US20170198403A1 - Catalytic coating and method of manufacturing thereof - Google Patents
Catalytic coating and method of manufacturing thereof Download PDFInfo
- Publication number
- US20170198403A1 US20170198403A1 US15/321,419 US201515321419A US2017198403A1 US 20170198403 A1 US20170198403 A1 US 20170198403A1 US 201515321419 A US201515321419 A US 201515321419A US 2017198403 A1 US2017198403 A1 US 2017198403A1
- Authority
- US
- United States
- Prior art keywords
- catalytic layer
- titanium
- ruthenium
- tantalum
- coating according
- 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.)
- Abandoned
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 27
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims description 25
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052715 tantalum Inorganic materials 0.000 claims description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 14
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 8
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000001680 brushing effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910001936 tantalum oxide Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 6
- 229910004537 TaCl5 Inorganic materials 0.000 description 5
- 229910010270 TiOCl2 Inorganic materials 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241001521328 Ruta Species 0.000 description 4
- 235000003976 Ruta Nutrition 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000005806 ruta Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C25B11/0484—
-
- 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
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
Definitions
- the invention relates to a catalytic coating of valve metal articles suitable for use in highly aggressive electrolytic environments, for example in hydrochloric acid electrolysis cells.
- Hydrochloric acid electrolysis is an electrochemical process gaining increasing interest at present, being hydrochloric acid the typical by-product of all major industrial processes making use of chlorine: the increase in the production capacity of plants of new conception entails the formation of significant amounts of acid, whose placement on the market presents significant difficulties.
- the electrolysis of the acid typically carried out in two-compartment electrolytic cells separated by an ion-exchange membrane, leads to the formation of chlorine at the anode compartment, which can be recycled upstream resulting in a substantially closed cycle of negligible environmental impact.
- valve metals such as titanium, niobium and zirconium are preferably employed, optionally alloyed titanium being the most common example for reasons of cost and ease of machining.
- Titanium alloys containing nickel, chromium and small amounts of noble metals such as ruthenium and palladium, like the AKOT® alloy commercialised by Kobe Steel, are for instance of widespread use.
- the anodes whereon the anodic evolution of chlorine is carried out consist for example of a valve metal article such as a titanium alloy substrate coated with a suitable catalyst, typically consisting of a mixture of oxides of titanium and ruthenium, capable of lowering the overvoltage of the anodic discharge of chlorine.
- a suitable catalyst typically consisting of a mixture of oxides of titanium and ruthenium, capable of lowering the overvoltage of the anodic discharge of chlorine.
- the same type of coating is also used to protect from corrosion some components of the anodic compartment not directly involved in the evolution of chlorine, with particular reference to interstitial areas subject to electrolyte stagnation.
- the lack of a sufficient electrolyte renewal may in fact lead to a local discontinuity of the passivation layer directed at protecting the valve metal, triggering corrosion phenomena, which are the more dangerous the more they are localised in small areas.
- the invention relates to a coating of valve metal surfaces including a titanium-free catalytic layer and consisting of the mixture of two phases, namely an amorphous phase of Ta 2 O 5 in admixture with a tetragonal ditetragonal dipyramidal crystalline phase containing RuO 2 , optionally in solid solution with SnO 2
- titanium-free coatings are more resistant to chloride attack in acidic solution, presumably because titanium oxides—whose function in a combination with ruthenium dioxide is to act as film-forming component—are present as a mixture of crystalline phases including an anatase TiO 2 phase, substantially weaker than the others.
- the inventors have also observed that mixtures of oxides of tantalum and ruthenium in an amorphous phase do not contribute to solving the problem in a decisive manner, even if completely free from titanium.
- the coating is formed from a mixture of RuO 2 in the typical crystalline form similar to rutile (i.e. tetragonal ditetragonal dipyramidal) and Ta 2 O 5 in a basically amorphous phase, the stability of the coating to acid attack is greatly increased.
- the overvoltage of the coating towards anodic chlorine evolution is surprisingly reduced.
- the weight ratio between the amorphous phase of Ta 2 O 5 and the crystalline phase is between 0.25 and 4, which defines the best range of functioning of the invention.
- the RuO 2 component in the tetragonal ditetragonal dipyramidal crystalline phase is partially replaced by SnO 2 (cassiterite).
- SnO 2 cassiterite
- the two dioxides of tin and of ruthenium, whose tetragonal ditetragonal dipyramidal crystalline form turns out to be the most stable, are capable of forming solid solutions in any weight ratio; in one embodiment, the Ru to Sn weight ratio in the tetragonal ditetragonal dipyramidal crystalline phase of the coating ranges between 0.5 and 2, which gives the best results in terms of protection of the substrate as well as of catalytic activity of the coating.
- the coating comprises two distinct catalytic layers, one as hereinbefore described in direct contact with the valve metal substrate coupled to an outermost one overlaid thereto with a higher content of ruthenium oxide.
- This can have the advantage of enhancing on one hand the protective function at the substrate surface and on the other hand the catalytic and conductive properties of the outermost layer, as required for example in the case wherein the coating is used for the catalytic activation of an anodic structure whose outer surface is in direct contact with the electrolyte.
- the inner catalytic layer has a weight ratio of amorphous Ta 2 O 5 phase to RuO 2 -containing crystalline phase (optionally including SnO 2 ) ranging between 0.25 and 2.5 and the outer catalytic layer consists of an amorphous phase of Ta 2 O 5 mixed with a tetragonal ditetragonal dipyramidal crystalline phase of RuO 2 with a Ru to Ta weight ratio between 3 and 5.
- a further protective pre-layer consisting of a mixture of oxides of titanium and tantalum.
- the magnitude of such resistive penalty can be however very limited, provided the pre-layer has a suitably limited thickness.
- a total loading of titanium and tantalum oxides of 0.6 to 4 g/m 2 is a suitable value for a pre-layer to be combined with a catalytic layer containing 20 g/m 2 of total oxides.
- the invention in another aspect, relates to a method for the manufacturing of a coating as hereinbefore described comprising the optional application of a solution of titanium and tantalum compounds, for example TiOCl 2 , TiCl 3 and TaCl 5 , to a valve metal substrate in one or more coats, with subsequent thermal decomposition after each coat; the application of a solution of compounds of tantalum, ruthenium and optionally tin in one or more coats, with subsequent thermal decomposition after each coat, until obtaining a first catalytic layer; the optional application of a solution of compounds of tantalum and ruthenium upon the first catalytic layer with subsequent thermal decomposition after each coat, until obtaining a second catalytic layer.
- a solution of titanium and tantalum compounds for example TiOCl 2 , TiCl 3 and TaCl 5
- the compounds of ruthenium and tin applied in view of the subsequent thermal decomposition are hydroxyacetochloride complexes; this can have the advantage of obtaining more regular and compact layers, having a more homogeneous composition, compared to hydrochloric or other precursors.
- the thermal decomposition step after each coat can be effected between 350 and 600° C., depending on the selected precursor compounds.
- thermal decomposition may for example be carried out between 450 and 550° C.
- a 1 mm thick AKOT® titanium alloy mesh was degreased with acetone in a ultrasonic bath and etched in 20% HCl at boiling temperature for 15 minutes. The mesh was cut into a plurality of pieces of 10 cm ⁇ 10 cm size for the subsequent preparation of electrode samples.
- a solution of precursors for the preparation of the protective pre-layer was obtained by mixing 150 g/l of TiOCl 2 and 50 g/l of TaCl 5 in 10% wt. hydrochloric acid.
- a first series of catalytic solutions was obtained by mixing 20% by weight RuCl 3 and 50 g/l TaCl 5 in 10% wt. hydrochloric acid according to various proportions.
- Solutions of hydroxyacetochloride complexes of Ru (0.9 M) and Sn (1.65 M) were obtained by dissolving the corresponding chlorides in 10% vol. aqueous acetic acid, evaporating the solvent, taking up with 10% aqueous acetic acid with subsequent evaporation of the solvent for two more times, finally dissolving the product again in 10% aqueous acetic acid to obtain the specified concentration.
- a second series of catalytic solutions was obtained by mixing the hydroxyacetochloride complexes of Ru and Sn according to various proportions.
- Electrode samples were obtained at different formulations with the following procedure:
- a 1 mm thick AKOT® titanium alloy mesh was degreased with acetone in a ultrasonic bath and etched in 20% HCl at boiling temperature for 15 minutes. The mesh was cut into a plurality of pieces of 10 cm ⁇ 10 cm size for the subsequent preparation of electrode samples.
- a solution of precursors for the preparation of the protective pre-layer was obtained by mixing 150 g/l of TiOCl 2 and 50 g/l of TaCl 5 in 10% hydrochloric acid.
- a series of catalytic solutions was obtained by mixing 20% by weight RuCl 3 and 150 g/l TiOCl 2 in 10% hydrochloric acid according to various proportions.
- the electrode samples shown in the table were subjected to a test of standard potential under anodic evolution of chlorine at the current density of 3 kA/m 2 , in 15% wt. HCl at a temperature of 60° C.
- the potential data obtained are reported in Table 3 (SEP).
- the table shows also the related data of an accelerated lifetime test, expressed in terms of hours of operation before deactivation under anodic evolution of chlorine at the current density of 6 kA/m 2 , in 20% wt. HCl at a temperature of 60° C., using a zirconium cathode as counterelectrode.
- the deactivation of the electrode is defined by a 1 V increase in the cell with respect to the initial value.
- Duplicates of electrode samples 2, 6 and C2 were subjected to a corrosion test which simulates the crevice corrosion conditions that can occur on the flanges of electrolysers for the production of chlorine or other occluded zones.
- a first series of samples was immersed in a known volume of 20% wt. HCl at 45° C. under nitrogen stream, to simulate electrolyte stagnation conditions; a second (control) series was immersed in the same volume of 20% wt. HCl at 40° C. under a stream of oxygen, in order to maintain passivation.
- the test was repeated with another set of samples, confirming a substantial increase in the corrosion resistance for the formulations of the invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Chemically Coating (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI2014A001363 | 2014-07-28 | ||
ITMI20141363 | 2014-07-28 | ||
PCT/EP2015/067273 WO2016016243A1 (en) | 2014-07-28 | 2015-07-28 | Catalytic coating and method of manufacturing thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
US20170198403A1 true US20170198403A1 (en) | 2017-07-13 |
Family
ID=51628367
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/321,419 Abandoned US20170198403A1 (en) | 2014-07-28 | 2015-07-28 | Catalytic coating and method of manufacturing thereof |
Country Status (11)
Country | Link |
---|---|
US (1) | US20170198403A1 (zh) |
EP (1) | EP3175019B1 (zh) |
JP (1) | JP6714576B2 (zh) |
CN (1) | CN106471159B (zh) |
AR (1) | AR101828A1 (zh) |
ES (1) | ES2712403T3 (zh) |
HU (1) | HUE041583T2 (zh) |
PT (1) | PT3175019T (zh) |
RU (1) | RU2689985C2 (zh) |
TW (1) | TWI679256B (zh) |
WO (1) | WO2016016243A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210238757A1 (en) * | 2018-06-21 | 2021-08-05 | Industrie De Nora S.P.A. | Anode for electrolytic evolution of chlorine |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7168729B1 (ja) * | 2021-07-12 | 2022-11-09 | デノラ・ペルメレック株式会社 | 工業用電解プロセス用電極 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3776834A (en) * | 1972-05-30 | 1973-12-04 | Leary K O | Partial replacement of ruthenium with tin in electrode coatings |
US3853739A (en) * | 1972-06-23 | 1974-12-10 | Electronor Corp | Platinum group metal oxide coated electrodes |
CN102703921A (zh) * | 2007-11-16 | 2012-10-03 | 阿克佐诺贝尔股份有限公司 | 电极 |
IT1391767B1 (it) * | 2008-11-12 | 2012-01-27 | Industrie De Nora Spa | Elettrodo per cella elettrolitica |
IT1403585B1 (it) * | 2010-11-26 | 2013-10-31 | Industrie De Nora Spa | Anodo per evoluzione elettrolitica di cloro |
CN102174704B (zh) * | 2011-02-20 | 2012-12-12 | 中国船舶重工集团公司第七二五研究所 | 一种含钽中间层金属氧化物电极的制备方法 |
JP5008043B1 (ja) * | 2011-09-13 | 2012-08-22 | 学校法人同志社 | 塩素発生用陽極 |
-
2015
- 2015-06-18 TW TW104119668A patent/TWI679256B/zh not_active IP Right Cessation
- 2015-07-21 AR ARP150102307A patent/AR101828A1/es active IP Right Grant
- 2015-07-28 EP EP15742289.0A patent/EP3175019B1/en active Active
- 2015-07-28 RU RU2017106084A patent/RU2689985C2/ru active
- 2015-07-28 CN CN201580034498.6A patent/CN106471159B/zh active Active
- 2015-07-28 PT PT15742289T patent/PT3175019T/pt unknown
- 2015-07-28 WO PCT/EP2015/067273 patent/WO2016016243A1/en active Application Filing
- 2015-07-28 JP JP2017505073A patent/JP6714576B2/ja not_active Expired - Fee Related
- 2015-07-28 HU HUE15742289A patent/HUE041583T2/hu unknown
- 2015-07-28 ES ES15742289T patent/ES2712403T3/es active Active
- 2015-07-28 US US15/321,419 patent/US20170198403A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210238757A1 (en) * | 2018-06-21 | 2021-08-05 | Industrie De Nora S.P.A. | Anode for electrolytic evolution of chlorine |
Also Published As
Publication number | Publication date |
---|---|
JP6714576B2 (ja) | 2020-06-24 |
JP2017522457A (ja) | 2017-08-10 |
PT3175019T (pt) | 2019-02-26 |
RU2689985C2 (ru) | 2019-05-30 |
RU2017106084A (ru) | 2018-08-28 |
ES2712403T3 (es) | 2019-05-13 |
HUE041583T2 (hu) | 2019-05-28 |
EP3175019A1 (en) | 2017-06-07 |
TWI679256B (zh) | 2019-12-11 |
RU2017106084A3 (zh) | 2019-01-15 |
WO2016016243A1 (en) | 2016-02-04 |
CN106471159B (zh) | 2019-04-05 |
CN106471159A (zh) | 2017-03-01 |
TW201604252A (zh) | 2016-02-01 |
AR101828A1 (es) | 2017-01-18 |
EP3175019B1 (en) | 2018-11-28 |
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Legal Events
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