EP0723038B1 - Procédé et dispositif de régénération d'une solution usagée de décapage d'éléments en alliage de zirconium - Google Patents
Procédé et dispositif de régénération d'une solution usagée de décapage d'éléments en alliage de zirconium Download PDFInfo
- Publication number
- EP0723038B1 EP0723038B1 EP96400097A EP96400097A EP0723038B1 EP 0723038 B1 EP0723038 B1 EP 0723038B1 EP 96400097 A EP96400097 A EP 96400097A EP 96400097 A EP96400097 A EP 96400097A EP 0723038 B1 EP0723038 B1 EP 0723038B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- acid
- water
- pickling
- regenerated
- 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.)
- Expired - Lifetime
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/01—Waste acid containing iron
Definitions
- the invention relates to a regeneration method. of a used acid pickling solution used for pickling of elements in zirconium alloy.
- Fuel assemblies for nuclear reactors and in particular the fuel assemblies for pressurized water nuclear reactors are generally consisting of a bundle of fuel rods parallel to each other and held by a frame comprising in particular longitudinal guide tubes and transverse spacer grids.
- Fuel rods can be made by a zirconium alloy sheath in which pellets of combustible material are introduced.
- the frame guide tubes can be also made up of zirconium tubes.
- zirconium tubes from of drafts requires several successive passes of cold rolling which are each followed by a treatment thermal annealing.
- degreasing is carried out and a chemical pickling of the laminated tube.
- the chemical pickling of zirconium alloy tubes such as Zircaloy 4 is carried out using a solution of hydrofluoric acid HF containing a certain proportion of nitric acid HNO 3 serving as catalyst for the attack of zirconium by hydrofluoric acid, according to the chemical reaction Zr + 4HF ⁇ ZrF 4 + 2H 2 .
- the used pickling solution which is recovered in a storage tank after pickling mainly contains hydrofluoric acid, water and nitric acid as well as zirconium fluoride ZrF 4 formed during pickling.
- Zirconium alloy pickling baths containing pollutants can be treated to separate most of the water from the solution of pollutants which must be destroyed, in approved treatment centers.
- Zirconium alloy tube production units must therefore bear significant costs relating to separation and destruction polluting products in approved centers and the purchase of new acid to reconstitute the pickling solution.
- Transport of the used solution to the treatment center is also accompanied by risks which are those of road transport of Hazardous Material.
- a process for the regeneration of alloy pickling solutions zirconium can therefore have both economic advantages and ecologically.
- a device for processing solutions is described pickling plants containing sulfuric acid and sulphates ferrous.
- the device comprises first and second evaporators under vacuum arranged in series and a crystallizer as well as vapor condensers produced by evaporators.
- An acid solution obtained by separation at the outlet of the crystallizer is incorporated into the distillate obtained in one condensers, then the solution obtained is heated and then stored in a container of regenerated solution.
- the object of the invention is therefore to propose a regeneration process a used pickling solution consisting mainly of hydrofluoric acid, nitric acid and water, after use for pickling of elements in zirconium alloy, this process making it possible to limit the operating costs of production lines for alloy elements of zirconium, the release of pollutants into the environment and the risks associated with the transport of hazardous materials.
- the single figure is a block diagram showing the different successive operations implemented to perform the regeneration a used fluonitric acid solution, used for pickling tubes made of zirconium alloy.
- the usual pickling process consists in preparing a solution of new pickling, mixing in a container 3, hydrofluoric acid, nitric acid and water in sufficient quantity to obtain good pickling efficiency.
- the pickling solution is used in a pickling unit 4 in which the zirconium alloy tubes are brought into contact with the pickling solution.
- Destruction of fluonitric acid solutions used in an approved center has the disadvantage of increasing manufacturing line operating costs of zirconium alloy tubes, due to the cost of transportation and processing for the destruction of the used solution and the obligation to prepare in the storage tank 3 a fresh acid solution to from commercial products.
- the regeneration process according to the invention as shown inside frame 2 is implemented by carrying out a separation treatment on the solution of used pickling stored in the tank 5.
- the solution stored in tank 5 mainly contains water, hydrofluoric acid and nitric acid as well as zirconium fluoride ZrF4 resulting from the attack of the zirconium alloy tubes by hydrofluoric acid, catalyzed with nitric acid HNO 3 .
- the separation operations necessary for the regeneration of the pickling solution by the process according to the invention are carried out successively in a vacuum evaporator 7 and in a vacuum-crystallizer evaporator 8.
- ZIRCOTUBE used a vacuum evaporator marketed under the name WTSE 1000 by LED ITALIA and an evaporator WTSE 150 from the same company modified to withstand aggression by concentrated acids and to constitute a crystallizer.
- the vacuum evaporators used include an evaporation chamber in which a low pressure, for example of the order of 5260 Pa (40 mm of mercury).
- the solution to be treated in the evaporation chamber is introduced and maintained at a moderate temperature, for example of the order of 35 ° C.
- the heating of the solution to be treated is obtained through a heat pump.
- Reduced chamber pressure allows to separate at least one of the constituents of the solution which is being treated, in the form of a vapor, at a moderate temperature.
- the vacuum evaporator has a stage of condensation in which the condensation of the vapor separated from the solution to be treated.
- the vacuum evaporator 7 and the crystallizer evaporator 8 make it possible to obtain a distillate which is condensed in a condensing stage and a concentrate remaining in the evaporation chamber.
- the vacuum evaporator 7 which can be constituted by a WTSE 1000 evaporator from LED ITALIA allows evaporation and condensation of a much of the water in the pickling solution used which is introduced into the evaporation chamber evaporator 7, from the storage tank 5.
- the concentrated acid solution contains hydrofluoric acid HF, nitric acid HNO 3 , a small amount of water and a pollutant consisting of zirconium fluoride ZrF 4 originating from the acid attack of the tubes of zirconium alloy, during stripping.
- the concentrated acid solution could be partially or totally sent for destruction but, according to the method of the invention, it is preferred to carry out a second treatment of this concentrated solution in the crystallizer 8.
- the crystallizer 8 which can be a vacuum evaporator operating according to the same principle as the vacuum evaporator 7 comprises, inside its condensation chamber, a container coated with a material resistant to concentrated acids and making it possible to collect the pollutant ZrF 4 in the form of solid crystals.
- the crystallizer 8 preferably comprises a plastic coating to allow it to resist the action of acids in concentrated form.
- the purified concentrated acid solution recovered in the condensing stage of the crystallizer 8 contains substantially all of the nitric acid from the initial pickling solution, because the acid nitric only plays a catalytic role during pickling of the zirconium alloy.
- the purified concentrated acid obtained at the outlet of the condensing stage of the crystallizer 8 is mixed with the slightly acidic water obtained at the outlet of the condensing stage of the vacuum evaporator 7, to obtain a regenerated pickling solution which can be returned to the solution storage tank 3 pickling.
- the title of the pickling solution is set at level of a processing unit 9 in which we do penetrate the mixture of concentrated acid and water supplied in outlet of the crystallizer 8 and the evaporator 7.
- the discount under the solution can be made for example by reintroducing pure water or the new acid in the mixture, at the unit of treatment 9.
- the title of the pickling solution is checked by a measurement unit 10 arranged on the recycling line 11 of the pickling solution regenerated inside storage tank 3.
- the regenerated acid reaching the reservoir storage 3 is rid of the pollutants formed when pickling zirconium alloy tubes.
- the regeneration treatment according to the invention allows to recover hydrofluoric acid from the solution pickling and almost all of the acid of the fluonitric mixture. This avoids the use large quantities of expensive new materials.
- the ZrF 4 crystals constituting a dry extract in the crystallizer can be easily extracted, because they are soluble in water.
- Pure water is therefore introduced into the crystallizer, which makes it possible to dissolve the ZrF 4 crystals.
- the liquid obtained is removed, so as to empty the crystallizer.
- An acid solution of ZrF4 is obtained in which the ZrF 4 can precipitate as soon as the pH of the solution reaches a value of approximately 5. It is therefore possible to recover the ZrF 4 from the aqueous solution, by neutralizing this solution.
- ZrF 4 zirconium fluoride obtained as a by-product in the regeneration process can be used as a base product in some manufacturing.
- the ZrF 4 produced by the regeneration process according to the invention can be separated from the aqueous solution on a filter such as a filter press and conditioned, by example, for its disposal in an underground storage center.
- the method according to the invention makes it possible to limit operating costs of element production units zirconium alloy such as tubes cladding and to avoid the transport of pickling solutions used containing pollutants and treatment expensive of these solutions used in specialized treatment.
- the invention is not limited to the embodiment that has been described.
- the invention applies to the regeneration of any fluonitric acid solution used for pickling elements made of zirconium alloy.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- ing And Chemical Polishing (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Description
- on évapore sous vide puis on condense une partie de l'eau contenue dans la solution usagée de manière à obtenir de l'eau légèrement acide et une solution acide concentrée polluée par du fluorure de zirconium ZrF4, représentant à peu près 30 % en volume de la solution usagée,
- on traite par évaporation sous vide dans un cristalliseur, la solution acide concentrée polluée, de manière à obtenir des cristaux de fluorure de zirconium ZrF4, et une solution acide concentrée épurée, et
- on mélange l'eau légèrement acide et la solution acide concentrée épurée en proportions voulues pour obtenir une solution de décapage régénérée.
Claims (5)
- Procédé de régénération d'une solution de décapage usagée constituée principalement par de l'acide fluorhydrique, de l'acide nitrique et de l'eau, après une utilisation pour le décapage d'éléments en alliage de zirconium, caractérisé par le fait :qu'on évapore sous vide puis qu'on condense une partie de l'eau contenue dans la solution usagée de manière à obtenir de l'eau légèrement acide et une solution acide concentrée polluée par du fluorure de zirconium ZrF4, représentant à peu près 30 % en volume de la solution usagée,qu'on traite par évaporation sous vide dans un cristalliseur (8),la solution acide concentrée polluée, de manière à obtenir des cristaux de zirconium ZrF4 et une solution acide concentrée épurée, etqu'on mélange l'eau légèrement acide et la solution acide concentrée épurée en proportion voulue pour obtenir une solution de décapage régénérée.
- Procédé suivant la revendication 1, caractérisé par le fait qu'on réalise une remise au titre de la solution régénérée obtenue par mélange de l'eau et de la solution acide concentrée épurée, avant sa réutilisation pour le décapage.
- Procédé suivant l'une quelconque des revendications 1 et 2,caractérisé par le fait qu'on effectue la dissolution par de l'eau des cristaux de fluorure de zirconium ZrF4 obtenus dans le cristalliseur (8) pour les évacuer du cristalliseur (8).
- Procédé suivant l'une quelconque des revendications 1 à 3, caractérisé par le fait que l'évaporation sous vide de l'eau contenue dans la solution usagée et de la solution acide concentrée polluée dans le cristalliseur (8) est réalisée sous une pression résiduelle de l'ordre de 5260 Pa (40 mm de mercure).
- Dispositif de régénération d'une solution de décapage usagée constituée principalement par de l'acide fluorhydrique, de l'acide nitrique et de l'eau, après une utilisation pour le décapage d'éléments en alliage de zirconium, comportant :un évaporateur sous vide (7), et un évaporateur sous vide cristalliseur (8) disposés en série, de manière que l'évaporateur sous vide cristalliseur (8) recueille le concentrat de l'évaporateur sous vide (7), l'évaporateur sous vide (7) et l'évaporateur cristalliseur (8) comprenant chacun un étage de condensation de distillat,des moyens de réalisation d'un mélange dosé des distillats produits dans l'évaporateur sous vide (7) et dans l'évaporateur cristalliseur (8),une unité de mélange et de remise au titre (9) de la solution de décapage régénérée,une ligne (11) de recyclage de la solution de décapage régénérée dans un réservoir de stockage de solution de décapage (3), et placé sur la ligne de recyclage (11) de la solution de décapage régénérée, un dispositif de mesure (10) du titre de la solution régénérée.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9500783A FR2729676B1 (fr) | 1995-01-24 | 1995-01-24 | Procede et dispositif de regeneration d'une solution usagee de decapage d'elements en alliage de zirconium |
FR9500783 | 1995-01-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0723038A1 EP0723038A1 (fr) | 1996-07-24 |
EP0723038B1 true EP0723038B1 (fr) | 2000-04-12 |
Family
ID=9475436
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96400097A Expired - Lifetime EP0723038B1 (fr) | 1995-01-24 | 1996-01-15 | Procédé et dispositif de régénération d'une solution usagée de décapage d'éléments en alliage de zirconium |
Country Status (5)
Country | Link |
---|---|
US (1) | US5788935A (fr) |
EP (1) | EP0723038B1 (fr) |
DE (1) | DE69607660T2 (fr) |
ES (1) | ES2145390T3 (fr) |
FR (1) | FR2729676B1 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6885845B1 (en) * | 1993-04-05 | 2005-04-26 | Ambit Corp. | Personal communication device connectivity arrangement |
FR2874220B1 (fr) * | 2004-08-10 | 2007-07-06 | Snecma Moteurs Sa | Procede de regeneration des acides d'usinage chimique, installation pour la mise en oeuvre du procede et procede d'usinage chimique associe. |
US7988946B2 (en) | 2005-06-30 | 2011-08-02 | Compagnie Europeenne Du Zirconium-Cezus | Method for recycling zirconium tetrafluoride into zirconia |
FR2887868B1 (fr) * | 2005-06-30 | 2007-08-17 | Cie Europ Du Zirconium Cezus S | Procede de recyclage de tetrafluorure de zirconium en zircone |
CN103241784A (zh) * | 2012-02-14 | 2013-08-14 | 库特勒自动化***(苏州)有限公司 | 太阳能电池刻蚀废物体系的处理方法及处理装置 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2993757A (en) * | 1958-07-07 | 1961-07-25 | Crucible Steel Co America | Process for recovering acid values from mixed acid waste |
US3540513A (en) * | 1968-10-14 | 1970-11-17 | Daido Chem Eng Corp | Apparatus for treating a pickling waste |
AT335251B (de) * | 1975-03-10 | 1977-03-10 | Ruthner Industrieanlagen Ag | Verfahren und vorrichtung zur wiedergewinnung von salpetersaure und flusssaure aus losungen |
FI58519C (fi) * | 1978-12-07 | 1981-02-10 | Rosenlew Ab Oy W | Foerfarande foer regenerering av betningssyror |
DE3009265A1 (de) * | 1980-03-11 | 1981-09-24 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zum regenerieren von zrf (pfeil abwaerts)4(pfeil abwaerts) enthaltenden beizloesungen |
AT374508B (de) * | 1982-07-01 | 1984-05-10 | Ruthner Industrieanlagen Ag | Verfahren zur aufarbeitung verbrauchter beizoder aetzloesungen auf der basis von salpeter-flussaeure |
US4572824A (en) * | 1984-11-01 | 1986-02-25 | General Electric Company | Process for recovery of zirconium and acid from spent etching solutions |
EP0331231B1 (fr) * | 1988-02-24 | 1991-10-16 | Metallgesellschaft Ag | Procédé pour régénérer des solutions de décapage contenant du ZrF4 |
FR2659956B1 (fr) * | 1990-03-21 | 1992-06-26 | Cogema | Procede de traitement d'une solution aqueuse contenant principalement de l'acide nitrique et de l'acide fluorhydrique. |
US5076884A (en) * | 1990-07-19 | 1991-12-31 | Westinghouse Electric Corp. | Process of precipitating zirconium or hafnium from spent pickling solutions |
-
1995
- 1995-01-24 FR FR9500783A patent/FR2729676B1/fr not_active Expired - Fee Related
-
1996
- 1996-01-15 DE DE69607660T patent/DE69607660T2/de not_active Expired - Fee Related
- 1996-01-15 ES ES96400097T patent/ES2145390T3/es not_active Expired - Lifetime
- 1996-01-15 EP EP96400097A patent/EP0723038B1/fr not_active Expired - Lifetime
- 1996-01-24 US US08/590,864 patent/US5788935A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE69607660D1 (de) | 2000-05-18 |
DE69607660T2 (de) | 2000-12-28 |
US5788935A (en) | 1998-08-04 |
FR2729676B1 (fr) | 1997-04-11 |
ES2145390T3 (es) | 2000-07-01 |
EP0723038A1 (fr) | 1996-07-24 |
FR2729676A1 (fr) | 1996-07-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101367507B (zh) | 废硫酸脱除气体过滤提浓方法 | |
CN207986863U (zh) | 一种废酸资源化利用处理*** | |
CA2062493C (fr) | Procede de traitement de gaz a base de fluor electrolytique et pouvant contenir des composes uraniferes | |
US6677482B2 (en) | Method of manufacturing (meth) acrylic acid | |
EP0723038B1 (fr) | Procédé et dispositif de régénération d'une solution usagée de décapage d'éléments en alliage de zirconium | |
CN101767847A (zh) | 一种基于膜技术的酸废液的纯化回收方法 | |
EP0145517B1 (fr) | Procédé de traitement d'un courant gazeux contenant des oxydes d'azote | |
EP1018500B1 (fr) | Procédé pour l'isolation de glycols | |
FR2515855A1 (fr) | Procede pour la decontamination de la surface radio-activement contaminee de matieres metalliques | |
EP0967003B1 (fr) | Procédé et système pour le traitement des gaz d'échappement | |
CH672321A5 (fr) | ||
CN110294462A (zh) | 一种含有重金属、氟化物及氯化物的废酸处理装置及方法 | |
EP0360866A1 (fr) | Procede et installation de nettoyage de pieces | |
CA2225798C (fr) | Procede de purification par extraction d'un milieu liquide | |
WO2007003769A1 (fr) | Procede de recyclage de tetrafluorure de zirconium en zircone | |
EP2427407B1 (fr) | Procédé de récupération et de recyclage d'ammoniac | |
CN208577599U (zh) | 一种处理高盐高cod废水的*** | |
CN105859004A (zh) | 一种含汞废盐酸液处理***及方法 | |
US20040050716A1 (en) | Electrochemical oxidation of matter | |
FR2795064A1 (fr) | Procede pour recueillir du brome | |
CN202201854U (zh) | 一种聚醚多元醇生产过程中废水再利用*** | |
WO1995032155A1 (fr) | Procede de valorisation d'un effluent liquide acide contenant des metaux lourds | |
FR2530856A1 (fr) | Procede de concentration des solutions residuaires de centrales nucleaires | |
FR2524338A1 (fr) | Dispositif pour realiser notamment des economies d'energie dans la recuperation des charbons actifs contenant des solvants adsorbes | |
FR2721919A1 (fr) | Procede et installation de recuperation du brome dans un effluent liquide |
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 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE CH DE ES FR GB LI SE |
|
17P | Request for examination filed |
Effective date: 19970111 |
|
17Q | First examination report despatched |
Effective date: 19980902 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE ES FR GB LI SE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 69607660 Country of ref document: DE Date of ref document: 20000518 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20000519 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2145390 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Free format text: ZIRCOTUBE TRANSFER- COMPAGNIE EUROPEENNE DU ZIRCONIUM-CEZUS Ref country code: CH Ref legal event code: NV Representative=s name: KIRKER & CIE SA |
|
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 |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20021216 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030107 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030108 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20030213 Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040115 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20040119 Year of fee payment: 9 |
|
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: 20040131 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040131 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040131 |
|
BERE | Be: lapsed |
Owner name: *CEZUS CIE EUROPEENNE DU ZIRCONIUM Effective date: 20040131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040803 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040115 |
|
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: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050117 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20050117 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20141211 Year of fee payment: 20 Ref country code: SE Payment date: 20150121 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |