EP1756251A1 - Utilisation de polysulfures organiques contre la corrosion par les bruts acides - Google Patents
Utilisation de polysulfures organiques contre la corrosion par les bruts acidesInfo
- Publication number
- EP1756251A1 EP1756251A1 EP05753703A EP05753703A EP1756251A1 EP 1756251 A1 EP1756251 A1 EP 1756251A1 EP 05753703 A EP05753703 A EP 05753703A EP 05753703 A EP05753703 A EP 05753703A EP 1756251 A1 EP1756251 A1 EP 1756251A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- sulfur
- compound
- corrosion
- hydrocarbon
- 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.)
- Withdrawn
Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 26
- 238000005260 corrosion Methods 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title description 11
- 150000008116 organic polysulfides Chemical class 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 20
- 125000005608 naphthenic acid group Chemical group 0.000 claims abstract description 12
- 229920001021 polysulfide Polymers 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Chemical group 0.000 claims description 8
- 239000011593 sulfur Chemical group 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 239000005077 polysulfide Substances 0.000 abstract description 3
- 150000008117 polysulfides Polymers 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000010779 crude oil Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- -1 organo thiophosphates Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/02—Stabilising gasoline by removing gases by fractioning
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
Definitions
- the present invention relates to the field of the treatment of acidic crude oils in refineries. More specifically, it relates to a process for combating corrosion of refining units which process acid crudes, including the use of specific poly sulfide compounds. Petroleum refineries can face a serious corrosion problem when they have to process certain so-called acid crudes. These crude acids contain essentially naphthenic acids which are at the origin of this very particular corrosion phenomenon, since it occurs in a liquid medium which does not conduct electric current. These naphthenic acids correspond to saturated cyclic hydrocarbons carrying one or more carboxylic groups. The acidity of a crude oil is described by a standardized measurement according to standard ASTM D 664-01.
- TAN Total Acid Number
- EP 742277 describes the inhibitory action of a combination of a trialkyl phosphate and an organic polysulfide.
- US patent 5552085 recommends the use of thiophosphorus compounds such as organo thiophosphates or thiophosphites.
- the patent AU 693975 discloses as an inhibitor a mixture of trialkyl phosphate and phosphoric esters of sulfurized phenol neutralized with lime.
- organophospores are very delicate to handle, due to their high toxicity. They are also poisons for the hydro-treatment catalysts installed to purify the hydrocarbon fractions from atmospheric distillations and under vacuum. For these two reasons at least, their use in the refining field is not desirable.
- the subject of the invention is therefore a method of combating corrosion by naphthenic acids of the metal walls of a refining unit, characterized in that it comprises the addition to the hydrocarbon stream to be treated by the unit d '' an effective amount of one or more hydrocarbon compound (s) of formula:
- - n is an integer between 2 and 15, and - the symbols R x and R 2 , identical or different, each represent an alkyl radical, linear or branched, comprising between 2 and 5 carbon atoms, these radicals possibly containing one or more heteroatoms such as oxygen or sulfur; or - R 1 and R 2 , identical or different, each represent a cycloalkyl radical comprising between 3 and 5 carbon atoms, these radicals possibly containing one or more heteroatoms such as oxygen or sulfur.
- the polysulphides of formula (I) are prepared according to methods known per se, such as those described in patents US2708199, US3022351 and US3038013. Some are commercial products.
- R 1 and R 2 are alkyl radicals, linear or branched, and n is between 2 and 6.
- the radicals R and R are identical, due to improved stability for the compound of corresponding formula (I).
- ditertiobutyl polysulphides are used as mixture of compounds of formula (I).
- These products, of industrial origin, are for example derived from the reaction of sulfur with ter-butyl mercaptan. The reaction conditions make it possible to prepare industrial products composed of a mixture of polysulphides with a number of sulfur atoms varying between 3 and 10, and having a number average value between 2 and 6.
- the quantity of compound (s) of formula (I) to be added to the hydrocarbon stream to be treated by the refining unit generally corresponds to a concentration, expressed in equivalent weight of sulfur of said compound relative to the weight of the hydrocarbon stream , between 1 and 5000 ppm, preferably between 5 and 500 ppm.
- a concentration, expressed in equivalent weight of sulfur of said compound relative to the weight of the hydrocarbon stream between 1 and 5000 ppm, preferably between 5 and 500 ppm.
- the method according to the invention advantageously makes it possible to treat hydrocarbon streams, in particular crude oils, whose TAN is greater than 0.2, and preferably greater than 1.
- the temperature for implementing the method corresponds to that at which occur the reactions of corrosion by naphthenic acids, and is generally between 200 and 450 ° C, and more particularly between 250 and 350 ° C.
- the addition of the compound of formula (I) in the hydrocarbon stream can be carried out very close to where the corrosion reaction takes place or else, at a lower temperature, upstream of the process of said unit. This addition can be carried out by any means known to a person skilled in the art, ensuring control of the injection rate and good dispersion of the additive in the hydrocarbon, for example by means of a nozzle or a mixer. .
- metal walls of the refining unit means all the walls capable of being in contact with the stream of acidic hydrocarbon to be treated. It can therefore be both the internal wall proper of units such as atmospheric and vacuum distillation towers, as the surface of the internal elements thereof as their trays or linings, or even peripheral elements to these, like their withdrawal and inlet lines, pumps, preheating furnaces, or heat exchangers, as soon as these elements are brought to a local temperature of between 200 and 450 ° C.
- a hydrocarbon stream to be treated in accordance with the process according to the invention there is petroleum crude oil, the residue from atmospheric distillation, the diesel fractions from atmospheric and vacuum distillation, as well as the distillate and vacuum from vacuum distillation.
- This test uses an iron powder simulating a metallic surface, and a mineral oil in which a mixture of naphthenic acids is dissolved, simulating a stream of acid crude.
- the characteristics of these reagents are as follows: - white mineral oil having a density of 0.838 - powder of spherical iron particles, with a particle size of -40 + 70 mesh (i.e. approximately 212 to 425 ⁇ m) - mixture of naphthenic acids having from 10 to 18 carbon atoms, a boiling point between 270 and 324 ° C and an average molar mass of 244 g / mol.
- the following are introduced into a 150 ml glass reactor, equipped with a dropping funnel and a water cooler, and provided with a stirring and temperature measurement system: - 70 ml (i.e. 58.8 g) mineral oil, - 2 g of iron powder, - 2.8 g of the mixture of naphthenic acid.
- the initial TAN of the reaction mixture is equal to 10.
- These reagents are kept in contact for 2 hours at a temperature of 250 ° C., under a dry nitrogen atmosphere to avoid oxidation reactions.
- the concentration of dissolved iron in the medium is determined by a conventional method implementing a mineralization of a sample, taking up the residue in acidified water and dosing by a plasma torch . This concentration of dissolved iron (expressed in ppm) is directly proportional to the rate of corrosion of the iron powder generated by the mixture of naphthenic acids present in the mineral oil.
- Example 1 is repeated by adding different types of alkyl polysulphides to the mineral oil when the reactor is charged. The added amount of these derivatives is calculated so as to obtain a concentration of 500 ppm expressed in equivalent weight of sulfur in the mineral oil present in the reactor.
- Table II The results obtained in Table II below are obtained.
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0403838A FR2868787B1 (fr) | 2004-04-13 | 2004-04-13 | Utilisation de polysulfures organiques contre la corrosion par les bruts acides |
| PCT/FR2005/000861 WO2005103208A1 (fr) | 2004-04-13 | 2005-04-08 | Utilisation de polysulfures organiques contre la corrosion par les bruts acides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1756251A1 true EP1756251A1 (fr) | 2007-02-28 |
Family
ID=34944754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP05753703A Withdrawn EP1756251A1 (fr) | 2004-04-13 | 2005-04-08 | Utilisation de polysulfures organiques contre la corrosion par les bruts acides |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US20070163922A1 (no) |
| EP (1) | EP1756251A1 (no) |
| JP (1) | JP2007532745A (no) |
| KR (1) | KR20070005676A (no) |
| CN (1) | CN1973021A (no) |
| AR (1) | AR050242A1 (no) |
| AU (1) | AU2005235761B2 (no) |
| BR (1) | BRPI0509789A (no) |
| CA (1) | CA2562102A1 (no) |
| EA (1) | EA010668B1 (no) |
| FR (1) | FR2868787B1 (no) |
| MX (1) | MXPA06011863A (no) |
| NO (1) | NO20065183L (no) |
| TW (1) | TWI314952B (no) |
| UA (1) | UA84741C2 (no) |
| WO (1) | WO2005103208A1 (no) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152192B (zh) * | 2013-05-13 | 2016-05-25 | 刘爱国 | 一种汽柴油防腐剂 |
| KR101990826B1 (ko) | 2019-03-18 | 2019-06-19 | 영화진흥위원회 | 청각장애인의 관람 환경 개선용 시각 제공장치 |
| US20210255609A1 (en) * | 2020-02-14 | 2021-08-19 | Exxonmobil Research And Engineering Company | Systems and methods for monitoring and predicting a risk state of an industrial process |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2708199A (en) * | 1951-10-24 | 1955-05-10 | Continental Oil Co | Preparation of organic polysulfides |
| US3022351A (en) * | 1957-03-07 | 1962-02-20 | Phillips Petroleum Co | Production of organic polysulfides |
| US3062612A (en) * | 1959-04-25 | 1962-11-06 | Inst Francais Du Petrole | Method of protecting metals against electrochemical corrosion of the acidic type |
| US3038013A (en) * | 1959-08-25 | 1962-06-05 | Phillips Petroleum Co | Color improvement in synthesis of polysulfides |
| DE3437936A1 (de) * | 1984-10-17 | 1986-04-17 | Peter, Siegfried, Prof.Dr., 8525 Uttenreuth | Verfahren und mittel zur bekaempfung der korrosion unter reduzierenden bedingungen |
| US5182013A (en) * | 1990-12-21 | 1993-01-26 | Exxon Chemical Patents Inc. | Naphthenic acid corrosion inhibitors |
| US5500107A (en) * | 1994-03-15 | 1996-03-19 | Betz Laboratories, Inc. | High temperature corrosion inhibitor |
| US5457234A (en) * | 1994-06-20 | 1995-10-10 | Phillips Petroleum Company | Process for treating organic polysulfide compounds |
| US5552085A (en) * | 1994-08-31 | 1996-09-03 | Nalco Chemical Company | Phosphorus thioacid ester inhibitor for naphthenic acid corrosion |
| US5464525A (en) * | 1994-12-13 | 1995-11-07 | Betz Laboratories, Inc. | High temperature corrosion inhibitor |
| US5630964A (en) | 1995-05-10 | 1997-05-20 | Nalco/Exxon Energy Chemicals, L.P. | Use of sulfiding agents for enhancing the efficacy of phosphorus in controlling high temperature corrosion attack |
| DE69719186T2 (de) * | 1996-05-30 | 2003-11-27 | Baker-Hughes Inc., Houston | Naphtensäurekorrosionskontrolle mit thiophosphorverbindungen |
-
2004
- 2004-04-13 FR FR0403838A patent/FR2868787B1/fr not_active Expired - Fee Related
-
2005
- 2005-04-08 CA CA002562102A patent/CA2562102A1/fr not_active Abandoned
- 2005-04-08 JP JP2007507813A patent/JP2007532745A/ja not_active Withdrawn
- 2005-04-08 EA EA200601679A patent/EA010668B1/ru not_active IP Right Cessation
- 2005-04-08 BR BRPI0509789-4A patent/BRPI0509789A/pt not_active IP Right Cessation
- 2005-04-08 AU AU2005235761A patent/AU2005235761B2/en not_active Expired - Fee Related
- 2005-04-08 KR KR1020067021376A patent/KR20070005676A/ko not_active Application Discontinuation
- 2005-04-08 UA UAA200610725A patent/UA84741C2/ru unknown
- 2005-04-08 US US11/547,920 patent/US20070163922A1/en not_active Abandoned
- 2005-04-08 EP EP05753703A patent/EP1756251A1/fr not_active Withdrawn
- 2005-04-08 WO PCT/FR2005/000861 patent/WO2005103208A1/fr active Application Filing
- 2005-04-08 MX MXPA06011863A patent/MXPA06011863A/es active IP Right Grant
- 2005-04-08 CN CNA2005800194186A patent/CN1973021A/zh active Pending
- 2005-04-11 TW TW094111355A patent/TWI314952B/zh not_active IP Right Cessation
- 2005-04-12 AR ARP050101429A patent/AR050242A1/es active IP Right Grant
-
2006
- 2006-11-10 NO NO20065183A patent/NO20065183L/no not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2005103208A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0509789A (pt) | 2007-10-23 |
| AU2005235761B2 (en) | 2009-12-17 |
| TW200606246A (en) | 2006-02-16 |
| US20070163922A1 (en) | 2007-07-19 |
| FR2868787A1 (fr) | 2005-10-14 |
| WO2005103208A1 (fr) | 2005-11-03 |
| CA2562102A1 (fr) | 2005-11-03 |
| FR2868787B1 (fr) | 2006-06-23 |
| AU2005235761A1 (en) | 2005-11-03 |
| JP2007532745A (ja) | 2007-11-15 |
| TWI314952B (en) | 2009-09-21 |
| AR050242A1 (es) | 2006-10-11 |
| UA84741C2 (ru) | 2008-11-25 |
| CN1973021A (zh) | 2007-05-30 |
| NO20065183L (no) | 2006-11-10 |
| EA200601679A1 (ru) | 2007-04-27 |
| EA010668B1 (ru) | 2008-10-30 |
| KR20070005676A (ko) | 2007-01-10 |
| MXPA06011863A (es) | 2007-04-16 |
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