US20090152104A1 - Molten salt electrolyzer for reducing metal, method for electrolyzing the same, and process for producing refractory metal with use of reducing metal - Google Patents

Molten salt electrolyzer for reducing metal, method for electrolyzing the same, and process for producing refractory metal with use of reducing metal Download PDF

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Publication number
US20090152104A1
US20090152104A1 US12/067,670 US6767006A US2009152104A1 US 20090152104 A1 US20090152104 A1 US 20090152104A1 US 6767006 A US6767006 A US 6767006A US 2009152104 A1 US2009152104 A1 US 2009152104A1
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molten salt
metal
calcium
reducing metal
wall
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Yuichi Ono
Masanori Yamaguchi
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Toho Titanium Co Ltd
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Assigned to TOHO TITANIUM CO., LTD. reassignment TOHO TITANIUM CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ONO, YUICHI, YAMAGUCHI, MASANORI
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements

Definitions

  • the present invention relates to an electrolyzer for production of a reducing metal by molten salt electrolysis, and the present invention also relates to a method for electrolyzing the reducing metal.
  • titanium metal is often used for aircraft materials and aircraft parts. Recently, titanium metal is more widely used, and it is now used for architectural materials, roads, sports products, etc. Conventionally, titanium metal is produced by the Kroll method in which titanium tetrachloride is reduced with molten magnesium and sponge titanium is obtained, and various improvements have been made to reduce the production cost. However, since the Kroll method is a batch process in which a series of operations is discontinuously repeated, it is difficult to further improve production efficiency.
  • titanium oxides are reduced with calcium in a molten salt so as to produce titanium metal (for example, see WO99/064638 and Japanese Unexamined Patent Application Publication No. 2003-129268).
  • EMR method a reductant containing a metal such as calcium or an alloy thereof is produced, and a titanium compound is reduced with electrons released from the reductant so as to yield titanium metal (for example, see Japanese Unexamined Patent Application Publication No. 2003-306725).
  • titanium metal is collected from a reaction system after electrolytic reaction. Then, calcium oxide, which is produced as a by-product, is dissolved in calcium chloride and is electrolyzed in a molten salt so as to collect calcium and reuse the calcium in a production process for titanium metal.
  • the temperature of an electrolytic bath during the above process is maintained at the melting point of calcium or higher, whereby calcium produced by electrolytic reaction exists in a liquid state.
  • molten calcium easily dissolves and disperses into calcium chloride because molten calcium has a high solubility with respect to calcium chloride, and the collection efficiency of calcium may be decreased.
  • U.S. Pat. No. 3,226,311 discloses a technique in which a complex molten salt having a lower melting point than that of calcium is used, and solid calcium is precipitated on a cathode. In this technique, however, additional complex molten salt is required, and production costs are not reduced.
  • an object of the present invention is to provide a device for producing a reducing metal which may be used for reducing oxides or chlorides of, for example, titanium, and to provide a method therefor.
  • the present invention provides a molten salt electrolyzer for efficiently producing a reducing metal by molten salt electrolysis, a method for electrolyzing the same, and process for producing a refractory metal with the use of the reducing metal.
  • the inventors have performed research in view of the above circumstances, and they found that reducing metal could be produced while maintaining high current efficiency by disposing walls so as to surround an anode and a cathode, respectively, which form a molten salt electrolytic cell. Thus, the inventors have completed the invention.
  • the present invention provides a molten salt electrolyzer for reducing metal
  • the molten salt electrolyzer comprises an electrolytic cell filled with a molten salt composed of a reducing metal chloride, and an anode and a cathode are immersed in the molten salt of the electrolytic cell.
  • a first wall surrounding the periphery of the anode and a second wall surrounding the periphery of the cathode are disposed in the electrolytic cell.
  • the anode and the cathode are surrounded by a wall, respectively, thereby preventing a back reaction that occurred by the dispersing of chlorine gas produced and an active metal in the electrolytic cell. Moreover, reducing metal is piled up in the inside of the second wall at a good yield ratio, and it can be efficiently collected, and as a result, molten salt electrolysis can be performed at high efficiency.
  • each of the first wall and the second wall preferably has an opening so that a molten salt can communicate each other therethrough.
  • the walls prevent dispersion of chlorine gas and a reducing metal while molten salts can communicate each other through the opening, whereby efficiency of molten salt electrolytic reaction may not be decreased.
  • the first wall preferably extends to the bottom of the electrolytic cell and preferably comprises a porous body. According to this structure, the chlorine gas that is produced forms bubbles, and they rise to the surface of the electrolytic bath without communicating through the porous body, whereas the reaction proceeds by contacting of chloride ions and the anode since the electrolytic bath can communicate through the porous body.
  • the first wall is preferably made of a metal oxide, a metal nitride, or a metal carbide
  • the second wall is preferably made of a metal, a metal nitride, or a metal carbide. According to this structure, chlorine gas will not corrode the first wall, and corrosion of the second wall caused by produced reducing metal is effectively prevented.
  • the above-mentioned molten salt electrolyzer is used.
  • a reducing metal with high purity can be efficiently produced while high current efficiency is maintained, by using the molten salt electrolyzer.
  • a refractory metal chloride selected from the group consisting of titanium, zirconium, tantalum, and niobium is reduced with the reducing metal produced by the above method.
  • FIG. 1 is a schematic section view showing a first and a second embodiments of a molten salt electrolyzer of the present invention.
  • FIG. 2 is a schematic section view showing a third embodiment of a molten salt electrolyzer of the present invention.
  • FIG. 3 is a schematic section view showing a fourth embodiment of a molten salt electrolyzer of the present invention.
  • FIG. 4 is a schematic section view showing a fifth embodiment of a molten salt electrolyzer of the present invention.
  • 1 a to 1 d denote a molten salt electrolyzer
  • 11 denotes an electrolytic cell
  • 12 denotes an electrolytic bath
  • 21 denotes an anode
  • 22 denotes a cathode
  • 31 denotes a first wall
  • 32 denotes a second wall
  • 33 denotes openings of a second wall
  • 34 denotes a wall of a cell
  • 35 denotes an opening of a wall of a cell
  • 36 denotes openings of a first wall
  • 37 denotes a wall
  • 37 a denotes a ceramic layer
  • 37 b denotes a metal layer
  • 41 denotes chlorine gas
  • 42 denotes a condensed layer of calcium
  • 51 denotes a nozzle for feeding an electrolytic bath
  • 52 denotes a nozzle for extracting chlorine gas
  • 53 denotes a nozzle for extracting a condensed layer of calcium
  • 54 denotes a nozzle for extract
  • FIG. 1 shows a structural example of a preferred molten salt electrolyzer for practicing the present invention.
  • a combination of an electrolytic bath and a reducing metal that can be produced may be appropriately selected.
  • an electrolytic bath consists of calcium chloride, the temperature thereof is not more than the melting point of calcium, and calcium is produced as a reducing metal.
  • FIG. 1 shows a molten salt electrolyzer 1 a equipped with an electrolytic cell 11 which is filled with an electrolytic bath 12 containing a molten calcium chloride and has an anode 21 and a cathode 22 arranged in immersed form therein.
  • a first wall 31 surrounding the periphery of the anode 21 , and a second wall 32 surrounding the periphery of the cathode 22 are immersed and disposed in the electrolytic cell 11 .
  • the first wall 31 consists of a porous body so that the electrolytic bath 12 can migrate between the outside and the inside of the first wall 31 surrounding the anode 21 by penetrating diffusion.
  • the second wall 32 is made of a dense material so that the electrolytic bath 12 cannot penetrate and diffuse, and it is provided with openings 33 of the second wall in proximity of the level below the cathode 22 so that the inside of the second wall 32 is communicated with the outside thereof.
  • the molten salt electrolytic cell 11 is heated to the temperature of the melting point of calcium chloride or higher by a heating device (not shown in the figure) so as to melt the electrolytic bath 12 .
  • a predetermined direct-current voltage is applied between the anode 21 and the cathode 22 so as to start a molten salt electrolysis of the electrolytic bath 12 .
  • Chloride ions in the electrolytic bath 12 reach the anode 21 by passing through the first wall 31 and supply electrons to the electrode, thereby producing chlorine gas 41 .
  • the produced chlorine gas 41 is collected and is transferred to another process (not shown in the figure), such as a chlorination process, and it is separately reused.
  • calcium ions included in the electrolytic bath 12 reach the cathode 22 by passing through the openings 33 of the second wall and receive electrons, thereby producing calcium.
  • the electrolytic bath 12 is maintained at a temperature that is not higher than the melting point of calcium, whereby calcium is precipitated in a solid state and rises to the surface of the electrolytic bath. Then, the calcium is collected and is transferred to a reduction process of titanium (not shown in the figure) so as to be used.
  • the molten salt electrolyzer 1 a having the above structure, bubbles of chlorine gas 41 produced at the anode 21 do not diffuse to the cathode 22 because of the first wall 31 , and most of them rise to the surface of the electrolytic bath.
  • the solid calcium produced at the cathode 22 does not diffuse to the anode 21 because of the second wall 32 , while a part of it dissolves into the electrolytic bath 12 .
  • the produced chlorine gas and the calcium do not diffuse and come into contact with each other because of the walls surrounding the electrodes, whereby a back reaction does not occur. Therefore, the efficiency of molten salt electrolysis is improved.
  • the electrolytic bath may be maintained at a temperature of the melting point of calcium or higher so as to collect calcium in a molten state.
  • the electrolytic bath dissolves into the electrolytic bath in the inside of the second wall 32 and forms a condensed layer 42 of calcium including calcium chloride.
  • the condensed layer 42 of calcium is appropriately extracted and is transferred to a reduction process of titanium (not shown in the figure) so as to be used.
  • the electrolytic cell 11 is preferably made of a material that can resist high temperatures during operation and may not react with a molten calcium chloride and a molten calcium. Specifically, the electrolytic cell 11 is preferably made of titanium, tantalum, or niobium.
  • the temperature of the electrolytic bath 12 differs according to cases in which calcium in a molten state is collected and calcium in a solid state is collected.
  • molten salt electrolysis is preferably performed in a temperature range that is higher than the melting point of calcium, and specifically, it is preferable that the temperature range be higher than the melting point of calcium by 5° C. to 50° C.
  • the temperature of the electrolytic bath is set to be 850° C. to 895° C.
  • the temperature range be higher than the melting point of calcium by 5° C. to 20° C. in view of the cost of heating and evaporation of calcium chloride. Since the melting point of calcium chloride is 780° C. and is lower than that of calcium, calcium chloride is maintained in a molten state in the condition that calcium is maintained in a molten state.
  • the electrolytic bath is preferably maintained in a temperature range that is not less than the melting point of calcium chloride and is not more than the melting point of calcium.
  • the temperature range is preferably not more than 845° C., which is the melting point of calcium, and is preferably not less than the melting point of calcium chloride.
  • electrolysis is preferably performed at a temperature that is slightly higher than the melting point of calcium chloride. Specifically, electrolysis is preferably performed at a temperature range from 785° C. to 800° C.
  • the electrolytic bath may consist of not only a single bath containing calcium chloride, but also a mixed salt of a potassium chloride and a calcium fluoride, so as to lower the melting point of the electrolytic bath.
  • the electrolysis temperature can be lowered compared to a case in which the electrolytic bath is a single bath consisting of calcium chloride, whereby solid calcium is easily precipitated.
  • the addition of only approximately 5 to 20 mol % of potassium chloride or calcium fluoride to calcium chloride is effective.
  • the anode is immersed in the molten salt of the electrolytic bath, and chlorine gas is produced thereat by electrolyzing calcium chloride contained in the electrolytic bath. Since the temperature of the electrolytic bath is high and is around 800° C., the anode is exposed to high-temperature chlorine gas and calcium chloride. Therefore, the anode is preferably made of a material that can resist high-temperature chlorine gas and molten salt, and graphite is preferable for industrial purpose. Since graphite is relatively inexpensive and is easily processed, and since it is superior in corrosion resistance with respect to high-temperature molten salt and chlorine gas, it is suitable for an anode of the present invention.
  • the cathode is immersed in the molten salt of the electrolytic bath, and calcium is precipitated thereat by electrolyzing calcium chloride. Since calcium is reducible, the cathode can be made of any material that can resist molten calcium chloride and is superior in electric conduction property, and it may be made of a carbon steel or a stainless steel, for example.
  • the end of the cathode is preferably processed in advance so as to have a surface that is as rough as possible. Specifically, the cathode is preferably sandblasted. In addition, the cathode is preferably threaded at the surface in advance. Such surface treatments can facilitate the precipitation of calcium at the cathode.
  • the first wall is provided in order to prevent a back reaction in which chlorine gas produced at the anode is reduced to calcium chloride by reacting with calcium produced at the cathode, and it is preferably disposed by surrounding the periphery of the anode. In this case, electrolytic reaction cannot continue if the electrolytic bath at the outside of the first wall cannot migrate to the inside thereof. Therefore, in a case in which a first wall without an opening, as shown in FIG. 1 , is mounted, the first wall is preferably made of a porous body in which chlorine gas does not diffuse but the electrolytic bath can communicate each other through.
  • the material for the porous body is preferably selected from the group consisting of a metal oxide, a metal nitride, and a metal carbide that have corrosion resistance with respect to chlorine gas and the molten salt.
  • the porous body is preferably made of a metal oxide that is selected from the group consisting of alumina, silica, zirconia, magnesia, and a compound material of these ceramics.
  • the porous body is preferably made of a metal nitride which is selected from the group consisting of silicon nitride, boron nitride, titanium nitride, zirconium nitride, and tantalum nitride.
  • the porous body is preferably made of a metal carbide that is selected from the group consisting of silicon carbide, boron carbide, titanium carbide, zirconium carbide, and tantalum carbide.
  • the porosity of the porous body is preferably in a range from 5 to 30%. Using a porous body having such a porosity prevents the diffusion of chlorine gas produced at the anode and facilitates the migration of the electrolytic bath.
  • the second wall is preferably disposed so as to surround the periphery of the cathode, thereby effectively preventing the diffusion of calcium produced at the cathode.
  • the second wall may be made of a porous body.
  • the second wall is preferably made of a material that is as dense as possible.
  • the second wall made of ceramics is often reductively corroded by molten calcium, it is preferably made of a metal, a metal nitride, or a metal carbide.
  • the metal is preferably selected from the group consisting of stainless steel, titanium, niobium, and tantalum that have corrosion resistance
  • the metal nitride is preferably selected from the group consisting of silicon nitride, boron nitride, titanium nitride, zirconium nitride, and tantalum nitride
  • the metal carbide is preferably selected from the group consisting of silicon carbide, boron carbide, titanium carbide, zirconium carbide, and tantalum carbide.
  • the second wall be dense as possible in order to prevent the diffusion of calcium produced at the cathode.
  • the second wall is preferably provided with an opening so as to facilitate migration of the electrolytic bath.
  • the opening of the second wall is preferably arranged at a level lower than the end of the cathode by 10 mm or more. If the opening is arranged at a level which is not lower than the lower end of the cathode by 10 mm, calcium, which diffuses from the surface of the bath to the bottom, undesirably disperses into the electrolytic bath at the outside of the second wall by passing through the opening.
  • a plurality of openings is preferably provided.
  • Calcium is produced by electrolytic reaction, and a condensed layer made of the calcium alone or the calcium dissolved in calcium chloride is formed in the electrolytic bath surrounded by the second wall.
  • the condensed layer of calcium may be used as a reductant for directly reducing titanium oxide and titanium chloride by immediately extracting from the electrolytic cell to another vessel.
  • FIG. 2 shows an electrolyzer 1 b of another preferred embodiment (third embodiment) relating to the present invention.
  • another wall 34 of cell is provided between the first wall 31 and the second wall 32 .
  • the wall 34 of cell is immersed and is disposed in the electrolytic cell 12 , thereby effectively preventing a phenomenon in which calcium that has flowed out from the second wall 32 diffuses and migrates to the anode. Moreover, it also effectively prevents a phenomenon in which chlorine gas that has flowed out from the first wall 31 diffuses to the cathode.
  • the wall 34 of cell that is immersed and disposed in the electrolytic bath 12 is preferably provided with an opening 35 of the wall of the cell so that the electrolytic bath 12 can migrate. Providing such an opening facilitates the migration of the bath between the anode and the cathode.
  • FIG. 3 shows an electrolyzer 1 c of the preferred embodiment (the fourth embodiment) when the present invention is applied to actual equipment.
  • some nozzles for feeding or extracting are added and are arranged on the basis of the third embodiment. Specifically, a nozzle 51 for feeding electrolytic bath 12 , a nozzle 53 for extracting condensed layer 42 of calcium so as to send the condensed layer 42 of calcium to a next process, and a nozzle 54 for extracting electrolytic bath are added and disposed.
  • the first wall 31 of the first and the second embodiments is modified in a shape for covering the entire anode 21 , and it is disposed as a nozzle 52 for extracting chlorine gas so that chlorine gas 41 produced at the anode 31 is extracted to the outside of the system without a leak.
  • the first wall 31 ( 52 ) is provided with openings 36 of first wall at the lower end so that the electrolytic bath 12 can migrate.
  • the first wall 31 is preferably made of a metal oxide, a metal nitride, or a metal carbide so as to avoid penetrative diffusion of the electrolytic bath 12 , and it is more preferable that a metal nitride be used therefor.
  • the openings 36 , 35 , and 33 are provided at the first wall 31 , the wall 34 of the cell, and the second wall 32 , respectively, and their positions are preferably not at the same level but at different level. Such an arrangement of the openings effectively prevents a back reaction, which occurs by a reaction of chlorine gas produced at the anode and calcium, even if calcium or a condensed layer 42 of calcium produced at the cathode 22 reaches the opening, because the electrolytic bath 12 flows up and down to the anode 21 .
  • FIG. 4 shows an electrolyzer 1 d of another preferred embodiment (the fifth embodiment) relating to the present invention.
  • This embodiment comprises an electrolytic cell 11 , an anode 21 , a cathode 22 , a wall 37 , and an electrolytic bath 12 , and it has the same basic features as the above first to the fourth embodiments.
  • the first wall 31 and the second wall 32 of the above first to the fourth embodiments are connected together and form a sheet as wall 37 .
  • the wall 37 is made of a cladding material comprising a ceramic layer 37 a at the anode side and a metal layer 37 b at the cathode side, which is different from the case of the above first to the fourth embodiments.
  • the ceramic layer 37 a and the metal layer 37 b forming the wall 37 are preferably made of the same material as the material for the above-mentioned first wall 31 and the second wall 32 , respectively.
  • the ceramic layer 37 a is preferably made of a metal oxide.
  • the metal layer 37 b is not required, and the wall 37 can be formed by only the ceramic layer 37 a.
  • the molten salt electrolysis requires little electric power, and the electric power consumption rate of calcium can be decreased.
  • Calcium can be effectively produced by molten salt electrolysis of calcium chloride using each of the above-mentioned embodiments of the present invention, whereas it has been difficult to do so by conventional techniques.
  • titanium can be produced by using calcium, which is produced by the above method, as a reductant for titanium tetrachloride.
  • Zirconium, tantalum, and niobium can be efficiently produced by using the calcium as a reductant for a chloride of zirconium, tantalum, or niobium instead of the titanium tetrachloride.
  • An electrolyzer shown in FIG. 1 comprising the following device configuration was used and was filled with calcium chloride (100%) as an electrolytic bath, and the electrolytic bath was maintained at 880° C.
  • Electrolytic cell titanium crucible
  • Molten salt electrolysis of calcium chloride was performed under the above conditions, and a black solution that seemed to be calcium was produced in the proximity of the surface of the bath at the cathode.
  • Current efficiency was obtained by comparing an amount of calcium collected by molten salt electrolysis and a theoretical amount of precipitated metal that was calculated from the amount of applied electric current. The current efficiency was 75%.
  • the collected calcium was analyzed, and the purity thereof was 80%.
  • Molten salt electrolysis was performed under the same condition as that of the first example, except that the temperature of the electrolytic bath was maintained at 800° C. so as to precipitate calcium in a solid state at the cathode. As a result, solid calcium was precipitated at the surface of the cathode.
  • the current efficiency was obtained by comparing the amount of the solid calcium and a theoretical amount of precipitated metal that was calculated from an amount of applied electric current. The current efficiency was 85%.
  • the precipitated calcium was analyzed, and the purity thereof was 90%.
  • Molten salt electrolysis of calcium chloride was performed under the same condition as that of the first example, except that the second wall 32 was not used.
  • the current efficiency was obtained by comparing the amount of the calcium collected by molten salt electrolysis and a theoretical amount of precipitated metal that was calculated from the amount of applied electric current. The current efficiency was 25%.
  • Molten salt electrolysis of calcium chloride was performed under the same conditions as that of the first example, except that the first wall 31 was not used.
  • the current efficiency was obtained by comparing the amount of the calcium collected by molten salt electrolysis and a theoretical amount of precipitated metal that was calculated from the amount of applied electric current. The current efficiency was 40%.
  • calcium can be efficiently produced and be collected by molten salt electrolysis of metal chloride, specifically, calcium chloride using the present invention. Moreover, a refractory metal chloride can be reduced by using the produced calcium.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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US12/067,670 2005-09-21 2006-06-21 Molten salt electrolyzer for reducing metal, method for electrolyzing the same, and process for producing refractory metal with use of reducing metal Abandoned US20090152104A1 (en)

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JP2005273658 2005-09-21
JP2005-273658 2005-09-21
PCT/JP2006/312436 WO2007034605A1 (ja) 2005-09-21 2006-06-21 還元性金属の溶融塩電解装置およびその電解方法並びに還元性金属を用いた高融点金属の製造方法

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JP4934012B2 (ja) * 2007-12-11 2012-05-16 東邦チタニウム株式会社 金属カルシウムの製造方法
JPWO2009107339A1 (ja) * 2008-02-27 2011-06-30 東邦チタニウム株式会社 還元性金属の製造方法およびこれに用いる溶融塩電解装置
JP5138465B2 (ja) * 2008-05-27 2013-02-06 東邦チタニウム株式会社 金属カルシウムの製造方法および製造装置
IT1396592B1 (it) * 2009-11-04 2012-12-14 Polimeri Europa Spa Procedimento per la produzione di dimetil carbonato ad elevata purezza
CN105220182B (zh) * 2015-10-29 2017-10-31 攀钢集团攀枝花钢铁研究院有限公司 一种制备多孔钛粉的方法
JP6823314B2 (ja) * 2016-11-22 2021-02-03 国立研究開発法人産業技術総合研究所 希土類金属の回収方法、溶融塩電解装置及びバイポーラー電極型隔膜
CN108754562B (zh) * 2018-06-14 2020-04-14 江西理工大学 一种TiN薄膜的制备方法
JP7333223B2 (ja) * 2019-07-30 2023-08-24 東邦チタニウム株式会社 溶融塩電解槽、溶融塩固化層の形成方法、金属の製造方法
CN111020228B (zh) * 2019-11-20 2022-03-22 攀钢集团攀枝花钢钒有限公司 一种电炉冶炼碳化渣送电方法

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AU2006293385A1 (en) 2007-03-29
WO2007034605A1 (ja) 2007-03-29

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