EP0384194A2 - Anodes dimensionnellement stables et leur utilisation pour la production de dichromates alcalins et d'acide chromique - Google Patents

Anodes dimensionnellement stables et leur utilisation pour la production de dichromates alcalins et d'acide chromique Download PDF

Info

Publication number: EP0384194A2
Authority: EP; European Patent Office
Prior art keywords: dimensionally stable; intermediate layer; platinum; stable anodes; anodes
Prior art date: 1989-02-18
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

EP90102143A

Other languages

German (de)

English (en)

Other versions

EP0384194A3 (fr

EP0384194B1 (fr

Inventor

Helmut Dr. Klotz

Rainer Dr. Weber

Norbert Dr. Lönhoff

Hans-Dieter Dr. Block

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.)

Bayer AG

Original Assignee

Bayer AG

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.)

1989-02-18

Filing date

1990-02-03

Publication date

1990-08-29

Family has litigation

First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6374469&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0384194(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.

1990-02-03 Application filed by Bayer AG filed Critical Bayer AG

1990-08-29 Publication of EP0384194A2 publication Critical patent/EP0384194A2/fr

1991-06-05 Publication of EP0384194A3 publication Critical patent/EP0384194A3/fr

1994-03-09 Application granted granted Critical

1994-03-09 Publication of EP0384194B1 publication Critical patent/EP0384194B1/fr

2010-02-03 Anticipated expiration legal-status Critical

Status Revoked legal-status Critical Current

Links

KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 title claims description 10
AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 title claims description 10
238000004519 manufacturing process Methods 0.000 title description 6
229910052751 metal Inorganic materials 0.000 claims abstract description 20
239000002184 metal Substances 0.000 claims abstract description 20
229910000510 noble metal Inorganic materials 0.000 claims abstract description 17
238000000576 coating method Methods 0.000 claims abstract description 14
239000011248 coating agent Substances 0.000 claims abstract description 10
239000013543 active substance Substances 0.000 claims abstract description 7
229910045601 alloy Inorganic materials 0.000 claims abstract description 7
239000000956 alloy Substances 0.000 claims abstract description 7
239000000155 melt Substances 0.000 claims abstract description 7
238000009713 electroplating Methods 0.000 claims abstract description 6
BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 33
RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
239000003513 alkali Substances 0.000 claims description 18
229910052719 titanium Inorganic materials 0.000 claims description 17
239000010936 titanium Substances 0.000 claims description 17
229910052697 platinum Inorganic materials 0.000 claims description 16
238000000034 method Methods 0.000 claims description 14
229910052741 iridium Inorganic materials 0.000 claims description 11
GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 9
238000005868 electrolysis reaction Methods 0.000 claims description 8
229910052758 niobium Inorganic materials 0.000 claims description 6
239000010955 niobium Substances 0.000 claims description 6
GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
229910052715 tantalum Inorganic materials 0.000 claims description 6
GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 5
229910000566 Platinum-iridium alloy Inorganic materials 0.000 claims description 3
QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 3
229910000457 iridium oxide Inorganic materials 0.000 claims description 3
-1 platinum metals Chemical class 0.000 claims description 3
229910003446 platinum oxide Inorganic materials 0.000 claims description 3
HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical class [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 claims description 3
229910052726 zirconium Inorganic materials 0.000 claims description 3
MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 2
238000002360 preparation method Methods 0.000 claims 1
239000010410 layer Substances 0.000 description 27
239000000243 solution Substances 0.000 description 16
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
239000001301 oxygen Substances 0.000 description 9
229910052760 oxygen Inorganic materials 0.000 description 9
LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 5
239000012528 membrane Substances 0.000 description 5
238000002161 passivation Methods 0.000 description 5
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
150000002739 metals Chemical class 0.000 description 4
MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
229910021639 Iridium tetrachloride Inorganic materials 0.000 description 2
KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
239000006227 byproduct Substances 0.000 description 2
238000005341 cation exchange Methods 0.000 description 2
229910052804 chromium Inorganic materials 0.000 description 2
239000011651 chromium Substances 0.000 description 2
238000000151 deposition Methods 0.000 description 2
230000008021 deposition Effects 0.000 description 2
YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
238000001035 drying Methods 0.000 description 2
238000004070 electrodeposition Methods 0.000 description 2
239000003792 electrolyte Substances 0.000 description 2
238000010438 heat treatment Methods 0.000 description 2
150000002500 ions Chemical class 0.000 description 2
NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
150000004706 metal oxides Chemical class 0.000 description 2
239000000203 mixture Substances 0.000 description 2
239000010970 precious metal Substances 0.000 description 2
239000010935 stainless steel Substances 0.000 description 2
229910001220 stainless steel Inorganic materials 0.000 description 2
238000009736 wetting Methods 0.000 description 2
229910009112 xH2O Inorganic materials 0.000 description 2
XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
229920000557 Nafion® Polymers 0.000 description 1
229910000978 Pb alloy Inorganic materials 0.000 description 1
BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical compound [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 1
239000003929 acidic solution Substances 0.000 description 1
239000012670 alkaline solution Substances 0.000 description 1
239000010405 anode material Substances 0.000 description 1
239000007864 aqueous solution Substances 0.000 description 1
239000002585 base Substances 0.000 description 1
239000010953 base metal Substances 0.000 description 1
239000000460 chlorine Substances 0.000 description 1
229910052801 chlorine Inorganic materials 0.000 description 1
JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
150000001875 compounds Chemical class 0.000 description 1
229910052802 copper Inorganic materials 0.000 description 1
239000010949 copper Substances 0.000 description 1
230000007797 corrosion Effects 0.000 description 1
238000005260 corrosion Methods 0.000 description 1
230000006378 damage Effects 0.000 description 1
150000002148 esters Chemical class 0.000 description 1
238000005530 etching Methods 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
229910052737 gold Inorganic materials 0.000 description 1
239000010931 gold Substances 0.000 description 1
229910001385 heavy metal Inorganic materials 0.000 description 1
239000011229 interlayer Substances 0.000 description 1
229910044991 metal oxide Inorganic materials 0.000 description 1
235000006408 oxalic acid Nutrition 0.000 description 1
229910052763 palladium Inorganic materials 0.000 description 1
VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
229910052703 rhodium Inorganic materials 0.000 description 1
239000010948 rhodium Substances 0.000 description 1
MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
229910052709 silver Inorganic materials 0.000 description 1
239000004332 silver Substances 0.000 description 1
229910000029 sodium carbonate Inorganic materials 0.000 description 1
PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 1
229910001415 sodium ion Inorganic materials 0.000 description 1
239000000725 suspension Substances 0.000 description 1
238000005979 thermal decomposition reaction Methods 0.000 description 1
229910052720 vanadium Inorganic materials 0.000 description 1
GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
229910052725 zinc Inorganic materials 0.000 description 1
239000011701 zinc Substances 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/22—Inorganic acids
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

Definitions

the invention further relates to a process for the production of alkali dichromates and chromic acid by electrolysis of alkali monochromate and / or alkali dichromate solutions using the electrodes according to the invention.
anodes that consist of an electrically conductive valve metal such as titanium, tantalum and niobium and are coated with an electrocatalytically active substance. These anodes are commonly called dimensionally stable (“dimensionally stable”) anodes or referred to as DSA®. Metals from the platinum group and their oxides, as well as lead dioxide and manganese dioxide, are primarily used as electrocatalytically active substances. Such anodes are described for example in BE-A 710 551, DE-B 2 300 422 and US-A 3 711 385.
This intermediate layer can consist of one or more metal oxides, such as oxides of platinum metals, oxides of titanium, vanadium, niobium, Tantalum and other base metals exist.
metal oxides such as oxides of platinum metals, oxides of titanium, vanadium, niobium, Tantalum and other base metals exist.
Such anodes are described for example in DE-A 3 219 003, DE-C 3 330 388, DE-A 3 715 444 and DE-A 3 717 972.
US-A 3 775 284 discloses anodes which have intermediate layers of precious metals such as platinum and iridium, which are applied by wet electroplating processes.
Typical processes in which oxygen is formed anodically are the electrolytic production of alkali dichromates, chromic acid, perchlorates, chlorates, persulphates and hydrogen peroxide, the electrolytic deposition of metals such as chromium, copper, zinc or noble metals and various electroplating processes or electroplating.
the object of the invention was to provide dimensionally stable anodes which do not have the disadvantages described.
the generation of such noble metal layers on valve metals by electrodeposition from melts containing noble metal salts is described, for example, in "G. Dick, Galvanotechnik 79 (1988), No. 12, pp. 4066-4071".
Dimensionally stable anodes the intermediate layer of platinum and / or iridium and / or are preferred a platinum-iridium alloy. Interlayers made of other precious metals such as gold, silver, rhodium and palladium, their base alloys with each other and their alloys with platinum and iridium are also possible.
the layer thickness of the intermediate layer according to the invention is preferably 1.5 to 30 ⁇ m, layer thicknesses of 1.5 to 5 ⁇ m being particularly preferred. However, layer thicknesses of less than 1.5 ⁇ m and greater than 30 ⁇ m are also possible.
valve metal of the dimensionally stable anode consists of titanium, tantalum, niobium, zirconium or their alloys, preference being given to titanium for cost reasons.
Niobium and tantalum are used particularly when voltages above 10 V are required.
the electrode coating can consist of all electrocatalytically active substances that are customary in practice. Electrode coatings which consist of one or more oxides of titanium, tantalum, niobium, zirconium and / or one or more oxides of platinum metals are preferred. Such electrode coatings can be produced by means of pyrolytic processes, for example by thermal decomposition of compounds of the metals mentioned. Electrode coatings consisting of a platinum oxide and / or iridium oxide are particularly preferred.
the dimensionally stable anodes according to the invention are notable for excellent durability when used in electrolytic processes in which oxygen is anodically formed as the main or by-product. Even at temperatures above 6 ° C, the service life of the anodes required for economic operation of electrolytic processes can be achieved with constant oxygen overvoltages over a long period of time. Of course, the dimensionally stable anodes according to the invention can also advantageously be used at temperatures below 60 ° C.
Another object of the invention is a process for the production of alkali dichromates and / or chromic acid by electrolysis of alkali monochromate and / or alkali dichromate solutions, which is characterized in that a dimensionally stable anode according to the invention is used.
alkali dichromates the electrolytic production of dichromates and chromic acid takes place in electrolysis cells, the electrode spaces of which are separated by cation exchange membranes.
alkali monochromate solutions or suspensions are introduced into the anode compartment of the cell and converted into an alkali dichromate solution by selectively transferring alkali ions through the membrane into the cathode compartment.
chromic acid alkali dichromate or alkali monochromate solutions are introduced into the anode compartment and into chromium transferred acidic solutions.
sodium monochromate and / or sodium dichromate are used for these processes.
an alkaline solution containing alkali ions is obtained in the cathode compartment, which can consist, for example, of an aqueous sodium hydroxide solution or, as described in CA-A 739 447, of an aqueous solution containing sodium carbonate.
anodes made of lead and lead alloys and dimensionally stable anodes with electrocatalytically active layers of noble metals or noble metal oxides are suitable as anode materials.
anodic current densities of 2 to 5 kA / m2 and electrolysis temperatures above 60 ° C however, these anodes only have an insufficient service life for the reasons mentioned above.
the electrolysis cells used in the examples consisted of anode compartments made of pure titanium and cathode compartments made of stainless steel. Cation exchange membranes from DuPont with the designation Nafion® 324 were used as membranes. The cathodes were made of stainless steel and the anodes were made of titanium with the electrocatalytically active coatings described in the individual examples. The distance between the electrodes and the membrane was 1.5 mm in all cases.
Sodium dichromate solutions containing 800 g / l Na2Cr2O7 ⁇ 2 H2O were introduced into the anode compartments. The rate of introduction was chosen so that a molar ratio of sodium ions to chromium (VI) of 0.6 was established in the anolytes leaving the cells.
the electrolysis temperature was 80 ° C. in all cases and the current density was 3 kA / m 2 projected front surface of the anodes and cathodes.
a titanium anode with an iridium layer was used, which was produced by the so-called baking process as follows: a titanium electrode with a front projected surface measuring 11.4 cm x 6.7 cm, after removal of the oxide layer and etching with oxalic acid, a solution with the following composition was wetted with a hair brush: 0.8 g IrCl4 ⁇ xH2O (51% Ir) 6.2 ml of 1-butanol 0.4 ml 37% hydrochloric acid 3 ml titanium tetrabutyl ester
the wetted anode was dried at 250 ° C. for 15 minutes and then annealed in an oven at 450 ° C. for 20 to 30 minutes. This measure was repeated six times, the heat treatment being carried out only after every second step after wetting and drying.
the wetted anode was dried at 250 ° C. for 15 minutes and then annealed in an oven at 450 ° C. for 20 to 30 minutes. This measure was repeated six times, the heat treatment being carried out only after every second step after wetting and drying.
An electrode coating containing approximately 200 mg of iridium was produced on the platinum intermediate layer of the titanium electrode.
a dimensionally stable titanium anode was used, the electrocatalytically active layer of which consisted exclusively of a platinum layer electrodeposited from the melt.
the platinum layer thickness was 2.5 ⁇ m.
Example 3 shows, however, that the anode of Example 3 has a significantly higher oxygen voltage.

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Chemical & Material Sciences (AREA)
Inorganic Chemistry (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Electrochemistry (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Electrodes For Compound Or Non-Metal Manufacture (AREA)
Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Electrolytic Production Of Metals (AREA)
Catalysts (AREA)

EP90102143A 1989-02-18 1990-02-03 Anodes dimensionnellement stables et leur utilisation pour la production de dichromates alcalins et d'acide chromique Revoked EP0384194B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE3905082		1989-02-18
DE3905082A DE3905082A1 (de)	1989-02-18	1989-02-18	Formstabile anoden und deren verwendung bei der herstellung von alkalidichromaten und chromsaeure

Publications (3)

Publication Number	Publication Date
EP0384194A2 true EP0384194A2 (fr)	1990-08-29
EP0384194A3 EP0384194A3 (fr)	1991-06-05
EP0384194B1 EP0384194B1 (fr)	1994-03-09

Family

ID=6374469

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP90102143A Revoked EP0384194B1 (fr)	1989-02-18	1990-02-03	Anodes dimensionnellement stables et leur utilisation pour la production de dichromates alcalins et d'acide chromique

Country Status (14)

Country	Link
US (1)	US5128000A (fr)
EP (1)	EP0384194B1 (fr)
JP (1)	JP2641584B2 (fr)
KR (1)	KR960016418B1 (fr)
AR (1)	AR246311A1 (fr)
BR (1)	BR9000721A (fr)
CA (1)	CA2010221A1 (fr)
DD (1)	DD298437A5 (fr)
DE (2)	DE3905082A1 (fr)
ES (1)	ES2050287T3 (fr)
MX (1)	MX173097B (fr)
RU (1)	RU1838450C (fr)
TR (1)	TR26579A (fr)
ZA (1)	ZA901196B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
FR2748495A1 (fr) *	1996-05-13	1997-11-14	Electricite De France	Anode a longevite amelioree et son procede de fabrication
US8758577B2 (en)	1999-06-30	2014-06-24	Chema Technology, Inc.	Electroplating apparatus
CN104593818A (zh) *	2014-12-24	2015-05-06	中南大学	一种钛基复合阳极及其制备方法和应用

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO1997028293A1 (fr) *	1996-02-01	1997-08-07	Motorola Inc.	Electrodes multicouches composites pour piles electrochimiques
US7556722B2 (en)	1996-11-22	2009-07-07	Metzger Hubert F	Electroplating apparatus
US6217729B1 (en)	1999-04-08	2001-04-17	United States Filter Corporation	Anode formulation and methods of manufacture
DE10029837B4 (de) *	2000-06-16	2005-02-17	Degussa Galvanotechnik Gmbh	Verfahren zur Herstellung von einseitig platinierten Platten und Streckmetallgittern aus Refraktärmetallen
JP4615847B2 (ja) *	2003-11-25	2011-01-19	株式会社フルヤ金属	耐食材及びその製造方法
JP2008156684A (ja) *	2006-12-22	2008-07-10	Tanaka Kikinzoku Kogyo Kk	塩酸電解用の陽極電極
US7713401B2 (en) *	2007-08-08	2010-05-11	Battelle Energy Alliance, Llc	Methods for performing electrochemical nitration reactions
WO2010001971A1 (fr) *	2008-07-03	2010-01-07	旭化成ケミカルズ株式会社	Cathode pour génération d'hydrogène et son procédé de production
US20110052896A1 (en) *	2009-08-27	2011-03-03	Shrisudersan Jayaraman	Zinc Oxide and Cobalt Oxide Nanostructures and Methods of Making Thereof
US20110086238A1 (en) *	2009-10-09	2011-04-14	Shrisudersan Jayaraman	Niobium Nanostructures And Methods Of Making Thereof
CN113355705B (zh) *	2021-06-02	2022-05-03	建滔（连州）铜箔有限公司	一种电解铜箔用钛阳极板以及背面处理工艺

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3454478A (en) *	1965-06-28	1969-07-08	Ppg Industries Inc	Electrolytically reducing halide impurity content of alkali metal dichromate solutions
US3663414A (en) *	1969-06-27	1972-05-16	Ppg Industries Inc	Electrode coating
DE2113676C2 (de) *	1971-03-20	1985-09-12	Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach	Elektrode für elektrochemische Prozesse
JPS5119429A (ja) *	1974-08-09	1976-02-16	Oki Electric Ind Co Ltd	Fusetsukyokushikibetsuhoshiki
JPS5325838A (en) *	1976-08-23	1978-03-10	Matsushita Electric Industrial Co Ltd	Storage battery electrode plate
FR2426095A1 (fr) *	1978-05-19	1979-12-14	Anger Roger	Electrode anodique stable en dimensions et procede de fabrication
US4157943A (en) *	1978-07-14	1979-06-12	The International Nickel Company, Inc.	Composite electrode for electrolytic processes
JPS565986A (en) *	1979-05-29	1981-01-22	Diamond Shamrock Corp	Cromic acid production by using three chambered electrolysis tank
JPS5940914A (ja) *	1982-08-31	1984-03-06	Mazda Motor Corp	車両の姿勢制御装置

1989
- 1989-02-18 DE DE3905082A patent/DE3905082A1/de not_active Withdrawn
1990
- 1990-01-29 MX MX019298A patent/MX173097B/es unknown
- 1990-02-03 ES ES90102143T patent/ES2050287T3/es not_active Expired - Lifetime
- 1990-02-03 DE DE90102143T patent/DE59004842D1/de not_active Revoked
- 1990-02-03 EP EP90102143A patent/EP0384194B1/fr not_active Revoked
- 1990-02-14 JP JP2031655A patent/JP2641584B2/ja not_active Expired - Lifetime
- 1990-02-16 BR BR909000721A patent/BR9000721A/pt not_active Application Discontinuation
- 1990-02-16 CA CA002010221A patent/CA2010221A1/fr not_active Abandoned
- 1990-02-16 AR AR90316181A patent/AR246311A1/es active
- 1990-02-16 KR KR1019900001875A patent/KR960016418B1/ko not_active Expired - Fee Related
- 1990-02-16 ZA ZA901196A patent/ZA901196B/xx unknown
- 1990-02-16 RU SU904743064A patent/RU1838450C/ru active
- 1990-02-16 DD DD90337917A patent/DD298437A5/de unknown
- 1990-03-13 TR TR90/0185A patent/TR26579A/xx unknown
1991
- 1991-04-01 US US07/680,602 patent/US5128000A/en not_active Expired - Lifetime

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
FR2748495A1 (fr) *	1996-05-13	1997-11-14	Electricite De France	Anode a longevite amelioree et son procede de fabrication
WO1997043465A1 (fr) *	1996-05-13	1997-11-20	Electricite De France Service National	Anode a longevite amelioree et son procede de fabrication
US8758577B2 (en)	1999-06-30	2014-06-24	Chema Technology, Inc.	Electroplating apparatus
CN104593818A (zh) *	2014-12-24	2015-05-06	中南大学	一种钛基复合阳极及其制备方法和应用
CN104593818B (zh) *	2014-12-24	2017-04-26	中南大学	一种钛基复合阳极及其制备方法和应用

Also Published As

Publication number	Publication date
EP0384194A3 (fr)	1991-06-05
JPH02247392A (ja)	1990-10-03
JP2641584B2 (ja)	1997-08-13
AR246311A1 (es)	1994-07-29
TR26579A (tr)	1995-03-15
DD298437A5 (de)	1992-02-20
RU1838450C (ru)	1993-08-30
US5128000A (en)	1992-07-07
DE59004842D1 (de)	1994-04-14
DE3905082A1 (de)	1990-08-23
ES2050287T3 (es)	1994-05-16
KR960016418B1 (ko)	1996-12-11
MX173097B (es)	1994-02-01
EP0384194B1 (fr)	1994-03-09
ZA901196B (en)	1990-11-28
CA2010221A1 (fr)	1990-08-18
BR9000721A (pt)	1991-01-22
KR900013109A (ko)	1990-09-03

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