[go: up one dir, main page]

EP1920087A1 - Reduction electrochimique d'oxydes metalliques - Google Patents

Reduction electrochimique d'oxydes metalliques

Info

Publication number
EP1920087A1
EP1920087A1 EP06760944A EP06760944A EP1920087A1 EP 1920087 A1 EP1920087 A1 EP 1920087A1 EP 06760944 A EP06760944 A EP 06760944A EP 06760944 A EP06760944 A EP 06760944A EP 1920087 A1 EP1920087 A1 EP 1920087A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
cao
concentration
titanium oxide
controlling
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.)
Granted
Application number
EP06760944A
Other languages
German (de)
English (en)
Other versions
EP1920087B1 (fr
EP1920087A4 (fr
Inventor
Ivan Ratchev
Rene Ignacio Olivares
Sergey Alexander Bliznyukov
Kannapar Mukunthan
Gregory David Rigby
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.)
Metalysis Ltd
Original Assignee
BHP Billiton Innovation Pty 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
Priority claimed from AU2005904121A external-priority patent/AU2005904121A0/en
Application filed by BHP Billiton Innovation Pty Ltd filed Critical BHP Billiton Innovation Pty Ltd
Publication of EP1920087A1 publication Critical patent/EP1920087A1/fr
Publication of EP1920087A4 publication Critical patent/EP1920087A4/fr
Application granted granted Critical
Publication of EP1920087B1 publication Critical patent/EP1920087B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/14—Refining in the solid state
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts

Definitions

  • the present invention relates to electrochemical reduction of metal oxides .
  • the present invention relates particularly, although by no means exclusively, to electrochemical reduction of metal oxides in the form of powders and/or pellets in an electrolytic cell containing a molten electrolyte to produce reduced material, namely metal having a low oxygen concentration, typically no more than 0.2% by weight.
  • the present invention is concerned with controlling electrochemical reduction of metal oxides.
  • the present invention applies to situations in which the process is carried out on a batch basis, a continuous basis, and a semi-continuous basis.
  • the present invention was made during the course of a research project on electrochemical reduction of metal oxides carried out by the applicant.
  • the research project focussed on the reduction of titania (TiO 2 ) .
  • the CaCl 2 -based electrolyte used in the experiments was a commercially available source of CaCl 2 , _ o —
  • the applicant operated the electrolytic cells at a potential above the decomposition potential of CaO and below the decomposition potential of CaCl 2 .
  • the applicant operated the laboratory electrolytic cells under a wide range of different operating parameters and conditions.
  • the applicant operated the laboratory electrolytic cells on a batch basis with titania in the form of pellets and larger solid blocks in the early part of the laboratory work and titania powder in the later part of the work.
  • the applicant also operated the laboratory electrolytic cells on a batch basis with other metal oxides.
  • Recent pilot plant work carried out by the applicant was carried out on a pilot plant electrolytic cell that was set up to operate initially on a continuous basis and subsequently on a batch basis.
  • the concentration of CaO in the electrolyte should be controlled by maintaining the concentration above a minimum CaO concentration and below a maximum CaO concentration in order to optimise operation of the process .
  • CaO and titania react spontaneously and form perovskite (CaTiO 3 ) .
  • the amount of CaO may decrease substantially as a consequence of the perovskite reaction.
  • An important physical characteristic is the surface area of titania in contact with electrolyte, particularly when this characteristic is considered in the context of a given mass of the electrolyte and a given mass of the titania.
  • the titania surface area for a given mass of titania is dependent on physical characteristics of the titania, such as powder/pellet shape and porosity.
  • the applicant also believes that the above- mentioned significance of the CaO concentration in a CaCl 2 - based electrolyte also applies to other alkali earth metal oxides , alkali metal oxides , and yttrium oxides . Specifically, the applicant believes that where one or more than one of the metal oxides is present in a CaCl 2 - based electrolyte, controlling the concentrations of the metal oxides within ranges is a means of optimising operation of an electrochemical reduction process for titanium oxide in a solid state in the electrolyte.
  • the metal oxides may be present as an impurity or impurites in the feed material used to produce the CaCl 2 - based electrolyte and/or by way of specific addition to the electrolyte.
  • a process for electrochemically reducing a titanium oxide in a solid state in an electrolytic cell that includes an anode, a cathode, a molten CaCl 2 -based electrolyte containing CaO, and titanium oxide feed material in contact with the molten electrolyte, which electrochemical process includes applying an electrical potential across the anode and the cathode and electrochemically reducing titanium oxide feed material in contact with the molten electrolyte and producing reduced material, and which process is characterised by controlling the process by controlling the concentration of CaO in the electrolyte.
  • the process includes controlling the concentration of CaO in the electrolyte by maintaining the concentration of CaO in the electrolyte between lower and upper concentration limits .
  • the maximum CaO concentration in the electrolyte is 0.5 wt . % .
  • the maximum CaO concentration in the electrolyte is 0.3 wt.%.
  • the minimum CaO concentration in the electrolyte is 0.005 wt.%.
  • the minimum CaO concentration in the electrolyte is 0.05 wt.%.
  • the minimum CaO concentration in the electrolyte is 0.1 wt.%.
  • the CaO concentration in the electrolyte is in the range of 0.1-0.3 wt.%.
  • the CaO concentration in the electrolyte is in the range of 0.15-0.25 wt.%.
  • the process includes controlling the concentration of CaO in the electrolyte by reference to the surface area of contact of the titanium oxide with the electrolyte .
  • the process includes controlling the concentration of CaO in the electrolyte by reference to the surface area of contact of the titanium oxide with the electrolyte when considered in the context of the mass of the electrolyte and the mass of the titanium oxide.
  • One practical option for controlling the CaO concentration in the electrolyte is to control the mass ratio of the electrolyte and the titanium oxide in the cell .
  • the process includes controlling the mass ratio of the electrolyte and titanium oxide in the cell to be at least 10:1 in situations where the initial CaO concentration is below 0.3, more preferably below 0.2 wt . % in the electrolyte and the titanium oxide is in a form of pellets and/or powders having a specific surface area of 0.1 to 100 m 2 /g of titanium oxide.
  • the process may include controlling the CaO concentration in the electrolyte by adding CaO to the electrolyte during the course of the process.
  • the process may include controlling the CaO concentration in the electrolyte by selecting an initial CaO concentration that is sufficiently high.
  • the electrochemical process may be carried out on any one of a batch basis, a semi-continuous basis, or a continuous basis .
  • the titanium oxide feed material is in a powder and/or a pellet form.
  • the titanium oxide feed material is titania .
  • the electrochemical reduction process includes applying a potential across the anode and the cathode that is above the decomposition potential of CaO and below the decomposition of CaCl2 •
  • the electrochemical reduction process may be carried out as a single stage or a multi-stage process .
  • a process for electrochemically reducing a titanium oxide in a solid state in an electrolytic cell that includes (a) an anode, (b) a cathode, (c) a molten CaCl 2 -based electrolyte containing any one or more than one metal oxide selected from the group including alkali earth metal oxides , alkali metal oxides, and yttrium oxides, and (d) a titanium oxide feed material in contact with the molten electrolyte, which electrochemical process includes applying an electrical potential across the anode and the cathode and electrochemically reducing titanium oxide feed material in contact with the molten electrolyte and producing reduced material, and which process is characterised by controlling the process by controlling the concentration of the selected metal oxide or metal oxides in the electrolyte .
  • the selected metal oxide is CaO.
  • the cell comprised a reaction vessel, a furnace, a crucible assembly, an electrode assembly, and a power supply.
  • the reaction vessel was manufactured from a high temperature stainless steel and had an internal diameter of 110mm and height of 430mm, and a water-cooled flange.
  • the vessel was contained within a resistance- heated furnace capable of reaching 1400 0 K.
  • a positioning pedestal within the vessel allowed for the crucible containing the molten salt to be properly fixed within the vessel .
  • a water-cooled lid was a critical feature of the reaction vessel and had provision for a viewing port which facilitated accurate positioning of the electrodes and the thermocouple within the molten salt bath.
  • the viewing port also allowed the surface of the molten salt to be monitored during the reaction.
  • Carbon monoxide and carbon dioxide are the main by-products of the electrochemical reduction process .
  • special care was taken in controlling the gas atmosphere .
  • a measured flow of high purity argon gas was passed through a furnace containing copper turnings at 873°K, then through a furnace containing magnesium flakes at 673 0 K before entering the vessel . After passing through the vessel, the gas stream was stripped of any chlorine- containing species and moisture and continuously analysed for CO and CO 2 .
  • a solid electrolyte based oxygen analyser monitored the partial pressure of O 2 in the off-gas immediately after the furnace.
  • the chemistry of the molten electrolyte was found to have a significant impact on the process operation. Consequently, the applicant ensured that the composition of the electrolyte at the start of a run was well controlled.
  • the electrolyte was prepared from analytical grade dihydrate, CaCl 2 .H 2 O obtained from AFS Chemicals. Typically, 68Og of molten salt were used in the experiments. Prior to melting, a dehydration step was carried out as follows .
  • the CaCl 2 .H 2 O was slowly heated under vacuum to 525K and kept at this temperature for at least 12 hours during which time the weight loss due to water removal was monitored. Once there was no more weight loss, the anhydrous salt was transferred from the vacuum oven into a platinum crucible and placed in a melting furnace . The salt was melted at 1275 0 K and kept at this temperature for 30 minutes to allow further removal of any residual water. The molten salt was then cast into a preheated steel mould, removed once solid, and transferred while hot to a drying oven held at 400K.
  • the titania pellets were prepared from 99.5% minimum purity rutile (Alfa Aesar) although occasionally other titania sources were used.
  • the titania pellets were prepared so that control of the total porosity and pore size was exercised by sintering at a predetermined temperature.
  • the concentration of CaO in the electrolyte was systematically increased up to 2.5 wt. %.
  • Figure 1 is a plot of cell current (in Amps) versus time (on seconds) for each of the above-mentioned experiments .
  • the Figure shows that there was a decrease in cell current over time with each of the CaO concentrations in the electrolyte.
  • the Figure also shows that the cell passed more current with increased concentrations of CaO in the electrolyte. This finding. Of itself, does not indicate that there was increased duction of titania at increased CaO concentrations .
  • Figure 2 is a plot of the concentration of oxygen in titanium in the reduced pellets versus the CaO concentration in the electrolyte at the end of the experimental runs of 4 hours .
  • the Figure shows that reduction of titania to titanium was inhibited as the concentration of CaO in the electrolyte increased.
  • the Figure shows that there were higher concentrations of oxygen in the titanium produced in the cell as the CaO concentrations in the electrolyte increased.
  • the Figure shows that the rate of reduction decreased as the concentration of CaO in the electrolyte increased.
  • Figures 1 and 2 indicate that significantly higher current consumption was required to achiev lower levels of reduction of titania at increased CaO concentrations.
  • operating at CaO concentrations of 0.5 wt.% or less produced high levels of reduction - to less than about 0.5 wt.% oxygen - with reasonable current consumption
  • Figure 3 is a plot of the amount of carbon removed from the anode in grams and the overall current efficiency versus the CaO concentration in the electrolyte at the end of the experimental runs of 4 hours .
  • the Figure shows that the amounts of electricity and carbon consumed in the process were proportionally higher as the concentration of CaO in the electrolyte increased.
  • the Figure shows that the current efficiency decreased as the concentration of CaO in the electrolyte increased.

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 Metals (AREA)

Abstract

L'invention concerne un processus de réduction électrochimique d'un oxyde de titane à l'état solide dans une cellule électrolytique qui contient une anode, une cathode, un électrolyte fondu à base de CaCl<SUB>2</SUB> et à teneur en CaO ainsi qu'une substance de base d'oxyde de titane en contact avec l'électrolyte fondu. Ce processus est caractérisé en ce que la régulation dudit processus s'effectue par une régulation de la concentration de CaO dans l'électrolyte.
EP06760944.6A 2005-08-01 2006-08-01 Reduction electrochimique d'oxyde de titane Active EP1920087B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2005904121A AU2005904121A0 (en) 2005-08-01 Electrochemical reduction of metal oxides
PCT/AU2006/001088 WO2007014422A1 (fr) 2005-08-01 2006-08-01 Reduction electrochimique d'oxydes metalliques

Publications (3)

Publication Number Publication Date
EP1920087A1 true EP1920087A1 (fr) 2008-05-14
EP1920087A4 EP1920087A4 (fr) 2011-07-27
EP1920087B1 EP1920087B1 (fr) 2017-03-22

Family

ID=37708485

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06760944.6A Active EP1920087B1 (fr) 2005-08-01 2006-08-01 Reduction electrochimique d'oxyde de titane

Country Status (3)

Country Link
EP (1) EP1920087B1 (fr)
EA (1) EA014138B1 (fr)
WO (1) WO2007014422A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007149508A2 (fr) 2006-06-19 2007-12-27 The University Of The Sciences In Philadelphia Antagonistes non compétitifs du récepteur nmda
GB201208698D0 (en) * 2012-05-16 2012-06-27 Metalysis Ltd Electrolytic method,apparatus and product
CN106947874B (zh) * 2017-04-18 2018-11-27 北京科技大学 一种两步法制备高纯钛的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPR602901A0 (en) * 2001-06-29 2001-07-26 Bhp Innovation Pty Ltd Removal of oxygen from metals oxides and solid metal solutions
JP2003129268A (ja) * 2001-10-17 2003-05-08 Katsutoshi Ono 金属チタンの精錬方法及び精錬装置
AUPS117002A0 (en) * 2002-03-13 2002-04-18 Bhp Billiton Innovation Pty Ltd Minimising carbon transfer in an electrolytic cell
AUPS107102A0 (en) * 2002-03-13 2002-04-11 Bhp Billiton Innovation Pty Ltd Electrolytic reduction of metal oxides
NZ531467A (en) * 2002-03-13 2007-06-29 Bhp Billiton Innovation Pty Reduction of metal oxides in an electrolytic cell operating above the threshold potential
AU2002952083A0 (en) * 2002-10-16 2002-10-31 Bhp Billiton Innovation Pty Ltd Minimising carbon transfer in an electrolytic cell
JP2004360025A (ja) * 2003-06-05 2004-12-24 Sumitomo Titanium Corp 直接電解法による金属チタンの製造方法

Also Published As

Publication number Publication date
EP1920087B1 (fr) 2017-03-22
EP1920087A4 (fr) 2011-07-27
EA200800526A1 (ru) 2008-08-29
WO2007014422A1 (fr) 2007-02-08
EA014138B1 (ru) 2010-10-29

Similar Documents

Publication Publication Date Title
CA2334237C (fr) Elimination d&#39;oxygene d&#39;oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
Fray et al. Reduction of titanium and other metal oxides using electrodeoxidation
Kilby et al. Current efficiency studies for graphite and SnO2-based anodes for the electro-deoxidation of metal oxides
CN1296520C (zh) 金属钛的炼制方法及炼制装置
KR101370007B1 (ko) 금속 제조를 위한 열적 및 전기화학적 방법
US20200095696A1 (en) Method and apparatus for electrolytic reduction of a feedstock comprising oxygen and a first metal
US20160194773A1 (en) Method and apparatus for producing metal by electrolytic reduction
US20060191799A1 (en) Electrochemical reduction of metal oxides
CA2535978A1 (fr) Procede thermique et electrochimique de production de metaux
MXPA04008887A (es) Reduccion de oxidos de metal en una celda electrolitica.
EP1581672B1 (fr) Reduction electrochimique d&#39;oxydes metalliques
EP3918113B1 (fr) Procédé de production d&#39;aluminium
Chen et al. Preparation of TiC/SiC composites from Ti-enriched slag by an electrochemical process in molten salts
EP1920087B1 (fr) Reduction electrochimique d&#39;oxyde de titane
KR101185836B1 (ko) 금속산화물로부터 금속을 제조하기 위한 전해환원공정
EP1789609A1 (fr) Reduction electrochimique d&#39;oxydes metalliques
AU2006275304B2 (en) Electrochemical reduction of metal oxides
JP4198434B2 (ja) 金属チタンの製錬方法
WO2010040231A1 (fr) Procédé d&#39;introduction de bore dans des anodes pour la production d&#39;aluminium
WO2008101290A1 (fr) Réduction électrochimique d&#39;oxydes métalliques
Zhao et al. Electrochemical evaluation of titanium production from porous Ti2O3 in LiCl-KCl-Li2O eutectic melt
ZA200407433B (en) Minimising carbon transfer in an electrolytic cell.
JP2004360025A (ja) 直接電解法による金属チタンの製造方法
AU2003286000B2 (en) Electrochemical reduction of metal oxides
WO2006084318A1 (fr) Injection d&#39;un electrolyte solide dans une cellule electrolytique

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080303

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: METALYSIS LIMITED

A4 Supplementary search report drawn up and despatched

Effective date: 20110629

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602006052044

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C25C0005000000

Ipc: C25C0005040000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C25C 5/04 20060101AFI20160829BHEP

Ipc: C25C 3/28 20060101ALI20160829BHEP

INTG Intention to grant announced

Effective date: 20161006

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 877870

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170415

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006052044

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170623

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 877870

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170322

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170622

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170722

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170724

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006052044

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

26N No opposition filed

Effective date: 20180102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170831

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170801

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170831

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NO

Payment date: 20180913

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20060801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190801

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20210812 AND 20210818

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230523

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250120

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250122

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20250128

Year of fee payment: 19

Ref country code: GB

Payment date: 20250120

Year of fee payment: 19