methylpyrazine, 9CI Chemical compound CCC1=NC=CN=C1C LNIMMWYNSBZESE-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 2
- 150000003216 pyrazines Chemical class 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- XYWDPYKBIRQXQS-UHFFFAOYSA-N di-isopropyl sulphide Natural products CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 claims 1
- 150000002019 disulfides Chemical class 0.000 claims 1
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 claims 1
- 125000003748 selenium group Chemical class *[Se]* 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- 238000003860 storage Methods 0.000 description 10
- 239000003205 fragrance Substances 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003345 natural gas Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- FINHMKGKINIASC-UHFFFAOYSA-N Tetramethylpyrazine Chemical compound CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- OXQOBQJCDNLAPO-UHFFFAOYSA-N 2,3-Dimethylpyrazine Chemical compound CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 description 2
- HJFZAYHYIWGLNL-UHFFFAOYSA-N 2,6-Dimethylpyrazine Chemical compound CC1=CN=CC(C)=N1 HJFZAYHYIWGLNL-UHFFFAOYSA-N 0.000 description 2
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 2
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 2
- INAXVXBDKKUCGI-UHFFFAOYSA-N 4-hydroxy-2,5-dimethylfuran-3-one Chemical compound CC1OC(C)=C(O)C1=O INAXVXBDKKUCGI-UHFFFAOYSA-N 0.000 description 2
- OALYTRUKMRCXNH-UHFFFAOYSA-N 5-pentyloxolan-2-one Chemical compound CCCCCC1CCC(=O)O1 OALYTRUKMRCXNH-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- XINCECQTMHSORG-UHFFFAOYSA-N Isoamyl isovalerate Chemical compound CC(C)CCOC(=O)CC(C)C XINCECQTMHSORG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 2
- KVFIJIWMDBAGDP-UHFFFAOYSA-N ethylpyrazine Chemical compound CCC1=CN=CC=N1 KVFIJIWMDBAGDP-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 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 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003342 selenium Chemical class 0.000 description 2
- UNYNVICDCJHOPO-UHFFFAOYSA-N sotolone Chemical compound CC1OC(=O)C(O)=C1C UNYNVICDCJHOPO-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IAEGWXHKWJGQAZ-UHFFFAOYSA-N trimethylpyrazine Chemical compound CC1=CN=C(C)C(C)=N1 IAEGWXHKWJGQAZ-UHFFFAOYSA-N 0.000 description 2
- PHXATPHONSXBIL-UHFFFAOYSA-N xi-gamma-Undecalactone Chemical compound CCCCCCCC1CCC(=O)O1 PHXATPHONSXBIL-UHFFFAOYSA-N 0.000 description 2
- QFXOXDSHNXAFEY-UHFFFAOYSA-N (+/-)-(Z)-6-dodecen-4-olide Natural products CCCCCC=CCC1CCC(=O)O1 QFXOXDSHNXAFEY-UHFFFAOYSA-N 0.000 description 1
- JLPUXFOGCDVKGO-TUAOUCFPSA-N (-)-geosmin Chemical compound C1CCC[C@]2(O)[C@@H](C)CCC[C@]21C JLPUXFOGCDVKGO-TUAOUCFPSA-N 0.000 description 1
- JZQKTMZYLHNFPL-BLHCBFLLSA-N (2E,4E)-deca-2,4-dienal Chemical compound CCCCC\C=C\C=C\C=O JZQKTMZYLHNFPL-BLHCBFLLSA-N 0.000 description 1
- HZYHMHHBBBSGHB-UHFFFAOYSA-N (2E,6E)-2,6-Nonadienal Natural products CCC=CCCC=CC=O HZYHMHHBBBSGHB-UHFFFAOYSA-N 0.000 description 1
- HZYHMHHBBBSGHB-ODYTWBPASA-N (2E,6Z)-nona-2,6-dienal Chemical compound CC\C=C/CC\C=C\C=O HZYHMHHBBBSGHB-ODYTWBPASA-N 0.000 description 1
- CZCBTSFUTPZVKJ-NXEZZACHSA-N (2S,4R)-rose oxide Chemical compound C[C@@H]1CCO[C@H](C=C(C)C)C1 CZCBTSFUTPZVKJ-NXEZZACHSA-N 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- 239000001075 (4R,4aR,8aS)-4,8a-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-4a-ol Substances 0.000 description 1
- BGRVQSWCQKFXPY-SOFGYWHQSA-N (5e)-nona-1,5-dien-4-one Chemical compound CCC\C=C\C(=O)CC=C BGRVQSWCQKFXPY-SOFGYWHQSA-N 0.000 description 1
- DVVATNQISMINCX-YTXTXJHMSA-N (E,E)-2,4-Octadienal Chemical compound CCC\C=C\C=C\C=O DVVATNQISMINCX-YTXTXJHMSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- DPCMFIRORYQTCL-NSCUHMNNSA-N (Z)-4-Hexenal Chemical compound C\C=C\CCC=O DPCMFIRORYQTCL-NSCUHMNNSA-N 0.000 description 1
- WOVJAWMZNOWDII-BQYQJAHWSA-N (e)-non-2-enenitrile Chemical compound CCCCCC\C=C\C#N WOVJAWMZNOWDII-BQYQJAHWSA-N 0.000 description 1
- 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 description 1
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical class CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 1
- APWZAIZNWQFZBK-UHFFFAOYSA-N 1-ethoxynaphthalene Chemical compound C1=CC=C2C(OCC)=CC=CC2=C1 APWZAIZNWQFZBK-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- GZXXANJCCWGCSV-UHFFFAOYSA-N 2,3-Diethylpyrazine Chemical compound CCC1=NC=CN=C1CC GZXXANJCCWGCSV-UHFFFAOYSA-N 0.000 description 1
- YKJOPQQFWPADLH-UHFFFAOYSA-N 2,3-diethyl-4-hydroxy-2h-furan-5-one Chemical compound CCC1OC(=O)C(O)=C1CC YKJOPQQFWPADLH-UHFFFAOYSA-N 0.000 description 1
- 239000001934 2,5-dimethylpyrazine Substances 0.000 description 1
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 1
- WTAYWTBOEQYGOG-QPJJXVBHSA-N 2-Nonen-4-one Chemical compound CCCCCC(=O)\C=C\C WTAYWTBOEQYGOG-QPJJXVBHSA-N 0.000 description 1
- GYTSBHDHXURGIV-UHFFFAOYSA-N 2-butyl-4-hydroxy-3-methyl-2h-furan-5-one Chemical compound CCCCC1OC(=O)C(O)=C1C GYTSBHDHXURGIV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZYDXKAHTGWQVMS-UHFFFAOYSA-N 3-(3-heptyloxiran-2-yl)prop-2-enal Chemical compound CCCCCCCC1OC1C=CC=O ZYDXKAHTGWQVMS-UHFFFAOYSA-N 0.000 description 1
- BGVBGAIWXAXBLP-UHFFFAOYSA-N 3-Methyl-2,4-nonanedione Chemical compound CCCCCC(=O)C(C)C(C)=O BGVBGAIWXAXBLP-UHFFFAOYSA-N 0.000 description 1
- HDVYRMMZBNOJRR-UHFFFAOYSA-N 3-ethyl-4-hydroxy-2-methyl-2h-furan-5-one Chemical compound CCC1=C(O)C(=O)OC1C HDVYRMMZBNOJRR-UHFFFAOYSA-N 0.000 description 1
- VKCZZKMSKYKKQB-SREVYHEPSA-N 4-[(Z)-non-3-enyl]oxetan-2-one Chemical compound CCCCC\C=C/CCC1CC(=O)O1 VKCZZKMSKYKKQB-SREVYHEPSA-N 0.000 description 1
- RSJIVJVBFQHLPW-UHFFFAOYSA-N 4-hydroxy-3-methyl-2-propyl-2h-furan-5-one Chemical compound CCCC1OC(=O)C(O)=C1C RSJIVJVBFQHLPW-UHFFFAOYSA-N 0.000 description 1
- IUFQZPBIRYFPFD-UHFFFAOYSA-N 5-ethyl-3-hydroxy-4-methyl-2(5H)-furanone Chemical compound CCC1OC(=O)C(O)=C1C IUFQZPBIRYFPFD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAFQYUQIAOWKSB-UHFFFAOYSA-N Ethyl undecanoate Chemical compound CCCCCCCCCCC(=O)OCC IAFQYUQIAOWKSB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SIMKGHMLPVDSJE-UHFFFAOYSA-N Mesifurane Chemical compound COC1=C(C)OC(C)C1=O SIMKGHMLPVDSJE-UHFFFAOYSA-N 0.000 description 1
- FRLZQXRXIKQFNS-UHFFFAOYSA-N Methyl 2-octynoate Chemical compound CCCCCC#CC(=O)OC FRLZQXRXIKQFNS-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005399 allylmethacrylate group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- GXANMBISFKBPEX-ARJAWSKDSA-N cis-3-hexenal Chemical compound CC\C=C/CC=O GXANMBISFKBPEX-ARJAWSKDSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 description 1
- 150000003959 diselenides Chemical class 0.000 description 1
- JLPUXFOGCDVKGO-UHFFFAOYSA-N dl-geosmin Natural products C1CCCC2(O)C(C)CCCC21C JLPUXFOGCDVKGO-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229940073505 ethyl vanillin Drugs 0.000 description 1
- ALCDAWARCQFJBA-UHFFFAOYSA-N ethylselanylethane Chemical compound CC[Se]CC ALCDAWARCQFJBA-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- OALYTRUKMRCXNH-QMMMGPOBSA-N gamma-Nonalactone Natural products CCCCC[C@H]1CCC(=O)O1 OALYTRUKMRCXNH-QMMMGPOBSA-N 0.000 description 1
- PHXATPHONSXBIL-JTQLQIEISA-N gamma-Undecalactone Natural products CCCCCCC[C@H]1CCC(=O)O1 PHXATPHONSXBIL-JTQLQIEISA-N 0.000 description 1
- 229940020436 gamma-undecalactone Drugs 0.000 description 1
- 229930001467 geosmin Natural products 0.000 description 1
- ORUJFMPWKPVXLZ-UHFFFAOYSA-N guaiacol carbonate Chemical compound COC1=CC=CC=C1OC(=O)OC1=CC=CC=C1OC ORUJFMPWKPVXLZ-UHFFFAOYSA-N 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- GXANMBISFKBPEX-UHFFFAOYSA-N hex-3c-enal Natural products CCC=CCC=O GXANMBISFKBPEX-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ORQWTLCYLDRDHK-UHFFFAOYSA-N phenylselanylbenzene Chemical compound C=1C=CC=CC=1[Se]C1=CC=CC=C1 ORQWTLCYLDRDHK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N trans-Rosenoxid Natural products CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
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
-
- 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
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/08—Inhibitors
- C10L2230/081—Anti-oxidants
-
- 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
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/08—Inhibitors
- C10L2230/088—Inhibitors for inhibiting or avoiding odor
-
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/50—Screws or pistons for moving along solids
Definitions
- the present invention relates to a process for odorizing cryogenic fluid, in particular in order to allow its olfactory detection and to alert of possible leaks, in particular when the cryogenic fluid may represent a danger by inhalation, a risk of explosion, and others.
- the present invention also relates to a device making it possible to odorize the cryogenic fluid by applying the method of the invention.
- odorizing gases are now well known, and in particular techniques for odorizing natural gas, as described for example in EP1758970 , EP1934314 and EP2038382 .
- an odorizing formulation liquid at ambient temperature, is added to a fuel in the gas state, for example natural gas.
- cryogenic fluid within the meaning of the present invention, is meant any fluid which can be stored in the liquid state under cryogenic conditions, that is to say at temperatures of the order of -150° C. and below -150°C.
- cryogenic fluids are, by way of non-limiting example, light alkanes (methane, ethane, propane), C 2 -C 5 alkenes, inert gases (for example nitrogen), industrial gases (oxygen, hydrogen ), and others.
- odorizing agent odorization
- odorization of a cryogenic fluid requires the dissolution of a generally very small and controlled quantity of the odorizing principle in said cryogenic fluid, so that the odorant is present homogeneously in the cryogenic fluid and that when vapors of said cryogenic fluid (for example in the event of a leak, when it is at ambient temperature) an effective quantity of odorant is definitely present in said vapors and that the olfactory detection threshold in the air is reached to allow the alert required.
- the document DE102004050419 describes a process for odorizing a liquid cryogenic fuel, the odorization operation being carried out on the fluid in the gaseous state, after evaporation of said cryogenic fluid.
- the diluent used must comply with imperative conditions in terms of crystallization point, with respect to the odorizer and with respect to the natural gas to be odorized, so that the diluent mainly mentioned, if not only mentioned, is propane.
- propane propane
- Another disadvantage linked to the aforementioned technique is the pollution of the fluid to be odorized by the appropriate diluent, (propane), which can be annoying, depending on the nature of the cryogenic fluid to be odorized and the use that is made of it subsequently. .
- the aim of the present invention is to propose a process that is simple to implement, particularly on an industrial level, that is to say for the odorization of very large quantities of cryogenic fluids, without having the known drawbacks of the techniques of the prior art, in particular those implementing a diluent that can pollute said cryogenic fluid to be odorized, and thus potentially be a nuisance for the use made of said cryogenic fluid.
- Another object of the invention is to provide a process that is simple to implement, particularly industrially, while allowing a controlled addition without restrictions with regard to the conditions of flow rates and pressure of an odorizing agent to be introduced.
- each of steps a), b) and c) of the process is carried out continuously.
- the flow rate of odorizing agent in the contact zone is proportional to the flow rate of the cryogenic fluid.
- the flow rate of odorizing agent in the contact zone is slaved to the flow rate of the cryogenic fluid.
- the amount of odorizing agent coming into contact with the cryogenic fluid to be odorized is between the minimum amount necessary to odorize said cryogenic fluid and the maximum to reach saturation. Too large an amount of odorizing agent in the cryogenic fluid can lead to solid deposits which could damage or even clog pipes, valves, and other components present on the industrial site for odorizing said cryogenic fluid.
- Step b) of supplying the buffer zone makes it possible to isolate the supply zone from the contact zone which is at the temperature of the cryogenic fluid.
- the odorizing agent (optionally in the form of an odorizing formulation) is, and remains, in the liquid state in the feed zone and is gradually brought to a temperature below 30°C above the temperature of the cryogenic fluid, or even the temperature of the cryogenic fluid, on leaving this buffer zone.
- the odorizing agent in step b), is brought to a temperature below 20° C., preferably below 10° C. above the temperature of the cryogenic fluid to be odorized.
- step c) the odorizing agent cooled in step b) is brought into contact with said cryogenic fluid to be odorized.
- the odorizing agent is most often in solid form, advantageously in the form of droplets of solidified odorizing agent or else in the form of a solidified spray.
- step c) the odorizing agent comes into contact with the cryogenic fluid and is entrained with the flow of cryogenic fluid, in which it dissolves, thus allowing the odorization of said cryogenic fluid.
- the odorizing agent is dispersed/mixed with the cryogenic fluid.
- This dispersion or mixing can be carried out according to any method known to those skilled in the art, for example by simple contact of the odorizing agent with a flow of cryogenic fluid, or even by means of any mechanical means, such as a static mixer, agitator, propeller, and others.
- the mixture is produced by simple contact of the odorizing agent with a flow of cryogenic fluid in a turbulent regime.
- turbulent regime we mean a flow defined by a Reynolds number greater than the critical Reynolds number, that is to say, for a flow in a tubular pipe, a Reynolds number greater than 2000, or even greater than 3000.
- the supply of odorizing agent is such that the concentration of odorizing agent in the cryogenic fluid is between 0.1 mg/m 3 (n) and 500 mg/m 3 (n), preferably between 0. 5 mg/m 3 (n) and 100 mg/m 3 (n), more preferably between 0.5 mg/m 3 (n) and 50 mg/m 3 (n).
- the concentration is measured relative to m 3 (n) corresponding to 1 m 3 of gas in the vapor state under normal temperature and pressure conditions (0°C and 1013.25 hPa).
- the odorizing agent implemented in the present invention can be of any kind, depending on the desired effect, the desired detection threshold, the expected odor, and others.
- the odorizing agent is advantageously chosen from the family of hydrocarbons, for example terpenes, from the family of alcohols and phenols, from the family of aldehydes, from the family of ethers, cyclic or not, from the family of esters, by for example the family of acrylates and (alkyl)acrylates, in the family of fatty acids, in the family of ketones, in the family of lactones, in the family of mercaptans, for example alkylmercaptans, (alkyl)thio-alkylmercaptans, the family of cyclic sulphides, the family of symmetrical or unsymmetrical dialkyl sulphides, the family of symmetrical or unsymmetrical dialkyl disulphides, or else in the family of selenium derivatives, for example selenides or diselenides of alkyl or dialkyl, that whether they are symmetrical or not.
- Mixtures of at least two of the odorizing agents mentioned above, in all proportions, can
- the odorizing agent is chosen from alcohols and phenols, such as, for example and without limitation, nerol, phenyl-3-propan-1-ol, linalool, geosmin, p-cresol, 3,5-dimethylphenol, 3-ethylphenol and 1-naphthol.
- alcohols and phenols such as, for example and without limitation, nerol, phenyl-3-propan-1-ol, linalool, geosmin, p-cresol, 3,5-dimethylphenol, 3-ethylphenol and 1-naphthol.
- the odorizing agent is chosen from the family of aldehydes, such as, for example and without limitation, trans-2,trans-4-decadienal, trans-2,trans-4-hexadienal, trans-2,trans-4-octadienal, trans-2,trans-4-nonadienal, ethyl vanillin, cis-3-hexenal, trans-4-hexenal, trans-2,cis-6-nonadienal , 4,5-epoxy-2-dodecenal and iso -valeraldehyde.
- aldehydes such as, for example and without limitation, trans-2,trans-4-decadienal, trans-2,trans-4-hexadienal, trans-2,trans-4-octadienal, trans-2,trans-4-nonadienal, ethyl vanillin, cis-3-hexenal, trans-4-hexenal, trans-2,cis-6-nonadien
- the odorizing agent is chosen from the family of ethers, such as, without limitation, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-ethoxynaphthalene, pyrans, for example cis -rose-oxide.
- the odorizing agent is chosen from the family of mercaptans, such as, without limitation, methyl mercaptan, ethyl mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, iso - butyl mercaptan, n-propyl mercaptan, iso -propyl mercaptan, pentyl mercaptans, cyclohexyl mercaptan, and n-dodecyl mercaptan.
- family of mercaptans such as, without limitation, methyl mercaptan, ethyl mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, iso - butyl mercaptan, n-propyl mercaptan, iso -propyl mercaptan, pentyl mercaptans, cyclohex
- the odorizing agent is chosen from the family of alkyl sulphides, disulphides or even polysulphides, such as, without limitation, methyl and ethyl sulphide (MES), sulphide (DMS) and diethyl sulfide (DES) or tetrahydrothiophene (THT).
- MES methyl and ethyl sulphide
- DMS sulphide
- DES diethyl sulfide
- TTT tetrahydrothiophene
- the odorizing agent is chosen from the family of esters, such as, without limitation, methyl, ethyl, allyl, n-propyl, iso -propyl, n-butyl, iso -butyl, tert -butyl, pentyl, hexyl, heptyl, octyl and dodecyl, methyl, ethyl, allyl methacrylates, n-propyl, iso -propyl, n-butyl, iso -butyl, tert -butyl, pentyl, hexyl, heptyl, octyl and dodecyl, iso -valerate propyl, iso -pentyl iso -valerate, methyl dodecanoate, ethyl dodecanoate, ethyl undecanoate, methylhepty
- the odorizing agent is chosen from the family of fatty acids such as, but not limited to, butyric acid, iso-valeric acid and methyl-2-propionic acid.
- the odorizing agent is chosen from the family of nitrogen compounds comprising, by way of non-limiting examples, lactones (such as caprolactone), nitriles (such as 2-nonenenitrile) and pyrazine compounds (such as 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- as well as 3,6,2-dimethylethylpyrazine), 2,3-methylethylpyrazine and tetramethylpyrazine, and others, as mentioned in document DE19837066 .
- lactones such as caprolactone
- nitriles such as 2-nonenen
- ketones also represents a family of preferred odorizing agents, ketones among which mention may be made, by way of nonlimiting examples, of 3-methylnonan-2,4-dione, 1-nonen-3-one, 3-hydroxy-4,5-dimethyl-2(5 H )-furanone, 3-hydroxy-4,5-diethyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5-ethyl- 2(5 H )-furanone, 3-hydroxy-4-ethyl-5-methyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5-butyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5- iso -butyl-2( 5H )-furanone, 3-hydroxy-4-methyl-5-propyl-2( 5H )-furanone, 2,5-dimethyl -4-methoxy-3(2 H )-furanone, ionones, damascenones, trans-2-nonen-4-one, furan
- lactones such as, for example, and in a non-limiting manner, 3,6-dimethyl-3a,4,5,7a-tetrahydro-2( 3H )-benzofuranone, ⁇ -nonalactone, ⁇ -undecalactone, (Z)-6-dodeceno- ⁇ -lactone, and coumarin.
- the odorizing agent is chosen from the family of selenium derivatives, among which mention may be made, by way of non-limiting examples, of dimethyl selenide, dimethyl diselenide, diethyl selenide , diphenyl selenide, diphenyl diselenide and ethylselenol, and others, such as those mentioned in the document WO2015050509 .
- the perception thresholds for the odorants cited above are all of the order of the order of magnitude of ten parts per billion (ppb), or even lower. They are mostly below 1 ppb.
- the odorizing agent which can be used in the present invention is chosen from methyl and ethyl sulphide, dimethyl sulphide, diethyl sulphide, dimethyl disulphide, diethyl disulphide, methyl mercaptan, ethyl mercaptan, tert -butyl mercaptan, sec -butyl mercaptan, iso propyl mercaptan, n-propyl mercaptan cyclohexyl mercaptan, tetrahydrothiophene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methylethylpyrazine, dimethyl selenide, and dimethyl diselenide.
- the odorizing agents which can be used in the context of the present invention can be used pure, as a mixture of two or more of them in all proportions or alternatively diluted with other compounds compatible with the cryogenic fluid chosen from C 5 - C 6 (for example n-pentane, isopentane , cyclohexane, methylpentane, petroleum ether, as well as mixtures of two or more of them), sulfones, sulfoxides, and preferably chosen from alkanes.
- C 5 - C 6 for example n-pentane, isopentane , cyclohexane, methylpentane, petroleum ether, as well as mixtures of two or more of them
- sulfones for example n-pentane, isopentane , cyclohexane, methylpentane, petroleum ether, as well as mixtures of two or more of them
- sulfones for example n-pent
- odorizing agents in the context of the present invention alone or in mixtures of two or more of them in all proportions, optionally, but not preferably, diluted with one or more solvents as indicated above, in proportions of solvent(s) however not exceeding 20%, better still not exceeding 10% by weight of solvent relative to the total weight (odorizing agent(s)+solvent(s)).
- the solvent is chosen from C 5 -C 6 alkanes whose physical properties allow easy handling, and typically those which are liquid at ambient temperature.
- the solvent is iso -pentane which makes it possible in particular to lower the crystallization point of the odorizing composition and to approach the temperature of the cryogenic fluid, which is for example -162° C. for LNG ("Liquefied Natural Gas”), and therefore close to the melting temperature of isopentane (-160°C).
- the odorizing agent that can be used in the context of the present invention can also comprise one or more additives chosen from heat stabilizers, dyes, antioxidants, such as for example those of the phenolic type, stable nitroxy radicals, for example of the tetramethylpiperidine oxide type (also known as TEMPO) and other derivatives, in particular described in “Synthetic Chemistry of Stable Nitroxides” by LB Volodarsky et al., CRC Press, (1993), ISBN: 0-8493-4590-1 .
- additives chosen from heat stabilizers, dyes, antioxidants, such as for example those of the phenolic type, stable nitroxy radicals, for example of the tetramethylpiperidine oxide type (also known as TEMPO) and other derivatives, in particular described in “Synthetic Chemistry of Stable Nitroxides” by LB Volodarsky et al., CRC Press, (1993), ISBN: 0-8493-4590-1 .
- the concentration of odorizing agent, when it is diluted in a solvent and/or when it is mixed with one or more additives can be comprised in large proportions, and generally between 0 1% and 100% by weight of odorizing agent relative to the total weight of the odorizing formulation.
- the odorizing agent represents 100% of the odorizing formulation, i.e. the odorizing agent is used without solvent.
- the odorizing agent will represent between 10 and 50% by weight of the odorizing formulation.
- the odorizing agent is used in the absence of solvent and/or in the absence of any other additive, making it possible to minimize pollution of the cryogenic fluid.
- the present invention consists of a process which continuously produces fine particles of a solid odorizing agent from said odorizing agent in liquid form, said fine particles of said solid odorizing agent then being continuously introduced into a cryogenic fluid in which they dissolve.
- odorizing the cryogenic fluid it is preferred to carry out the process for odorizing the cryogenic fluid continuously, this embodiment being very particularly suitable for facilitating mixing and in particular ensuring the homogeneity of the odorized cryogenic fluid.
- the odorization process according to the invention can also be carried out discontinuously, this embodiment typically being able to be carried out by introducing a charge of odorizing agent (optionally in the form of an odorizing formulation) into at least part of the cryogenic fluid to be odorized, for example in a stream of static cryogenic fluid, in a bypass or bypass, and the like, then dilution of this at least part of the odorized cryogenic fluid in said cryogenic fluid to be odorized.
- the supply zone consists of any system allowing the odorant to be transferred from its storage to the buffer zone.
- the supply zone is supplied, preferably continuously, with an odorizing agent which is in liquid or gaseous form, preferably in liquid form, said supply preferably being carried out at ambient temperature. Feeding the odorizing agent in the solid state is not preferred, for obvious reasons of handling and dosage, particularly when the odorization process according to the present invention is carried out in continuous mode.
- the transfer of the odorizing agent into the supply zone can be carried out using a pump or any other pumping technology, or else by pressure difference between the storage and the buffer zone, or alternatively by pressure differential when injecting pre-loaded doses into intermediate storage. It is also possible to control the flow rate, for example using a flow meter, possibly combined with a control valve.
- the odorizing agent can thus be supplied by any means known per se, for example by means of a pump or any other device making it possible to apply a pressure differential.
- the supply pressure is between 0.1 MPa and 10 MPa, preferably between 0.1 MPa and 5 MPa.
- the pressure values indicated above are values corresponding to absolute pressures.
- the odorizing agent can be stored and used in a wide range of temperatures, for example being able to go from -100°C and +100°C, typically from -50°C to +60 °C.
- the storage temperature is the temperature of the odorization site.
- the storage pressure is most generally atmospheric pressure, the operating pressure possibly being different from the storage pressure in order to ensure the transport of the odorizing agent to the supply zone.
- the supply of odorizing agent can be carried out by any device allowing the transfer of fluid (in the liquid or gaseous state), advantageously in a controlled manner, and preferably in a controlled and regulated manner.
- the arrival in the buffer zone b) of the odorizing agent, typically when the latter is liquid, can be achieved by any means known per se, and for example by means of at least one or more elements chosen from cannula, nozzle , injector or any other means allowing the supply by drip or spray, and others, said aforementioned elements being able to be used alone or in combination of one or more of them.
- This arrival in the buffer zone b) can also be carried out, typically when the odorizing agent is in gaseous form, by driving said odorizing agent (vapor pressure), possibly with a vector gas, as described for example in the international application WO1997019746 , or such as nitrogen, helium, argon, hydrogen, natural gas, methane, or any other light alkane, or even a part of the cryogenic fluid to be odorized, that -it having been previously vaporized, for example with a bypass system, as described for example in the patent US2058508 .
- a vector gas as described for example in the international application WO1997019746 , or such as nitrogen, helium, argon, hydrogen, natural gas, methane, or any other light alkane, or even a part of the cryogenic fluid to be odorized, that -it having been previously vaporized, for example with a bypass system, as described for example in the patent US2058508 .
- the odorizing agent can be thermostatically controlled in the supply zone a) and/or optionally upstream of said supply zone, in order to regulate/control the concentration of odorizing agent in the carrier gas .
- the odorizing agent is injected in the form of a spray, said spray being able to be obtained by any technique known to those skilled in the art.
- the supply zone is (are) equipped with means making it possible to maintain a temperature above the crystallization temperature of the odorizing agent, so that said odorizing agent is maintained in the fluid state (liquid or gaseous state), these means typically being one or more thermal insulation systems well known to those skilled in the art, and for example vacuum insulation, or circulation of a gas whose boiling point is less than or equal to the temperature of the cryogenic fluid.
- thermal insulation systems well known to those skilled in the art, and for example vacuum insulation, or circulation of a gas whose boiling point is less than or equal to the temperature of the cryogenic fluid.
- the thermal insulation can be achieved by heating the supply zone with a heat transfer fluid, possibly thermostatically controlled, by heating by means of a heating resistor, by induction, conduction, or the like.
- the buffer zone b) makes it possible in particular to bring the odorizing agent, liquid or gaseous, to a temperature below 30° C. above the temperature of the cryogenic fluid.
- This buffer zone has the effect of isolating the supply zone from the contact zone which is at the temperature of the cryogenic fluid.
- the odorizing agent is, and remains, in a fluid state (liquid or gaseous) in the feed zone and is gradually brought to a temperature below 30°C above the temperature of the cryogenic fluid, or even at the temperature of the cryogenic fluid, on leaving the buffer zone b).
- the temperature of the buffer zone is maintained, at least in part, at a temperature above the melting point of the odorizing agent, in order to avoid the cooling of said odorizing agent below its melting point. Crystallization, due to the proximity of the contact zone whose temperature, typically equal to that of the cryogenic fluid.
- This temperature can be maintained by any means known to those skilled in the art, for example by means of a gas blanket in at least part of the supply zone and/or of the buffer zone, by preheating of the optionally formulated odorizing agent, heating of the supply zone and/or of the buffer zone, use of thermally insulating materials, and the like, or combination of two or more of the aforementioned techniques.
- the gas sky is generally created by feeding a gas whose liquefaction point is less than or equal to the boiling temperature of the cryogenic fluid.
- gases are nitrogen, argon, helium, hydrogen, methane, natural gas, and the like, and mixtures thereof.
- This gas can be introduced into at least part of the supply zone and/or at least part of the buffer zone.
- the rate of introduction of this gas is generally between 0.1 L.min -1 and 500 L.min -1 , preferably between 0.2 L.min -1 and 10 L.min -1 .
- the gas flow can also make it possible to apply a pressure differential allowing a controlled and regulated supply of the odorizing agent in the supply zone.
- the gas flow is slaved to a temperature measurement carried out within the supply zone.
- the heating of the supply zone and/or the preheating of the odorizing agent makes it possible to maintain the temperature of the supply zone and/or at least part of the buffer zone at a temperature above the set point. fusion of the odorizing agent.
- the buffer zone b) represents the space between the supply zone in which the odorizing agent is in liquid or vapor form, and the contact zone (or surface of the cryogenic fluid) in which the odorizing agent comes into contact with the cryogenic fluid.
- This buffer zone has a temperature gradient between the temperature of the supply zone and the temperature of the contact zone.
- the temperature gradient (typically cooling) is obtained by the cryogenic fluid considered.
- the buffer zone b) can be equipped with mechanical assistance allowing improved transport of said odorizing agent to the cryogenic fluid, as described later in the description.
- the introduction of the odorizing agent into the cryogenic fluid is carried out in the contact zone c).
- Said contact zone c) is preferentially agitated in order to facilitate the dispersion of the odorizing agent to facilitate rapid dissolution in the medium.
- This agitation can be generated by any means known to those skilled in the art, for example mechanical agitation, convection, circulation or recirculation by means of pumps or any other device allowing the generation of a flow at a greater or lesser rate.
- the contact of the odorizing agent with the surface of the cryogenic fluid will be made in a flow of cryogenic fluid, thus making it possible to promote the dispersion of the odorizing agent, and this in a homogeneous manner, within the fluid. cryogenic which thus becomes an odorized cryogenic fluid.
- the passage from the supply zone to the contact zone, through the buffer zone can be carried out by gravity and/or with mechanical assistance, making it possible to convey the odorizing agent, possibly in the form of odorizing formulation, towards the cryogenic fluid in order to ensure contact.
- the method of the present invention thus has several advantages and more particularly that of not having to resort to the preparation of a pre-mixture containing the odorizing agent in a matrix as for example described in the patent application FR2201424 .
- the method of the present invention is therefore easier to implement in that it does not require the use of additional solvent or else in small quantities, therefore no storage, and therefore little or no pollutant in the cryogenic fluid. odorized.
- the addition of the odorizing agent in the cryogenic fluid is simplified, without the need for prior preparation of an odorizing concentrate, for example in a hydrocarbon such as propane, as described for example in FR2201424 .
- the device for odorizing a cryogenic fluid described above can take various forms and aspects.
- the figures 1 and 2 appended show two possible but non-limiting embodiments.
- the Figure 1 represents an example of a device making it possible to implement the cryogenic fluid odorization method, according to the present invention.
- This device comprises a supply zone (A), a buffer zone (B), and a contact zone (C).
- the odorizing agent optionally in the form of an odorizing formulation, is introduced with a vector gas via the pipe (2) into the upper part of the endless screw (4) which is subjected to a rotational movement, via the motor (3 ), so that the odorizing agent (or the odorizing formulation) reaches, in the form of dispersed particles (5), the flow of cryogenic fluid (1) which flows in the direction indicated.
- the Figure 2 represents another example of a device making it possible to implement the cryogenic fluid odorization method, according to the present invention, the device also comprising a supply zone (A), a buffer zone (B), and a contact zone (VS).
- A supply zone
- B buffer zone
- VS contact zone
- the odorizing agent (possibly in the form of an odorizing formulation) is introduced via line (2), with a vector gas via line (3), into the supply zone (A) comprising a heating resistor (4) intended to maintain a temperature above the solidification temperature of the odorizing agent (or of the odorizing formulation) which passes by gravity, via the buffer zone (B), into the contact zone (C) where it is dispersed ( e) (5) in the cryogenic fluid (1) flowing in the direction indicated.
- a heating resistor (4) intended to maintain a temperature above the solidification temperature of the odorizing agent (or of the odorizing formulation) which passes by gravity, via the buffer zone (B), into the contact zone (C) where it is dispersed ( e) (5) in the cryogenic fluid (1) flowing in the direction indicated.
- the odorizing device presented in this invention has many advantages, among which the great ease of use can be mentioned. Indeed, because of its small size and its easy installation, the device can be easily installed at the places where it is desired to practice the odorization of a cryogenic fluid. The method of the invention therefore finds a particularly advantageous application when it is implemented by means of the device according to the present invention.
- cryogenic fluids can be implemented in many situations, such as, by way of non-limiting examples, when loading/filling tank trucks, tanks, boats, barges, gas cylinders, and others, from tanks, boats, barges or during the very process of liquefaction of the cryogenic fluid during transfer to/or within the storage, and others.
- the odorization process according to the invention finds a very particularly advantageous application for the odorization of Liquefied Natural Gas (LNG), in particular when loading tank trucks or static or mobile storage from LNG carriers, by whether or not through one or more reservoirs.
- LNG Liquefied Natural Gas
- the odorizing agent belongs to the family of odorants conventionally used to odorize natural gas and is typically chosen from mercaptans and sulphides.
- This embodiment is particularly suitable for the odorization of LNG, which then has a characteristic smell of gas, which allows the detection and identification of leaks during the transport, storage and use of said LNG, in order to warn of any danger linked to the accumulation of natural gas in the air.
- the method of the present invention in particular when it is implemented for the odorization of LNG, it is now possible to dispense with gas odorization stations during the LNG regasification step. Indeed, the odorization process of the present invention can be carried out at a single centralized point.
- This centralization thus makes it possible to limit the number of places involved in the storage and handling of odorizing agents and odorizing formulations and thus the risks of olfactory pollution, the costs associated with the maintenance of injection stations, and others.
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)
- Cosmetics (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
- Gas Separation By Absorption (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
La présente invention concerne un procédé d'odorisation de fluide cryogénique, notamment afin d'en permettre la détection olfactive et alerter de fuites éventuelles, en particulier lorsque le fluide cryogénique peut représenter un danger par inhalation, un risque d'explosion, et autres.The present invention relates to a process for odorizing cryogenic fluid, in particular in order to allow its olfactory detection and to alert of possible leaks, in particular when the cryogenic fluid may represent a danger by inhalation, a risk of explosion, and others.
La présente invention concerne également un dispositif permettant d'odoriser le fluide cryogénique en appliquant le procédé de l'invention.The present invention also relates to a device making it possible to odorize the cryogenic fluid by applying the method of the invention.
Les techniques permettant d'odoriser des gaz sont maintenant bien connues, et notamment les techniques pour odoriser le gaz naturel, comme décrit par exemple dans
Cependant, aucun des odorisants classiquement utilisés pour le gaz naturel n'est liquide aux températures des fluides cryogéniques. À ces températures, les odorisants classiques se trouvent à l'état solide, ce qui pose des problèmes de compatibilité des systèmes d'odorisation connus aujourd'hui. Il n'est donc pas possible de transposer les technologies d'odorisation des gaz connues jusqu'à présent pour odoriser les fluides cryogéniques.However, none of the odorants conventionally used for natural gas are liquid at the temperatures of cryogenic fluids. At these temperatures, the conventional odorants are in the solid state, which poses problems of compatibility of the odorization systems known today. It is therefore not possible to transpose the gas odorization technologies known hitherto to odorize cryogenic fluids.
Par « fluide cryogénique » au sens de la présente invention, on entend tout fluide qui peut être stocké à l'état liquide dans des conditions cryogéniques, c'est-à-dire à des températures de l'ordre de -150°C et inférieures à -150°C. Des exemples de fluides cryogéniques sont, à titre d'exemple non limitatifs les alcanes légers (méthane, éthane, propane), les alcènes en C2-C5, les gaz inertes (par exemple azote), les gaz industriels (oxygène, hydrogène), et autres. Il doit être compris que l'invention s'intéresse à l'addition d'un agent odorisant (odorisation) dans des fluides cryogéniques à l'état liquide, et non à l'addition d'agent odorisant dans des fluides à l'état gazeux.By "cryogenic fluid" within the meaning of the present invention, is meant any fluid which can be stored in the liquid state under cryogenic conditions, that is to say at temperatures of the order of -150° C. and below -150°C. Examples of cryogenic fluids are, by way of non-limiting example, light alkanes (methane, ethane, propane), C 2 -C 5 alkenes, inert gases (for example nitrogen), industrial gases (oxygen, hydrogen ), and others. It should be understood that the invention is concerned with the addition of an odorizing agent (odorization) in cryogenic fluids in the liquid state, and not with the addition of odorizing agent in fluids in the liquid state. gaseous.
Ainsi, le fait d'introduire un agent odorisant, éventuellement sous forme de formulation odorisante, connu(e) de l'homme du métier et présentant des points de cristallisation bien supérieurs à -150°C, comme indiqué précédemment, dans un fluide cryogénique, aurait pour conséquence une cristallisation dudit agent ou de ladite formulation au sein des systèmes d'injections. L'introduction directe sous forme de spray, telle que décrite par exemple dans le brevet
Or une odorisation efficace d'un fluide cryogénique nécessite la dissolution d'une quantité généralement très faible et maîtrisée du principe odorisant dans ledit fluide cryogénique, de sorte que l'odorisant soit présent de manière homogène dans le fluide cryogénique et que lorsque des vapeurs dudit fluide cryogénique (par exemple en cas de fuite, lorsque celui-ci se trouve à température ambiante) une quantité efficace d'odorisant soit présente de manière certaine dans lesdites vapeurs et que le seuil olfactif de détection dans l'air soit atteint pour permettre l'alerte requise.However, effective odorization of a cryogenic fluid requires the dissolution of a generally very small and controlled quantity of the odorizing principle in said cryogenic fluid, so that the odorant is present homogeneously in the cryogenic fluid and that when vapors of said cryogenic fluid (for example in the event of a leak, when it is at ambient temperature) an effective quantity of odorant is definitely present in said vapors and that the olfactory detection threshold in the air is reached to allow the alert required.
Le document
L'odorisation de gaz naturel liquéfié a fait l'objet d'une demande de brevet publiée sous le n°
La présente invention a pour objectif de proposer un procédé simple à mettre en œuvre, tout particulièrement sur le plan industriel c'est-à-dire pour l'odorisation de très grandes quantités de fluides cryogéniques, sans présenter les inconvénients connus des techniques de l'art antérieur, notamment celles mettant en œuvre un diluant pouvant venir polluer ledit fluide cryogénique à odoriser, et ainsi être potentiellement une gêne pour l'utilisation qui est faite dudit fluide cryogénique.The aim of the present invention is to propose a process that is simple to implement, particularly on an industrial level, that is to say for the odorization of very large quantities of cryogenic fluids, without having the known drawbacks of the techniques of the prior art, in particular those implementing a diluent that can pollute said cryogenic fluid to be odorized, and thus potentially be a nuisance for the use made of said cryogenic fluid.
Un autre objectif de l'invention est de proposer un procédé simple à mettre en œuvre, tout particulièrement sur le plan industriel, tout en permettant une addition contrôlée sans restrictions vis-à-vis des conditions de débits et pression d'un agent odorisant à introduire. D'autres objectifs et avantages apparaîtront encore dans la description qui suit de la présente invention.Another object of the invention is to provide a process that is simple to implement, particularly industrially, while allowing a controlled addition without restrictions with regard to the conditions of flow rates and pressure of an odorizing agent to be introduced. Other objects and advantages will become apparent from the following description of the present invention.
Ainsi, et selon un premier aspect, la présente invention concerne un procédé d'odorisation d'un fluide cryogénique à l'état liquide comprenant au moins les étapes suivantes :
- a) alimentation, à une température supérieure à la température du fluide cryogénique et supérieure à la température de cristallisation de l'agent odorisant, par exemple à température ambiante, en continu, d'un agent odorisant sous forme liquide ou gazeuse, de préférence sous forme liquide, dans une zone d'alimentation,
- b) alimentation dudit agent odorisant sous forme liquide ou gazeuse de l'étape a) dans une zone tampon dans laquelle l'agent odorisant liquide ou gazeux est amené à une température inférieure à 30°C au-dessus de la température du fluide cryogénique, et
- c) alimentation dudit agent odorisant refroidi à l'étape b), dans la zone de contact, où ledit agent odorisant sous forme solide entre en contact avec ledit fluide cryogénique à odoriser.
- a) feeding, at a temperature above the temperature of the cryogenic fluid and above the crystallization temperature of the odorizing agent, for example at room temperature, continuously, an odorizing agent in liquid or gaseous form, preferably in liquid form, in a feed zone,
- b) feeding said odorizing agent in liquid or gaseous form from step a) into a buffer zone in which the liquid or gaseous odorizing agent is brought to a temperature below 30°C above the temperature of the cryogenic fluid, and
- c) feeding said odorizing agent cooled in step b), into the contact zone, where said odorizing agent in solid form comes into contact with said cryogenic fluid to be odorized.
Selon un aspect préféré de la présente invention, chacune des étapes a), b) et c) du procédé est réalisée en continu. Selon un autre aspect préféré de la présente invention, le débit d'agent odorisant dans la zone de contact est proportionnel au débit du fluide cryogénique. Selon un aspect tout particulièrement préféré, le débit d'agent odorisant dans la zone de contact est asservi au débit du fluide cryogénique.According to a preferred aspect of the present invention, each of steps a), b) and c) of the process is carried out continuously. According to another preferred aspect of the present invention, the flow rate of odorizing agent in the contact zone is proportional to the flow rate of the cryogenic fluid. According to a very particularly preferred aspect, the flow rate of odorizing agent in the contact zone is slaved to the flow rate of the cryogenic fluid.
La quantité d'agent odorisant entrant en contact avec le fluide cryogénique à odoriser est comprise entre la quantité minimale nécessaire pour odoriser ledit fluide cryogénique et le maximum pour arriver à saturation. Une quantité trop importante d'agent odorisant dans le fluide cryogénique peut conduire à des dépôts de solide qui pourraient endommager, voire boucher des canalisations, des vannes, et autres organes présents sur le site industriel d'odorisation dudit fluide cryogénique.The amount of odorizing agent coming into contact with the cryogenic fluid to be odorized is between the minimum amount necessary to odorize said cryogenic fluid and the maximum to reach saturation. Too large an amount of odorizing agent in the cryogenic fluid can lead to solid deposits which could damage or even clog pipes, valves, and other components present on the industrial site for odorizing said cryogenic fluid.
L'étape b) d'alimentation de la zone tampon permet d'isoler la zone d'alimentation de la zone de contact qui se trouve à la température du fluide cryogénique. En d'autres termes, l'agent odorisant (éventuellement sous forme de formulation odorisante) est, et reste, à l'état liquide dans la zone d'alimentation et est progressivement amené à une température inférieure à 30°C au-dessus de la température du fluide cryogénique, voire à la température, du fluide cryogénique, au sortir de cette zone tampon.Step b) of supplying the buffer zone makes it possible to isolate the supply zone from the contact zone which is at the temperature of the cryogenic fluid. In other words, the odorizing agent (optionally in the form of an odorizing formulation) is, and remains, in the liquid state in the feed zone and is gradually brought to a temperature below 30°C above the temperature of the cryogenic fluid, or even the temperature of the cryogenic fluid, on leaving this buffer zone.
Selon un mode de réalisation préféré, dans l'étape b), l'agent odorisant est amené à une température inférieure à 20°C de préférence inférieure à 10°C au-dessus de la température du fluide cryogénique à odoriser.According to a preferred embodiment, in step b), the odorizing agent is brought to a temperature below 20° C., preferably below 10° C. above the temperature of the cryogenic fluid to be odorized.
Dans l'étape c), l'agent odorisant refroidi à l'étape b) est amené au contact dudit fluide cryogénique à odoriser. Lors du contact, l'agent odorisant se trouve le plus souvent sous forme solide, avantageusement sous forme de gouttelettes d'agent odorisant solidifié ou encore sous forme de spray solidifié.In step c), the odorizing agent cooled in step b) is brought into contact with said cryogenic fluid to be odorized. During contact, the odorizing agent is most often in solid form, advantageously in the form of droplets of solidified odorizing agent or else in the form of a solidified spray.
Ainsi, dans l'étape c), l'agent odorisant entre en contact avec le fluide cryogénique et est entraîné avec le flux de fluide cryogénique, dans lequel il se dissout, permettant ainsi l'odorisation dudit fluide cryogénique.Thus, in step c), the odorizing agent comes into contact with the cryogenic fluid and is entrained with the flow of cryogenic fluid, in which it dissolves, thus allowing the odorization of said cryogenic fluid.
De manière optionnelle, mais préférée, l'agent odorisant est dispersé/mélangé au fluide cryogénique. Cette dispersion ou mélange peut être réalisée selon toute méthode connue de l'homme du métier, par exemple par simple contact de l'agent odorisant avec un flux de fluide cryogénique, ou bien encore au moyen de tout moyen mécanique, tel que mélangeur statique, agitateur, hélice, et autres.Optionally, but preferably, the odorizing agent is dispersed/mixed with the cryogenic fluid. This dispersion or mixing can be carried out according to any method known to those skilled in the art, for example by simple contact of the odorizing agent with a flow of cryogenic fluid, or even by means of any mechanical means, such as a static mixer, agitator, propeller, and others.
Parmi les systèmes d'assistance mécanique tout particulièrement adaptés pour véhiculer l'agent odorisant vers le fluide cryogénique, on peut citer, à titre d'exemples non limitatifs, les lames, racles, racleurs, couteaux, vis-sans-fin utilisés seuls ou combinés ou toute autre technologie permettant de convoyer des liquides ou des solides.Among the mechanical assistance systems that are particularly suitable for conveying the odorizing agent to the cryogenic fluid, mention may be made, by way of non-limiting examples, of the blades, doctor blades, scrapers, knives, endless screws used alone or combined or any other technology for conveying liquids or solids.
De manière préférée, le mélange est réalisé par simple contact de l'agent odorisant avec un flux de fluide cryogénique en régime turbulent. Par régime turbulent, on entend un flux défini par un nombre de Reynolds supérieur au nombre Reynolds critique, c'est-à-dire, pour un écoulement dans une canalisation tubulaire, un nombre de Reynolds supérieur à 2000, voire supérieur à 3000.Preferably, the mixture is produced by simple contact of the odorizing agent with a flow of cryogenic fluid in a turbulent regime. By turbulent regime, we mean a flow defined by a Reynolds number greater than the critical Reynolds number, that is to say, for a flow in a tubular pipe, a Reynolds number greater than 2000, or even greater than 3000.
De manière générale, l'alimentation en agent odorisant est telle que la concentration en agent odorisant dans le fluide cryogénique est comprise entre 0,1 mg/m3 (n) et 500 mg/m3 (n), de préférence entre 0,5 mg/m3 (n) et 100 mg/m3 (n), de préférence encore entre 0,5 mg/m3 (n) et 50 mg/m3 (n). La concentration est mesurée par rapport à des m3 (n) correspondant à 1 m3 de gaz à l'état vapeur dans les conditions normales de température et de pression (0°C et 1013,25 hPa).In general, the supply of odorizing agent is such that the concentration of odorizing agent in the cryogenic fluid is between 0.1 mg/m 3 (n) and 500 mg/m 3 (n), preferably between 0. 5 mg/m 3 (n) and 100 mg/m 3 (n), more preferably between 0.5 mg/m 3 (n) and 50 mg/m 3 (n). The concentration is measured relative to m 3 (n) corresponding to 1 m 3 of gas in the vapor state under normal temperature and pressure conditions (0°C and 1013.25 hPa).
Grâce à la présente invention, il est ainsi possible de disposer d'un procédé simple et efficace d'odorisation de fluide cryogénique, pouvant fonctionner en continu ou en discontinu, sans risque de colmatage ou bouchage de canalisations, tubulures, vannes ou autres dispositifs dans lesquels coule ledit fluide cryogénique, ledit procédé comprenant les étapes ci-dessus définies, dans lesquels un agent odorisant est mis au contact dudit fluide cryogéniqueThanks to the present invention, it is thus possible to have a simple and effective process for odorizing cryogenic fluid, which can operate continuously or discontinuously, without the risk of clogging or clogging of pipes, pipes, valves or other devices in which flows said cryogenic fluid, said method comprising the steps defined above, in which an odorizing agent is brought into contact with said cryogenic fluid
L'agent odorisant mis en œuvre dans la présente invention peut être de toute nature, selon l'effet recherché, le seuil de détection souhaité, l'odeur attendue, et autres.The odorizing agent implemented in the present invention can be of any kind, depending on the desired effect, the desired detection threshold, the expected odor, and others.
L'agent odorisant est avantageusement choisi dans la famille des hydrocarbures, par exemple les terpènes, dans la famille des alcools et des phénols, dans la famille des aldéhydes, dans la famille des éthers, cycliques ou non, dans la famille des esters, par exemple la famille des acrylates et des (alkyl)acrylates, dans la famille des acides gras, dans la famille des cétones, dans la famille des lactones, dans la famille des mercaptans, par exemple les alkylmercaptans, les (alkyl)thio-alkylmercaptans, la famille des sulfures cycliques, la famille des sulfures de dialkyle symétriques ou non, la famille des disulfures de dialkyle symétriques ou non, ou encore dans la famille des dérivés du sélénium, par exemple les séléniures ou diséléniures d'alkyle ou de dialkyle, qu'ils soient symétriques ou non. Des mélanges d'au moins deux des agents odorisants cités ci-dessus, en toutes proportions, peuvent également être envisagés.The odorizing agent is advantageously chosen from the family of hydrocarbons, for example terpenes, from the family of alcohols and phenols, from the family of aldehydes, from the family of ethers, cyclic or not, from the family of esters, by for example the family of acrylates and (alkyl)acrylates, in the family of fatty acids, in the family of ketones, in the family of lactones, in the family of mercaptans, for example alkylmercaptans, (alkyl)thio-alkylmercaptans, the family of cyclic sulphides, the family of symmetrical or unsymmetrical dialkyl sulphides, the family of symmetrical or unsymmetrical dialkyl disulphides, or else in the family of selenium derivatives, for example selenides or diselenides of alkyl or dialkyl, that whether they are symmetrical or not. Mixtures of at least two of the odorizing agents mentioned above, in all proportions, can also be envisaged.
Selon un mode de réalisation préféré, l'agent odorisant est choisi parmi les alcools, et les phénols, tels que, par exemple et de manière non limitative, le nérol, le phényl-3-propan-1-ol, le linalol, la géosmine, le p-crésol, le 3,5-diméthylphénol, le 3-éthylphénol et le 1-naphtol. Selon un autre mode de réalisation préféré, l'agent odorisant est choisi dans la famille des aldéhydes, tels que par exemple et de manière non limitative trans-2,trans-4-décadiénal, le trans-2,trans-4-hexadiénal, le trans-2,trans-4-octadiénal, le trans-2,trans-4-nonadiénal, l'éthylvanilline, le cis-3-hexénal, le trans-4-hexénal, le trans-2,cis-6-nonadiénal, le 4,5-époxy-2-dodécénal et l'iso-valéraldéhyde.According to a preferred embodiment, the odorizing agent is chosen from alcohols and phenols, such as, for example and without limitation, nerol, phenyl-3-propan-1-ol, linalool, geosmin, p-cresol, 3,5-dimethylphenol, 3-ethylphenol and 1-naphthol. According to another preferred embodiment, the odorizing agent is chosen from the family of aldehydes, such as, for example and without limitation, trans-2,trans-4-decadienal, trans-2,trans-4-hexadienal, trans-2,trans-4-octadienal, trans-2,trans-4-nonadienal, ethyl vanillin, cis-3-hexenal, trans-4-hexenal, trans-2,cis-6-nonadienal , 4,5-epoxy-2-dodecenal and iso -valeraldehyde.
Selon encore un autre mode de réalisation préféré, l'agent odorisant est choisi dans la famille des éthers, tels que, de manière non limitative, le 1-méthoxynaphtalène, le 2-méthoxynaphtalène, le 1-éthoxynaphtalène, les pyranes, par exemple le cis-rose-oxyde.According to yet another preferred embodiment, the odorizing agent is chosen from the family of ethers, such as, without limitation, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-ethoxynaphthalene, pyrans, for example cis -rose-oxide.
Selon encore un autre mode de réalisation préféré, l'agent odorisant est choisi dans la famille des mercaptans, tels que, de manière non limitative, le méthylmercaptan, l'éthylmercaptan, le tert-butylmercaptan, le sec-butylmercaptan, l'iso-butylmercaptan, le n-propylmercaptan, l'iso-propylmercaptan, les pentylmercaptans, le cyclohexylmercaptan, et le n-dodécylmercaptan.According to yet another preferred embodiment, the odorizing agent is chosen from the family of mercaptans, such as, without limitation, methyl mercaptan, ethyl mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, iso - butyl mercaptan, n-propyl mercaptan, iso -propyl mercaptan, pentyl mercaptans, cyclohexyl mercaptan, and n-dodecyl mercaptan.
Selon encore un autre mode de réalisation préféré, l'agent odorisant est choisi dans la famille des sulfures, disulfures voire polysulfures d'alkyle, tels que, de manière non limitative, le sulfure de méthyle et d'éthyle (MES), le sulfure de diméthyle (DMS) et le sulfure de diéthyle (DES) ou le tetrahydrothiophène (THT).According to yet another preferred embodiment, the odorizing agent is chosen from the family of alkyl sulphides, disulphides or even polysulphides, such as, without limitation, methyl and ethyl sulphide (MES), sulphide (DMS) and diethyl sulfide (DES) or tetrahydrothiophene (THT).
Dans encore un autre mode de réalisation préféré, l'agent odorisant est choisi dans la famille des esters, tels que, de manière non limitative, les acrylates de méthyle, d'éthyle, d'allyle, de n-propyle, d'iso-propyle, de n-butyle, d'iso-butyle, de tert-butyle, de pentyle, d'hexyle, d'heptyle, d'octyle et de dodécyle, les méthacrylates de méthyle, d'éthyle, d'allyle, de n-propyle, d'iso-propyle, de n-butyle, d'iso-butyle, de tert-butyle, de pentyle, d'hexyle, d'heptyle, d'octyle et de dodécyle, l'iso-valérate de propyle, l'iso-valérate d'iso-pentyle, le dodécanoate de méthyle, le dodécanoate d'éthyle, l'undécanoate d'éthyle, le carboxylate de méthylheptyne et le carbonate de di-(méthoxy-2-phényle).In yet another preferred embodiment, the odorizing agent is chosen from the family of esters, such as, without limitation, methyl, ethyl, allyl, n-propyl, iso -propyl, n-butyl, iso -butyl, tert -butyl, pentyl, hexyl, heptyl, octyl and dodecyl, methyl, ethyl, allyl methacrylates, n-propyl, iso -propyl, n-butyl, iso -butyl, tert -butyl, pentyl, hexyl, heptyl, octyl and dodecyl, iso -valerate propyl, iso -pentyl iso -valerate, methyl dodecanoate, ethyl dodecanoate, ethyl undecanoate, methylheptyne carboxylate and di-(2-methoxy-phenyl)carbonate.
Selon encore un autre mode de réalisation préféré, l'agent odorisant est choisi dans la famille des acides gras tels que, de manière non limitative, l'acide butyrique, l'acide iso-valérique et l'acide méthyl-2-propionique.According to yet another preferred embodiment, the odorizing agent is chosen from the family of fatty acids such as, but not limited to, butyric acid, iso-valeric acid and methyl-2-propionic acid.
Selon encore un autre mode de réalisation préféré, l'agent odorisant est choisi dans la famille des composés azotés comprenant, à titre d'exemples non limitatifs, les lactones (telles que la caprolactone), les nitriles (tels que le 2-nonènenitrile) et les composés de type pyrazines (tels que la 2-méthylpyrazine, la 2,3-diméthylpyrazine, la 2,6-diméthylpyrazine, la 2,3,5-triméthylpyrazine, la tétraméthylpyrazine, la 2-éthylpyrazine, la 2,3-diéthylpyrazine, la 5,2-méthyléthylpyrazine, la 2,3-méthyléthylpyrazine, la 5,2,3-méthyldiéthylpyrazine et la 3,5,2- ainsi que la 3,6,2-diméthyléthylpyrazine), la 2,3-méthyléthylpyrazine et la tétraméthylpyrazine, et autres, tels que mentionnés dans le document
La famille des cétones représente également une famille d'agents odorisants préférée, cétones parmi lesquelles on peut citer, à titre d'exemples non limitatifs, la 3-méthylnonan-2,4-dione, la 1-nonén-3-one, la 3-hydroxy-4,5-diméthyl-2(5H)-furanone, la 3-hydroxy-4,5-diethyl-2(5H)-furanone, la 3-hydroxy-4-méthyl-5-éthyl-2(5H)-furanone, la 3-hydroxy-4-ethyl-5-methyl-2(5H)-furanone, la 3-hydroxy-4-méthyl-5-butyl-2(5H)-furanone, la 3-hydroxy-4-méthyl-5-iso-butyl-2(5H)-furanone, la 3-hydroxy-4-méthyl-5-propyl-2(5H)-furanone, la 2,5-diméthyl-4-méthoxy-3(2H)-furanone, les ionones, les damascénones, la trans-2-nonén-4-one, le furanéol, et la 1-(2,2,6-triméthylcyclohexyl)-2-buténone.The family of ketones also represents a family of preferred odorizing agents, ketones among which mention may be made, by way of nonlimiting examples, of 3-methylnonan-2,4-dione, 1-nonen-3-one, 3-hydroxy-4,5-dimethyl-2(5 H )-furanone, 3-hydroxy-4,5-diethyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5-ethyl- 2(5 H )-furanone, 3-hydroxy-4-ethyl-5-methyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5-butyl-2(5 H )-furanone, 3-hydroxy-4-methyl-5- iso -butyl-2( 5H )-furanone, 3-hydroxy-4-methyl-5-propyl-2( 5H )-furanone, 2,5-dimethyl -4-methoxy-3(2 H )-furanone, ionones, damascenones, trans-2-nonen-4-one, furaneol, and 1-(2,2,6-trimethylcyclohexyl)-2-butenone .
Une autre famille d'odorisants préférés est constituée des lactones, telles que par exemple, et de manière non limitative, la 3,6-diméthyl-3a,4,5,7a-tétrahydro-2(3H)-benzofuranone, la γ-nonalactone, la γ-undécalactone, la (Z)-6-dodécéno-γ-lactone, et la coumarine.Another family of preferred odorants consists of lactones, such as, for example, and in a non-limiting manner, 3,6-dimethyl-3a,4,5,7a-tetrahydro-2( 3H )-benzofuranone, γ -nonalactone, γ-undecalactone, (Z)-6-dodeceno-γ-lactone, and coumarin.
Selon encore un autre mode de réalisation préféré, l'agent odorisant est choisi dans la famille des dérivés du sélénium, parmi lesquels on peut citer, à titre d'exemples non limitatifs le séléniure de diméthyle, le diséléniure de diméthyle, le séléniure de diéthyle, le séléniure de diphényle, le diséléniure de diphényle et l'éthylsélénol, et autres, tels que ceux mentionnés dans le document
Les seuils de perception des odorisants cités ci-dessus sont tous de l'ordre de l'ordre de grandeur de la dizaine de partie par milliard (ppb), voire inférieurs. Ils sont pour la plupart inférieurs à 1 ppb.The perception thresholds for the odorants cited above are all of the order of the order of magnitude of ten parts per billion (ppb), or even lower. They are mostly below 1 ppb.
Selon un mode de réalisation tout particulièrement préféré, l'agent odorisant utilisable dans la présente invention est choisi parmi le sulfure de méthyle et d'éthyle, le sulfure de diméthyle, le sulfure de diéthyle, le disulfure de diméthyle, le disulfure de diéthyle, le méthylmercaptan, l'éthylmercaptan, le tert-butylmercaptan, le sec-butylmercaptan, l'isopropylmercaptan, le n-propylmercaptan le cyclohexylmercaptan, le tétrahydrothiophène, l'acrylate de méthyle, l'acrylate d'éthyle, le méthacrylate de méthyle, le méthacrylate d'éthyle, la méthyléthylpyrazine le séléniure de diméthyle, et le diséléniure de diméthyle.According to a very particularly preferred embodiment, the odorizing agent which can be used in the present invention is chosen from methyl and ethyl sulphide, dimethyl sulphide, diethyl sulphide, dimethyl disulphide, diethyl disulphide, methyl mercaptan, ethyl mercaptan, tert -butyl mercaptan, sec -butyl mercaptan, iso propyl mercaptan, n-propyl mercaptan cyclohexyl mercaptan, tetrahydrothiophene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methylethylpyrazine, dimethyl selenide, and dimethyl diselenide.
Les agents odorisants utilisables dans le cadre de la présente invention peuvent être utilisés purs, en mélange de deux ou plusieurs d'entre eux en toutes proportions ou encore dilués avec d'autres composés compatibles avec le fluide cryogénique choisis parmi les alcanes en C5-C6 (par exemple le n-pentane, l'iso-pentane, le cyclohexane, le méthylpentane, l'éther de pétrole, ainsi que les mélanges de deux ou plusieurs d'entre eux), les sulfones, les sulfoxydes, et de préférence choisis parmi les alcanes.The odorizing agents which can be used in the context of the present invention can be used pure, as a mixture of two or more of them in all proportions or alternatively diluted with other compounds compatible with the cryogenic fluid chosen from C 5 - C 6 (for example n-pentane, isopentane , cyclohexane, methylpentane, petroleum ether, as well as mixtures of two or more of them), sulfones, sulfoxides, and preferably chosen from alkanes.
On préfère cependant utiliser les agents odorisants dans le cadre de la présente invention seuls ou en mélanges de deux ou plusieurs d'entre eux en toutes proportions, éventuellement, mais de manière non préférée, dilués avec un ou plusieurs solvants comme indiqué ci-dessus, dans des proportions de solvant(s) n'excédant toutefois pas 20%, mieux encore n'excédant pas 10% en poids de solvant par rapport au poids total (agent(s) odorisant(s) + solvant(s)).It is however preferred to use the odorizing agents in the context of the present invention alone or in mixtures of two or more of them in all proportions, optionally, but not preferably, diluted with one or more solvents as indicated above, in proportions of solvent(s) however not exceeding 20%, better still not exceeding 10% by weight of solvent relative to the total weight (odorizing agent(s)+solvent(s)).
Dans un mode de réalisation préféré, le solvant est choisi parmi les alcanes en C5-C6 dont les propriétés physiques permettent une manipulation facilitée, et typiquement ceux qui sont liquides à température ambiante.In a preferred embodiment, the solvent is chosen from C 5 -C 6 alkanes whose physical properties allow easy handling, and typically those which are liquid at ambient temperature.
Dans un mode de réalisation préférée, le solvant est l'iso-pentane qui permet notamment d'abaisser le point de cristallisation de la composition odorisante et de se rapprocher de la température du fluide cryogénique, qui est par exemple de -162°C pour le GNL (« Gaz Naturel Liquéfié »), et donc proche de la température de fusion de l'isopentane (-160°C).In a preferred embodiment, the solvent is iso -pentane which makes it possible in particular to lower the crystallization point of the odorizing composition and to approach the temperature of the cryogenic fluid, which is for example -162° C. for LNG ("Liquefied Natural Gas"), and therefore close to the melting temperature of isopentane (-160°C).
Outre l'éventuel solvant, l'agent odorisant utilisable dans le cadre de la présente invention peut également comprendre un ou plusieurs additifs choisis parmi les stabilisants thermiques, les colorants, les anti-oxydants, tels que par exemple ceux de type phénolique, les radicaux nitroxy stable, par exemple de type oxydes de tétraméthylpipéridine (également connus sous le nom de TEMPO) et autres dérivés, notamment décrits dans
La concentration d'agent odorisant, lorsqu'il est dilué dans un solvant et/ou lorsqu'il est mélangé à un ou plusieurs additifs (on parle alors de « formulation odorisante ») peut être comprise dans de larges proportions, et généralement entre 0,1% et 100% en poids d'agent odorisant par rapport au poids total de la formulation odorisante. Dans un mode de réalisation préféré, l'agent odorisant représente 100% de la formulation odorisante, i.e. l'agent odorisant est utilisé sans solvant.The concentration of odorizing agent, when it is diluted in a solvent and/or when it is mixed with one or more additives (we then speak of “odorizing formulation”) can be comprised in large proportions, and generally between 0 1% and 100% by weight of odorizing agent relative to the total weight of the odorizing formulation. In a preferred embodiment, the odorizing agent represents 100% of the odorizing formulation, i.e. the odorizing agent is used without solvent.
Dans une autre solution préférée, l'agent odorisant représentera entre 10 et 50% en poids de la formulation odorisante. Dans un autre mode de réalisation préféré, l'agent odorisant est utilisé en l'absence de solvant et/ou en l'absence de tout autre additif, permettant de minimiser les pollutions du fluide cryogénique.In another preferred solution, the odorizing agent will represent between 10 and 50% by weight of the odorizing formulation. In another preferred embodiment, the odorizing agent is used in the absence of solvent and/or in the absence of any other additive, making it possible to minimize pollution of the cryogenic fluid.
Sans vouloir être lié par la théorie, la présente invention consiste en un procédé qui produit en continu de fines particules d'un agent odorisant solide à partir dudit agent odorisant sous forme liquide, lesdites fines particules dudit agent odorisant solide étant ensuite introduites en continu dans un fluide cryogénique dans lequel elles se dissolvent.Without wishing to be bound by theory, the present invention consists of a process which continuously produces fine particles of a solid odorizing agent from said odorizing agent in liquid form, said fine particles of said solid odorizing agent then being continuously introduced into a cryogenic fluid in which they dissolve.
On préfère réaliser le procédé d'odorisation du fluide cryogénique en continu, ce mode de réalisation étant tout particulièrement adapté pour faciliter le mélange et en particulier assurer l'homogénéité du fluide cryogénique odorisé. Le procédé d'odorisation selon l'invention peut également être réalisé en discontinu, ce mode de réalisation pouvant typiquement être effectué par introduction d'une charge d'agent odorisant (éventuellement sous forme de formulation odorisante) dans au moins une partie du fluide cryogénique à odoriser, par exemple dans une veine de fluide cryogénique statique, dans un by-pass ou dérivation, et autre, puis dilution de cette au moins une partie du fluide cryogénique odorisé dans ledit fluide cryogénique à odoriser.It is preferred to carry out the process for odorizing the cryogenic fluid continuously, this embodiment being very particularly suitable for facilitating mixing and in particular ensuring the homogeneity of the odorized cryogenic fluid. The odorization process according to the invention can also be carried out discontinuously, this embodiment typically being able to be carried out by introducing a charge of odorizing agent (optionally in the form of an odorizing formulation) into at least part of the cryogenic fluid to be odorized, for example in a stream of static cryogenic fluid, in a bypass or bypass, and the like, then dilution of this at least part of the odorized cryogenic fluid in said cryogenic fluid to be odorized.
Selon un autre aspect, la présente invention concerne un dispositif d'introduction d'un agent odorisant dans un fluide cryogénique à l'état liquide, ledit dispositif étant adapté pour la mise en œuvre du procédé selon la présente invention. Dans un mode de réalisation préféré le dispositif comprend :
- 1) une zone d'alimentation, laquelle est alimentée en agent odorisant sous forme liquide ou gazeuse, de préférence liquide,
- 2) une zone tampon dans laquelle l'agent odorisant liquide ou gazeux est amené à une température inférieure à 30°C au-dessus de la température du fluide cryogénique, et
- 3) une zone de contact, où ledit agent odorisant sous forme solide entre en contact avec ledit fluide cryogénique à odoriser.
- 1) a supply zone, which is supplied with odorizing agent in liquid or gaseous form, preferably liquid,
- 2) a buffer zone in which the liquid or gaseous odorant is brought to a temperature lower than 30°C above the temperature of the cryogenic fluid, and
- 3) a contact zone, where said odorizing agent in solid form comes into contact with said cryogenic fluid to be odorized.
La zone d'alimentation consiste en tout système permettant de transférer l'odorisant depuis son stockage vers la zone tampon. La zone d'alimentation est alimentée, de préférence en continu, avec un agent odorisant qui se présente sous forme liquide ou gazeuse, de préférence sous forme liquide, ladite alimentation étant de préférence réalisée à température ambiante. L'alimentation de l'agent odorisant à l'état solide n'est pas préférée, pour des raisons évidentes de manipulation et de dosage, particulièrement lorsque l'on met en œuvre le procédé d'odorisation selon la présente invention en mode continu.The supply zone consists of any system allowing the odorant to be transferred from its storage to the buffer zone. The supply zone is supplied, preferably continuously, with an odorizing agent which is in liquid or gaseous form, preferably in liquid form, said supply preferably being carried out at ambient temperature. Feeding the odorizing agent in the solid state is not preferred, for obvious reasons of handling and dosage, particularly when the odorization process according to the present invention is carried out in continuous mode.
Le transfert de l'agent odorisant dans la zone d'alimentation peut être réalisé, à l'aide d'une pompe ou toute autre technologie de pompage, ou bien par différence de pression entre le stockage et la zone tampon, ou en alternative par différentiel de pression lors de l'injection de doses pré-chargées dans un stockage intermédiaire. On peut en outre contrôler le débit, par exemple à l'aide d'un débitmètre, éventuellement combiné à une vanne de régulation.The transfer of the odorizing agent into the supply zone can be carried out using a pump or any other pumping technology, or else by pressure difference between the storage and the buffer zone, or alternatively by pressure differential when injecting pre-loaded doses into intermediate storage. It is also possible to control the flow rate, for example using a flow meter, possibly combined with a control valve.
L'agent odorisant peut ainsi être alimenté par tout moyen connu en soi, par exemple au moyen de pompe ou tout autre dispositif permettant d'appliquer un différentiel de pression. Selon un mode de réalisation préféré, la pression d'alimentation est comprise entre 0,1 MPa et 10 MPa, de préférence entre 0,1 MPa et 5 MPa. Les valeurs de pression indiquées ci-dessus sont des valeurs correspondant à des pressions absolues.The odorizing agent can thus be supplied by any means known per se, for example by means of a pump or any other device making it possible to apply a pressure differential. According to a preferred embodiment, the supply pressure is between 0.1 MPa and 10 MPa, preferably between 0.1 MPa and 5 MPa. The pressure values indicated above are values corresponding to absolute pressures.
Un des avantages de la présente invention est que l'agent odorisant peut être stocké et utilisé dans une large gamme de de températures, par exemple pouvant aller de -100°C et +100°C, typiquement de -50°C à +60°C. Selon un mode de réalisation tout particulièrement préféré, la température de stockage est la température du site d'odorisation. La pression de stockage est le plus généralement la pression atmosphérique, la pression d'utilisation pouvant être différente de la pression de stockage afin d'assurer le transport de l'agent odorisant vers la zone d'alimentation.One of the advantages of the present invention is that the odorizing agent can be stored and used in a wide range of temperatures, for example being able to go from -100°C and +100°C, typically from -50°C to +60 °C. According to a very particularly preferred embodiment, the storage temperature is the temperature of the odorization site. The storage pressure is most generally atmospheric pressure, the operating pressure possibly being different from the storage pressure in order to ensure the transport of the odorizing agent to the supply zone.
Ainsi, l'alimentation en agent odorisant peut être réalisée par tout dispositif permettant le transfert de fluide (à l'état liquide ou gazeux), avantageusement de manière contrôlée, et de préférence de manière contrôlée et régulée.Thus, the supply of odorizing agent can be carried out by any device allowing the transfer of fluid (in the liquid or gaseous state), advantageously in a controlled manner, and preferably in a controlled and regulated manner.
L'arrivée dans la zone tampon b) de l'agent odorisant, typiquement lorsque celui-ci est liquide peut être réalisée par tout moyen connu en soi, et par exemple au moyen d'au moins un ou plusieurs éléments choisis parmi canule, buse, injecteur ou tout autre moyen permettant l'alimentation par goutte à goutte ou en spray, et autres, lesdits éléments précités pouvant être utilisés seuls ou en combinaison de un ou plusieurs d'entre eux.The arrival in the buffer zone b) of the odorizing agent, typically when the latter is liquid, can be achieved by any means known per se, and for example by means of at least one or more elements chosen from cannula, nozzle , injector or any other means allowing the supply by drip or spray, and others, said aforementioned elements being able to be used alone or in combination of one or more of them.
Cette arrivée dans la zone tampon b) peut également être réalisée, typiquement lorsque l'agent odorisant est sous forme gazeuse, par entrainement dudit agent odorisant (tension de vapeur), éventuellement avec un gaz vecteur, comme décrit par exemple dans la demande internationale
Selon un mode de réalisation préféré, l'agent odorisant peut être thermostaté dans la zone d'alimentation a) et/ou éventuellement en amont de ladite zone d'alimentation, afin de réguler/contrôler la concentration d'agent odorisant dans le gaz vecteur.According to a preferred embodiment, the odorizing agent can be thermostatically controlled in the supply zone a) and/or optionally upstream of said supply zone, in order to regulate/control the concentration of odorizing agent in the carrier gas .
Dans un mode d'alimentation préféré, l'agent odorisant est injecté sous forme de spray, ledit spray pouvant être obtenu par toute technique connue de l'homme du métier.In a preferred mode of supply, the odorizing agent is injected in the form of a spray, said spray being able to be obtained by any technique known to those skilled in the art.
Dans un autre mode de réalisation préférée, la zone d'alimentation, ainsi que de préférence la zone tampon, est(sont) équipée(s) de moyens permettant de maintenir à une température supérieure à la température de cristallisation de l'agent odorisant, de sorte que ledit agent odorisant est maintenu à l'état fluide (état liquide ou gazeux), ces moyens étant typiquement un ou plusieurs systèmes d'isolation thermique bien connus de l'homme du métier, et par exemple une isolation par le vide, ou une circulation d'un gaz dont la température d'ébullition est inférieure ou égale à la température du fluide cryogénique. On entend par cela le fait qu'un tel gaz ne se condensera pas en se refroidissant à la température du fluide cryogénique, permettant ainsi le maintien d'un zone libre de fluide cryogénique (zone tampon).In another preferred embodiment, the supply zone, as well as preferably the buffer zone, is (are) equipped with means making it possible to maintain a temperature above the crystallization temperature of the odorizing agent, so that said odorizing agent is maintained in the fluid state (liquid or gaseous state), these means typically being one or more thermal insulation systems well known to those skilled in the art, and for example vacuum insulation, or circulation of a gas whose boiling point is less than or equal to the temperature of the cryogenic fluid. By this is meant the fact that such a gas will not condense on cooling to the temperature of the cryogenic fluid, thus allowing the maintenance of a zone free of cryogenic fluid (buffer zone).
Dans un autre mode de réalisation préféré, l'isolation thermique pourra être réalisée par réchauffage de la zone d'alimentation avec un fluide caloporteur, éventuellement thermostaté, par réchauffage au moyen d'une résistance chauffante, par induction, conduction, ou autre.In another preferred embodiment, the thermal insulation can be achieved by heating the supply zone with a heat transfer fluid, possibly thermostatically controlled, by heating by means of a heating resistor, by induction, conduction, or the like.
La zone tampon b) permet notamment d'amener l'agent odorisant, liquide ou gazeux, à une température inférieure à 30°C au-dessus de la température du fluide cryogénique. Cette zone tampon a pour effet d'isoler la zone d'alimentation de la zone de contact qui se trouve à la température du fluide cryogénique. En d'autres termes, l'agent odorisant est, et reste, à l'état fluide (liquide ou gazeux) dans la zone d'alimentation et est progressivement amené à une température inférieure à 30°C au-dessus de la température du fluide cryogénique, voire à la température, du fluide cryogénique, au sortir de la zone tampon b).The buffer zone b) makes it possible in particular to bring the odorizing agent, liquid or gaseous, to a temperature below 30° C. above the temperature of the cryogenic fluid. This buffer zone has the effect of isolating the supply zone from the contact zone which is at the temperature of the cryogenic fluid. In other words, the odorizing agent is, and remains, in a fluid state (liquid or gaseous) in the feed zone and is gradually brought to a temperature below 30°C above the temperature of the cryogenic fluid, or even at the temperature of the cryogenic fluid, on leaving the buffer zone b).
Dans un mode de réalisation préféré, la température de la zone tampon est maintenue, au moins en partie, à une température supérieure au point de fusion de l'agent odorisant, afin d'éviter le refroidissement dudit agent odorisant en dessous de son point de cristallisation, en raison de la proximité de la zone de contact dont la température, typiquement égale à celle du fluide cryogénique. Le maintien de cette température peut être réalisé par tous moyens connus de l'homme du métier, par exemple au moyen d'un ciel de gaz dans au moins une partie de la zone d'alimentation et/ou de la zone tampon, par préchauffage de l'agent odorisant éventuellement formulé, chauffage de la zone d'alimentation et/ou de la zone tampon, utilisation de matériaux thermiquement isolants, et autres, ou combinaison de deux ou plusieurs des techniques précitées.In a preferred embodiment, the temperature of the buffer zone is maintained, at least in part, at a temperature above the melting point of the odorizing agent, in order to avoid the cooling of said odorizing agent below its melting point. crystallization, due to the proximity of the contact zone whose temperature, typically equal to that of the cryogenic fluid. This temperature can be maintained by any means known to those skilled in the art, for example by means of a gas blanket in at least part of the supply zone and/or of the buffer zone, by preheating of the optionally formulated odorizing agent, heating of the supply zone and/or of the buffer zone, use of thermally insulating materials, and the like, or combination of two or more of the aforementioned techniques.
Le ciel de gaz est généralement créé par alimentation d'un gaz dont le point de liquéfaction est inférieur ou égal à la température d'ébullition du fluide cryogénique. Des exemples typiques de gaz sont l'azote, l'argon, l'hélium, l'hydrogène, le méthane, le gaz naturel, et autres, ainsi que leurs mélanges.The gas sky is generally created by feeding a gas whose liquefaction point is less than or equal to the boiling temperature of the cryogenic fluid. Typical examples of gases are nitrogen, argon, helium, hydrogen, methane, natural gas, and the like, and mixtures thereof.
Ce gaz peut être introduit dans au moins une partie de la zone d'alimentation et/ou au moins une partie de la zone tampon. Le débit d'introduction de ce gaz est généralement compris entre 0,1 L.min-1 et 500 L.min-1, de préférence entre 0,2 L.min-1 et 10 L.min-1. Dans un mode de réalisation plus particulier, le débit de gaz peut également permettre d'appliquer un différentiel de pression permettant une alimentation contrôlée et régulée de l'agent odorisant dans la zone d'alimentation. Dans une solution préférée, le débit de gaz est asservi à une mesure de température réalisée au sein de la zone d'alimentation.This gas can be introduced into at least part of the supply zone and/or at least part of the buffer zone. The rate of introduction of this gas is generally between 0.1 L.min -1 and 500 L.min -1 , preferably between 0.2 L.min -1 and 10 L.min -1 . In a more particular embodiment, the gas flow can also make it possible to apply a pressure differential allowing a controlled and regulated supply of the odorizing agent in the supply zone. In a preferred solution, the gas flow is slaved to a temperature measurement carried out within the supply zone.
Le chauffage de la zone d'alimentation et/ou le préchauffage de l'agent odorisant permet(tent) de maintenir la température de la zone d'alimentation et/ou au moins une partie de la zone tampon à une température supérieure au point de fusion de l'agent odorisant.The heating of the supply zone and/or the preheating of the odorizing agent makes it possible to maintain the temperature of the supply zone and/or at least part of the buffer zone at a temperature above the set point. fusion of the odorizing agent.
La zone tampon b) représente l'espace entre la zone d'alimentation dans laquelle l'agent odorisant est sous forme liquide ou vapeur, et la zone de contact (ou surface du fluide cryogénique) dans laquelle l'agent odorisant vient au contact du fluide cryogénique.The buffer zone b) represents the space between the supply zone in which the odorizing agent is in liquid or vapor form, and the contact zone (or surface of the cryogenic fluid) in which the odorizing agent comes into contact with the cryogenic fluid.
Cette zone tampon présente un gradient de température entre la température de la zone d'alimentation et la température de la zone de contact. Dans un mode de réalisation préférée, le gradient de température (typiquement refroidissement) est obtenu par le fluide cryogénique considéré.This buffer zone has a temperature gradient between the temperature of the supply zone and the temperature of the contact zone. In a preferred embodiment, the temperature gradient (typically cooling) is obtained by the cryogenic fluid considered.
Dans un mode de réalisation de l'invention, la zone tampon b) peut être équipée d'une assistance mécanique permettant un transport amélioré dudit agent odorisant vers le fluide cryogénique, comme décrit plus loin dans la description.In one embodiment of the invention, the buffer zone b) can be equipped with mechanical assistance allowing improved transport of said odorizing agent to the cryogenic fluid, as described later in the description.
L'introduction de l'agent odorisant dans le fluide cryogénique est réalisée dans la zone de contact c). Ladite zone de contact c) est préférentiellement agitée afin de faciliter la dispersion de l'agent odorisant pour faciliter une dissolution rapide dans le milieu. Cette agitation peut être générée par tout moyen connu de l'homme du métier, par exemple agitation mécanique, convection, circulation ou recirculation au moyens de pompes ou tout autre dispositif permettant la génération d'un flux à débit plus ou moins important.The introduction of the odorizing agent into the cryogenic fluid is carried out in the contact zone c). Said contact zone c) is preferentially agitated in order to facilitate the dispersion of the odorizing agent to facilitate rapid dissolution in the medium. This agitation can be generated by any means known to those skilled in the art, for example mechanical agitation, convection, circulation or recirculation by means of pumps or any other device allowing the generation of a flow at a greater or lesser rate.
Dans un mode de réalisation préféré, le contact de l'agent odorisant avec la surface du fluide cryogénique sera réalisé dans un flux de fluide cryogénique permettant ainsi de favoriser la dispersion de l'agent odorisant, et ceci de façon homogène, au sein du fluide cryogénique qui devient ainsi un fluide cryogénique odorisé.In a preferred embodiment, the contact of the odorizing agent with the surface of the cryogenic fluid will be made in a flow of cryogenic fluid, thus making it possible to promote the dispersion of the odorizing agent, and this in a homogeneous manner, within the fluid. cryogenic which thus becomes an odorized cryogenic fluid.
Comme indiqué précédemment, le passage de la zone d'alimentation vers la zone de contact, au travers de la zone tampon, peut être réalisé de manière gravitaire et/ ou avec une assistance mécanique, permettant de véhiculer l'agent odorisant, éventuellement sous forme de formulation odorisante, vers le fluide cryogénique afin d'assurer la mise en contact.As indicated previously, the passage from the supply zone to the contact zone, through the buffer zone, can be carried out by gravity and/or with mechanical assistance, making it possible to convey the odorizing agent, possibly in the form of odorizing formulation, towards the cryogenic fluid in order to ensure contact.
Le procédé de la présente invention présente ainsi plusieurs avantages et tout particulièrement celui de ne pas faire appel à la préparation d'un pré-mélange contenant l'agent odorisant dans une matrice comme par exemple décrit dans la demande de brevet
En effet, grâce au procédé de l'invention utilisant le dispositif décrit ci-dessus, l'addition de l'agent odorisant dans le fluide cryogénique est simplifiée, sans nécessité d'une préparation préalable d'un concentré odorisant, par exemple dans un hydrocarbure tel que le propane, comme décrit par exemple dans
Le dispositif d'odorisation d'un fluide cryogénique décrit plus haut peut se présenter sous diverses formes et aspects. Les
La
L'agent odorisant, éventuellement sous forme de formulation odorisante, est introduit avec un gaz vecteur via la canalisation (2) dans la partie supérieure de la vis sans fin (4) qui est soumise à un mouvement de rotation, via le moteur (3), de sorte que l'agent odorisant (ou la formulation odorisante) atteigne, sous forme de particules dispersées (5), le flux de fluide cryogénique (1) qui s'écoule dans le sens indiqué.The odorizing agent, optionally in the form of an odorizing formulation, is introduced with a vector gas via the pipe (2) into the upper part of the endless screw (4) which is subjected to a rotational movement, via the motor (3 ), so that the odorizing agent (or the odorizing formulation) reaches, in the form of dispersed particles (5), the flow of cryogenic fluid (1) which flows in the direction indicated.
La
L'agent odorisant (éventuellement sous forme de formulation odorisante) est introduit via la canalisation (2), avec un gaz vecteur via la canalisation (3), dans la zone d'alimentation (A) comprenant une résistance chauffante (4) destinée à maintenir une température supérieure à la température de solidification de l'agent odorisant (ou de la formulation odorisante) qui transite par gravité, via la zone tampon (B), dans la zone de contact (C) où il(elle) est dispersé(e) (5) dans le fluide cryogénique (1) qui s'écoule dans le sens indiqué.The odorizing agent (possibly in the form of an odorizing formulation) is introduced via line (2), with a vector gas via line (3), into the supply zone (A) comprising a heating resistor (4) intended to maintain a temperature above the solidification temperature of the odorizing agent (or of the odorizing formulation) which passes by gravity, via the buffer zone (B), into the contact zone (C) where it is dispersed ( e) (5) in the cryogenic fluid (1) flowing in the direction indicated.
Le dispositif d'odorisation présenté dans cette invention présente de nombreux avantages, parmi lesquels on peut citer la grande facilité d'utilisation. En effet, en raison de son encombrement réduit et de son installation aisée, le dispositif peut être facilement installé aux endroits où l'on souhaite pratiquer l'odorisation d'un fluide cryogénique. Le procédé de l'invention trouve par conséquent une application tout particulièrement intéressante lorsqu'il est mis en œuvre au moyen du dispositif selon la présente inventionThe odorizing device presented in this invention has many advantages, among which the great ease of use can be mentioned. Indeed, because of its small size and its easy installation, the device can be easily installed at the places where it is desired to practice the odorization of a cryogenic fluid. The method of the invention therefore finds a particularly advantageous application when it is implemented by means of the device according to the present invention.
Ainsi, de tels procédés d'odorisation, en continu ou en discontinu, de fluides cryogéniques peuvent être mis en œuvre dans de nombreuses situations, telles que , à titre d'exemples non limitatifs, lors de chargement/remplissage de camions-citernes, de réservoirs, de bateaux, de barges, de bouteilles de gaz, et autres, à partir de réservoirs, bateaux, barges ou lors du procédé même de liquéfaction du fluide cryogénique lors du transfert vers / ou au sein du stockage, et autres.Thus, such processes for the odorization, continuously or discontinuously, of cryogenic fluids can be implemented in many situations, such as, by way of non-limiting examples, when loading/filling tank trucks, tanks, boats, barges, gas cylinders, and others, from tanks, boats, barges or during the very process of liquefaction of the cryogenic fluid during transfer to/or within the storage, and others.
Plus spécifiquement, le procédé d'odorisation selon l'invention trouve une application tout particulièrement intéressante pour l'odorisation du Gaz Naturel Liquéfié (GNL), notamment lors du chargement de camions-citernes ou de stockages statiques ou mobiles à partir de méthaniers, par l'intermédiaire ou non d'un ou plusieurs réservoirs.More specifically, the odorization process according to the invention finds a very particularly advantageous application for the odorization of Liquefied Natural Gas (LNG), in particular when loading tank trucks or static or mobile storage from LNG carriers, by whether or not through one or more reservoirs.
Dans un mode de réalisation tout particulièrement préféré, l'agent odorisant appartient à la famille des odorisants classiquement utilisés pour odoriser le gaz naturel et est typiquement choisi parmi les mercaptans et les sulfures. Ce mode de réalisation est tout particulièrement adapté à l'odorisation du GNL, qui présente alors une odeur caractéristique de gaz, ce qui permet la détection et l'identification de fuites lors du transport, du stockage et l'utilisation dudit GNL, afin d'avertir tout danger lié à l'accumulation de gaz naturel dans l'air.In a very particularly preferred embodiment, the odorizing agent belongs to the family of odorants conventionally used to odorize natural gas and is typically chosen from mercaptans and sulphides. This embodiment is particularly suitable for the odorization of LNG, which then has a characteristic smell of gas, which allows the detection and identification of leaks during the transport, storage and use of said LNG, in order to warn of any danger linked to the accumulation of natural gas in the air.
Grâce au procédé de la présente invention en particulier lorsqu'il est mis en œuvre pour l'odorisation du GNL, il est désormais possible de s'affranchir des stations d'odorisation du gaz lors de l'étape de regazéification du GNL. En effet le procédé d'odorisation de la présente invention peut être réalisé en un seul point centralisé.Thanks to the method of the present invention, in particular when it is implemented for the odorization of LNG, it is now possible to dispense with gas odorization stations during the LNG regasification step. Indeed, the odorization process of the present invention can be carried out at a single centralized point.
Cette centralisation permet ainsi de limiter le nombre de lieux concernés par le stockage et la manipulation des agents odorisants et des formulations odorisantes et ainsi les risques de pollutions olfactives, les frais liés à la maintenance des stations d'injections, et autres.This centralization thus makes it possible to limit the number of places involved in the storage and handling of odorizing agents and odorizing formulations and thus the risks of olfactory pollution, the costs associated with the maintenance of injection stations, and others.
Claims (11)
- Process for odorizing a cryogenic fluid in the liquid state, comprising at least the following steps:a) continuously feeding an odorizing agent in liquid or gaseous form, preferably in liquid form, into a feed zone, said feeding being carried out at a temperature above the temperature of the cryogenic fluid and above the crystallization temperature of the odorizing agent,b) feeding said odorizing agent in liquid or gaseous form from step a) into a buffer zone in which the odorizing agent is brought to a temperature less than 30°C above the temperature of the cryogenic fluid, andc) feeding said odorizing agent cooled in step b), into the contact zone, wherein said odorizing agent in solid form comes into contact with said cryogenic fluid to be odorized.
- Process according to Claim 1, in which the flow rate of odorizing agent in the contact zone is proportional to the flow rate of the cryogenic fluid, preferably, the flow rate of the odorizing agent in the contact zone is automatically controlled by the flow rate of the cryogenic fluid.
- Process according to Claim 1 or Claim 2, in which the odorizing agent is brought, in step b), to a temperature less than 20°C, more preferably less than 10°C, above the temperature of the cryogenic fluid to be odorized.
- Process according to any one of the preceding claims, in which the concentration of odorizing agent in the cryogenic fluid is between 0.1 mg/m3 (n) and 500 mg/m3 (n), preferably between 0.5 mg/m3 (n) and 100 mg/m3 (n), more preferably between 0.5 mg/m3 (n) and 50 mg/m3 (n).
- Process according to any one of the preceding claims, in which the odorizing agent is chosen from terpenes, alcohols, phenols, aldehydes, ethers, esters, fatty acids, ketones, lactones, nitriles, pyrazine compounds, mercaptans, cyclic sulfides, dialkyl sulfides, dialkyl disulfides, or else from selenium derivatives, alone or in mixtures of two or more, in any proportions.
- Process according to any one of the preceding claims, in which the odorizing agent is chosen from methyl ethyl sulfide, dimethyl sulfide, diethyl sulfide, dimethyl disulfide, diethyl disulfide, methyl mercaptan, ethyl mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, iso-propyl mercaptan, n-propyl mercaptan, cyclohexyl mercaptan, tetrahydrothiophene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methylethylpyrazine, dimethyl selenide and dimethyl diselenide.
- Process according to any one of the preceding claims, in which the odorizing agent is used pure, mixed or diluted with other solvents compatible with the cryogenic fluid, chosen from C5-C6 alkanes, sulfones and sulfoxides; in proportions of solvent(s) not exceeding 20%, by weight of solvent relative to the total weight of the odorizing agent(s) and of the solvent(s).
- Process according to any one of the preceding claims, in which the odorizing agent also comprises one or more additives chosen from heat stabilizers, dyes and antioxidants, thus forming an odorizing formulation.
- Process according to any one of the preceding claims, in which the cryogenic fluid is Liquefied Natural Gas.
- Device for introducing an odorizing agent into a cryogenic fluid in the liquid state, said device comprising:1) a feed zone, which is fed with odorizing agent in liquid or gaseous form, preferably liquid form,2) a buffer zone in which the liquid or gaseous odorizing agent is brought to a temperature less than 30°C above the temperature of the cryogenic fluid, and3) a contact zone, wherein said odorizing agent in solid form comes into contact with said cryogenic fluid to be odorized.
- Device according to Claim 10, in which the buffer zone b) is equipped with mechanical assistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HRP20221080TT HRP20221080T1 (en) | 2017-04-25 | 2018-04-18 | Process for cryogenic fluid odorisation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1753565A FR3065375B1 (en) | 2017-04-25 | 2017-04-25 | METHOD FOR ODORIZING CRYOGENIC FLUID |
| PCT/FR2018/050980 WO2018197783A1 (en) | 2017-04-25 | 2018-04-18 | Process for cryogenic fluid odorisation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3615638A1 EP3615638A1 (en) | 2020-03-04 |
| EP3615638B1 true EP3615638B1 (en) | 2022-07-27 |
Family
ID=59253724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP18722690.7A Active EP3615638B1 (en) | 2017-04-25 | 2018-04-18 | Process for cryogenic fluid odorisation |
Country Status (14)
| Country | Link |
|---|---|
| US (2) | US11279895B2 (en) |
| EP (1) | EP3615638B1 (en) |
| KR (2) | KR20220017002A (en) |
| CN (1) | CN110520509B (en) |
| AU (1) | AU2018259133B2 (en) |
| CA (1) | CA3060506C (en) |
| DK (1) | DK3615638T3 (en) |
| ES (1) | ES2926190T3 (en) |
| FR (1) | FR3065375B1 (en) |
| HR (1) | HRP20221080T1 (en) |
| PL (1) | PL3615638T3 (en) |
| PT (1) | PT3615638T (en) |
| SG (1) | SG11201909909YA (en) |
| WO (1) | WO2018197783A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117929677B (en) * | 2024-03-20 | 2024-06-14 | 普利莱（天津）燃气设备有限公司 | Multifunctional natural gas odorizing agent concentration analyzer and analysis method |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2058508A (en) | 1934-08-13 | 1936-10-27 | Standard Oil Co California | Proportional odorizer |
| US2430050A (en) * | 1945-01-24 | 1947-11-04 | Charles E Gill | Gas odorizing |
| US3761232A (en) * | 1971-05-10 | 1973-09-25 | Inst Gas Technology | Method for odorizing cryogenic liquids |
| US4025315A (en) * | 1971-05-19 | 1977-05-24 | San Diego Gas & Electric Co. | Method of odorizing liquid natural gas |
| CA1006353A (en) * | 1972-10-02 | 1977-03-08 | David K. Mulliner | Method and system for odorizing liquid natural gas with thiophene |
| US3907515A (en) * | 1972-10-02 | 1975-09-23 | San Diego Gas & Electric Co | Apparatus for odorizing liquid natural gas |
| FR2238113A1 (en) * | 1973-07-18 | 1975-02-14 | Inst Gas Technology | Odorising cryogenic liquids - esp liquid fuels, by addn of solutions of sulphur cpds in liquid hydrocarbon gases |
| JPS5392802A (en) * | 1977-01-25 | 1978-08-15 | Bridgestone Liquefied Gas Co | Addition of odorant to fuel gas |
| US5167867A (en) * | 1989-09-26 | 1992-12-01 | Exxon Production Research Company | Test-fluid composition and method for detecting leaks in pipelines and associated facilities |
| SE505635C2 (en) * | 1995-11-28 | 1997-09-22 | Aga Ab | Method and apparatus for adding an odorant to a gas piping system |
| DE19837066A1 (en) | 1998-08-17 | 2000-02-24 | Haarmann & Reimer Gmbh | Odorizing a gas, e.g. city gas comprises adding an acrylic acid, nitrogen compound and antioxidant to the gas |
| US20010047621A1 (en) * | 1999-06-29 | 2001-12-06 | Joe Frank Arnold | Injection system and method for odorizing natural gas |
| AU2002243760A1 (en) | 2001-01-30 | 2002-08-12 | Board Of Regents University Of Texas System | Process for production of nanoparticles and microparticles by spray freezing into liquid |
| DE10240028A1 (en) * | 2002-08-27 | 2004-03-11 | Symrise Gmbh & Co. Kg | Mixture e.g. for odorizing liquefied gas comprises at least two alkyl acrylates, sulfur compound, third component and optionally an antioxidant |
| JP2004315566A (en) * | 2003-04-11 | 2004-11-11 | Ishikawajima Harima Heavy Ind Co Ltd | Method for odorizing gas and apparatus therefor |
| FR2868790B1 (en) | 2004-04-08 | 2008-07-25 | Arkema Sa | ODORIZING MIXTURE FOR GASEOUS FUEL ODORLESS |
| DE102004050419A1 (en) | 2004-10-15 | 2006-04-27 | Linde Ag | Odorization of fuel medium e.g. cryogenic medium for a vehicle has accumulator which stores fluid medium in liquid, gaseous and/or in hydride form and/or at least one fuel medium leading line |
| JP5055883B2 (en) * | 2005-09-07 | 2012-10-24 | トヨタ自動車株式会社 | Hydrogen supply device |
| FR2891841B1 (en) | 2005-10-11 | 2007-12-28 | Arkema Sa | ODORIZING MIXTURE FOR GASEOUS FUEL ODORLESS |
| FR2902798B1 (en) | 2006-06-26 | 2009-04-24 | Arkema France | ODORIZING MIXTURE FOR GASEOUS FUEL ODORLESS |
| CN202691601U (en) * | 2012-07-05 | 2013-01-23 | 北京普发兴业动力科技发展有限责任公司 | Odorizing device of high-pressure compressed natural gas pipeline |
| AU2014330092B2 (en) * | 2013-10-01 | 2017-11-30 | Aygaz Anonim Sirketi | Sulphur-free gas odorant |
| CN106352238B (en) * | 2016-11-24 | 2019-09-03 | 四川蜀谷仪表科技有限公司 | Making gas ordorous control device and making gas ordorous system |
-
2017
- 2017-04-25 FR FR1753565A patent/FR3065375B1/en active Active
-
2018
- 2018-04-18 DK DK18722690.7T patent/DK3615638T3/en active
- 2018-04-18 WO PCT/FR2018/050980 patent/WO2018197783A1/en unknown
- 2018-04-18 EP EP18722690.7A patent/EP3615638B1/en active Active
- 2018-04-18 KR KR1020227002858A patent/KR20220017002A/en not_active Application Discontinuation
- 2018-04-18 CN CN201880027068.5A patent/CN110520509B/en active Active
- 2018-04-18 SG SG11201909909Y patent/SG11201909909YA/en unknown
- 2018-04-18 HR HRP20221080TT patent/HRP20221080T1/en unknown
- 2018-04-18 CA CA3060506A patent/CA3060506C/en active Active
- 2018-04-18 AU AU2018259133A patent/AU2018259133B2/en active Active
- 2018-04-18 US US16/604,683 patent/US11279895B2/en active Active
- 2018-04-18 ES ES18722690T patent/ES2926190T3/en active Active
- 2018-04-18 PL PL18722690.7T patent/PL3615638T3/en unknown
- 2018-04-18 KR KR1020197031124A patent/KR102519249B1/en active IP Right Grant
- 2018-04-18 PT PT187226907T patent/PT3615638T/en unknown
-
2022
- 2022-02-25 US US17/681,102 patent/US11814596B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US20220220402A1 (en) | 2022-07-14 |
| CA3060506C (en) | 2023-09-26 |
| KR20220017002A (en) | 2022-02-10 |
| KR20190126429A (en) | 2019-11-11 |
| US20200157446A1 (en) | 2020-05-21 |
| AU2018259133B2 (en) | 2020-10-22 |
| WO2018197783A1 (en) | 2018-11-01 |
| PL3615638T3 (en) | 2022-10-03 |
| KR102519249B1 (en) | 2023-04-06 |
| CA3060506A1 (en) | 2018-11-01 |
| FR3065375B1 (en) | 2019-06-28 |
| US11814596B2 (en) | 2023-11-14 |
| EP3615638A1 (en) | 2020-03-04 |
| SG11201909909YA (en) | 2019-11-28 |
| DK3615638T3 (en) | 2022-09-05 |
| FR3065375A1 (en) | 2018-10-26 |
| HRP20221080T1 (en) | 2022-12-23 |
| AU2018259133A1 (en) | 2019-11-14 |
| CN110520509B (en) | 2022-04-08 |
| US11279895B2 (en) | 2022-03-22 |
| ES2926190T3 (en) | 2022-10-24 |
| PT3615638T (en) | 2022-09-08 |
| CN110520509A (en) | 2019-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3615638B1 (en) | Process for cryogenic fluid odorisation | |
| FR2888245A1 (en) | METHOD AND SYSTEM FOR THE INTENSIVE SEPARATION OF HEAVY OIL BY GRANULATING ASPHALT RESIDUE AFTER COUPLED EXTRACTION. | |
| EP2794762B1 (en) | Method for producing a cross-linked bitumen/polymer composition while reducing h2s emissions | |
| US20100018712A1 (en) | Method of transitioning to kinetic hydrate inhibitors in multiple tie-in well systems | |
| WO2013178930A1 (en) | Low-viscosity liquid sulphur | |
| EP3369800B1 (en) | Improved method for regenerating an alkaline solution used in a method for extracting sulphurous compounds not comprising a washing step | |
| EP3369799B1 (en) | Improved method for regenerating an alkaline solution used in a method for extracting sulphurous compounds comprising a washing step | |
| FR2815120A1 (en) | METHOD AND DEVICE FOR TAKING A CIRCULATING EMULSION IN A PIPELINE | |
| CA3155368A1 (en) | Method for removing acid compounds from a gaseous effluent using a tertiary amine-based absorbent solution | |
| FR2866346A1 (en) | Extracting anti-hydrate compounds contained in condensed-hydrocarbon liquid feedstock, useful in processing natural gas involves contacting feedstock with non-aqueous ionic liquid; and regenerating ionic liquid charged with anti-hydrates | |
| FR2983206A1 (en) | IMPROVED DEVICE FOR EXTRACTING SULFUR COMPOUNDS BY LIQUID LIQUID EXTRACTION USING A SODA SOLUTION WITH OPTIMIZED FINAL WASHING STEP | |
| EP2782981A1 (en) | Improved device for the extraction of sulphur compounds, comprising a first pre-treatment reactor operating in a non-continuous manner, followed by a second piston-type pre-treatment reactor | |
| FR2924033A1 (en) | Essential oil's e.g. citrus fruit essential oil, stable emulsion realizing method, involves cooling oil and water before oil and water return to atmospheric pressure for obtaining droplets whose average size is less than micrometer | |
| CA3174487A1 (en) | Method for storing a biogas in a tank and associated system | |
| EP0039289B1 (en) | Process for fractionating a charge of hydrocarbons composed essentially of saturated hydrocarbons having 2 to 4 carbon atoms | |
| WO2013076385A1 (en) | Improved process and improved device for extracting sulphur-containing compounds from a hydrocarbon-based cut by liquid-liquid extraction with a solution of sodium hydroxide | |
| FR2983738A1 (en) | GAS SELECTIVE STRIPPING OF A VOLATILE PHASE CONTAINED IN AN EMULSION WHOSE PHASE CONTINUES IS LESS VOLATILE | |
| BE505570A (en) | ||
| FR3125441A1 (en) | CLC process and installation with recovery of gaseous oxygen produced by an oxygen carrier | |
| FR3051477A1 (en) | SOLID BITUMEN AT AMBIENT TEMPERATURE | |
| BE525863A (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| REG | Reference to a national code |
Ref country code: HR Ref legal event code: TUEP Ref document number: P20221080T Country of ref document: HR |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20191031 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) | ||
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
| 17Q | First examination report despatched |
Effective date: 20210324 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20220215 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1507080 Country of ref document: AT Kind code of ref document: T Effective date: 20220815 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602018038438 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 Effective date: 20220901 |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Ref document number: 3615638 Country of ref document: PT Date of ref document: 20220908 Kind code of ref document: T Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20220902 Ref country code: FI Ref legal event code: FGE |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2926190 Country of ref document: ES Kind code of ref document: T3 Effective date: 20221024 |
|
| REG | Reference to a national code |
Ref country code: NO Ref legal event code: T2 Effective date: 20220727 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
| REG | Reference to a national code |
Ref country code: HR Ref legal event code: T1PR Ref document number: P20221080 Country of ref document: HR |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1507080 Country of ref document: AT Kind code of ref document: T Effective date: 20220727 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221127 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221028 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 |
|
| REG | Reference to a national code |
Ref country code: HR Ref legal event code: ODRP Ref document number: P20221080 Country of ref document: HR Payment date: 20230315 Year of fee payment: 6 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602018038438 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 |
|
| 26N | No opposition filed |
Effective date: 20230502 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20230418 Year of fee payment: 6 Ref country code: NO Payment date: 20230412 Year of fee payment: 6 Ref country code: ES Payment date: 20230512 Year of fee payment: 6 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FI Payment date: 20230411 Year of fee payment: 6 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230418 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220727 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230430 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230430 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230418 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20240315 Year of fee payment: 7 |
|
| REG | Reference to a national code |
Ref country code: HR Ref legal event code: ODRP Ref document number: P20221080 Country of ref document: HR Payment date: 20240311 Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230418 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240229 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20240315 Year of fee payment: 7 Ref country code: IT Payment date: 20240313 Year of fee payment: 7 Ref country code: HR Payment date: 20240311 Year of fee payment: 7 Ref country code: FR Payment date: 20240308 Year of fee payment: 7 Ref country code: BE Payment date: 20240319 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240306 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20240411 Year of fee payment: 7 |