DE2213084A1 - Electrodes for electrochemical processes - Google Patents

Description

The Torlisgesid © BrfincUmg "refers to llaktrodea f eloktroch ^ Msclie Verjfalire: a measure. Insfeesoncl © ^« aiai ¹ which are electrochemically "effective" Bsiag on il "oeiiadet ,, the from © in®ai lcorroaioIce-resistant ^ n metal

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Xu. egg?.?' Brxvd's patent specification i 244 630 is already ßählz.gi53. _t bJ.3 Slektrod © bei ei & em ©! © ktrcohe ^ ischea • 'ii'-jyi- riv:.? - ak -! -' a: e au T ^ rwsndea, = feei dar © is. elolctrocheialseh ni-Ä'-iCJ. "·? -i7.ß.2V _f " b <2f: 't © h'3nö from a large quantity © eiBeia M o.Tr' ..? / :. ac-r ? J fvi;:;. ngi: 'uppe imci © tesr largerB Mang © ßei ¹ - Ö2 £ ia <?. voa ί?. ^ · - ;. Ρίύ? ocio: r ^s i ^ ehi'srferi dar JSlsment; © ώίκΏ. _? Aatimon \ mcl G-eriaaniim

2098A2 / 1039 BAO ORIGINAL

is located on a carrier "which has been prepared from a film-forming metal such as beispzslswaiBe 'Xitsn orliegende" The i "invention nunmohr relates to an improved electrode of the provided with a coating film-forming 2yp © ₅ wherein said document from a Katalloxid the platinum group and Oxides of one or more of the elements of tin, antimony and germanium ".

(According to the invention, an electrode for electrochemical processes is proposed, which consists of a carrier part made of a film-forming metal or an alloy, depending on the relevant issue, which consists of the following three components: (a) Rutheaiiamdioxids (b) Xltandioxld ond (o) one or more of Binndioxid, <Jöraanditamdio3Cid and oxides of antimony, and in this Mi "" schu & g the amount of component (a) is not no less than% Gerwor $ _{r is} the slope of the component (b) more than 50 0ew _o -Si _f the length of component (c) within the range from i to öewo- ^ and the weight ratio a & r component (a) component (b) less than 2i1 is ₀

Under a fiüabildendnn metal odor alloy are ■ '. Zirconium, niobium, tungsten, or an alloy that builds up on one of these metals and eliminates the anodic polarization inherent properties? similar to 'den-Jenig-sn of pure MeHfcalles sied * The preferred metal for the production of the carrier part is titanium or its »it-fashionable polarization-affiliations - linear from " ■: "

• 53.i3k; :: - odex5. according to a-2r invention is more breucnber than Arao j ··. : /. _: 2-iion xtir oi © Mskt ^ cryas by .Lliralin ^ ti-illnhloriö-löeung

2098A2 / 1039

BATH ORIGINAL

especially 1λ skins with flowering seeds s

• because aar $ l8ktrod © nbelag auegeiseiaMiet adheres to the transforming metal carrier _} sis a suitably low ijfoerpotential Bvm Freimachen Ton G & Lor mid "© ine yefe © resistance g damage due to occasional contact with then amalgam feeeitsskodsäj the solTast Tdeail'work the aeccöimal'quec ^ B.sölles -araf tretsa kasa. " The electrocatalysis can be used just as well as other olectroehemiaciisa.Yerfshrea einaolili ^ eslieh otherji "l €> jfctrolytisea®n methods" are used, for example, for electrocatalysis, fe ^ ispislsynthese® ia B3? EiiJisifcoffs ©: U.on.isifcoffs timd ittr the cathodieclxeo. SehutaV

according to the Irfindian-gg the as A & e & en for di © electrolysis γοη AlicaliajetallchloyAdlSswagan ^ © rw ^ ndöt can be »besteaen from © in © m Srägartsil from Eitaa or'siner

the one. Topping on know? ά © 3? from 20 to 50. ^ , 40 Με 50 # Sitaadiosid -and 5 Ma, 25 dioside

An electrode according to the invention is aweok-wise Weis © made j that on an Ir & gstrteil from a ^ i Bild «nde-n metal or alloy a 4BStx * ichmii-t © l

«That from a - diirch heat © eiaw.1.rkuiig ssersetalwwen IT he toh Ruth © ilii7a, an 'dujroh Mraesto ^ irkuaag serseta" barbar organization overbipjaung you ! Esersetsfear ^ rertoinduajgsn uad du, rca. Heat © inxiirlcimg · oxidizable aaopgaaiscb.en Yerfeiadimgen Yon gizm · »SeriGasiniiaa \ mß. Antimony in an organic inert fluid _? Whereupon the coating is coated by evaporation of the Dräger fluid and then with the de.i! Sölag \ ^p erssiK5V) @ ad © n

2098A2 / 1039

BAD OR [QINAL

e within the range before ;. 400 t & s _?

e.rhitst t / irclr. x * m the compounds of ruthenium ^ titanium, tin *

and antimony in the oxides of these llesmnte tiberz & l · «· Further orders of Asastrichmittels can vwd then brought .f on the provided with the covering iDrägerteil & x? In the same way dried and wärmebehamdslt iferdejij. 13m aw so the strength of the gemiseiiten Oxidsehichis aui, 1 ^e .'des Mass.

Paint consists of Ye ^ MadEsiigen of Si tan tmd 2iim in an organic

The strength of the finished system is in no way is critical vzd in general, selected in the insight to the Aformtztuag, soft, the electrode of the währead Gebrauche in the elekisioohemisohen 2eil unterworfea ^ _f the self ucat'er andeai * 9Ei of current density _r depends on the the electrode work

For electrodes that are used as anodes in the electrolysis of alkali metal fluoride solutions, a thickness corresponding to a weight of the finished coating in the range of 5 and 40 g / m of the coated surface of the carrier file is generally suitable, thinner However, or thicker coverings can be used if desired.

In the an8triehiaittel: a _? the zuia separating according to the invention can be used, can the replaceable by the action of heat ε? Ruthenimverbimdung, for example, consist of ruthenium trichloride or Rutheniumreainat, ffeeignete by Wärra-süinxclrkung aersetzbare organic Yerbindun- gene of l'ITAA SSTR-d. l'itaaalkoxides _for titanium alkoxy halides »la which the halogen consists of oil, bromine or fluorine, as well as

209842/1039

The preferred citane compounds are the alkoxides and alkoxy halides, also known as alkyl titanates and alkyl halotitanates, particularly the alkyl titanates and al © titanates, in which the alkyl groups each contain 2 to 4 carbon atoms "Organocompounds of 55inn, germanium and antimony which can be replaced by the action of heat are alkosides and alkosihalog @ nides of these llem ^ ateo Gewttnöokteafallg can be oxidized by Wäimeeln effect asjorgaaiseixeia halide", 0oj3d © r9 the chlorides is particularly a lower alkanol or a mixture of niadsr® »iaefcesondere d« r ^ 9nigen »which contains 3 " to 6 carbon atoms in the molecule «» *.

The invention is explained in more detail in the following examples without being limited to this «

Bin Sitanbleohstreifen ron 35 om I _"ength? β jam width w && 1 starch was poured in ozalic acid solution, washed and dried. Sia anatriohaittel was prepared by dissolving 5.9 g of partially hydrated Etttheniiantriohlorid and $$ 6 g Setratomtylorthotitanat in 19.5 g n-j-pentanol and zueata of 5 g a solution made by dissolving 20 * 8 g of chloride in 60 g of n-pentanol. was dried at 180 ⁰ C and then wänaebehandelt duroh Br? · overheat in air for 15 minutes at 45O ⁰ Oo That Tells a finished coating was obtained 20 g / m of occupied! was titanium · ■ surface and in terms of weight of 40 % ruthenium dioxide? 45 % 21tandlO3cid and 15 fi tin & ioxiä

2098A2 / 1039

»· O β

From cLiösan. with the cover strip provided with sample pieces were cut and tested as anodes in dor producing chlorine from Natriumchloridsola which contained and 21 _# 5? S HACL with a pH 2-3 was at a {(temperature of 65 ⁰ C d. The samples were operated under a low, over-potential (50 to 70 m? At a current density of 8 kA / m) and the samples showed a gate resistance to damage when they came into contact with the cathode amalgam in a mercury cell came, in which Hatriurn Glorid brine was electrolyzed.

, 3 _r

Bin © anode, the working surface of which was in the form of a (fitter, was made from strips of oil and it had a projected surface of., 0.1 m _o This anode was made in

Etched, washed and dried for 16 hours. The anode grid was then sprayed with a Anstrichmittelstoffau, -aaiaiaensetaung consisting of 55 g Sutheniumtrichlori4, 136 g of tetra-n-butylorthotitauat and 29? P g Stannoootoat dissolved in 264 g was n »Pentaßor" wurd The Anstriehsauftrag * in an oven for 15 minutes dried at 18O ⁰ C and then wärmebehaadelt by Srhitsen in air in an oven oei 45O ⁰ C for 20 minutes, to thereby form a coating of the composition ra "40 J * RuOg, 45% SiOg and 15% snop, based on the weight A further seven coats of the same paint were sprayed onto the anode and each coat was dried and heat treated in the same way as the coating? to "a © total deposition of mixed oxides aur o.em Ti'sangittör · in an amount of 32 g / m is in this way configured zn surface yield.

209842/1039

se; ait dom covering v © rsab325.e SitajiasiQde warde darm ia © ine

BilberkathooLe-Bselle built in _for »the latrilumefcloricLsole el $ kt>? Ol; ymert -furde * This anode was worked satisfactorily for 6 months AbBntamig or Varringermig der

Example 3

Am T-ita'aanoclerigittar with ö ,. ' ^! st "pro3 © $ ti jrber Oberfläohe gemäGG Example 2 was provided with a coating with the Abwancllimg that the ABstricloraittel of 62.5 g 136 g HutlieniiMti'iohloridj Sstra ~ n-" btitylortlio "fcitaaat mid _20? 1 g in 266 g Stannoootoat TarS@niam.ol "bestando 'Dies® StoffsussiBjnsrisetsixag resulted in its covering of the ansaicmensetaraag τοϊι 45 f» EuOg »45 $ iSiOg and 10 $ 3n0 _o o Di ^ 6 A & strichmltt © lseMoäi · © s resulted in Eis © & 8sa3ntaT

Kig of mixed oxides on the Sita & lattice -of 32 g / m ■

projected Oborfl ^ ohs-o Idea © Anode Ufurd © © bsnfalls in Qu «! c] i: isilberkatlioß.i? nselie euib Electrolysis of. Uatriiam. Ohloridßol® uses xmä sssigto After δ months no or less · the effectiveness with- Yerwadtmg an anode 3trcia.es τοη up to 900 amperes ,.

Pat fc.üt

2098 4 2/1039

Claims (1)

EE ΪΔ3Ϊ SPSÜÜEE s Electrode for electrochemical processes ,, consisting
from a <a carrier part made from a forming metal or
Alloy, which has a coating that consists of a consists of three components? (a) ruthenia dioxide,
d and (c) one or more of tin dioxide,
Germanium dioxide and the oxides of antimony * being in this
Mix the amount of component (a) not less than
1. Gewo ~ 5S _? the amount of component (b) does not exceed 5%
the amount of component (g) is within the range from 1 to 80 β-ewn · "^ and the weight ratio of component (a)
s'or component (b) is less than 2i \ , 2o electrode according to claim 1 characterized gekennaeiohnet _{f #} that dor 2ragsr-Ge.il av.8 iUitan or a titanium alloy "
the similar anoic polarization axes such as
self 5o electrode according to claim 2 _t characterized in that the coating of 20 to 50 ^ Rutheniumdioxiä.?. 40 to 50 ^
dioacid and 5 to 25 % sin dioxide, based on the weight, consists. 4 «electrode according to one of the preceding claims,
It is clearly identified that the weight of the covering is within the range τοη 5 to 40 g / m of the covered surface
is o 5ο method ζην production of an electrode according to claim Ι «thereby gekemisw-iahnet ,, öasss on a carrier part from buckets . MeteXl ocia ;? Alloy a covering made of a material 209842/1039 is applied »which is made of sdner by heat Blsaren compound τοώ ruthenium j of an organic bond of itan and d at least one compound selected from by heat-decomposable organic compounds tmd by heat-oxidizable inorganic ¥ @ rl): Lnduiigan of ZiSHi consists of ₅ 6-ermanium xmä antimony- in an organic carrier liquid the covering is covered and then the beam part provided with a covering is heated to a temperature of at least 35O ⁰ G _{in an OEidiöxwdan atmosphere.} .um di © of ruthenium «, .'Sit ^ i., Zi: m _? Crei ^ isnium and antimony in oxides of these elements 60 Method according to claim 5, daduroh g © kesmgsichn © t _? The fact that the carrier part is made of titanium or an even titanium alloy admits that similar polarization characteristics are similar to that of. Si tan 7o? Experience according to one of claims 5 and 6 in that the sequence of the Aiifbrin ^ jas and Troekaene d ^ s B ^ lay «5s and the Brhitgung de _: ß with the Selag v © 3 ? · * · Is repeated at least once in order to build up a thicker layer of oxides. 8. The method according to any one of claims 5 to 7 * thereby ge · * kezmseichnet. that the total amount & © ß topping _? which is applied to the carrier part, sufficient iet _y mm one layer the oxide © zn result in _P the "5 Ms 40 g / m of the covered surface of the carrier part is _o Method n & oh one of the claims © 5 "to B _t in that the leather application after drying is © in the © r 209842/1039 • OK - oxidizing atmosphere at θ ± β · 3γ iiiape.t>: -. üiu- iuriü;, iialb of the range from 400 "to 5SO ⁰ CJ., lOc ancestors after 3ii «3m of the imaprücb / a 3 Mf; 9 ₅ by the fact that the material KU8Ks?. <; «N? Jet: -3wr. £ from compounds of Ruthaniroa, 2itcJi" and Sirrn ia. An organic carrier- 11 »Method according to claim 10, thereby <ilaae the shares ö.or .Verbiadnagön -Jon Rutlicnivei _# 2itsa ubö. 2i; iiB in the Stoffau.sam3Gaeas «ta« sig 4orart it was räiilt ^ Qn ^ that after the! TrookneK and the Srhit & an des Bela ^ as In an oxidizing atmosphere the "arch-sen CDicid"? Within the Bersiob. "Of 2G to 50 # Huthesiunaäloxid, 40 to 50 ■ / »! Titanium dioxide and others 5 'to 25 S ^ Eijßioxicl, bssogsn au :? dae 3-3wioli ^; ; d'5s toppings. "? or lie* 12o method according to one of claims 5 to 11 _f characterized j daae die d ^ rch VJärsiesiaB-irkang sers (!! • gano connection iron titanium is an alkyl titanate or ain aikjlhalotitstnat _{? In} which the halogen consists of chlorine> bromine or fluorine, 13 * Method according to claim 12, aaaui'ch characterized in that the alkyl groups of the alfeyl ^ itanate ode ie 2 to 4 carbon atoms contain, 14- electrode according to the Aneprii.eho 't bit 4 _; in that aie is used as an anode for the Elsk »roly3 ^ τοη OM or- uses ν ± ν &. 15, Slsictrode according to claim '' 4 <dadureii ge're-Mnzeich, δ.: \ Εε the cathode aue ^ eiaer flieseendo-n Q λ λ _Λ RATeNTANWALT * 209842/1039! 14.-INe ₁ RFiNCIaS, dipl-ing.h. »Oh« WPHNO. t. > TAK »H BATH ORIGINAL