WO2005009577A2 - Modular pressure swing adsorption process and apparatus - Google Patents
Modular pressure swing adsorption process and apparatus Download PDFInfo
- Publication number
- WO2005009577A2 WO2005009577A2 PCT/US2004/011258 US2004011258W WO2005009577A2 WO 2005009577 A2 WO2005009577 A2 WO 2005009577A2 US 2004011258 W US2004011258 W US 2004011258W WO 2005009577 A2 WO2005009577 A2 WO 2005009577A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- psa
- modules
- manifold
- pressurized
- pressurized adsorbent
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
- B01D53/0446—Means for feeding or distributing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/10—Nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/12—Oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/18—Noble gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Definitions
- PSA pressure swing adso ⁇ tion
- gases gases
- Exemplary applications include separation of hydrogen from gas mixtures, separation of helium from natural gas, purification of landfill gas, and air separation for production of oxygen, nitrogen and/or argon.
- PSA systems of all types are also subject to severe limitations due to their very high complexity and attendant high parts count. Not only does this complexity significantly increase the probability of a component failure, it also significantly increases the system size, assembly time, and material cost.
- Most PSA systems are single point of failure systems, with notable exceptions being the processes revealed in U.S. Patent No. 4,234,322 to De Meyer et al. and U.S. Application Ser. No. 10/269,064.
- the PSA plant must eventually be shut-down to conduct maintenance on the defective component. Such shutdowns are extremely undesirable as they incur a significant amount of lost production time for the entire process facility.
- the lifetime of the connected process equipment may be greatly reduced due to the high mechanical stresses incurred during a shutdown and restart event.
- U.S. Patent No. 6,051,050 to Keefer et al. describes systems using multiple rotary PSA modules in parallel in order to achieve greater overall system capacity, but fails to disclose a method or strategy for operating these modules in the event of a malfunction.
- the rotary modules of the Keefer et al. patent are quite different than those accepted in industrial practice, and are not subject to the same type of single point valve failure as valved PSA apparatuses. Their mode of failure is through gradual seal failure.
- the modules of the Keefer et al. patent also have a very large number of active beds, and they are thus less concerned with variations in product and raffinate gas flowrate pulsation.
- the present invention advantageously provides a valved pressure swing adso ⁇ tion system with reduced flow pulsations.
- the pressure swing adso ⁇ tion system of the present invention can be repaired while operating.
- the present invention further advantageously provides a pressure swing adso ⁇ tion system with increased reliability.
- the present invention provides an apparatus for pressure swing adso ⁇ tion systems that eliminates bending moments at the adsorbent vessel end connections.
- the present invention also advantageously provides a pressure swing adso ⁇ tion apparatus with an integral structural cover.
- Figure 1 is a flow schematic of a PSA system of the present invention
- Figure 2 is a graph showing the reduction in flow pulsation achieved with the PSA system of the present invention.
- Figure 3a shows a perspective view of a first embodiment of the PSA apparatus of the present invention
- Figure 3b shows a side section view through one adsorbent chamber of the first embodiment of the PSA apparatus of the present invention
- Figure 4 shows a section view of the flow manifolds of the first embodiment of the
- Figure 5a shows an exploded view of a second embodiment of the PSA apparatus of the present invention
- Figure 5b shows an assembled view of the second embodiment of the PSA apparatus of the present invention.
- FIG. 6 shows a PSA system of the present invention implemented using the first embodiment of the PSA apparatus of the present invention.
- DETAILED DESCRIPTION OF THE INVENTION [0022] Embodiments of the present invention will be described hereinafter with reference to the accompanying drawings. In the following description, the constituent elements having substantially the same function and arrangement are denoted by the same reference numerals, and repetitive descriptions will be made only when necessary.
- FIG. 1 is a flow schematic for a PSA system 1 of the present invention having a pressurized feed gas manifold 2, a pressurized product manifold 3, and a low-pressure raffinate manifold 4.
- Product manifold 3 is provided with a product surge tank 5 while raffinate manifold 4 is provided with raffinate surge tank 6.
- at least a first PSA module 10 and a second PSA module 20 are connected to the feed, product and raffinate manifolds.
- eight PSA modules 10, 20, 30, 40, 50, 60, 70 and 80 are operated in parallel. Any number of parallel modules may be employed in the process of the present invention, and the choice of eight modules is adopted only as an example.
- the PSA modules are connected to the feed manifold 2 by their respective isolation valves 11, 21, 31, 41, 51, 61, 71, and 81.
- the PSA modules are connected to the product manifold 3 by their respective isolation valves 12, 22, 32, 42, 52, 62, 72, and 82.
- the PSA modules are connected to the raffinate manifold 4 by their respective valves 13, 23, 33, 43, 53, 63, 73, and 83. When all of these valves are in their open positions, every PSA module is fluidly connected in parallel.
- Individual PSA modules may be isolated from the fluid manifolds by closing the valves connecting that module to the manifolds. For instance, module 20 may be isolated by closing valves 21, 22 and 23.
- FIG. 1 illustrates another advantage of the PSA process of the present invention.
- Figure 2 is a graph showing low-pressure raffinate flowrate versus time for four different operating strategies for the PSA system 1 of Figure 1. These traces are for a three- equalization, seven bed PSA after the process of U.S. Application Ser. No. 10/269,064, but the effect is similar for any PSA cycle. PSA cycles using less than three equalizations would show even more pronounced pulsation in the raffinate flowrate. [0026] If the PSA system is operated with every module synchronized to run their individual PSA cycles in phase, the flow pulsations are the same as operating a single process train, and the total flowrate varies between less than 1,000 units and over 17,000 units, a factor of 17:1.
- the array of PSA modules is operated out of phase, such that periods of raffinate gas generation are offset from one another.
- the eight modules of the PSA system are operated in two groups of four, with each group operated 180 degrees out of phase with one another.
- Figure 2 shows that this results in the raffinate flowrate varying between roughly 1,500 and 9,000 units. This is a ratio of about 6:1, which is nearly three times less than was the case with the prior art method of operating a single process train, or operating many modules both in parallel and in phase.
- each group uses half of the total available modules. For the example of an eight module system, this results in four groups of modules.
- each group have the same number of vessels in order to minimize flow variations for the entire system as well as flowrate variations through any given module in order to avoid the problems of adsorbent fluidization and fluid shocks.
- the balance between the number of groups and the number of modules per group must be optimized for each application of the present invention. In an application where minimized downtime for the connected equipment is the highest priority, a system with fewer groups each having a greater number of modules in parallel is preferred. In a system where reliability is of less importance than flowrate pulsation, a greater number of groups with fewer modules will be desired.
- FIG. 3a illustrates a preferred apparatus for the PSA module of the present invention.
- the PSA module 100 has seven adsorbent chambers 101 arrayed between a feed manifold 102 and a product manifold 103.
- the pressurized adsorbent chambers are held in a fixed relationship with the manifolds via tie bolts 104.
- Both the feed and product manifolds are provided with a plurality of valves 105, which are used to execute the PSA cycle.
- the PSA module 100 illustrated in Figure 3 a is an especially-preferred embodiment for executing the seven adsorbent vessel, three pressure equalization cycle described in U.S.
- the apparatus of the present invention may also preferably be used to execute other cycles disclosed therein, as well as other PSA cycles of the related art.
- Side section view 3b shows a single adsorbent chamber 101 provided with an adsorbent mass 110.
- the adsorbent mass may be a single type of adsorbent, or may be made up of mixtures of adsorbent or distinct layers of adsorbent. The choice of adsorbent mass composition and size is dictated by the process flow conditions, the separation of interest and the PSA cycle, and does not limit the present invention in any way.
- the adsorbent chamber is sealingly connected to the inlet manifold 102 and the outlet manifold 103.
- Figure 4 shows an exploded section view of the adsorbent chamber and manifolds of Figure 3b.
- the adsorbent chamber 101 is advantageously mated to a sealing boss 111 provided on both the inlet and outlet manifolds. These are shown as identical features in the figure, but may be differently shaped if desired.
- Each sealing boss is provided with at least one sealing member 112 which affects the fluid seal between the adsorbent chamber and the manifold.
- compression seals or external radial seals may be provided. Neither the seals, nor the sealing boss affects a rigid structural joint between the manifolds and the adsorbent chamber.
- the adsorbent chamber is fixed in rigid structural relation to an end flange feature or manifold.
- Such rigid connections undesirably give rise to localized bending stresses. Due to the cyclic nature of the stress state in a PSA apparatus, this bending moment can undesirably give rise to substantial problems with premature fatigue failure of the apparatus. Such premature failure is especially dramatically accelerated in the case of hydrogen PSA, as hydrogen embrittlement can affect many metallic construction materials.
- the non-structural sealing feature of the present invention is especially desirable as it facilitates the use of far thinner structural elements for equivalent fatigue life.
- Another advantage of the sealing apparatus of the present invention is that different materials may be used to manufacture the adsorbent chamber, manifolds and tie bolt features.
- a material that has good strength but little stiffness could be used for the adsorbent chambers, such as fiberglass-reinforced plastic, while a stiff material with less strength may be used for the manifolds, such as aluminum or closed-cell polymer foam.
- a third material can be used for the tie bolts. This freedom to optimize each material individually facilitates potentially dramatic decreases in weight and or materials cost when required for a particular application.
- Figure 4 shows that the sealing bosses 111 are provided with a concave internal form to aid in flow distribution from the outlet and inlet radial flow distributors 113 and 114.
- the radial flow distributor is in fluid communication with a fluid channel 115 in the inlet manifold and fluid channel 116 in the outlet manifold. Flowing fluid from the channel 115 through the flow distributor 114 communicates with a chamber 120.
- the chamber is defined by the concave feature of the sealing boss as well as the adsorbent retainer plate 122, which is supported by a snap ring 123.
- the PSA apparatus of Figures 3 and 4 is shown for the case with the inlet manifold on the bottom of the apparatus and the outlet manifold on the top. If the apparatus is mounted in the opposite direction, the snap ring 123 would be on the other side of the retainer plate.
- the retainer plate 122 may advantageously be supplied with a fine mesh layer 124 to retain small diameter adsorbent particles.
- This mesh layer may be made from wire mesh, woven or non- woven polymer, glass or other fabric.
- the mesh layer 124 and the retainer plate 122 are preferably assembled with a radial seal ring 125 which holds them together for assembly and provides a radial seal to present bypassing of fluid or particles.
- this composite retainer assembly is preferred, other adsorbent support means may be used with equal success, such as metal, polymer or ceramic foams with an open structure, nonwoven mats, or other means apparent to one skilled in the art.
- the outlet manifold is preferably supplied with a similar retainer plate assembly, except that the snap ring 123 is positioned to hold the retainer plate from above. It is most preferable to supply an elastic layer 130 between the upper retainer plate and the adsorbent.
- Preferred elastic materials also serve a filtration function to exclude fluidized dust particles from entering the manifolds.
- prefe ⁇ ed materials are reticulated polymer foam, woven or non- woven elastomer mat, or elastomer-impregnated mat such as those made from natural fibers such as coconut fiber.
- an elastic element may also be provided at the inlet, or bottom end of the adsorbent chamber.
- the inlet manifold 102 is provided with a feed valve 135 and a waste valve 136.
- Inlet valve 135 communicates between parallel feed flow channel 137 and adsorbent chamber 101 through the channel 115 and the radial flow distributor 114.
- Feed flow channel 137 communicates with all of the adsorbent chambers in the apparatus through their respective valves. It may be appreciated from Figure 4, which shows the valve 135 in its closed position, that flow through feed channel 137 between adsorbent chambers in the apparatus is not materially-impeded by the valve 135, whether it is in the open or closed position. This feature may be ensured by providing a flow channel 137 of sufficient cross-sectional area to ensure the ready flow through the channel, which is critical to the implementation of the PSA cycles of U.S.
- the waste valve 136 likewise communicates with a parallel waste flow channel 138, which is in fluid communication with all of the adsorbent chambers 101 of the apparatus through their respective valves.
- the figures show a manifold that is machined, and the channel features 115 are formed by drilling. Thus, plugs 140 are provided to seal the ends of the channel 115. If the manifold is formed by a net shape process such as casting, plugs 140 are not required. Likewise, the pugs could be replaced with sensors, safety relief valves or other appurtenances. Further, the flow channels 115 and/or
- 137 can be provided with additional features to provide connections for sensors, sample withdrawal, etc.
- additional features to provide connections for sensors, sample withdrawal, etc. The provision of such additional features does not limit the present invention in any way.
- the outlet manifold 103 is similarly provided with product valve 141, equalization valve 142 and equalization valve 143. These valves communicate with product conduit 144, first equalization conduit 145 and second equalization conduit 146. Each of these conduits is in fluid connection with each of the adsorbent chambers of the PSA apparatus through the respective valves for each chamber.
- the apparatus shown is for the especially-prefe ⁇ ed PSA cycle with seven adsorbent vessels and three pressure equalizations of US app 10/269,064 by the present inventor. Other PSA cycles would use different numbers of valves and conduits.
- the six or five adsorbent chamber cycles of the above-named application would omit one of the equalization conduits and valves depicted in the figures for each adsorbent chamber.
- the equalization conduit 145 is additionally provided with porous flow restriction element 147 which is retained by retaining ring 148.
- the retaining ring may be used to secure a flow control orifice plate.
- Other elements such as check valves or flow control valves may also be provided. Such features may be provided only for one parallel flow channel as shown here, or for more than one channel.
- valves may be solenoid operated, hydraulically-operated or mechanically-operated via a mechanical drive system such as a camshaft.
- a mechanical drive system such as a camshaft.
- the choice of valve actuation does not limit the present invention, and does not detract from the advantages thereof.
- the apparatus depicted uses all valves of a single size. Valves of varying sizes and types may be advantageously combined in the present apparatus to achieve desired combination of flow properties. Further, although the most-prefe ⁇ ed apparatus employing parallel flow conduits is depicted, traditional PSA cycle not employing parallel flow conduits may also be executed by providing the required internal flow features.
- the manifolds of the present invention may be made by machining from solid stock, or by machining from a near net shape part made by casting or by joining together layers of material by brazing, soldering or adhesive bonding. Further, the manifolds may be made as a monolithic assembly, or be fashioned in a number of pieces held together by fasteners or other means and sealed by means of fluid seals such as gaskets. The choice of manufacturing technique does not limit the advantages of the present invention.
- Figure 5a shows a second embodiment of the PSA apparatus of the present invention.
- the tie rods of the first embodiment are omitted, and are replaced by structural panels 200 and 201. These panels are secured to the manifolds 102 and 103 by fasteners 202.
- a prefe ⁇ ed fastener being a machine screw, although other types of fasteners may be employed.
- the joining means between the structural panels and the manifolds may be via an adhesive bond, brazing, soldering or welding.
- any load- bearing connection joining the manifolds to the structural panels may be advantageously used. This connection allows the pressure load separating the two manifolds to be borne by the structural panels in a state of substantially-pure tensile stress. Design of a flat panel in tension is straightforward, and common construction materials such as metallic or polymer sheet excel in bearing tensile load.
- FIG. 5 a also shows similar panels 203 and 204 which serve as structural supports for the module. Again, these are advantageously mechanically-attached to the manifold using means that are adequate to support the mechanical loadings imposed by the module weight, as well as any additional loads posed by wind, seismic action, shipping loads, service loads, etc.
- Such structural panels may advantageously be provided with interconnecting features
- the module may also be advantageously provided with a top cover 208 which provides weather protection to the valves. This cover may be provided with valve actuation port 209 to permit installation of the required valve actuation means, whether they are pneumatic or electrical lines.
- the valve control apparatus may be advantageously located inside the valve cover 208, protected from the weather. In this case, only a main electrical and/or pneumatic supply line would be required.
- Figure 5b shows an assembled view of the second embodiment of the PSA apparatus 210. It is readily apparent that if the structural panels of the present invention are applied on all sides of the module, they provide a substantial degree of protection against accidental damage to the adsorbent chambers. Such damage can easily occur during shipping and installation. The valves are also well-protected. It is, therefore, apparent that it may be advantageous in some situations to combine the panels of the second embodiment with the tie bolts of the first embodiment. A prime example being the case where local pressure vessel laws do not allow the structural panels of the present invention, but permit the tie bolts.
- the PSA apparatus may be provided with panels on only two or three sides provided that the structural strength of the remaining panels is suitably increased.
- the panels of the PSA apparatus of the present invention advantageously reduce the complexity of assembly. They also facilitate a reduction in weight, as they reduce localized stresses associated with the tie bolts. These advantages are combined with improved shipping and handling durability, weather protection, and increased aesthetics compared to prior art methods.
- Figure 6 is a perspective view of the PSA system of the present invention implemented using the prefe ⁇ ed PSA apparatus of the present invention.
- the elements described in Figure 1 are indicated by their numbers in Figure 6.
- the site footprint of the PSA system of the present invention is indicated by their numbers in Figure 6.
- PSA system may be reduced significantly if no space is provided between the modules for maintenance access. Using the prefe ⁇ ed apparatus, this may be accomplished as all maintenance tasks may be executed with access only to the top and bottom of the modules.
- the present invention provides numerous advantages. For example, the present invention provides a pressure swing adso ⁇ tion apparatus that does not require fluid connectors between adsorbent vessels. Additionally, the present invention provides a pressure swing adso ⁇ tion apparatus that does not require welding for construction. The present invention also provides a pressure swing adso ⁇ tion apparatus that has minimal empty volume. Furthermore, the present invention provides a pressure swing adso ⁇ tion apparatus that does not require structural support for the adsorbent vessels. While these structural advantages may be useful in certain circumstances, such structural features are not required by the present invention.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020067000365A KR101125316B1 (en) | 2003-07-09 | 2004-04-26 | Modular pressure swing adsorption process and apparatus |
AT04750032T ATE511908T1 (en) | 2003-07-09 | 2004-04-26 | MODULAR PRESSURE CHANGE ADSORPTION METHOD AND MODULAR PRESSURE CHANGE ADSORPTION DEVICE |
PL04750032T PL1641549T3 (en) | 2003-07-09 | 2004-04-26 | Modular pressure swing adsorption process and apparatus |
AU2004258810A AU2004258810B2 (en) | 2003-07-09 | 2004-04-26 | Modular pressure swing adsorption process and apparatus |
JP2006518608A JP4800938B2 (en) | 2003-07-09 | 2004-04-26 | Modular pressure swing adsorption process and apparatus |
CA2525639A CA2525639C (en) | 2003-07-09 | 2004-04-26 | Modular pressure swing adsorption process and apparatus |
EP04750032A EP1641549B1 (en) | 2003-07-09 | 2004-04-26 | Modular pressure swing adsorption process and apparatus |
AU2010201960A AU2010201960B2 (en) | 2003-07-09 | 2010-05-17 | Modular pressure swing adsorption system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/615,244 | 2003-07-09 | ||
US10/615,244 US6918953B2 (en) | 2003-07-09 | 2003-07-09 | Modular pressure swing adsorption process and apparatus |
Publications (2)
Publication Number | Publication Date |
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WO2005009577A2 true WO2005009577A2 (en) | 2005-02-03 |
WO2005009577A3 WO2005009577A3 (en) | 2005-06-16 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/US2004/011258 WO2005009577A2 (en) | 2003-07-09 | 2004-04-26 | Modular pressure swing adsorption process and apparatus |
Country Status (12)
Country | Link |
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US (1) | US6918953B2 (en) |
EP (2) | EP1641549B1 (en) |
JP (1) | JP4800938B2 (en) |
KR (1) | KR101125316B1 (en) |
CN (2) | CN100366323C (en) |
AT (2) | ATE497827T1 (en) |
AU (2) | AU2004258810B2 (en) |
CA (2) | CA2809165C (en) |
DE (1) | DE602004031389D1 (en) |
ES (2) | ES2358374T3 (en) |
PL (2) | PL1980311T3 (en) |
WO (1) | WO2005009577A2 (en) |
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EP1641549B1 (en) | 2011-06-08 |
ES2358374T3 (en) | 2011-05-10 |
CN1805777A (en) | 2006-07-19 |
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ES2367393T3 (en) | 2011-11-03 |
CN100366323C (en) | 2008-02-06 |
AU2004258810A1 (en) | 2005-02-03 |
JP2007527307A (en) | 2007-09-27 |
WO2005009577A3 (en) | 2005-06-16 |
ATE511908T1 (en) | 2011-06-15 |
PL1641549T3 (en) | 2011-10-31 |
CN101157001B (en) | 2013-03-27 |
KR101125316B1 (en) | 2012-03-28 |
EP1641549A2 (en) | 2006-04-05 |
AU2004258810B2 (en) | 2010-03-04 |
EP1980311B1 (en) | 2011-02-09 |
PL1980311T3 (en) | 2011-06-30 |
US20050005771A1 (en) | 2005-01-13 |
JP4800938B2 (en) | 2011-10-26 |
CA2809165C (en) | 2017-07-04 |
CA2525639C (en) | 2013-06-11 |
CA2525639A1 (en) | 2005-02-03 |
DE602004031389D1 (en) | 2011-03-24 |
CN101157001A (en) | 2008-04-09 |
US6918953B2 (en) | 2005-07-19 |
EP1641549A4 (en) | 2007-04-11 |
AU2010201960A1 (en) | 2010-06-03 |
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