WO2002070759A1 - Procede et appareil de production de titane - Google Patents

Procede et appareil de production de titane Download PDF

Info

Publication number
WO2002070759A1
WO2002070759A1 PCT/AU2002/000212 AU0200212W WO02070759A1 WO 2002070759 A1 WO2002070759 A1 WO 2002070759A1 AU 0200212 W AU0200212 W AU 0200212W WO 02070759 A1 WO02070759 A1 WO 02070759A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
accordance
compound
plasma
reduction reaction
Prior art date
Application number
PCT/AU2002/000212
Other languages
English (en)
Inventor
Jawad Haidar
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
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 Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Publication of WO2002070759A1 publication Critical patent/WO2002070759A1/fr

Links

Classifications

    • 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
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/005—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys using plasma jets

Definitions

  • the present invention relates to a method and apparatus for the production of metal and, particularly, but not exclusively, to a method and apparatus for the production of titanium.
  • Titanium is a metal with a number of highly desirable properties. It is stronger than steel, but is of lighter weight. Further, it is highly resistant to corrosion. Titanium finds extensive use in industries such as the aerospace industry and other industries were these properties are prized. A major problem, however, is that titanium is very expensive. This limits its use virtually to applications where its properties are essential so that the cost must be incurred.
  • the main reason for the expense of titanium is the difficulty in obtaining titanium from its ore.
  • Present processes are very expensive.
  • titanium minerals are chlorinated in the presence of carbon to form TiCl 4 that is then reduced to Ti metal using magnesium.
  • By-products of the process such as MgCl 2 is separated from the titanium sponge by washing and then the titanium sponge is crushed for further purification using vacuum arc distillation. The vacuum arc is also used to make ingot out of the crushed sponge.
  • the Kroll process is multi-stage and expensive.
  • the present invention preferably enables the production of titanium by way of a direct extraction process, preferably in the absence of any reducing agent. Removal of a requirement for an agent simplifies the reaction, results in less likelihood of impurity and, preferably, lowers the expense of production.
  • the titanium is extracted from titanium tetrachloride.
  • a method for the production of titanium from a compound containing titanium comprising the steps of implementing a direct reduction reaction of the compound in the absence of any reducing agent, and driving the reduction reaction away from equilibrium whereby-to facilitate the precipitation of titanium metal.
  • the reduction reaction is driven away from equilibrium rapidly.
  • the compound is preferably a titanium halide, and is preferably titanium chloride (TiCl 4 ) .
  • Driving the reduction reaction away from equilibrium is preferably achieved by a process of rapid cooling of the reaction constituents, to rapidly drive the reduction reaction away from equilibrium.
  • the reduction reaction is implemented by way of a plasma discharge to produce the reaction constituents within the plasma.
  • the rapid cooling is implemented by rapidly quenching the plasma.
  • the rapid cooling is preferably implemented by driving the plasma into contact with relatively strongly cooled surfaces .
  • the rapid cooling may also be implemented by mixing the plasma with other gases (as an alternative to driving into contact with strongly cooled surfaces or in addition to) .
  • the titanium species condense at the cooled surface in the form of powders that can be continuously removed from the surface.
  • the powder may be exposed to heat from the plasma for a short period so that it forms large crystals, and then the crystals are subsequently removed from the cooling surface.
  • an apparatus for the production of titanium from a compound containing titanium comprising a reaction vessel including a reaction means for implementing a reduction reaction of the compound, and means for driving the reduction reaction away from equilibrium.
  • the reaction implementation means preferably comprises -means for creating a plasma arc
  • the means for driving a reaction away from equilibrium may comprise means for rapidly cooling the reaction components .
  • This may comprise means for presenting a cooling surface within the reaction chamber, or means for introducing a gas to mix the plasma and therefore cause the plasma to cool, or both.
  • titanium metal produced by a method in accordance with the first aspect of the present invention .
  • reacting gases may be introduced to facilitate titanium production or to produce titanium compounds .
  • a method for the production of titanium from a compound containing titanium comprising the steps of implementing a reduction reaction, and rapidly driving the reduction reaction away from equilibrium whereby to facilitate the precipitation of titanium metal .
  • gases may be introduced to either increase the yield of titanium (reactive gas such as hydrogen may do this) or to produce compounds such as titanium nitride and titanium oxide (nitrogen and oxygen may be introduced to do this) .
  • a similar reaction as described above in relation to the first aspect of the present invention may be used to prepare other metals .
  • a method of producing a metal from a compound containing the metal comprising the steps of implementing a reduction reaction of the compound, and then rapidly driving the reaction away from equilibrium whereby to facilitate the precipitation of the metal.
  • the reduction reaction is implemented in the absence of a reducing agent and is a direct reduction.
  • the compound may be a metal halide.
  • the reduction reaction may be driven away from equilibrium by any of the means discussed above in relation to the first aspect of the present invention.
  • a method for the production of titanium from a compound containing titanium comprising the steps of implementing a direct extraction of titanium from the titanium compound utilising a plasma arc process.
  • the titanium compound is a titanium halide, and is preferably titanium tetrachloride.
  • the plasma arc process operates to dissociate the titanium atoms from the chlorine atoms directly.
  • the reaction is preferably driven rapidly away from equilibrium to enable titanium to be obtained.
  • Figure 1 is a schematic diagram of an apparatus in accordance with an embodiment of the present invention for the production of titanium
  • Figure 2 is a photograph illustrating titanium produced by the apparatus of figure 1
  • Figure 3 is an EDX trace of the titanium material produced by the apparatus of figure 1.
  • Figure 1 schematically shows a reaction apparatus which can be used to prepare titanium metal, according to an embodiment of the present invention.
  • a direct reduction process is employed, in the absence of any reducing agent. Attempting such a process is counterintuitive. Under equilibrium conditions, the direct reduction is thermodynamically unfeasible and one would expect the components of the reduction merely to recombine due to the reactivity, so that no or little titanium would be obtained.
  • the present invention avoids this recombination by rapidly driving the reaction away from equilibrium.
  • the reduction reaction is implemented by a plasma arc .
  • Driving the reaction away from equilibrium is achieved by quenching the reactive' plasma by bringing the plasma into contact with strongly cooled surfaces and also by first mixing with inert gases .
  • the temperature of its atomic species Ti and Cl
  • the effects of the gas flow is somewhat similar to that of the cooled surface in that the gas flow causes a sharp decrease in the plasma temperature, resulting in a low reaction rate between the Ti species and the chlorine species in the plasma.
  • the reaction rate between Ti and Cl is lower than between Ti and Cl in the gas phase of the plasma.
  • Ti vapour condenses at the cool surface in the form of powders that can be continually removed from the surface so as to avoid increasing the temperatures of the collecting surfaces, hence avoiding a higher reaction rate between the collected Ti metal and the remaining chlorine gas in the plasma.
  • the temperature of the cooled surface can be regulated so as to avoid condensation of titanium chloride species such as TiCl 2 , TiCl 3 and TiCl .
  • the powder may be exposed to heat from the plasma for a short period so that it forms large crystals, and then the crystals are subsequently removed from the cooling surfaces . Formation of large crystals may be favoured over powders as it lowers contamination of the metal upon exposure to air.
  • inert gases and strongly cooled surfaces are used together. It may be possible to use merely a strongly cooled surface or alternatively mixing with inert gases, each alone.
  • figure 1 is a schematic diagram of an apparatus for carrying out the pro ⁇ ess.
  • a plasma is created by operating an electric discharge 1 between a first electrode 2 (which in this embodiment is a cathode) and a second electrode 3 (which in this embodiment is an anode) .
  • Titanium chloride is introduced into the arc through nozzles 5 distributed in an annular fashion about the arc, and a plasma 1 is formed.
  • the main body of the arc 1 is surrounded by a cooling cylinder 4.
  • the cooling cylinder 4 is a water-cooled metal cylindrical tube (the water cooling arrangement is not shown in the diagram but it will be appreciated by a skilled person how this is achieved) .
  • the cooling tube 4 may also serve as an auxiliary anode and then the arc may be operated between the cathode 2 and the auxiliary anode 4.
  • inert or reactive gases may be introduced into the arc together with the titanium chloride or independently through the gas nozzle 6 surrounding the cathode 2.
  • inert gases such as noble gases are introduced in order to facilitate driving the reduction reaction occurring in the arc away from equilibrium.
  • Gases from the plasma can exit the arc region through the gaps between the gas nozzle 6 and the titanium chloride nozzle 5 or alternatively through the region between the cooling tube and electrode 3.
  • the length of these gaps may be adjusted by adjusting the position of the cooling tube 4 and the cathode 2, relative to the anode 2, so as to force the gas through either of the 2 exit regions.
  • the gas nozzle 6 together with the cathode 2 may be driven downwards so as to close the gap between the gas nozzle 6 and the titanium chloride nozzle 5 and hence prevent gas from exiting the plasma arc 1 region through the upper part of that gap.
  • the TiCl 4 is driven through the arc discharge 1, dissociated in the plasma due to atomic and radiative plasma processes, and the Ti species condenses on the surface of the cooling tube 4 and elsewhere in the vessel 7, including the surface of the anode 3.
  • the cooling tube 4 should be long enough to allow complete dissociation of the TiCl 4 .
  • Titanium metal collected on the surfaces may be continuously removed so as to optimise titanium metal production.
  • the apparatus of figure 1 is enclosed in the vessel 7.
  • Working gases in the vessel including argon, chlorine and gaseous titanium chloride are continuously removed from the vessel using a pumping system 8 connected to the vessel.
  • the pressure in the vessel is kept below one atmosphere and the process of Ti production is preferably carried out at pressure below 300 torrs .
  • the gas flow through the nozzle 6 has a large influence on arc properties and hence on the titanium production process and yield.
  • a low argon gas flow of a few litres per minute injected through the gas nozzle 6, using the configuration of figure 1 but with a closed gap between gas nozzle' 6 and titanium chloride nozzle 5 most of the titanium found is produced on the internal surfaces of the cooling tube.
  • black titanium powder is collected from the external surface of the cooling tube and the internal walls of the vessel.
  • Titanium chloride nozzle 6 is of ceramic and. has outlet diameter of 20 millimetres.
  • All other electrodes are water-cooled copper. This results in a titanium product in the form of a tubeless cylinder with large crystals on its surface.
  • Figure 2 shows an example of the product collected from the inner walls of the cooling tube, for the example parameters given above.
  • the material is in a tubular form with the length of the tubular part around 5 centimetres .
  • the materials shown in this figure have been washed in alcohol to remove residual powder that may exist in the collected materials.
  • Figure 3 shows a trace for an energy dispersive X-ray analysis of the crystals of figure 2. Impurities in the crystals are below the detection limits of the " analysis system and purity of the crystals exceeds 99.6%. Impurities due to corrosion of the internal part of the system due to reaction with chlorine are minimal. This high purity illustrates the advantages of the present process starting from titanium chloride, over reduction processes starting from titanium minerals. For the present process, impurities in the titanium products are minimal as purification occurs at the chlorination stage leading to the formation of very pure titanium chloride .
  • titanium chloride is used in the process of this embodiment, it will be appreciated that other starting compounds may be used. In particular, other titanium halides may be utilised or a mixture of titanium halides.
  • This process may also be used for the production of other metals, in some cases.
  • the apparatus illustrated in figure 1 and described above is only exemplary. Other configurations based on the same physical principle may also be used.
  • the inner surface of the cooling tube may be non- cylindrical and also the anode may not be a non-disc shape so as to maximise the contact area between the cooling surfaces in the plasma.
  • Titanium powder may also be formed on the surface of the anode and the internal walls of the chamber.
  • the system may be surrounded by other cooling surfaces so as to increase contact with the escaping plasma gas and increase the yield of titanium metal production. Reactive gases such as hydrogen, nitrogen and oxygen may also be injected into the vessel or into the arc in order to increase the yield of titanium production or to produce titanium compounds such as titanium nitride and titanium oxide.
  • One advantage of using hydrogen is that it increases the plasma enthalpy, resulting in increasing energy dissipation in the plasma. This increases the rate of dissociation of the titanium tetrachloride (where titanium tetrachloride is the compound which is used as the starting material) . Hydrogen has no reducing role in this case.
  • Titanium crystals may be produced by exposing deposited titanium to heat from the plasma for a short period. This can be done in any way, but in one example the flow of titanium tetrachloride may be stopped and the plasma gas becomes only argon. Increasing the arc power to increase heat and radiation from the arc causes the titanium to heat up and crystallise.
  • the process of the present invention may be implemented on an industrial scale for the industrial production of titanium or selected titanium compounds.
  • a series of reaction vessels may be utilised in parallel similar to the reaction vessels described in figure 1.
  • a further preferred step in the method of the present invention would be to recirculate undissociated titanium tetrachloride (or whatever metal halide is being used as the starting product) back through the arc to increase yield.
  • Titanium or other metal which is produced may be continuously removed from the cooled surface.
  • There are a number of possibilities for achieving this including mechanically scrubbing and also shaking of the collection surface using an ultrasound transducer and other possibilities.
  • the above example and description relates to the production of titanium from titanium tetrachloride.
  • the present invention could be applied to produce titanium from other halides or compounds, and even to produce other metals from metal halides or other compounds and is not limited to the production of titanium.

Abstract

L'invention concerne un procédé et un appareil de production de titane. Actuellement, la production de titane est très coûteuse. Cette invention propose un procédé de production moins onéreux impliquant une réduction directe d'un halogénure de titane, par exemple du chlorure de titane, dans un arc plasma. En vue d'empêcher la recombinaison des produits réactifs, la réaction est déséquilibrée par refroidissement rapidement des produits réactifs, afin de précipiter le titane.
PCT/AU2002/000212 2001-02-28 2002-02-27 Procede et appareil de production de titane WO2002070759A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPR9546 2001-02-28
AUPR954601 2001-02-28

Publications (1)

Publication Number Publication Date
WO2002070759A1 true WO2002070759A1 (fr) 2002-09-12

Family

ID=3833161

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2002/000212 WO2002070759A1 (fr) 2001-02-28 2002-02-27 Procede et appareil de production de titane

Country Status (1)

Country Link
WO (1) WO2002070759A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019139777A1 (fr) * 2018-01-12 2019-07-18 General Electric Company Procédés de formation de particules métalliques sphériques
US11193185B2 (en) 2016-10-21 2021-12-07 General Electric Company Producing titanium alloy materials through reduction of titanium tetrachloride
US11478851B2 (en) 2016-10-21 2022-10-25 General Electric Company Producing titanium alloy materials through reduction of titanium tetrachloride

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5256930A (en) * 1992-02-10 1993-10-26 Commonwealth Scientific Corporation Cooled plasma source
US5478429A (en) * 1993-01-20 1995-12-26 Tokyo Electron Limited Plasma process apparatus
US5571366A (en) * 1993-10-20 1996-11-05 Tokyo Electron Limited Plasma processing apparatus
JPH10107012A (ja) * 1996-09-27 1998-04-24 Tokyo Electron Ltd プラズマ処理装置
US5749937A (en) * 1995-03-14 1998-05-12 Lockheed Idaho Technologies Company Fast quench reactor and method
US5879575A (en) * 1995-11-29 1999-03-09 Applied Materials, Inc. Self-cleaning plasma processing reactor
US5980688A (en) * 1994-06-02 1999-11-09 Micron Technology, Inc. Plasma reactors and method of cleaning a plasma reactor
JP2000100790A (ja) * 1998-09-22 2000-04-07 Canon Inc プラズマ処理装置及びそれを用いた処理方法
JP2000164580A (ja) * 1998-09-22 2000-06-16 Canon Inc プラズマ処理装置及びそれを用いた処理方法
US6079357A (en) * 1997-10-21 2000-06-27 Tokyo Electron Yamanashi Limited Plasma processing apparatus
US6149760A (en) * 1997-10-20 2000-11-21 Tokyo Electron Yamanashi Limited Plasma processing apparatus
US6177149B1 (en) * 1997-12-24 2001-01-23 Tokyo Electron Limited Method of forming titanium film by CVD
US6214162B1 (en) * 1996-09-27 2001-04-10 Tokyo Electron Limited Plasma processing apparatus
US6311638B1 (en) * 1999-02-10 2001-11-06 Tokyo Electron Limited Plasma processing method and apparatus
US6321681B1 (en) * 1997-10-10 2001-11-27 European Community (Ec) Method and apparatus to produce large inductive plasma for plasma processing
US6350497B1 (en) * 1997-09-24 2002-02-26 Canon Kabushiki Kaisha Plasma processing method

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5256930A (en) * 1992-02-10 1993-10-26 Commonwealth Scientific Corporation Cooled plasma source
US5478429A (en) * 1993-01-20 1995-12-26 Tokyo Electron Limited Plasma process apparatus
US5571366A (en) * 1993-10-20 1996-11-05 Tokyo Electron Limited Plasma processing apparatus
US5980688A (en) * 1994-06-02 1999-11-09 Micron Technology, Inc. Plasma reactors and method of cleaning a plasma reactor
US5749937A (en) * 1995-03-14 1998-05-12 Lockheed Idaho Technologies Company Fast quench reactor and method
US5879575A (en) * 1995-11-29 1999-03-09 Applied Materials, Inc. Self-cleaning plasma processing reactor
US5935373A (en) * 1996-09-27 1999-08-10 Tokyo Electron Limited Plasma processing apparatus
US6214162B1 (en) * 1996-09-27 2001-04-10 Tokyo Electron Limited Plasma processing apparatus
JPH10107012A (ja) * 1996-09-27 1998-04-24 Tokyo Electron Ltd プラズマ処理装置
US6350497B1 (en) * 1997-09-24 2002-02-26 Canon Kabushiki Kaisha Plasma processing method
US6321681B1 (en) * 1997-10-10 2001-11-27 European Community (Ec) Method and apparatus to produce large inductive plasma for plasma processing
US6149760A (en) * 1997-10-20 2000-11-21 Tokyo Electron Yamanashi Limited Plasma processing apparatus
US6079357A (en) * 1997-10-21 2000-06-27 Tokyo Electron Yamanashi Limited Plasma processing apparatus
US6177149B1 (en) * 1997-12-24 2001-01-23 Tokyo Electron Limited Method of forming titanium film by CVD
JP2000164580A (ja) * 1998-09-22 2000-06-16 Canon Inc プラズマ処理装置及びそれを用いた処理方法
JP2000100790A (ja) * 1998-09-22 2000-04-07 Canon Inc プラズマ処理装置及びそれを用いた処理方法
US6311638B1 (en) * 1999-02-10 2001-11-06 Tokyo Electron Limited Plasma processing method and apparatus

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ATKINS P.W.: "Physical chemistry", 1986, OXFORD UNIVERSITY PRESS *
DATABASE WPI Derwent World Patents Index; Class L03, AN 2000-342646/30 *
DATABASE WPI Derwent World Patents Index; Class L03, AN 2000-468483/41 *
DATABASE WPI Derwent World Patents Index; Class X14, AN 1998-303553/27 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11193185B2 (en) 2016-10-21 2021-12-07 General Electric Company Producing titanium alloy materials through reduction of titanium tetrachloride
US11478851B2 (en) 2016-10-21 2022-10-25 General Electric Company Producing titanium alloy materials through reduction of titanium tetrachloride
WO2019139777A1 (fr) * 2018-01-12 2019-07-18 General Electric Company Procédés de formation de particules métalliques sphériques

Similar Documents

Publication Publication Date Title
JP5427452B2 (ja) 金属チタンの製造方法
US3825415A (en) Method and apparatus for the production of liquid titanium from the reaction of vaporized titanium tetrachloride and a reducing metal
KR101148573B1 (ko) 금속 화합물의 제조를 위한 방법 및 장치
JP5702428B2 (ja) 金属チタン又はチタンベース合金を連続生成するための方法及び装置
EP1866449B1 (fr) Procédé de préparation du métal de tantalum or niobium primaire
JPS6330062B2 (fr)
CN1182456A (zh) 快速骤冷反应器和方法
WO1999061670A1 (fr) Cible de pulverisation cathodique de tantale et procede de fabrication de ladite cible
JPS6035417B2 (ja) 塩化物からの金属還元法
US6197082B1 (en) Refining of tantalum and tantalum scrap with carbon
WO2002070759A1 (fr) Procede et appareil de production de titane
US5648530A (en) Manufacture of carbonyl floride
JP2960652B2 (ja) 高純度金属の精製方法およびその精製装置
JPS6139372B2 (fr)
RU2401874C2 (ru) Способ волкова для производства химически активных металлов и устройство для его осуществления
JPH0925522A (ja) 高純度金属材料の製造方法
Peterson et al. The preparation of high-purity thorium by the magnesium reduction of thorium tetrachloride
RU2370558C1 (ru) Способ получения высокочистого кобальта для распыляемых мишеней
JP2784324B2 (ja) チタンの製造方法
RU2298588C2 (ru) Способ получения вещества, выбранного из ряда тугоплавких металлов или ряда неметаллов: кремний, бор, фосфор, мышьяк, сера
JP2016530986A (ja) ボーキサイトから、ボーキサイトの処理から生じた赤泥から、及び化学的に類似した物質から、工業的に重要な生成物を相互に分離して抽出する方法
RU2293060C2 (ru) Способ получения мононитрида урана и смеси мононитридов урана и плутония
RU2541244C1 (ru) Способ очистки висмута
JP3564852B2 (ja) 高純度金属ルテニウム粉末の製造方法
EP0591411B1 (fr) Recuperation de metal niobium

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 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 NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ 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 CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE 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
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

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