WO2000028553A2 - Verfahren zum entsorgen von metallkationen - Google Patents
Verfahren zum entsorgen von metallkationen Download PDFInfo
- Publication number
- WO2000028553A2 WO2000028553A2 PCT/DE1999/003405 DE9903405W WO0028553A2 WO 2000028553 A2 WO2000028553 A2 WO 2000028553A2 DE 9903405 W DE9903405 W DE 9903405W WO 0028553 A2 WO0028553 A2 WO 0028553A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- metal cations
- exchange resin
- cations
- organic compound
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 150000001768 cations Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- 229910052742 iron Inorganic materials 0.000 claims description 24
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003729 cation exchange resin Substances 0.000 claims description 19
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229940081066 picolinic acid Drugs 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 230000005855 radiation Effects 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000003588 decontaminative effect Effects 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Definitions
- the invention relates to a method for disposing of metal cations by binding to a cation exchange resin.
- metal cations are produced which have to be disposed of. These cations, which are often cations of dissolved corrosion products, are continuously bound to ion exchange resins. However, cations can also be involved, which can be traced back to protective layers that are no longer required. Such protective layers are necessary in order to avoid a base metal attack during decontamination. The cations can also be radioactive.
- a cleaning method which is used in particular for the decontamination of the surface of a metallic component, is known from DE 41 17 625 C2.
- this method provides that metal cations are bound to cation exchange resin from a solution in order to regenerate cleaning chemicals.
- iron-III is reduced to iron-II, since iron-III cannot be completely removed from the solution. So the only thing that matters is to regenerate the cleaning chemicals.
- the invention is based on the object of specifying a method for disposing of metal cations which requires significantly less cation exchange resin than was previously the case.
- the capacity of the cation exchange resin should therefore be improved so that less loaded cation exchange resin is obtained than before, which is to be disposed of as waste.
- the object is achieved according to the invention in that the valency of the metal forming the metal cations on the lowest possible value is reduced, and that the metal cations, the metal of which has the lowest possible valence, are bound to the cation exchange resin.
- the invention is based on the finding that more metal cations can be bound on the same amount of cation exchange resin if the valence of the metal of the metal cations is smaller. This has the advantage that less cation exchange resin can be used to bind the same amount of metal cations, provided that the value of the metal is reduced to the lowest possible value, as provided for by the method according to the invention. Since less loaded cation exchange resin is obtained, less final storage capacity for the resins is advantageously required.
- the value of the metal is reduced, for example, by reducing the metal cations in a solution. Such a chemical process is relatively easy to carry out.
- an organic compound is added to the solution and the solution is then irradiated with UV light.
- Particularly suitable organic compounds are ethylenediaminetetraacetic acid (EDTA) or picolinic acid. A mixture of these acids can also be used.
- the method can be modified so that the organic compound is formed again with the binding of the metal cations to the cation exchange resin and can be reused in a cycle. This has the particular advantage that the organic compound, for example EDTA, does not have to be replenished continuously. You get by with a relatively small amount of organic compound.
- the metal of the metal cations is, for example, iron, nickel and / or chromium.
- the metal is iron, which is initially at least partially trivalent. The trivalent iron is then converted into divalent iron.
- iron In oxidic layers that are to be removed, besides divalent nickel and trivalent chromium, iron often has two stable values, namely two and three. Iron is the main component of such layers.
- the proportion of trivalent iron in a layer of oxides can be greater than 90% depending on the type of nuclear facility to be decontaminated. This means that simply converting trivalent iron into divalent iron reduces the amount of waste to be disposed of by around 30%. Consequently, 30% cation exchange resin is advantageously saved, so that one can manage with a significantly lower repository volume.
- the method according to the invention has the particular advantage that less cation exchange resin has to be disposed of, but that the cations formed are also more firmly bound to the resin due to the lower valency of the metals, which means that a breakdown of the cation exchange resin becomes less likely. It follows that the slip of cations by the cation exchanger is also reduced. Finally, the cleaning time for a plant, which is also the time span for the Removing cations from a used solution involves significantly shortening. The downtime of a plant, which is in particular a nuclear plant, for the purpose of decontamination is advantageously shorter than before.
- Oxides of trivalent iron can be part of a layer carrying the contamination or a protective layer in a nuclear facility.
- such an oxide of trivalent iron is formed by means of an organic compound, for example by means of EDTA, into an organic compound of trivalent iron which is present in aqueous solution.
- aqueous solution an organic compound of trivalent iron which is present in aqueous solution.
- the solution of the organic compound of trivalent iron is irradiated with UV light. This creates a solution of an organic compound of divalent iron and carbon dioxide, which is released. UV radiation to reduce iron can be found in EP 0 753 196 B1.
- a third step the now existing solution of an organic compound of divalent iron is passed over a cation exchange resin.
- the cations of divalent iron are bound there.
- the organic compound for example EDTA, which was used in the first step.
- the organic compound formed in the third step can be reused for the first step if further oxides of trivalent iron are to be removed.
- all trivalent iron oxides are removed, a small amount of the organic compound remains. This can be destroyed using known methods, for example using the method of EP 0 527 416 B1.
- water, carbon dioxide and a much smaller amount of cation exchange resin remain than known processes, which only contain cations of the divalent iron.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Physical Water Treatments (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002350206A CA2350206A1 (en) | 1998-11-10 | 1999-10-25 | Method for disposing of metal cations |
KR1020017005902A KR20010080404A (ko) | 1998-11-10 | 1999-10-25 | 금속 양이온을 처리하기 위한 방법 |
JP2000581656A JP2002529751A (ja) | 1998-11-10 | 1999-10-25 | 金属陽イオンの除去方法 |
EP99962033A EP1141975A2 (de) | 1998-11-10 | 1999-10-25 | Verfahren zum entsorgen von metallkationen |
US09/854,261 US20010031232A1 (en) | 1998-11-10 | 2001-05-10 | Method for disposing of metal cations |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19851850 | 1998-11-10 | ||
DE19851850.1 | 1998-11-10 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/854,261 Continuation US20010031232A1 (en) | 1998-11-10 | 2001-05-10 | Method for disposing of metal cations |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2000028553A2 true WO2000028553A2 (de) | 2000-05-18 |
WO2000028553A3 WO2000028553A3 (de) | 2000-08-17 |
Family
ID=7887330
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE1999/003405 WO2000028553A2 (de) | 1998-11-10 | 1999-10-25 | Verfahren zum entsorgen von metallkationen |
Country Status (7)
Country | Link |
---|---|
US (1) | US20010031232A1 (de) |
EP (1) | EP1141975A2 (de) |
JP (1) | JP2002529751A (de) |
KR (1) | KR20010080404A (de) |
CA (1) | CA2350206A1 (de) |
TW (1) | TW494087B (de) |
WO (1) | WO2000028553A2 (de) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3664870A (en) * | 1969-10-29 | 1972-05-23 | Nalco Chemical Co | Removal and separation of metallic oxide scale |
JPS62176914A (ja) * | 1986-01-29 | 1987-08-03 | Sumitomo Chem Co Ltd | 希有金属の回収方法 |
WO1990000085A1 (en) * | 1988-06-27 | 1990-01-11 | Autotrol Corporation | Photodegradation of metal chelate complexes |
DE4117625A1 (de) * | 1991-05-29 | 1992-12-03 | Siemens Ag | Reinigungsverfahren |
US5205999A (en) * | 1991-09-18 | 1993-04-27 | British Nuclear Fuels Plc | Actinide dissolution |
DE4423398A1 (de) * | 1994-07-04 | 1996-01-11 | Siemens Ag | Verfahren und Einrichtung zum Entsorgen eines Kationenaustauschers |
EP0753196B1 (de) * | 1994-03-28 | 1998-09-30 | Siemens Aktiengesellschaft | Verfahren und einrichtung zum entsorgen einer lösung, die eine organische säure enthält |
-
1999
- 1999-10-25 CA CA002350206A patent/CA2350206A1/en not_active Abandoned
- 1999-10-25 EP EP99962033A patent/EP1141975A2/de not_active Withdrawn
- 1999-10-25 WO PCT/DE1999/003405 patent/WO2000028553A2/de not_active Application Discontinuation
- 1999-10-25 JP JP2000581656A patent/JP2002529751A/ja active Pending
- 1999-10-25 KR KR1020017005902A patent/KR20010080404A/ko not_active Application Discontinuation
- 1999-11-06 TW TW088119436A patent/TW494087B/zh not_active IP Right Cessation
-
2001
- 2001-05-10 US US09/854,261 patent/US20010031232A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3664870A (en) * | 1969-10-29 | 1972-05-23 | Nalco Chemical Co | Removal and separation of metallic oxide scale |
JPS62176914A (ja) * | 1986-01-29 | 1987-08-03 | Sumitomo Chem Co Ltd | 希有金属の回収方法 |
WO1990000085A1 (en) * | 1988-06-27 | 1990-01-11 | Autotrol Corporation | Photodegradation of metal chelate complexes |
DE4117625A1 (de) * | 1991-05-29 | 1992-12-03 | Siemens Ag | Reinigungsverfahren |
US5205999A (en) * | 1991-09-18 | 1993-04-27 | British Nuclear Fuels Plc | Actinide dissolution |
EP0753196B1 (de) * | 1994-03-28 | 1998-09-30 | Siemens Aktiengesellschaft | Verfahren und einrichtung zum entsorgen einer lösung, die eine organische säure enthält |
DE4423398A1 (de) * | 1994-07-04 | 1996-01-11 | Siemens Ag | Verfahren und Einrichtung zum Entsorgen eines Kationenaustauschers |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 012, no. 022 (C-470), 22. Januar 1988 (1988-01-22) & JP 62 176914 A (SUMITOMO CHEM CO LTD), 3. August 1987 (1987-08-03) * |
Also Published As
Publication number | Publication date |
---|---|
EP1141975A2 (de) | 2001-10-10 |
TW494087B (en) | 2002-07-11 |
KR20010080404A (ko) | 2001-08-22 |
US20010031232A1 (en) | 2001-10-18 |
CA2350206A1 (en) | 2000-05-18 |
WO2000028553A3 (de) | 2000-08-17 |
JP2002529751A (ja) | 2002-09-10 |
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