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(11) | EP 0 004 880 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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Electrodes for electrolytic processes, especially perchlorate production Elektroden für elektrolytische Verfahren, insbesondere zur Herstellung von Perchloraten Electrodes pour procédés électrolytiques, en particulier pour la production de perchlorate |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
Technical field
[0001] The invention relates to electrodes for use in electrolytic processes, of the type comprising an electrically-conductive and corrosion-resistant substrate having an electrocatalytically-active surface coating, and to electrolytic processes using such electrodes, especially (but not exclusively) as anodes for the production of chlorates, perchlorates and other persalts and percompounds including organic peroxyacids.
Background art
[0002] For the production of perchlorate, various anode materials have been used commercially, including smooth massive platinum, platinized titanium or tantalum (despite a tendency to produce excess oxygen) and lead dioxide coated on titanium or graphite, although these lead dioxide anodes have a high overvoltage and wear rapidly.
[0003] Some proposals have already been made to combine platinum group metals and tin dioxide in electrode coating materials. For example, U.S. Patent Specification 3,701,724 mentioned an anode for chlorine production having a coating consisting essentially of a minor amount of a platinum group metal and/or platinum group metal oxides with a major amount of Sn02' Sb205, Sb203 or Ge02 and mixtures thereof. However, the claims and examples of this patent are directed solely to such coatings containing platinum group metal oxides and there is no enabling disclosure of a coating containing a platinum group metal. Also, U.S. Patent Specification 3,882,002 proposed an anode for chlorine production having a valve metal substrate coated with an intermediate layer of tin dioxide which was covered with an outer layer of a platinum group metal or oxide thereof. Neither of these proposals was directed to improving electrolytic performance in the production of percompounds.
Disclosure of invention
[0004] An object of the invention therefore is to provide an improved electrode suitable for use as an anode for the production of perchlorates and other persalts, but which may also be used in other applications, such as chlorate production.
[0005] According to a main aspect of the invention, an electrode comprises an electrically-conductive corrosion-resistant substrate having an electrocatalytic coating and is characterised in that the coating consists of a mixture of at least one platinum group metal and tin dioxide dispersed in one another throughout the coating in the ratio of 8.5:1 to 3:2 by weight of the platinum group metal(s) to the tin (as metal) of the tin dioxide and, optionally, as dopant of the tin dioxide in a total quantity of up to about 30% by weight of the tin, at least one additional metal or oxide of zinc, cadmium, arsenic, antimony, bismuth, selenium and tellurium. The coating may contain one or more oxides of antimony and/or bismuth in an amount of at most 1 part by weight of Sb/Bi to 4 parts by weight of Sn. In the case of antimony trioxide or bismuth trioxide as dopant, the preferred amount corresponds to a ratio expressed as parts by weight of Sb/Bi:Sn (as metal) of at most about 1:4 to about 1:10 or even as low as 1:100.
[0006] The platinum group metals are ruthenium, rhodium, palladium, osmium, oridium and platinum. Platinum is the preferred platinum group metal in the coating, when a single metal is present, especially in anodes for perchlorate production. However, it is understood that alloys such as platinum-iridium and platinum- rhodium are also useful for other applications. An alloy of platinum-palladium containing up to 20% palladium by weight of the alloy has given very satisfactory results for perchlorate production.
[0007] The substrate may consist of any of the valve metals, namely titanium, zirconium, hafnium, vanadium, niobium and tantalum, or alloys thereof, porous sintered titanium being preferred. However, other electrically-conductive and corrosion-resistant substrates may be used, such as expanded graphite.
[0008] The platinum group metal(s) and tin dioxide with possible additional dopants, such as antimony trioxide or bismuth trioxide, may be co-deposited chemically from solutions of appropriate salts which are painted, sprayed or otherwise applied on the substrate and then subjected to heat treatment, this process being repeated until a sufficiently thick layer has been built up.
[0009] Alternatively, thin layers of different components (e.g. alternate platinum or Pt/Pd alloy layers and layers of pure or doped tin dioxide) can be built up in such a way that the components are effectively mixed and dispersed in one another throughout the coating, possibly with diffusion between the layers, in contrast to the known prior art coatings such as that of U.S. Patent Specification 3,882,002, in which the tin dioxide was applied as a separate intermediate layer covered by a platinum group metal. Using this procedure of applying alternate layers, it is possible to deposit thin layers of platinum galvanically, which is advantageous, because galvanically-deposited platinum has a lower oxygen evolution potential than chemi-deposited platinum.
[0010] The platinum-group metal or alloy/tin dioxide layer may be applied directly to the substrate, or to an intermediate layer, e.g. of co-deposited tin and antimony oxides or tin and bismuth oxides, or to intermediate layers consisting of one or more platinum group metals or their oxides, mixtures or mixed crystals of platinum group metals and valve metal oxides, intermetallics of platinum group metals and non-platinum group metals.
[0011] In a preferred embodiment, the coating comprises 40 to 85 parts by weight of platinum, 0 to 20 parts by weight of palladium and 15 to 40 parts by weight (as Sn metal) of tin dioxide on a titanium, tantalum or titanium- tantalum alloy substrate. This embodiment of an electrode of the invention, when used as anode for perchlorate or persulphate production, has been found to have selective properties favouring the persalt production while hindering oxygen evolution. The platinum metal acts as a catalyst for persalt production. The tin dioxide acts as an oxygen evolution inhibitor by blocking peroxide decomposition, which can be regarded as the intermediate step of the unwanted oxygen evolution reaction. Finally, the palladium acts as a diluent for the relatively more expensive platinum, without adversely affecting the oxygen inhibition effect of the tin dioxide.
[0012] Another aspect of the invention is a process for the production of chlorates, perchlorates and other percompounds, e.g. persulphates, which is characterised by using as anode an electrode according to the invention, as defined above.
Brief description of drawings
[0013] In the accompanying drawings:
Fig. 1 shows a graph of the faraday efficiency of oxygen evolution as ordinate plotted against the tin content of the electrode coating as abscissa, the electrode being that described below in detail in Example I;
Fig. 2 shows a graph of the faraday efficiency of oxygen evolution as ordinate plotted against the palladium content of the electrode coating as abscissa, the electrode being that described below in detail in Example I1.
Best modes for carrying out the invention
Example I
[0015] Titanium coupons measuring 10×10×1 mm were sandblasted and etched in 20% hydrochloric acid and were thoroughly washed in water. The coupons were then coated with an aqueous solution of chlorides of platinum and tin in different weight ratios, dried at 95° to 100°C and then heated at 450°C for 15 minutes in an oven with forced air ventilation. The procedure was repeated five times and the coupons were given a final heat treatment at 450°C for 60 minutes. The coatings so produced contained Sn02 and platinum metal dispersed in one another.
[0016] The coated coupons were tested as anodes for the production of sodium perchlorate by the electrolysis of a solution consisting of 100 g/I NaClO3, 400 g/i NaC104 and 5 g/I Na2Cr04 at 30°C using a stainless steel cathode and a current density of 2 KA/m2. Sodium chlorate was supplied and sodium perchlorate removed to maintain the concentrations in the electrolyte at a steady state. The faraday efficiency of the oxygen evolution reaction (i.e. the unwanted side reaction in perchlorate production) was measured as a function of the percentage by weight of tin (as metal) in the mixed Pt-Sn02 coating. The results obtained are shown in Fig. 1, from which it can be seen that there is an optimum oxygen-inhibition effect for a tin content in the range of about 25%-35% of the total weight of tin and platinum metals, and a very appreciable inhibition of oxygen evolution for a tin content in the larger range from about 15% to about 40%.
Example II
[0017] Titanium coupons were coated as in Example I, but using various coating solutions containing platinum, palladium and tin chlorides, to produce mixed Pt-Pd-Sn02 coatings having compositions as follows:
[0018] These coupons were tested as anodes for perchlorate production under the same conditions as used in Example I. The faraday efficiency of the unwanted oxygen evolution reaction was measured as a function of the palladium metal content, and the results are shown in Fig. 2. This graph shows that, for a palladium content up to 20%, the faraday efficiency remained low, i.e. the palladium did not adversely affect the performance of the coating to inhibit oxygen evolution. However, above the critical Pd content of 20%, the faraday efficiency abruptly increased, the stability of the coating was lowered and some electrochemical corrosion took place.
1. An electrode for use in electrolytic processes, comprising an electrically-conductive
corrosion-resistant substrate having an electrocatalytic coating, characterised in
that the coating consists of a mixture of at least one platinum group metal and tin
dioxide dispersed in one another throughout the coating in the ratio of from 8.5:1
to 3:2 by weight of the platinum group metal(s) to the tin of the tin dioxide and,
optionally, a total quantity of up to about 30% by weight of the tin of at least one
additional metal or oxide of zinc, cadmium, arsenic, antimony, bismuth, selenium and
tellurium.
2. An electrode according to Claim 1, characterised in that the platinum group metal
is platinum.
3. An electrode according to Claim 1, characterised in that the coating comprises
40 to 85 parts by weight of platinum, 0 to 20 parts by weight of palladium and 15
to 40 parts by weight of tin.
4. An electrode according to Claim 1, 2 or 3, characterised in that the coating contains
one or more oxides of antimony and/or bismuth in an amount of at most 1 part by weight
of Sb/Bi to 4 parts by weight of Sn.
5. A process for the production of chlorates, perchlorates and other percompounds
by electrolysis, characterised by using as anode an electrode as claimed in any preceding
claim.
1. Elektrode zur Verwendung in elektrolytischen Prozessen, die ein elektrisch leitfähiges,
korrosionsbeständiges Substrat mit einer elektrokatalytischen Beschichtung aufweist,
dadurch gekennzeichnet, daß die Beschichtung aus einer Mischung von mindestens einem
Platinmetall und Zinndioxid, die über die gesamte Beschichtung im Gewichtsverhältnis
von Platinmetall(en) zu Zinn des Zinndioxids von 8,5:1 bis 3:2 ineinander dispergiert
sind, und gegebenenfalls einer Gesamtmenge von bis zu etwa 30 Gew.% bezogen auf das
Zinn mindestens eines zusätzlichen Metalls oder Oxids von Zink, Cadmium, Arsen, Antimon,
Wismut, Selen und Tellur besteht.
2. Elektrode nach Anspruch 1, dadurch gekennzeichnet, daß das Platinmetall Platin
ist.
3. Elektrode nach Anspruch 1, dadurch gekennzeichnet, daß die Beschichtung 40 bis
85 Gewichtsteile Platin, 0 bis 20 Gewichtsteile Palladium und 15 bis 40 Gewichtsteile
Zinn enthält.
4. Elektrode nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß die Beschichtung
eine oder mehrere Oxide von Antimon und/oder Wismut in einer Menge von höchstens 1
Gewichtsteil Sb/Bi zu 4 Gewichtsteilen Sn enthält.
5. Verfahren zur Herstellung von Chloraten, Perchloraten und anderen Perverbindungen
durch Elektrolyse, dadurch gekennzeichnet, daß als Anode eine Elektrode gemäß eines
der vorangegangenen Ansprüche verwendet wird.
1. Electrode pour procédés électrolytiques, comprenant un substrat électriquement
conducteur et résistant à la corrosion, ce substrat étant doté d'un revêtement électro-
catalytique, caractérisée par le fait que le revêtement est composé d'un mélange d'au
moins un métal du groupe du platine et de dioxyde d'étain dispersés l'un dans l'autre
dans tout le revêtement, avec une proportion comprise entre 8,5:1 et 3:2 du poids
du métal ou des métaux du groupe du platine au poids d'étain du dioxyde d'étain, et,
éventuellement, d'une quantité totale pouvant atteindre environ 30% du poids de l'étain
d'au moins un métal additionnel, pouvant être sous forme d'oxyde, choisit dans le
groupe formé par le zinc, le cadmium, l'arsenic, l'antimoine, le bismuth, le sélénium
et le tellure.
2. Electrode selon la revendication 1, caractérisée par le fait que le métal du groupe
du platine est le platine.
3. Electrode selon la revendication 1, caractérisée par le fait que le revêtement
comprend de 40 à 85 parties en poids de platine, de 0 à 20 parties en poids de palladium
et de 15 à 40 parties en poids d'étain.
4. Electrode selon la revendication 1, 2 ou 3, caractérisé par le fait que le revêtement
contient un ou plusieurs oxydes d'antimoine et/ou de bismuth en une quantité maximale
de 1 partie en poids de Sb/Bi pour 4 parties en poids de Sn.
5. Procédé de production de chlorates, de perchlorates et d'autres per-composés par
électrolyse, caractérisé par l'utilisation en tant qu'anode d'une électrode selon
l'une quelconque des revendications précédentes.