WO2008025254A1 - A process for starting up fluidized catalytic reaction means used for producing lower olefin - Google Patents
A process for starting up fluidized catalytic reaction means used for producing lower olefin Download PDFInfo
- Publication number
- WO2008025254A1 WO2008025254A1 PCT/CN2007/002549 CN2007002549W WO2008025254A1 WO 2008025254 A1 WO2008025254 A1 WO 2008025254A1 CN 2007002549 W CN2007002549 W CN 2007002549W WO 2008025254 A1 WO2008025254 A1 WO 2008025254A1
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- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- catalyst
- regenerator
- temperature
- reaction
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the invention relates to a starting method for preparing a low-carbon olefin fluidization catalytic reaction device from methanol or/and dimethyl ether, which is suitable for the completion of an exothermic reaction type circulating fluidized catalytic reaction device, and is particularly suitable for methanol or / Fluidization of a dimethyl ether to produce a low-carbon olefin such as ethylene or propylene.
- Background technique
- Ethylene and propylene are the two basic materials used in the chemical industry with the largest amount and many uses. They are known as the mother of modern organic synthesis industry, and their production technology is the focus of competition in developed countries.
- the main route for the preparation of these two low-carbon olefins is light oil cracking, and other methods include catalytic conversion of lower alcohol ethers, aldehydes, mercaptans, and halogenated hydrocarbons.
- the impact of two oil crises in the 1970s promoted the research and development of low-carbon olefins technology for non-petroleum feedstock routes.
- the medium-alcohol conversion method has been greatly developed, showing great commercial application prospects.
- the US Mobile Company introduced a process technology for the preparation of low-carbon olefins using ZSM-5 zeolite as a catalyst and methanol as a raw material.
- the device itself has no heating components, and the device is heated by an external auxiliary heating facility during the start-up phase.
- this type of plant is very large, with up to hundreds of tons of catalysts being started, so the heat required to raise the reactor and regenerator bed temperatures above 500 °C is very large, especially at 400. When it is above °C, it is very difficult to use external heat to raise the temperature.
- a commonly used method in the FCC process is to spray light diesel into the bed when the regenerator catalyst bed temperature reaches above 370 ° C, and use the combustion heat release of the diesel to warm the device.
- the advantage of this method is that it can heat up the device quickly and greatly shorten the start-up time.
- the maintenance of the catalyst bed temperature also requires the catalyst to carry heat from the regenerator. Therefore, in actual operation, it is necessary to continuously spray the fuel oil to the regenerator to maintain the temperature of the regenerator.
- the present invention provides a method for preparing a low-carbon olefin fluidization catalytic reaction device, which comprises using a mixture of methanol and methanol and dimethyl ether as a raw material, and using a starting auxiliary heat source to circulate a fluidized catalytic reaction device.
- a method for preparing a low-carbon olefin fluidization catalytic reaction device which comprises using a mixture of methanol and methanol and dimethyl ether as a raw material, and using a starting auxiliary heat source to circulate a fluidized catalytic reaction device.
- the starting method of the invention can also use dimethyl ether as a raw material, and use the starting auxiliary heat source to heat the catalyst bed of the circulating fluidized catalytic reaction device to 300 ° C to transport the raw materials to the reactor, and the raw material reacts exotherm to make the reactor fast.
- the coking catalyst in the reactor is circulated to the regenerator and then burns to release heat, so that the regenerator rapidly heats up to 540 ,, so that the system can quickly reach normal operation.
- a method for preparing a low carbon olefin fluidization catalytic reaction apparatus wherein the catalytic reaction is based on methanol and a mixture of methanol and dimethyl ether, and the reaction apparatus includes a reactor for a catalyst bed and a regenerator having a regenerated bed layer, the method comprising the steps of:
- a method for preparing a low carbon olefin fluidization catalytic reaction apparatus wherein the catalytic reaction uses dimethyl ether as a raw material, and the reaction apparatus includes a reaction having a catalyst bed And regenerator, the method includes the following steps:
- the reaction unit is a circulating fluidized catalytic reaction unit consisting of a reactor and a regenerator.
- the catalyst in the reactor catalyst bed is a hydrogen type molecular sieve catalyst.
- the catalyst in the reactor catalyst bed is a solid acid catalyst.
- the present invention provides a start-up method for an exothermic reaction type circulating fluidization process such as conversion of methanol or/and dimethyl ether to lower olefins, which can save the start-up cost and ensure the long-term stability of various solid acid catalysts. Stable, rapid start-up of production systems, and improved economic efficiency.
- the embodiment of the present invention is as follows:
- the circulating fluidized catalytic reaction device is heated to above 200 ° C by using a start-up auxiliary heat source, and then the raw material is transported to the reactor, the raw material is methanol or a mixture of methanol and dimethyl ether;
- the reactor is rapidly warmed to the specified temperature.
- the coked catalyst is burned in the regenerator, causing the regenerator to rapidly heat up to 540 ° C or higher, so that the system can quickly reach normal operation.
- the reaction raw materials are used In the case of ether, the reaction apparatus can be fed only when it is heated above 300 °C.
- the hydrogen type molecular sieve is a solid acid catalyst, and under the action thereof, the reaction mechanism is:
- the reaction device is a circulating fluidized catalytic reaction device composed of a reactor and a regenerator;
- the catalyst is a hydrogen type molecular sieve catalyst or other solid acid acid catalyst
- the methanol conversion reaction causes the catalyst to coke. After the coking catalyst enters the regenerator with the circulation of the system, the regenerator temperature rises to a given range when the regenerator catalyst bed temperature reaches 34 CTC.
- the method of the present invention avoids the use of a conventional circulating fluidized catalytic reaction device which must be taken at the start-up stage by spraying light diesel oil into the catalyst bed of the regenerator and burning the regenerator, thereby shortening the start-up time while The catalyst is protected, the corresponding resource consumption is saved, and the economic benefit is improved.
- Figure 1 is a schematic view showing the process flow of the reaction-regeneration portion of Example 1.
- FIG. 2 is a graph showing changes in the reaction bed and regenerated bed layers and methanol conversion rate of an industrial amplifying apparatus having a methanol treatment amount of 60 B ⁇ /day in a temperature rising stage according to the method of the present invention.
- All devices in the production system used were tested and confirmed to be in a standby state, after which air was supplied to the regenerator and nitrogen was passed to the reactor. The air and nitrogen are heated by an external auxiliary heat source to effect heating of the circulating fluidization device.
- the active catalyst is added to the apparatus to a predetermined amount.
- the catalyst circulation is controlled to be as low as possible, and methanol is started to be sent to the reactor, and the methanol conversion reaction is started.
- the heat causes the reactor catalyst bed to heat up rapidly.
- the catalyst circulation is increased to stabilize the reactor temperature at 450 Torr, while the coke catalyst having a higher temperature is supplied to the regenerator, and the bed temperature of the regenerator catalyst is accelerated.
- the regenerator catalyst bed temperature reaches above 340 Torr, the coked catalyst initiates combustion and the temperature rise of the regenerator catalyst bed is accelerated.
- the process is basically the same, the only difference being that the reactor is heated when it is heated to 30 (TC above).
- Example 1 The technical features of the present invention are described below by way of examples, but the present invention is not limited thereto.
- Example 1
- Fig. 1 is a schematic view showing the process flow of a reaction-regeneration portion in this embodiment.
- 101 is a heater for preheating nitrogen or steam
- 102 is a reactor
- 103 is a regenerator
- 104 is an auxiliary heater for preheating air
- 105 is a nitrogen inlet line
- 106 is a steam inlet line
- 107 is a nitrogen or steam entering the reaction.
- Pipeline, 108 methanol feed line, 109 is the product gas to the cooling system line
- 110 is the transfer line from the regenerator to the reactor after regeneration
- 111 is the coking catalyst from the reactor to the regenerator after the reaction.
- the transfer line, 112 is the regenerated flue gas discharge line
- 113 is the transfer line of the catalyst from the catalyst storage tank to the regenerator
- 114 is the large line of air from the auxiliary heater to the regenerator
- 115 is the transport of the catalyst from the regenerator to the catalyst storage tank.
- Line, 116 is the air inlet line.
- the total catalyst inventory in the system during the operation of the system is 1.2 to 1.6 times the amount of methanol processed per hour.
- Pass The reactors 102, 106, 107 are purged with nitrogen and are passed through lines 116, 114 to the regenerator.
- Heating devices 101 and 104 are then activated to heat the nitrogen and air to heat the reactor and regenerator.
- the catalyst delivery device is turned on, and the catalyst is added to the regenerator via line 113.
- the nitrogen and air flow rates are adjusted at any time depending on the temperature of the reactor and the regenerator, so that the cyclone separator of the reactor and the regenerator can work effectively.
- the opening of the reactor and the regenerator bottom slide valve are simultaneously adjusted to adjust the catalyst circulation.
- the reactor catalyst bed temperature was lowered to 149 ° C
- the regenerator catalyst bed temperature was lowered to 263 ° C
- the reactor and regenerator were heated.
- the catalyst circulation of the reactor and regenerator is first controlled to the lowest possible state, and then the reaction is carried out through line 108.
- the catalyst bed of the vessel 102 delivers methanol and the reaction is initiated immediately.
- the methanol feed rate is gradually increased from small to large to ensure complete conversion of methanol.
- the reaction product of methanol is mainly dimethyl ether, and the amount of coking of the catalyst is small.
- dimethyl ether begins to be converted into hydrocarbons, and the conversion rate increases with temperature rise, and the catalyst coking amount also increases.
- the conversion of methyl-alcohol to dimethyl ether and further conversion to hydrocarbons is strongly exothermic, thereby increasing the temperature of the reactor.
- the reactor and regenerator catalyst bed temperatures were raised to 492 ° C and 62 (TC, respectively, to further enhance heat exchange and other measures to stabilize the reactor and regenerator temperatures.
- control methanol into The weight of the material is 5 If 1 , which achieves stable operation of the system.
- Fig. 2 is a graph showing the temperature change curve and the methanol conversion rate of the reaction bed and the regenerated bed in the heating stage of the industrial amplifying device with a methanol treatment capacity of 60 tons/day.
- the dotted line in Fig. 2 is the methanol conversion curve.
- the solid line on the left and the right side is the temperature curve of the reaction bed, and the solid line on the left and right sides is the regenerative bed.
- the temperature profile of the layer is the temperature profile of the layer.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Catalysts (AREA)
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/374,733 US20100004118A1 (en) | 2006-08-23 | 2007-08-23 | Process for Starting up a Fluidized Catalytic Reaction Apparatus Used for Producing Lower Olefins |
AU2007291793A AU2007291793B2 (en) | 2006-08-23 | 2007-08-23 | A process for starting up fluidized catalytic reaction means used for producing lower olefin |
BRPI0712628-0A BRPI0712628B1 (pt) | 2006-08-23 | 2007-08-23 | Aperfeiçoamento introduzido em um processo para inicializar um aparato de reação catalítia fluidizada utilizado para a produção de olefinas leves |
JP2009524889A JP5009370B2 (ja) | 2006-08-23 | 2007-08-23 | 低級オレフィンを製造するための流動化触媒反応装置の始動方法 |
DK07800769.7T DK2055690T3 (en) | 2006-08-23 | 2007-08-23 | PROCEDURE FOR STARTING FLUIDIZED CATALYTIC REACTION DEVICE USED FOR PREPARING LOWER OLEFIN |
EP07800769.7A EP2055690B1 (en) | 2006-08-23 | 2007-08-23 | A process for starting up fluidized catalytic reaction apparatus used for producing lower olefin |
US14/886,305 US20160039725A1 (en) | 2006-08-23 | 2015-10-19 | Process for Starting Up a Fluidized Catalytic Reaction Apparatus Used for Producing Lower Olefins |
US15/936,754 US10259757B2 (en) | 2006-08-23 | 2018-03-27 | Method for starting up a fluidized catalytic reaction apparatus used for producing lower olefins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200610112558.4 | 2006-08-23 | ||
CN2006101125584A CN101130466B (zh) | 2006-08-23 | 2006-08-23 | 制取低碳烯烃流态化催化反应装置的开工方法 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/374,733 A-371-Of-International US20100004118A1 (en) | 2006-08-23 | 2007-08-23 | Process for Starting up a Fluidized Catalytic Reaction Apparatus Used for Producing Lower Olefins |
US14/886,305 Continuation-In-Part US20160039725A1 (en) | 2006-08-23 | 2015-10-19 | Process for Starting Up a Fluidized Catalytic Reaction Apparatus Used for Producing Lower Olefins |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008025254A1 true WO2008025254A1 (en) | 2008-03-06 |
Family
ID=39127899
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2007/002549 WO2008025254A1 (en) | 2006-08-23 | 2007-08-23 | A process for starting up fluidized catalytic reaction means used for producing lower olefin |
Country Status (11)
Country | Link |
---|---|
US (1) | US20100004118A1 (zh) |
EP (1) | EP2055690B1 (zh) |
JP (1) | JP5009370B2 (zh) |
KR (1) | KR101092899B1 (zh) |
CN (1) | CN101130466B (zh) |
AU (1) | AU2007291793B2 (zh) |
BR (1) | BRPI0712628B1 (zh) |
DK (1) | DK2055690T3 (zh) |
MY (1) | MY154377A (zh) |
WO (1) | WO2008025254A1 (zh) |
ZA (1) | ZA200900700B (zh) |
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US10259757B2 (en) | 2006-08-23 | 2019-04-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for starting up a fluidized catalytic reaction apparatus used for producing lower olefins |
CN102020523B (zh) * | 2009-09-10 | 2013-06-05 | 中国石油化工股份有限公司 | 一种烯烃转化装置的开工方法 |
US8506795B2 (en) | 2010-06-04 | 2013-08-13 | Uop Llc | Process for fluid catalytic cracking |
CN102371137A (zh) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | 甲醇或二甲醚转化为低碳烯烃的反应装置 |
WO2012142727A1 (en) * | 2011-04-21 | 2012-10-26 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for use in production of saturated hydrocarbons from synthesis gas |
CN102285855A (zh) * | 2011-06-27 | 2011-12-21 | 渭南高新区爱心有限责任公司 | 一种由二甲醚或二甲醚与甲醇的混合物制备低碳烯烃的方法 |
CN102367217B (zh) * | 2011-11-25 | 2013-12-18 | 神华集团有限责任公司 | 一种甲醇制烯烃装置及其开工方法 |
CN103193574B (zh) | 2012-01-10 | 2015-01-07 | 中国石油化工股份有限公司 | 甲醇制低碳烯烃反应-再生装置的开车方法 |
CN102863307A (zh) * | 2012-07-23 | 2013-01-09 | 李小燕 | 一种甲醇制烯烃开工方法及流程 |
CN104193569B (zh) * | 2014-08-07 | 2016-06-01 | 清华大学 | 醇醚制烯烃反应-再生装置的开车方法 |
CN105435803B (zh) * | 2014-08-27 | 2018-04-06 | 中国石油化工股份有限公司 | 微球状合成气制低碳烃的催化剂及其制备方法 |
CN110678258A (zh) | 2017-05-31 | 2020-01-10 | 国立大学法人北海道大学 | 功能性结构体以及功能性结构体的制造方法 |
JP7316935B2 (ja) | 2017-05-31 | 2023-07-28 | 古河電気工業株式会社 | 接触分解用又は水素化脱硫用触媒構造体、該触媒構造体を有する接触分解装置及び水素化脱硫装置、並びに接触分解用又は水素化脱硫用触媒構造体の製造方法 |
CN110709166A (zh) * | 2017-05-31 | 2020-01-17 | 古河电气工业株式会社 | 甲醇重整催化剂结构体、甲醇重整用装置、甲醇重整催化剂结构体的制造方法以及烯烃或芳香族烃中的至少一种的制造方法 |
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EP3632554A4 (en) | 2017-05-31 | 2021-04-21 | Furukawa Electric Co., Ltd. | EXHAUST GAS PURIFICATION OXIDATION CATALYST STRUCTURE AND PRODUCTION PROCESS, VEHICLE EXHAUST GAS TREATMENT DEVICE, CATALYST MOLDED BODY AND GAS PURIFICATION PROCESS. |
CN110691645A (zh) | 2017-05-31 | 2020-01-14 | 国立大学法人北海道大学 | 功能性结构体以及功能性结构体的制造方法 |
US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
EP3632542A4 (en) | 2017-05-31 | 2021-01-06 | Furukawa Electric Co., Ltd. | DIRECT OR REVERSE CONVERSION CATALYST STRUCTURE AND PRODUCTION PROCESS OF THE SAME, DIRECT OR REVERSE REACTION DEVICE, PROCESS FOR THE PRODUCTION OF CARBON DIOXIDE AND HYDROGEN, AND PROCESS FOR THE PRODUCTION OF CARBON MONOXIDE AND WATER |
JP7352910B2 (ja) | 2017-05-31 | 2023-09-29 | 国立大学法人北海道大学 | 機能性構造体及び機能性構造体の製造方法 |
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KR20210030355A (ko) | 2018-07-05 | 2021-03-17 | 다우 글로벌 테크놀로지스 엘엘씨 | 촉매 가공을 위한 보충 연료를 함유하는 수소를 이용하는 화학 처리 |
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2006
- 2006-08-23 CN CN2006101125584A patent/CN101130466B/zh active Active
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2007
- 2007-08-23 MY MYPI20090203A patent/MY154377A/en unknown
- 2007-08-23 BR BRPI0712628-0A patent/BRPI0712628B1/pt not_active IP Right Cessation
- 2007-08-23 US US12/374,733 patent/US20100004118A1/en not_active Abandoned
- 2007-08-23 JP JP2009524889A patent/JP5009370B2/ja active Active
- 2007-08-23 EP EP07800769.7A patent/EP2055690B1/en active Active
- 2007-08-23 DK DK07800769.7T patent/DK2055690T3/en active
- 2007-08-23 AU AU2007291793A patent/AU2007291793B2/en not_active Ceased
- 2007-08-23 WO PCT/CN2007/002549 patent/WO2008025254A1/zh active Application Filing
- 2007-08-23 ZA ZA200900700A patent/ZA200900700B/xx unknown
- 2007-08-23 KR KR1020097005638A patent/KR101092899B1/ko active IP Right Grant
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DK2055690T3 (en) | 2017-08-28 |
KR101092899B1 (ko) | 2011-12-12 |
AU2007291793B2 (en) | 2010-11-25 |
BRPI0712628B1 (pt) | 2018-02-06 |
BRPI0712628A2 (pt) | 2012-10-23 |
KR20090064391A (ko) | 2009-06-18 |
EP2055690A4 (en) | 2010-03-31 |
JP5009370B2 (ja) | 2012-08-22 |
JP2010501496A (ja) | 2010-01-21 |
MY154377A (en) | 2015-06-15 |
US20100004118A1 (en) | 2010-01-07 |
ZA200900700B (en) | 2010-04-28 |
CN101130466A (zh) | 2008-02-27 |
AU2007291793A1 (en) | 2008-03-06 |
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EP2055690B1 (en) | 2017-07-19 |
CN101130466B (zh) | 2011-05-04 |
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