EP3175019B1 - Catalytic coating and method of manufacturing thereof - Google Patents
Catalytic coating and method of manufacturing thereof Download PDFInfo
- Publication number
- EP3175019B1 EP3175019B1 EP15742289.0A EP15742289A EP3175019B1 EP 3175019 B1 EP3175019 B1 EP 3175019B1 EP 15742289 A EP15742289 A EP 15742289A EP 3175019 B1 EP3175019 B1 EP 3175019B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalytic layer
- ruthenium
- titanium
- valve metal
- tantalum
- 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.)
- Active
Links
- 230000003197 catalytic effect Effects 0.000 title claims description 41
- 238000000576 coating method Methods 0.000 title claims description 19
- 239000011248 coating agent Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 25
- 229910052707 ruthenium Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 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
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 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
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 6
- 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
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 8
- 229910001936 tantalum oxide Inorganic materials 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
- 239000002243 precursor Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 229910010270 TiOCl2 Inorganic materials 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 241001521328 Ruta Species 0.000 description 4
- 235000003976 Ruta Nutrition 0.000 description 4
- 229910004537 TaCl5 Inorganic materials 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
- 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 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
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 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
- 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
- 230000004913 activation Effects 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
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 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
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 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
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- -1 platinum group metal oxides Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- C25B11/051—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
-
- 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
-
- 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
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.
- EP 2 757179 A1 describes chlorine evolution anodes which, in addition to amorphous ruthenium oxide, may comprise crystalline ruthenium oxide in an intermediate layer or in a catalytic layer.
- US 3 875 043 A describes a catalytic coating comprising tantalum oxide and ruthenium oxide.
- US 3,853,739 A describes a coating made from a solid solution of platinum group metal oxides in an amorphous tantalum binder. Carl-Erik Boman et al. describe in Acta Chemica Scandinavica, vol. 24, 1 January 1970, pp. 116-122 the preparation and characterization of crysatls of ruthenium dioxide having a rutile structure.
- US 2011/0209992 A1 describes an electrode for an electrolysis cell comprising a catalytic layer containing tin, ruthenium, iridium, palladium and niobium oxides using precursor solutions of hydroxyacetochloride complexes of tin, iridium or ruthenium.
- the invention relates to a coated valve metal substrate, having a coating as defined in claim 1.
- the coating includes 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 .
- the inventors have in fact observed that 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 2.5, 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 coated valve metal substrate 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% HCI at boiling temperature for 15 minutes. The mesh was cut into a plurality of pieces of 10 cm x 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 x 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 (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI20141363 | 2014-07-28 | ||
| PCT/EP2015/067273 WO2016016243A1 (en) | 2014-07-28 | 2015-07-28 | Catalytic coating and method of manufacturing thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3175019A1 EP3175019A1 (en) | 2017-06-07 |
| EP3175019B1 true EP3175019B1 (en) | 2018-11-28 |
Family
ID=51628367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15742289.0A Active EP3175019B1 (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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT201800006544A1 (it) * | 2018-06-21 | 2019-12-21 | Anodo per evoluzione elettrolitica di cloro | |
| 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 |
| WO2024184552A1 (en) * | 2023-03-09 | 2024-09-12 | Magneto Special Anodes B.V. | Mixed metal oxide coatings applied using spatial atomic layer deposition and uses thereof |
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 |
| EP2217744A2 (en) * | 2007-11-16 | 2010-08-18 | Akzo Nobel N.V. | Electrode |
| 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 CN CN201580034498.6A patent/CN106471159B/zh active Active
- 2015-07-28 US US15/321,419 patent/US20170198403A1/en not_active Abandoned
- 2015-07-28 WO PCT/EP2015/067273 patent/WO2016016243A1/en active Application Filing
- 2015-07-28 HU HUE15742289A patent/HUE041583T2/hu unknown
- 2015-07-28 RU RU2017106084A patent/RU2689985C2/ru active
- 2015-07-28 ES ES15742289T patent/ES2712403T3/es active Active
- 2015-07-28 PT PT15742289T patent/PT3175019T/pt unknown
- 2015-07-28 JP JP2017505073A patent/JP6714576B2/ja not_active Expired - Fee Related
- 2015-07-28 EP EP15742289.0A patent/EP3175019B1/en active Active
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| AR101828A1 (es) | 2017-01-18 |
| CN106471159B (zh) | 2019-04-05 |
| TWI679256B (zh) | 2019-12-11 |
| JP6714576B2 (ja) | 2020-06-24 |
| CN106471159A (zh) | 2017-03-01 |
| RU2017106084A3 (zh) | 2019-01-15 |
| HUE041583T2 (hu) | 2019-05-28 |
| WO2016016243A1 (en) | 2016-02-04 |
| US20170198403A1 (en) | 2017-07-13 |
| RU2689985C2 (ru) | 2019-05-30 |
| EP3175019A1 (en) | 2017-06-07 |
| ES2712403T3 (es) | 2019-05-13 |
| TW201604252A (zh) | 2016-02-01 |
| RU2017106084A (ru) | 2018-08-28 |
| JP2017522457A (ja) | 2017-08-10 |
| PT3175019T (pt) | 2019-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2643499B1 (en) | Anode for electrolytic evolution of chlorine | |
| EP3314041B1 (en) | Electrode for electrolytic processes | |
| KR101707811B1 (ko) | 전해 분야를 위한 전극 | |
| US11643746B2 (en) | Electrode for oxygen evolution in industrial electrochemical processes | |
| KR101789358B1 (ko) | 전기 화학적 산업 공정에 있어서 산소를 발생시키기 위한 전극 | |
| EP3175019B1 (en) | Catalytic coating and method of manufacturing thereof | |
| EP3224392B1 (en) | Anode for electrolytic evolution of chlorine | |
| JP2017522457A5 (zh) | ||
| US20190338147A1 (en) | Anticorrosive coating and method for obtaining same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| 17P | Request for examination filed |
Effective date: 20170104 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| 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 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) | ||
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
| 17Q | First examination report despatched |
Effective date: 20180201 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20180601 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1070327 Country of ref document: AT Kind code of ref document: T Effective date: 20181215 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602015020442 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Ref document number: 3175019 Country of ref document: PT Date of ref document: 20190226 Kind code of ref document: T Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20190219 |
|
| REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1070327 Country of ref document: AT Kind code of ref document: T Effective date: 20181128 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190228 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190228 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190328 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2712403 Country of ref document: ES Kind code of ref document: T3 Effective date: 20190513 |
|
| REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E041583 Country of ref document: HU |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190301 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015020442 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| 26N | No opposition filed |
Effective date: 20190829 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20190728 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20190731 |
|
| 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: 20190728 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190728 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190731 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190728 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20200727 Year of fee payment: 6 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20200717 Year of fee payment: 6 Ref country code: ES Payment date: 20200922 Year of fee payment: 6 Ref country code: FR Payment date: 20200723 Year of fee payment: 6 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20200724 Year of fee payment: 6 Ref country code: SE Payment date: 20200727 Year of fee payment: 6 Ref country code: HU Payment date: 20200905 Year of fee payment: 6 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20210801 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210729 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210729 Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220128 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210801 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181128 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210728 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20220905 |
|
| 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: 20210729 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240719 Year of fee payment: 10 |