EP2516596A2 - Emulgierung von kohlenwasserstoffgasölen zur erhöhung der effizienz von wasserbasierten wasserstoffsulfid-scavengern - Google Patents
Emulgierung von kohlenwasserstoffgasölen zur erhöhung der effizienz von wasserbasierten wasserstoffsulfid-scavengernInfo
- Publication number
- EP2516596A2 EP2516596A2 EP10770692A EP10770692A EP2516596A2 EP 2516596 A2 EP2516596 A2 EP 2516596A2 EP 10770692 A EP10770692 A EP 10770692A EP 10770692 A EP10770692 A EP 10770692A EP 2516596 A2 EP2516596 A2 EP 2516596A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- heavy oil
- scavenger
- aqueous
- hydrogen sulfide
- processing equipment
- 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- Withdrawn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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 12
- 229930195733 hydrocarbon Natural products 0.000 title claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 12
- 239000003921 oil Substances 0.000 title claims description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 9
- 239000007789 gas Substances 0.000 title description 4
- 238000004945 emulsification Methods 0.000 title description 3
- 239000000295 fuel oil Substances 0.000 claims abstract description 49
- 239000002516 radical scavenger Substances 0.000 claims abstract description 40
- 238000012545 processing Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 6
- 230000003068 static effect Effects 0.000 claims abstract description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 24
- 229940015043 glyoxal Drugs 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 230000002000 scavenging effect Effects 0.000 abstract description 2
- -1 giyoxal Chemical class 0.000 abstract 1
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
- C10G29/24—Aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4075—Limiting deterioration of equipment
Definitions
- This invention relates generally to processing heavy oil, and more particularly, to methods for removing hydrogen sulfide in heavy oil with an aqueous- based scavenger/oil emulsion.
- H 2 S hydrogen sulphide
- Hydrogen sulfide scavengers can be used to remove hydrogen sulfide from heavy oil. It is known to be possible to reduce the hydrogen sulphide content present in aqueous mediums by using aqueous solutions of aldehydes such as formaldehyde, glyoxal, and glutaraldehyde (see for example the U.S. Pat. Nos. 4,680, 127 and 5,284,635). However, simple addition of water-based hydrogen sulfide scavengers to heavy oil provides poor results.
- aldehydes such as formaldehyde, glyoxal, and glutaraldehyde
- water-based scavengers such as glyoxal will eventually settle out of the heavy oil into an acidic aqueous phase and settle to the bottom of processing equipment.
- This aqueous phase may run along the bottom of the processing or refinery equipment as small tributaries in pipelines or stagnate at the bottom of holding tanks.
- This acidic aqueous phase is highly corrosive and can cause troughing in the processing or refinery equipment.
- the invention is directed to a method for reducing the amount of hydrogen sulfide present in heavy oil and reducing the amount of corrosion in processing equipment contacting the heavy oil.
- the method includes the steps of adding an aqueous-based scavenger containing one or more aldehydes to the heavy oil using a static mixer injection system and creating an aqueous-based scavenger/heavy oil emulsion using a high shear/high velocity pump.
- the method further includes diverting a portion of the heavy oil into a scavenger addition branch, adding the aqueous-based scavenger to the portion of the heavy oil and forming the emulsion in the addition branch, and adding the aqueous-based scavenger/oil emulsion to the heavy oi l in the processing equipment.
- the aqueous-based scavenger is glyoxal.
- FIG. 1 is a schematic diagram of an aqueous-based scavenger addition system for use with hydrocarbon media processing equipment.
- a hydrogen sulfide scavenger addition system 10 is fluidically connected to processing equipment 12 for hydrocarbon media.
- the scavenger system 10 reduces the amount of hydrogen sulfide present in the hydrocarbon media, such as heavy oils, by adding an aqueous-based scavenger in a manner so as to desirably avoid causing significant corrosion to processing equipment 1 2.
- Aqueous- based scavengers are useful for the elimination of hydrogen sulphide present in various fluids and notably are particularly effective at eliminating the hydrogen sulphide present in heavy oi ls which can ex ist in the form of water in oi l or oil in water emulsions.
- the processing equipment 12 in contact with the heavy oi l may be any type of equipment that can be used for processing the hydrocarbon media, such as pipelines and holding tanks. Processing equipment 1 2 subject to corrosion is general ly processing equipment made of carbon steel, but any type of processing equipment may be protected.
- the heavy oi l may be any type of heavy oi l containing hydrogen sulfide.
- the heavy oil includes, but is not limited to, gas oi l, naphtha, FCC slurry, diesel fuel, fuel oi l, jet fuel, gasoline, kerosene or vacuum residua.
- the heavy oil may be at an elevated temperature to aid in transport in the processing equipment 1 2. For example, the heavy oil may be at a temperature of from about ambient to about 1 50 °C. Typically, the temperatures required to move the heavy oil in the processing equipment 12 is about 80 °C.
- a portion of the heavy oil flowing through the processing equipment 12 is diverted from the processing equipment 12 into the scavenger addition system 10 via a scavenger addition branch 14.
- a static mixer 1 6 is used to initially mix the scavenger with the portion of heavy oil flowing through the system 10.
- the static mixer 16 comprises an injection quill dispersion system 18.
- the scavenger is added to the diverted heavy oil flow in a continuous manner with the injection quill 1 8 located generally at the center of the addition branch 14 in the direction of the heavy oil flow.
- the injection quill 18 desirably has an open-ended tube (not shown) cut at about a 45° angle with a slot.
- the scavenger injection rate is controlled with an injection pump 20 or shut-off valve 22 in addition line 24.
- a suitable injection quill 1 8 is available from Metal Samples Corrosion Monitoring Systems of Munford, AL.
- the scavenger may be injected into the heavy oil by any conventional inline injection system and may be injected at any point in-line suitable to allow the scavenger to mix with the heavy oil.
- an aqueous-based scavenger/oil micro-emulsion is formed using a high shear/high velocity mixer or pump 30.
- a high shear/high velocity mixer or pump 30 such as one available from Silverson Machines, Inc. of East Longmeadow, MA.
- the diverted portion of the heavy oil flow in the scavenger addition system 10, now containing the micro-emulsion, is then returned to the heavy oil flow in the processing equipment 12.
- the scavenger may be added to the heavy oil flowing through the processing equipment without diverting a portion of the flow such that the entire heavy oil flow flows through the scavenger addition system 10.
- the scavenger is a dispersed aqueous phase containing about 20 to 70% of one or more aldehydes chosen from the group constituted by formaldehyde, glyoxal, glutaraldehyde, glycolaldehyde or glyoxylic acid.
- the water-based scavenger added to the heavy oil to reduce the hydrogen sulfide is Glyoxal.
- Glyoxal is a water-soluble aldehyde and may include oligomers of glyoxal.
- Glyoxal is commercially available as a 40 weight percent aqueous solution.
- the scavenger may also contain an enhancing additive to catalyze the reaction of actives with the hydrogen sulfide.
- the enhancing catalyst is a quaternary ammonium salt.
- the quaternary ammonium salt desirably is added in an amount of about 2.5 wt %.
- the glyoxal is added to the heavy oil in an amount sufficient to reduce the levels of hydrogen sulfide in the heavy oil.
- glyoxal may be added in an amount of from about I ppm to about 2000 ppm, and desirably between about I ppm and about 500 ppm by volume, based on the velocity of the heavy oil through the processing equipment and the concentration of hydrogen sulfide.
- glyoxal may be added in an amount of from about 10 ppm to about 200 ppm by volume. Any amount of hydrogen sulfide in the heavy oil may be reduced and the actual amount of residual hydrogen sulfide will vary depending on the starting amount.
- the hydrogen sulfide levels are reduced to 1 50 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 100 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 50 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil. In another embodiment, the hydrogen sulfide levels are reduced to 20 ppm by volume or less, as measured in the vapor phase, based on the volume of the heavy oil.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/646,432 US20110147272A1 (en) | 2009-12-23 | 2009-12-23 | Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers |
| PCT/US2010/053457 WO2011087540A2 (en) | 2009-12-23 | 2010-10-21 | Emulsification of hydrocarbon gas oils to increase efficacy of water based hydrogen sulfide scavengers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2516596A2 true EP2516596A2 (de) | 2012-10-31 |
Family
ID=44149590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP10770692A Withdrawn EP2516596A2 (de) | 2009-12-23 | 2010-10-21 | Emulgierung von kohlenwasserstoffgasölen zur erhöhung der effizienz von wasserbasierten wasserstoffsulfid-scavengern |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US20110147272A1 (de) |
| EP (1) | EP2516596A2 (de) |
| JP (1) | JP2013515818A (de) |
| KR (1) | KR20120123348A (de) |
| CN (1) | CN102762696A (de) |
| AR (1) | AR079659A1 (de) |
| AU (1) | AU2010341783A1 (de) |
| BR (1) | BR112012015563A2 (de) |
| CA (1) | CA2785532A1 (de) |
| CL (1) | CL2012001711A1 (de) |
| MX (1) | MX2012007493A (de) |
| RU (1) | RU2012127278A (de) |
| SG (1) | SG181925A1 (de) |
| TW (1) | TW201137108A (de) |
| WO (1) | WO2011087540A2 (de) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112014006986A2 (pt) | 2011-09-23 | 2017-04-04 | Lonza Ag | processo e composição para a remoção de sulfeto de hidrogênio a partir de fluidos de processo industrial |
| WO2013049027A1 (en) * | 2011-09-27 | 2013-04-04 | General Electric Company | Hydrogen sulfide scavenger compositions, methods for making and processes for removing hydrogen sulfide from liquid hydrocarbon media |
| SG11201501042WA (en) | 2012-08-21 | 2015-03-30 | Lonza Ag | Method of scavenging hydrogen sulfide and/or sulfhydryl compounds |
| CN106103659B (zh) * | 2014-03-17 | 2018-07-06 | 株式会社可乐丽 | 含硫化合物除去用的组合物 |
| WO2016121747A1 (ja) * | 2015-01-29 | 2016-08-04 | 株式会社クラレ | 含硫黄化合物除去用の組成物 |
| EA035710B1 (ru) | 2015-10-14 | 2020-07-29 | Хальдор Топсёэ А/С | Способ удаления соединений серы из технологических потоков |
| CA3038037A1 (en) | 2016-09-27 | 2018-04-05 | Kuraray Co., Ltd. | Metal corrosion suppressing method |
| WO2018097108A1 (ja) | 2016-11-22 | 2018-05-31 | 株式会社クラレ | 含硫黄化合物除去用の組成物 |
| US10513662B2 (en) * | 2017-02-02 | 2019-12-24 | Baker Hughes, A Ge Company, Llc | Functionalized aldehydes as H2S and mercaptan scavengers |
| CN108732940B (zh) * | 2017-04-24 | 2021-05-07 | 西门子（中国）有限公司 | 优化汽油柴油切割过程的催化裂化分馏塔的顶循环油流量的方法和系统 |
| KR20220035200A (ko) | 2019-07-17 | 2022-03-21 | 비엘 테크놀러지스 인크. | 정유 탈염장치에서의 아민의 제거 및 전환 방법 |
| FI130591B (en) | 2020-06-30 | 2023-11-28 | Andritz Oy | Crude methanol purification method |
| CN112710812B (zh) * | 2020-11-17 | 2023-02-24 | 中国石油天然气股份有限公司 | 检测与处理油田产出原油中有毒气体的一体化工艺 |
| WO2024081958A2 (en) * | 2022-10-14 | 2024-04-18 | Solugen, Inc. | Compositions to control level of undesirable materials |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4344842A (en) * | 1979-05-31 | 1982-08-17 | Irwin Fox | Reactive iron oxide agents for scavenging hydrogen sulfide from hydrocarbon liquids |
| US4680127A (en) * | 1985-12-13 | 1987-07-14 | Betz Laboratories, Inc. | Method of scavenging hydrogen sulfide |
| US5284635A (en) * | 1989-09-05 | 1994-02-08 | Societe Francaise Hoechst | Process for the elimination of hydrogen sulfide by using water-in-oil emulsions |
| US5397708A (en) * | 1993-05-13 | 1995-03-14 | Nalco Chemical Company | Method for detection of sulfides |
| DE4342620C1 (de) * | 1993-12-14 | 1995-07-06 | Starck H C Gmbh Co Kg | Verfahren zur Herstellung von Metallhydroxiden |
| US5674377A (en) * | 1995-06-19 | 1997-10-07 | Nalco/Exxon Energy Chemicals, L.P. | Method of treating sour gas and liquid hydrocarbon |
| US5744024A (en) * | 1995-10-12 | 1998-04-28 | Nalco/Exxon Energy Chemicals, L.P. | Method of treating sour gas and liquid hydrocarbon |
| US6063346A (en) * | 1998-06-05 | 2000-05-16 | Intevep, S. A. | Process for scavenging hydrogen sulfide and mercaptan contaminants from a fluid |
| GB9915214D0 (en) * | 1999-06-29 | 1999-09-01 | Bp Exploration Operating | Microemulsions |
| GB0031710D0 (en) * | 2000-12-27 | 2001-02-07 | Dyno Oil Field Chemicals | Process for the reduction or elimination of hydrogen sulphide |
| US7314545B2 (en) * | 2004-01-09 | 2008-01-01 | Lyondell Chemical Technology, L.P. | Desulfurization process |
| EP1812150B1 (de) * | 2004-10-01 | 2018-06-27 | Propure AS | Mehrfluidinjektionsmischer |
| US7267477B1 (en) * | 2004-10-07 | 2007-09-11 | Broad Reach Companies, Llc | Fluid blending utilizing either or both passive and active mixing |
| US7576136B2 (en) * | 2005-06-07 | 2009-08-18 | Ge Betz, Inc. | Emulsified feedstock for hydrocarbon process units that incorporate spray atomization |
| US8162048B2 (en) * | 2008-09-09 | 2012-04-24 | Tetra Technologies, Inc. | Method of delivering frac fluid and additives |
-
2009
- 2009-12-23 US US12/646,432 patent/US20110147272A1/en not_active Abandoned
-
2010
- 2010-10-21 EP EP10770692A patent/EP2516596A2/de not_active Withdrawn
- 2010-10-21 CN CN2010800646589A patent/CN102762696A/zh active Pending
- 2010-10-21 RU RU2012127278/04A patent/RU2012127278A/ru unknown
- 2010-10-21 WO PCT/US2010/053457 patent/WO2011087540A2/en not_active Ceased
- 2010-10-21 SG SG2012047007A patent/SG181925A1/en unknown
- 2010-10-21 MX MX2012007493A patent/MX2012007493A/es unknown
- 2010-10-21 JP JP2012545940A patent/JP2013515818A/ja not_active Withdrawn
- 2010-10-21 BR BR112012015563A patent/BR112012015563A2/pt not_active IP Right Cessation
- 2010-10-21 AU AU2010341783A patent/AU2010341783A1/en not_active Abandoned
- 2010-10-21 CA CA2785532A patent/CA2785532A1/en not_active Abandoned
- 2010-10-21 KR KR1020127019030A patent/KR20120123348A/ko not_active Withdrawn
- 2010-12-21 AR ARP100104815A patent/AR079659A1/es unknown
- 2010-12-23 TW TW099145621A patent/TW201137108A/zh unknown
-
2012
- 2012-06-22 CL CL2012001711A patent/CL2012001711A1/es unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2011087540A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112012015563A2 (pt) | 2017-09-05 |
| WO2011087540A3 (en) | 2011-11-17 |
| SG181925A1 (en) | 2012-07-30 |
| CA2785532A1 (en) | 2011-07-21 |
| TW201137108A (en) | 2011-11-01 |
| MX2012007493A (es) | 2012-08-03 |
| WO2011087540A2 (en) | 2011-07-21 |
| US20110147272A1 (en) | 2011-06-23 |
| JP2013515818A (ja) | 2013-05-09 |
| CL2012001711A1 (es) | 2013-04-12 |
| RU2012127278A (ru) | 2014-01-27 |
| KR20120123348A (ko) | 2012-11-08 |
| CN102762696A (zh) | 2012-10-31 |
| AU2010341783A1 (en) | 2012-07-19 |
| AR079659A1 (es) | 2012-02-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 |
|
| 17P | Request for examination filed |
Effective date: 20120723 |
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