EP1610081A1 - Heat exchange process and heat exchanger - Google Patents

Heat exchange process and heat exchanger Download PDF

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Publication number
EP1610081A1
EP1610081A1 EP05013053A EP05013053A EP1610081A1 EP 1610081 A1 EP1610081 A1 EP 1610081A1 EP 05013053 A EP05013053 A EP 05013053A EP 05013053 A EP05013053 A EP 05013053A EP 1610081 A1 EP1610081 A1 EP 1610081A1
Authority
EP
European Patent Office
Prior art keywords
fluid
heating zone
heat exchanger
zone
heat exchange
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Withdrawn
Application number
EP05013053A
Other languages
German (de)
English (en)
French (fr)
Inventor
Henrik Otto Stahl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of EP1610081A1 publication Critical patent/EP1610081A1/en
Withdrawn legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/082—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/06—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits having a single U-bend
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/10—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
    • F28D7/163—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation with conduit assemblies having a particular shape, e.g. square or annular; with assemblies of conduits having different geometrical features; with multiple groups of conduits connected in series or parallel and arranged inside common casing
    • F28D7/1669—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation with conduit assemblies having a particular shape, e.g. square or annular; with assemblies of conduits having different geometrical features; with multiple groups of conduits connected in series or parallel and arranged inside common casing the conduit assemblies having an annular shape; the conduits being assembled around a central distribution tube
    • F28D7/1676—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation with conduit assemblies having a particular shape, e.g. square or annular; with assemblies of conduits having different geometrical features; with multiple groups of conduits connected in series or parallel and arranged inside common casing the conduit assemblies having an annular shape; the conduits being assembled around a central distribution tube with particular pattern of flow of the heat exchange media, e.g. change of flow direction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F9/00—Casings; Header boxes; Auxiliary supports for elements; Auxiliary members within casings
    • F28F9/22—Arrangements for directing heat-exchange media into successive compartments, e.g. arrangements of guide plates

Definitions

  • the invention concerns a heat exchanger and a process for heat exchange in which the heat exchanger is applicable.
  • the invention relates to a heat exchanger useful as a steam super heater and having improved resistance to metal dusting and stress corrosion.
  • Steam reforming is most often an essential step in the production of carbon monoxide rich synthesis gas.
  • methane and steam is hereby converted under supply of heat to a gas composition comprising hydrogen, carbon dioxide, carbon monoxide, steam and methane.
  • the temperature of the synthesis gas after reforming is most often between 750°C and 1050°C.
  • the hot synthesis gas is subsequently cooled in a boiler or in a boiler and a super heater.
  • Metal dusting is a deteriorating attack of the carbon monoxide rich gas on alloys based on iron and/or nickel.
  • a basic reaction by metal dusting is the decomposition of carbon monoxide in a reduction reaction or the bouduard-reaction.
  • Metal dusting only takes place when the metal surface temperature is below the equilibrium temperature of these reactions. That will typically be between 750°C and 850°C. However, if the temperature is lower, typically below 450°C, the reaction will not take place at a significant rate. This means that there is a metal temperature surface intermediate, which should be avoided for contact with gas in reformed gas coolers. These temperature ranges are between 450-800°C for nickel based high alloys and 400-800°C for low alloy steels.
  • waste heat boilers are cooled by the effective heat transfer to the boiling water and can therefore normally be designed to avoid conditions of metal dusting.
  • super heaters when applied as coolers for synthesis gasses have to be considered as subject to metal dusting attack.
  • Nickel based alloys are very sensitive to stress corrosion, whereas low alloy steels are not. Nickel based alloys should therefore only be in contact with dry steam.
  • the invention provides a heat exchange process comprising sequentially cooling of a first fluid by indirect heat exchange with a second fluid and comprising the following steps:
  • the invention also provides a heat exchanger for use in the above process, the heat exchanger for use in the above heat exchange process, the heat exchanger comprising a plurality of U-tubes securing a heat exchange surface for allowing heat transfer between a first and a second fluid, the U-tubes arranged in at least two sequential concentric tube bundles, the tube bundles defining at least a first and second heating zone respectively, each heating zone partially separated from the other by a wall, the first heating zone being a colder zone and the second heating zone being a hotter zone, the tube bundle of the first colder heating zone being made of a low alloy steel and the tube bundle of the second hotter heating zone being made of a temperature and corrosion resistant alloy.
  • the invention concerns a heat exchanger which is useful as a super heater and is designed to avoid metal dusting and stress corrosion by a proper selection of a combination of metal alloys and gas/steam flow through a pre-defined pattern of heat exchange tube bundles.
  • the heat exchanger is suitable for heat exchange between a first and a second fluid.
  • An example of such fluids is steam (first fluid) and synthesis gas (second fluid).
  • the hot synthesis gas from a steam reforming reactor is cooled by steam in the heat exchanger.
  • the heat exchanger is of the U-tube type with a thick tube sheet.
  • a plurality of U-tubes for transfer of the first fluid are arranged parallel and spaced apart with a central inlet and a peripheral outlet for the second fluid.
  • the shell side heat exchange is enhanced by disc and doughnut baffles.
  • the plurality of tubes is arranged in tube bundles, each tube bundle corresponding to a particular heating zone.
  • the first fluid for instance steam
  • the second fluid for instance reformed gas
  • the essential principle of the invention is that at least two tube bundles are present in the heat exchanger and they are connected to one tube sheet in concentric rings.
  • the compartments for each tube bundle are separated by metallic walls with openings in their middle or at their ends through which the second fluid passes and is divided into several streams when flowing from one compartment to the other.
  • the second fluid flows both countercurrent- and concurrent to the first fluid within each tube bundle compartment, as shown by the arrows in figures 1 and 3.
  • Figure 1 relates to an embodiment of the invention having two heating zones separated by a wall.
  • the first fluid for instance steam, enters the heat exchanger through inlet 1.
  • the first fluid then enters a compartment comprising U-tubes in a first tube bundle and defining a first heating zone 2.
  • the first fluid After passing through the U-tubes in the first heating zone in indirect heat exchange with the second fluid, the first fluid enters a second compartment comprising the U-tubes in a second tube bundle and defining a second heating zone 3.
  • the U-tubes of the second tube bundle are placed sequentially after the U-tubes of the first tube bundle.
  • the tube bundle defining the second heating zone 3 is placed innermost in the heat exchanger while the tube bundle defining the first heating zone 2 is placed outermost and the two tube bundles are separated by a wall 12.
  • the wall 12 can be of metal and it is positioned and constructed to provide openings 15 and 16 allowing division of the flow of the second fluid into several streams, when flowing from one compartment to the other.
  • the first fluid passes through the U-tubes in the second heating zone 3 in indirect heat exchange with the second fluid. After passing through the second heating zone 3 the first fluid is now heated and it leaves the heat exchanger through the outlet 4.
  • the second fluid for instance synthesis gas, or any other hot gas that requires cooling, enters the heat exchanger through inlet 5.
  • Inlet 5 leads to a central pipe 13 placed in the middle of the innermost tube bundle.
  • This central pipe 13 has openings 14 allowing the second fluid to leave the central pipe 13 and enter the second heating zone 3 on the shell side of the tube bundles defining this heating zone. It is preferable that the openings 14 are not located at the ends of the central pipe 13, in order to ensure both concurrent and countercurrent flow.
  • the second fluid enters the middle of heating zone 3 through the openings 14 and the fluid is then divided to flow towards the two ends of the tube bundle.
  • the second fluid thus contacts the external surfaces i.e. the shell side of the U-tubes of the innermost tube bundle and is cooled in indirect heat exchange with the first fluid.
  • the second fluid thereafter passes through end openings 15 and 16 in the wall 12 separating the two tube bundles defining the first and second heating zones 2 and 3.
  • the opening 15 is at the lower end of the wall 12 and the opening 16 is at the upper end of the wall 12.
  • the second fluid then passes across the shell side of the tube bundles defining the first heating zone 2, which surrounds the innermost bundle defining the second heating zone 3.
  • the gas then flows in the tube bundle from the end openings 15 and 16 towards the middle of the heating zone 2.
  • the further cooled second fluid then leaves the first heating zone 2 and the heat exchanger through outlet 6.
  • Figure 2 shows the placement of the tube bundles relative to each other in the heat exchanger.
  • the wall 12 divides the heating zones into two compartments resulting in heating zones 2 and 3.
  • the tube bundles are placed in the heat exchanger with the tube bundle of heating zone 2 placed outermost and the tube bundles of heating zone 3 placed innermost.
  • the heat exchanger can have three heating zones, as shown in figure 3.
  • the third bundle also defines a heating zone 11 allowing further heat exchange of the first fluid with the second.
  • the second fluid enters the middle of this heating zone through a central opening 17 in the wall 18 separating the outermost tube bundle from the two innermost tube bundles.
  • the wall 18 separates thereby heating zone 11 from heating zones 2 and 3.
  • the fluid is then divided into streams flowing towards the two ends of the tube bundle.
  • the walls separating the compartments can therefore have openings at either their ends (15 and 16) or in their middle (17).
  • the openings in each subsequent wall therefore alternate by being either at the end of the wall or in its middle. This ensures that the flow of the second fluid is both concurrent and counter current to the flow of the first fluid in each heating zone. Effective heat exchange is thereby realised.
  • the second fluid is in this way cooled by subsequent flow (divided flow) through the two or three tube bundles.
  • first fluid is heated by subsequent flow through the tubes, starting in the outermost bundle, which is coldest and has the lowest temperature and leaving after flow through the innermost bundle, which is hottest and therefore has the highest temperature.
  • the outmost tube bundle defining the heating zone 2 therefore corresponds to a cold zone (a low temperature zone) and the innermost bundle defining the heating zone 3 therefore corresponds to a hot zone (a high temperature zone).
  • the heating zone 2 in the middle between heating zones 3 and 11 has intermediate temperatures between the hottest (high temperature zone) and the coldest (low temperature zone) zones.
  • Baffles can be placed in the heating zones in order to improve the heat distribution.
  • Baffles particularly suitable for the heat exchanger are of the disc and doughnut type. These have the effect of allowing the second fluid to travel through the heating zones in a zig-zag movement and additionally they assist in positioning the U-tubes.
  • the baffles 7, 8 and 9 shown in figure 1 are held in place by rods.
  • Baffle 7 is hot i.e. experiences high temperature
  • baffle 8 is cold i.e. experiences low temperature.
  • the baffles 10 in the central pipe are hot baffles.
  • Baffles can also be placed in the embodiment shown in figure 3.
  • the hot (high temperature) tube bundle defining heating zone 3 must be made of a material resistant to metal dusting. This could for example be a high alloy such as austenitic nickel/chromium/iron alloy, for instance Inconel®.
  • the baffles, rods and walls defining the channels in which the tube bundles are situated must also be resistant to metal dusting.
  • the cold (low temperature) tube bundle defining heating zone 2 may be of low alloy steel and in most cases the baffles and rods may also be of low alloy material. If a third bundle of tubes are present as shown in figure 3, the tubes of the middle/intermediate bundle may be of low alloy steel, whereas the rods, baffles and walls/channels may be of Inconel®.
  • the low alloy steel could for example be a ferritic iron, chromium, molybdenum, carbon steel.
  • Characteristic for the heat exchanger of the invention is that the U-tubes are of materials resistant to metal dusting when the material surface is hot enough to give a risk of metal dusting.
  • the U-tubes can be of cheaper low alloy steel when situated in colder zones. Low alloy steel is not sensitive to wet stress corrosion. When the first fluid is steam, it enters U-tubes of low alloy steel, and the steam will not come in contact with the U-tubes of high alloys before it is completely dry.
  • the heat exchanger of the invention shows an improvement in its heat exchange performance due to it enhanced resistance towards metal dusting and stress corrosion.
  • a typical process in which the heat exchanger is useful is in a steam reforming process as described in the following:

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Geometry (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
EP05013053A 2004-06-25 2005-06-16 Heat exchange process and heat exchanger Withdrawn EP1610081A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA200400998 2004-06-25
DK200400998 2004-06-25

Publications (1)

Publication Number Publication Date
EP1610081A1 true EP1610081A1 (en) 2005-12-28

Family

ID=34937511

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05013053A Withdrawn EP1610081A1 (en) 2004-06-25 2005-06-16 Heat exchange process and heat exchanger

Country Status (9)

Country Link
US (2) US20050284606A1 (ja)
EP (1) EP1610081A1 (ja)
JP (1) JP2006010309A (ja)
KR (1) KR101175993B1 (ja)
CN (1) CN1715743A (ja)
AU (1) AU2005202782B2 (ja)
CA (1) CA2510916C (ja)
RU (1) RU2374587C2 (ja)
ZA (1) ZA200505145B (ja)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1017747A3 (nl) * 2007-08-29 2009-05-05 Atlas Copco Airpower Nv Warmtewisselaar.
WO2009156085A3 (en) * 2008-06-26 2010-08-26 Haldor Topsøe A/S Process for the production of ammonia and stream superheater
DE102010040278A1 (de) * 2010-09-06 2012-03-08 Siemens Aktiengesellschaft Wärmetauscher
ES2558027R1 (es) * 2013-03-07 2016-04-06 Foster Wheeler Usa Corporation Método y sistema para prolongar la duración de funcionamiento de un horno utilizando materiales con diferentes propiedades térmicas
EP3406999A1 (en) 2017-05-26 2018-11-28 ALFA LAVAL OLMI S.p.A. Shell-and-tube heat exchanger
IT202200026172A1 (it) 2022-12-21 2024-06-21 Giovanni Manenti Scambiatore di calore con fluidi in configurazione controcorrente invertita e relativo metodo operativo

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JP5644102B2 (ja) * 2009-12-28 2014-12-24 三浦工業株式会社 熱交換器
RU2635673C1 (ru) * 2010-12-22 2017-11-15 Флексэнерджи Энерджи Системз, Инк. Теплообменник с вторичной складчатостью
JP5628067B2 (ja) * 2011-02-25 2014-11-19 株式会社荏原製作所 研磨パッドの温度調整機構を備えた研磨装置
US20130292089A1 (en) * 2012-05-01 2013-11-07 Norcross Corporation Dual passage concentric tube heat exchanger for cooling/heating of fluid in a low pressure system
WO2014187560A1 (de) * 2013-05-21 2014-11-27 Linde Aktiengesellschaft Wärmeübertrager, verfahren zur wartung bzw. herstellung und zum betreiben eines wärmeübertragers, kraftwerk und verfahren zur erzeugung elektrischer energie
DE102014216974A1 (de) * 2014-08-26 2016-03-03 Mahle International Gmbh Thermoelektrisches Modul
US10414018B2 (en) * 2016-02-22 2019-09-17 Ebara Corporation Apparatus and method for regulating surface temperature of polishing pad
RU173350U1 (ru) * 2016-11-22 2017-08-23 Андрей Александрович Виноградов Градирня сухая для жаркого климата
EP3543637A1 (en) * 2018-03-22 2019-09-25 Casale Sa Shell and tube heat exchanger

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EP0390420A1 (en) * 1989-03-22 1990-10-03 C F Braun Inc Combined heat exchanger system such as for ammonia synthesis reactor effluent
US6153152A (en) * 1990-04-03 2000-11-28 The Standard Oil Company Endothermic reaction apparatus and method
US20020155061A1 (en) * 2001-04-24 2002-10-24 Ravi Prasad Syngas production method utilizing an oxygen transport membrane
EP1273866A1 (en) * 2000-04-13 2003-01-08 Tetsuto Tamura Rapid cooling device and method of rapidly cooling the device
US6623869B1 (en) * 2001-06-19 2003-09-23 Sumitomo Metal Ind Metal material having good resistance to metal dusting
US20030213854A1 (en) * 2002-05-15 2003-11-20 Stickford George H. Evaporator configuration for a micro combined heat and power system

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US2774575A (en) * 1952-03-07 1956-12-18 Worthington Corp Regenerator
EP0390420A1 (en) * 1989-03-22 1990-10-03 C F Braun Inc Combined heat exchanger system such as for ammonia synthesis reactor effluent
US6153152A (en) * 1990-04-03 2000-11-28 The Standard Oil Company Endothermic reaction apparatus and method
EP1273866A1 (en) * 2000-04-13 2003-01-08 Tetsuto Tamura Rapid cooling device and method of rapidly cooling the device
US20020155061A1 (en) * 2001-04-24 2002-10-24 Ravi Prasad Syngas production method utilizing an oxygen transport membrane
US6623869B1 (en) * 2001-06-19 2003-09-23 Sumitomo Metal Ind Metal material having good resistance to metal dusting
US20030213854A1 (en) * 2002-05-15 2003-11-20 Stickford George H. Evaporator configuration for a micro combined heat and power system

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1017747A3 (nl) * 2007-08-29 2009-05-05 Atlas Copco Airpower Nv Warmtewisselaar.
WO2009156085A3 (en) * 2008-06-26 2010-08-26 Haldor Topsøe A/S Process for the production of ammonia and stream superheater
CN102137817A (zh) * 2008-06-26 2011-07-27 赫多特普索化工设备公司 生产氨的方法
US8261700B2 (en) 2008-06-26 2012-09-11 Haldor Topsoe A/S Steam superheater
CN102137817B (zh) * 2008-06-26 2015-02-18 赫多特普索化工设备公司 生产氨的方法
DE102010040278A1 (de) * 2010-09-06 2012-03-08 Siemens Aktiengesellschaft Wärmetauscher
ES2558027R1 (es) * 2013-03-07 2016-04-06 Foster Wheeler Usa Corporation Método y sistema para prolongar la duración de funcionamiento de un horno utilizando materiales con diferentes propiedades térmicas
US9850431B2 (en) 2013-03-07 2017-12-26 Amec Foster Wheeler Usa Corporation Method and system for utilizing materials of differing thermal properties to increase furnace run length
US10557087B2 (en) 2013-03-07 2020-02-11 Amec Foster Wheeler Usa Corporation Method and system for utilizing materials of differing thermal properties to increase furnace run length
US10889759B2 (en) 2013-03-07 2021-01-12 Amec Foster Wheeler Usa Corporation Method and system for utilizing materials of differing thermal properties to increase furnace run length
EP3406999A1 (en) 2017-05-26 2018-11-28 ALFA LAVAL OLMI S.p.A. Shell-and-tube heat exchanger
WO2018215160A1 (en) 2017-05-26 2018-11-29 Alfa Laval Olmi S.P.A Shell-and-tube heat exchanger
US11054196B2 (en) 2017-05-26 2021-07-06 Alfa Laval Olmi S.P.A. Shell-and-tube heat exchanger
IT202200026172A1 (it) 2022-12-21 2024-06-21 Giovanni Manenti Scambiatore di calore con fluidi in configurazione controcorrente invertita e relativo metodo operativo

Also Published As

Publication number Publication date
AU2005202782B2 (en) 2009-12-10
RU2374587C2 (ru) 2009-11-27
US20050284606A1 (en) 2005-12-29
KR20060049684A (ko) 2006-05-19
CN1715743A (zh) 2006-01-04
RU2005119478A (ru) 2006-12-27
KR101175993B1 (ko) 2012-08-23
JP2006010309A (ja) 2006-01-12
CA2510916C (en) 2013-08-13
US20100218931A1 (en) 2010-09-02
ZA200505145B (en) 2006-04-26
AU2005202782A1 (en) 2006-01-12
CA2510916A1 (en) 2005-12-25

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