[go: up one dir, main page]

WO2004029309A1 - Processus ameliore pour eliminer l'oxygene des oxydes metalliques par electrolyse dans un sel fondu - Google Patents

Processus ameliore pour eliminer l'oxygene des oxydes metalliques par electrolyse dans un sel fondu Download PDF

Info

Publication number
WO2004029309A1
WO2004029309A1 PCT/GB2003/004049 GB0304049W WO2004029309A1 WO 2004029309 A1 WO2004029309 A1 WO 2004029309A1 GB 0304049 W GB0304049 W GB 0304049W WO 2004029309 A1 WO2004029309 A1 WO 2004029309A1
Authority
WO
WIPO (PCT)
Prior art keywords
current
threshold
electrolysis
exceed
anode
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.)
Ceased
Application number
PCT/GB2003/004049
Other languages
English (en)
Inventor
Alastair Bryan Godfrey
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.)
Qinetiq Ltd
Original Assignee
Qinetiq Ltd
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 Qinetiq Ltd filed Critical Qinetiq Ltd
Priority to AU2003264905A priority Critical patent/AU2003264905A1/en
Publication of WO2004029309A1 publication Critical patent/WO2004029309A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/18—Reducing step-by-step
    • 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
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium

Definitions

  • the present invention relates to an improved method for removing oxygen from metal oxides by electrolysis in a fused salt to produce elements or alloys. It is particularly concerned with extraction processes for producing titanium or titanium alloys, especially ones conducted upon a large scale.
  • Electro-winning of elements from their ores has become well-established over the last two hundred years.
  • a new process has come to light in which a metal oxide is fabricated as an electrode with an electrolytic collector and is cathodically reduced to the metal in the presence of a fused electrolyte and applied direct current voltage.
  • Such an “electro-deoxidation” or “electro-reduction” process hereinafter generically referred to as an "EDO" process, is described in WO 99/64638 to Fray, and is generally applicable to oxides of metals, metalloids and mixtures of oxides.
  • WO 99/64638 the disclosure of which is incorporated herein by reference, is especially concerned with the extraction of titanium from its oxide, although it teaches that the process may also be applied to decompose electrolytically oxides of ⁇ , Mg, Al, Zr, Hf, Nb, Mo and rare earths such as Nd and S , as well as oxides of metalloids such as Ge and Si.
  • WO 99/64638 teaches that it is important for the potential of the cathode to be maintained and controlled potentiostatically so that only oxygen removal occurs and not the more usual decomposition of the fused salt electrolyte.
  • Fray on the application of a voltage via a power source, a current will not start to flow until balancing reactions occur at both the anode and the cathode.
  • the cathode At the cathode there are two possible reactions, the discharge of the cation from the salt or the removal of oxygen. The latter reaction occurs at a more positive potential than the discharge of the metal cation and, therefore, will occur first.
  • a method is provided of extracting a metal, metalloid or alloy from a metal oxide, metalloid oxide or mixture of oxides of alloying elements, by conducting electrolysis in a cell comprising a carbon anode and a fused electrolyte under conditions so as to remove oxygen from the oxide or oxides, wherein the current is controlled so that it does not exceed a selected threshold throughout substantially all of the electrolysis process.
  • the current needs to be limited for at least a first portion of the process, typically for up to the first quarter or first third of the overall reaction time, where it would otherwise be too high.
  • the active control may merely comprise setting the voltage to a suitably low value, preferably having regard to the resulting anodic current density, and may optionally include periodic testing at a higher, more desirable operating voltage to check if the threshold is still being exceeded.
  • the present invention relates, in particular, to the production of titanium from titanium dioxide by an EDO process; thus the metal or alloy preferably comprises titanium.
  • the method is applicable to all elements that can be extracted using an EDO process and such elements include, for example, V, U, Mg, Al, Zr, Hf, Nb, Mo and rare earths such as Nd and Sm, as well as metalloids such as Ge and Si.
  • Figure 1 shows a typical current profile for the electro- deoxidation of a metal, metalloid or mixed oxide using an EDO process at constant voltage
  • Figure 2 shows a preferred current profile for the electro-deoxidation of a metal, metalloid or mixed oxide using the process according to the present invention.
  • the present invention is of especial application in scaled up processes, for example where more than 0.5kg, preferably 1kg, and usually more than 10kg of oxide undergoes electro-deoxidation in a single cell, or especially in industrial scale processes where oxide batches exceed 30kg/cell, 40kg/cell or even 80kg/cell, and more than 20kg or even more than 50kg of metal is extracted per cell per day. This is because larger scale cells have been found to be increasingly more susceptible to the problems outlined above.
  • carbon anodes are known to be capable of withstanding high current densities without a problem, for example, current densities of the order of 10,000A/m 2 are commonly applied to the anodes of Hall cells.
  • the formation of the crust can be prevented by controlling the current in the electrolysis cell such that the current does not exceed a selected threshold value, which value appears to be related to a critical anodic current density, above which anode degradation occurs.
  • the current generated and, hence, the anode current density is directly related to the size of the oxide sample.
  • Limitation of the current is effective in preventing the build-up of deposits on the surface of the electrolyte, irrespective of the magnitude of the applied voltage, provided, of course, that the voltage remains within the required range for electro-deoxidation by an EDO process. Whenever an EDO process is conducted by the usual constant voltage method, the cell current is not constant.
  • the overall electrolysis time was approximately 50 hours.
  • the peak current which typically occurs after approximately 30 minutes, had a magnitude of around 200A.
  • a current threshold for the electro- deoxidation of lkg titanium dioxide was then selected at approximately 70A, using a 3.5kg, cylindrical carbon anode arranged concentrically about the cathode.
  • WO 99/64638 refers briefly to the possibility of controlling current in order to address a charge imbalance problem created in the first few minutes of operation, but that is a different problem to the one addressed by the present invention.
  • the present process may be conducted substantially as a two-stage process comprising a first current controlled phase, wherein the current is limited and held below an identified threshold, but preferably kept as high as possible, and a second voltage limited phase wherein the voltage is held at the maximum allowable for electro-deoxidation by an EDO process .
  • FIG. 2 A typical current profile for electro-deoxidation according to the present invention is illustrated in Figure 2.
  • ⁇ I' represents the cell current in Amps and ⁇ t' represents the time in hours.
  • the dotted line delimits the two electro-deoxidation stages.
  • the cell current is prevented from exceeding the selected threshold for substantially all of that part of the process when it would otherwise do so.
  • the voltage is capped to prevent decomposition of the electrolyte.
  • the second stage commences when a transition point is reached at which, even at maximum voltage, the current is no longer able to exceed the threshold. This transition point, represented by A on Figure 2, occurs toward the end of the deoxidation process, typically after three quarters of the oxygen has been removed.
  • the voltage is still capped, so as to prevent chlorine evolution.
  • the current is maintained as close as possible to the selected threshold value.
  • the current is maintained within 20%, and ideally within 10%, of the selected threshold until, even at maximum voltage, the current cannot exceed the threshold. In other words, the current is maintained as close as possible to the threshold until the transition point mentioned above is reached.
  • the two-stage process will be conducted using automated control means that steadily increase the voltage in the first stage, and then maintain constant high voltage once the above-mentioned transition point has been reached.
  • One preferred method of limiting the cell current to the required value is to vary the applied cell voltage within the limits required for electro-deoxidation.
  • the current is prevented from exceeding the selected threshold by use of a control means.
  • the control means comprises a current measuring device and a variable voltage supply.
  • the control means may comprise a fixed voltage supply and a variable resistor, which resistor limits the current drawn by the cell.
  • Other control means will suggest themselves to the skilled addressee. Automated control means under computer control will usually be preferred, and may be programmed to follow various operating modes.
  • the selected threshold may lie at any point on the profile illustrated in Figure 1, and may, for example, be at a current threshold below the second plateau.
  • the current threshold is selected such that no substantial visible deposits are formed on the surface of the electrolyte under selected atmospheric conditions. More preferably, the current threshold is selected such that no short circuiting is caused by surface deposits.
  • the degree of crust formation is dependent on the surface area of the anode and, hence, the actual operating current density. Therefore, the current threshold may alternatively be selected such that the current density at the anode is prevented from exceeding a critical limit.
  • the current threshold is selected such that the current density at the anode does not exceed 200 A/m 2 , although in some cell arrangements current densities of up to 500 or. even 600 A/m 2 may still be achievable, for example at reduced pressure. Current densities of up to 1000 A/m 2 may even be possible in certain instances, for example, where the operating conditions, electrolyte and anode are carefully selected.
  • the anode size and configuration may also be selected having regard to the required current density.
  • An additional benefit of the present invention is that the peak power consumption of the electrolytic cell is reduced compared with a cell operating at constant voltage. This is an important factor in scaling up the process, in that it permits the use of less expensive power supplies.
  • the electrolyte must consist of salts which are preferably more stable than the equivalent salts of the metal which is being refined and, ideally, the salt should be as stable as possible to remove the oxygen to as low as concentration as possible.
  • the electrolyte may be a halide salt, preferably a chloride salt, and the cation may be selected from barium, calcium, caesium, lithium, strontium and yttrium. Mixtures of salts may also be used.
  • Calcium chloride, or a mixed salt containing calcium chloride is inexpensive and commonly employed, providing a wide temperature of operation without excessive vaporisation.
  • the applied operating voltage should lie in the range 1.4 to 3.4V, and more preferably in the range 1.7 to 3.2V.
  • the atmosphere is maintained at a reduced pressure for at least part of the electrolysis process, for example, at least in the first stage identified above, using, for example, a means such as a vacuum pump.
  • the pressure is below lOOmBar. More preferably the pressure is in the range 1 to 10 mBar.
  • Operating the electrolysis cell at reduced pressure causes vigorous agitation of the electrolyte surface, which assists in breaking down and oxidising the crust.
  • the crust can be removed in 5 to 10 minutes.
  • the atmosphere will often comprise an inert gas, such as argon, and may optionally include small amounts of oxygen. This may encourage the oxidation and removal of carbonaceous deposits.
  • an inert gas such as argon
  • a cathode was constructed by threading lkg of porous titanium dioxide tiles onto a stainless steel rod.
  • the cathode was mounted in an electrolytic cell containing calcium chloride electrolyte at approximately 1000°C and a 3.5 kg carbon anode .
  • the titanium dioxide was electrolysed for 50 minutes at 2.2V, at the end of which time the current had increased to 88A and deposits were starting to form on the surface of the electrolyte.
  • the voltage was reduced to 2.0V, which resulted in the current decreasing to 70A and no further formation of deposits.
  • the run was continued for a further 17 hours at a maximum current of 70A, during which time no crust was observed on the electrolyte.
  • Example 2 shows that crust formation can be prevented by operating the cell at a current slightly below that at which substantial deposits are observed to form.
  • Porous tiles were formed by sintering a mixture of titanium, aluminium and vanadium oxides, and a cathode was subsequently constructed by threading 439g of the tiles onto a stainless steel rod.
  • the cathode was ⁇ mounted in an electrolytic cell containing calcium chloride electrolyte at approximately 950°C.
  • the cylindrical anode consisted of industrial quality carbon (density 1.8g/cm 3 ) with a surface area of 1650cm 2 .
  • the mixed oxide was electrolysed for 77 ⁇ hours at a fixed current of 20A (current density 12lA/m 2 ) , using a constant current transformer to apply the cell voltage.
  • a voltage cap of 3.2V was set up, but during the run the voltage did not, in fact, exceed 2.6V. Therefore, the electro-deoxidation process was not completed and had not yet reached the second stage described above and illustrated in Figure 2.
  • the cathode had been partially reduced to a Ti/Al/V alloy with approximately 10wt% remaining oxygen.
  • this Example 3 shows that controlling the current, and hence the anode current density, such that it does not exceed a selected threshold is an effective method of preventing crust formation.
  • a cathode was constructed by threading lkg of porous titanium dioxide tiles onto a stainless steel rod.
  • the cathode was mounted in an electrolytic cell containing calcium chloride electrolyte at approximately 1000°C and a carbon anode .
  • the titanium dioxide was electrolysed for 1 hours at 2.0V, at an average current of 49A, after which time a significant crust was observed on the surface of the electrolyte.
  • a vacuum was applied to the cell for 2 minutes at a pressure of lOmBar and the crust was observed to decrease, but not disappear. The pressure was increased again to atmospheric pressure and electrolysis continued, with the crust subsequently reforming.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un procédé d'élimination d'oxygène de métaux ou d'oxydes métalloïdes, par électrolyse dans un sel fondu, ce qui permet de produire des éléments ou des alliages améliorés, de façon à éviter les problèmes de contamination des cellules et une efficacité de puissance faible, en particulier dans des processus d'électrodésoxydation améliorés. Le courant de cellule (I) est régulé, de sorte qu'il ne dépasse pas un seuil prédéterminé pendant, sensiblement, tout le processus d'électrolyse. Ledit processus comprend une première phase de courant constante et une seconde phase de courant constant.
PCT/GB2003/004049 2002-09-27 2003-09-24 Processus ameliore pour eliminer l'oxygene des oxydes metalliques par electrolyse dans un sel fondu Ceased WO2004029309A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003264905A AU2003264905A1 (en) 2002-09-27 2003-09-24 Improved process for removing oxygen from metal oxides by electrolysis in a fused salt

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0222382.4A GB0222382D0 (en) 2002-09-27 2002-09-27 Improved process for removing oxygen from metal oxides by electrolysis in a fused salt
GB0222382.4 2002-09-27

Publications (1)

Publication Number Publication Date
WO2004029309A1 true WO2004029309A1 (fr) 2004-04-08

Family

ID=9944822

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2003/004049 Ceased WO2004029309A1 (fr) 2002-09-27 2003-09-24 Processus ameliore pour eliminer l'oxygene des oxydes metalliques par electrolyse dans un sel fondu

Country Status (4)

Country Link
US (1) US20040060826A1 (fr)
AU (1) AU2003264905A1 (fr)
GB (1) GB0222382D0 (fr)
WO (1) WO2004029309A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006010229A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
GB2527266A (en) * 2014-02-21 2015-12-23 Metalysis Ltd Method of producing metal

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003903150A0 (en) * 2003-06-20 2003-07-03 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
CA2540234A1 (fr) * 2003-09-26 2005-04-07 Bhp Billiton Innovation Pty Ltd. Reduction electrochimique d'oxydes metalliques
CN1894440B (zh) * 2003-10-14 2010-06-16 Bhp比利顿创新公司 金属氧化物的电化学还原
CN101006204A (zh) * 2004-06-22 2007-07-25 Bhp比利顿创新公司 金属氧化物的电化学还原
CA2575580A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
WO2006027612A2 (fr) * 2004-09-09 2006-03-16 Cambridge Enterprise Limited Procede, appareil et produit electrolytiques ameliores
WO2007092398A2 (fr) * 2006-02-06 2007-08-16 E. I. Du Pont De Nemours And Company cathode pour la production Electrolytique de poudres de titane et d'autres mEtaux
US9758881B2 (en) * 2009-02-12 2017-09-12 The George Washington University Process for electrosynthesis of energetic molecules
BR112015020000A2 (pt) * 2013-03-15 2017-07-18 Gp Cellulose Gmbh fibra kraft quimicamente modificada e métodos de fabricação da mesma
EP4235054A3 (fr) 2015-02-26 2023-10-18 C2Cnt Llc Procédés de production de nanofibres de carbone
WO2017066295A1 (fr) 2015-10-13 2017-04-20 Clarion Energy Llc Procédés et systèmes de production de nanofibres de carbone
CN115449855B (zh) * 2022-10-24 2023-07-28 青岛国韬钛金属产业研究院有限公司 一种钛合金的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064638A1 (fr) * 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
GB2359564A (en) * 2000-02-22 2001-08-29 Secr Defence Electrolytic reduction of metal oxides
WO2002066711A1 (fr) * 2001-02-16 2002-08-29 Bhp Billiton Innovation Pty Ltd Extraction de metaux
US6540902B1 (en) * 2001-09-05 2003-04-01 The United States Of America As Represented By The United States Department Of Energy Direct electrochemical reduction of metal-oxides

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2845386A (en) * 1954-03-16 1958-07-29 Du Pont Production of metals
US2773023A (en) * 1954-04-26 1956-12-04 Horizons Titanium Corp Removal of oxygen from metals
US2844499A (en) * 1955-11-08 1958-07-22 Horizons Titanium Corp Method of removing oxygen from titanium metal
US3271277A (en) * 1962-04-30 1966-09-06 Leonard F Yntema Refractory metal production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064638A1 (fr) * 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
GB2359564A (en) * 2000-02-22 2001-08-29 Secr Defence Electrolytic reduction of metal oxides
WO2002066711A1 (fr) * 2001-02-16 2002-08-29 Bhp Billiton Innovation Pty Ltd Extraction de metaux
US6540902B1 (en) * 2001-09-05 2003-04-01 The United States Of America As Represented By The United States Department Of Energy Direct electrochemical reduction of metal-oxides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006010229A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
GB2527266A (en) * 2014-02-21 2015-12-23 Metalysis Ltd Method of producing metal

Also Published As

Publication number Publication date
AU2003264905A1 (en) 2004-04-19
US20040060826A1 (en) 2004-04-01
GB0222382D0 (en) 2002-11-06

Similar Documents

Publication Publication Date Title
AU758931C (en) Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt
US11261532B2 (en) Method and apparatus for electrolytic reduction of a feedstock comprising oxygen and a first metal
AU2011293904B2 (en) Extraction of liquid element by electrolysis of oxides
US20040060826A1 (en) Process for removing oxygen from metal oxides by electrolysis in a fused salt
US20080110764A1 (en) Electrolytic Reduction of Metal Oxides
CN1163637C (zh) 稀土类金属的制法
JPWO1997015701A1 (ja) 希土類金属の製造法
US7628904B2 (en) Minimising carbon transfer in an electrolytic cell
MXPA03007326A (es) Extraccion de metales.
US5810993A (en) Electrolytic production of neodymium without perfluorinated carbon compounds on the offgases
JP3700564B2 (ja) スクラップから混合希土類金属を回収する方法
JPS61253391A (ja) プラセオジム−鉄若しくはプラセオジム−ネオジム−鉄合金の製造方法並びにその製造装置
EP1483431B1 (fr) Minimisation du transfert de carbone dans une cellule electrolytique
JPS6187888A (ja) ネオジム−鉄母合金の製造方法並びにその製造装置
US5346608A (en) Method for obtaining neodymium or neodymium-iron alloy by electrolysis of melts containing neodymium compounds
AU2003206430B2 (en) Removal of substances from metal and semi-metal compounds
MXPA00011878A (es) Eliminacion de oxigeno de oxidos de metal y soluciones solidas por electrolisis en una sal fusionada
AU2006203344A1 (en) Removal of substances from metal and semi-metal compounds
AU2003209825A1 (en) Minimising carbon transfer in an electrolytic cell
AU2002245948A1 (en) Electrolytic reduction of metal oxides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP