CS271059B1 - Electrode for electrolysis of aqueous solutions containing alcaline metals chlorides - Google Patents

Abstract

The solution relates to the area of electrochemical equipment, to electrodes for aqueous solution electrolysis of alkaline metal chlorides in particular, with the aim to obtaining chlorine and caustic soda, chlorates and hypochlorites. The subject thereof is an electrode for aqueous solution electrolysis of alkaline metal chlorides containing an electro-conducting material base with an active coating of titanium, iridium and ruthenium oxides mix, while the components are used in the following relation expressed in molar per cents: <IMAGE>. The designed electrode ensures stability of anode potential during the electrolysis practically until the active coating is fully worn down, as well as the increase of the electrode resistance against anolyte pollution, the increase of the oxygen content in anode gases and the increase of the chlorine quantity. The solution can be used in chlorine, chlorates and hypochlorites production technology by electrochemical methods.

Description

1 271 059 OIIMCAIIHE H3OBPETEIIH31 K ABTOPCKOM CBHAETEJIbCTBy 3aflBjietio = 03.06.81 3asiBKa No.3298834 / 23-26 MKM3 C25B 11/10

Abtopu: B. B. Bycce-MaMyKac, Φ. H. JlbBOBHM. E.K. CnaccKad, B.A.KyeacoB, Α.Φ.Μβ33Ηκο. 3. A. Apywmimi. A.II.MapTUHOB u JI.H.IleJiHna 3asiBHTe.ni>: aBTop

IlaseaiiHe H3OrtpeTeiiHSi 3JIEKTP0A AJ1ÍI 3ΑΕΚΤΡΟΑΜ3Λ BOAHUX PACTBOPOB XAOPHAOB UIEJ10MIIUX METAJUIOB

HaoapeTenne othochtch to oejiacTH 3JieKTpoxHMH * iecKHX προηββοαοτβ, κοηκρθτηο. κ J KT KT po po J AH p AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH AH ΟΤΒΟΡΟΒ CT CT CT CT CT CT CT CT CT CT CT CT CT CT CT CT CT CT. XJlOpaTOB. ΓΗΠΟΧΑΟΡΗΤΟΒ. H3BecTen ajiexTpoA ajih 3JieiCTPOXHMH'iecKHX npoueccoB, coflepwamHfi BjieKTponpoBoaiiyio ocHoey.HanpHMep H3 THTaHa, on KOTOpyn iianeceno aKTHBiioe ποκρητηβ h3 cMecn okhcjiob THTana. hphahh hpyTeHMa; πρηίθμ coaepmaiiHe okhcjiob THTana b ποκρυτΗΗ siuJiaeTcsi 3na'iHTeAbHUM h cocTaBJísieT eojiee75 moji. *. llanpHMep.B H3BecTiioM ojieKTpoae noKpuTHe Jββτ cJieAyiomHH cocTae (moa. *) =

Ir02-3.94: Ru02-7.48 Η T102-8B.58 (oepaseu "B" H oepa3en "Λ") H IrO2-7,91; Ru02-15.l.l6 η T102-77.03 (oepa3eu “C”).

TaKHM oepa3OM. η ηίβμτηομ ojieKTpoae HiirpeAHeHTU b3situ b cjieaynuiHX cooTiiaiueiiHsix (my. *): Ti02 = (Ir02 + Ru02) - <3.3 - 7.8): 1 H Ir02: Ru02-0.5: 1 [11.

IEaTaTaTaTaTaNTaTaNTaTaNTaTiOnTiTaTiNTaTcViHnocTb atioAiioro noTeHunaJia πρηajieKTpojiHse. hhukhh buxoa no Toxy. iieaocTaTOHiiasi ctoSkoctb οαθκτρολβ. KpoMe τογο, iieaocTaTKOMajieKTpoaa HBJiae * rca iienoJinoe cpaeaTueaHHe aKTHBiiofl Maccu - noTeiiuHaji ajiexTpoaa ρβ3κο'BO3pacTaeT iiph itajiHMHH eiae AocTaTonnoro KOJiHH & cTBa Maccu aKTHBHoro ποκρμτηη.

Tax. riPH HcnuTaiiHsix oepaauoB "B". "C" h "A" b nacuiueiiHoM pacTBope NaCl πρη ujiothocth

Tone 1 Λ / cm2 h TexnepaType 65 ° aiioAiiuò ποτθιιηηοα oepaaua * 'B “H3MeiiHJica b npeaejiax 1.53-1.62 B3a BpeMH 3JiexTpojiH3a 2000 nacoB (~ 83 cztok), oepaaua“ C ”- n npeaejiax 1.35-1.38 B 3a npeMsianeKTpoJiH3a 2300 <iacoB ( ~ 96 cyTOK) h oepaaua “A · '- n npeaejiax 1.44-1.50 B 3a HpeMH 3jieKTpoJiH3a 816 <iacoB (34 cvtok).

HaHeojiee 6jih3Khm H3 HaaecTtiux TexiiHMecKHX peuieiiHn κ anHCUBaeMOMy ΗοαβρθτβΠΗίο noTex »iH * iecKofi cyuwocTH h aocraraeMOMy pesyjibTary aBAaeTca ojieKTpoa ajih ojieKTpojiH3a boahuxpacTBopoB xjiophaob uibjiomhux MeTaJijiob. coaepmamnň ociioey hs BettTHJibHoro MeTajuia c HaHecennuMHa Ηββ noxpuTHeM H3 cmbch okhcjiob eeHTHJibiiux MeTajuioB, HanpHMep THTaHa h okhcjiob MeTajuioB pyTeHHH, πρΗΊβΜ coaepjKaiiHe oKHCJia βθητηαβηογο MeTajuia aB H3BecTHOM ajieKTpoae ποκρητηβ κοικβτ coAepmaTb KaK cMecbnJiaTHiiu. HanpHMep pyTeHHM. τβκ h cnecb okhcjiob THTaHa h rpynnu ιυιβτΗΐιιι. HanpHMep hphahh hcmbch cocTaBJisieT eojiee 50 my. * .Okhcjiob THTana h oAiioro MeTaJiJia HBCKOJiiKHX MeTajuioB rpynnu njiaTHiiu. HanpHMep hphahh h pyTeiiHii Í2J.

HeAocTaTKOM H3BecTiioro sjíeKTpoaa ηβληθτοη ΗβΑοατβτοΊΐιβΗ ctoRkoctb.

UeJib H3oepeTeiiHH HBJisieTca noaumeiiHe ctoHkocth oJieKTpnaa. nocTaBJíeinian not eat aocTHraeTca ojieKTpoAOM ajih 3JieKTpojiH3a boahux pacTBopoB xjiophaobweJlOHHNX HeTajuifJB. coAepmauiHM ocnoey ho BeHTHJibiioro MeTaajia c HaiiecemiUM Ha hub ni xputhem hoCMeCH OKHCJIOB THTaHa, ΗΡΗΑΗΗ H pyTeilHH. ΠΡΗΜβΜ COAepmaHHe OKHCH THTaHa B CMBCH COCTaBJIHBTeojiee 50 moji. *, OcoeeiiHOCTbw κοτοροτο HUJiaeTca το. · Ιτο noKpuTHe coAepiHHT okhcjiu hphjihh hpyTeiiHfl πρη mojimicim cooTHOiueHHH (0.75-3) = 1.

J TJIHHHTeJlbHUM ΠΡΗ3ΗβΚΟΜ IiPeAJlOWeHHOrO OJIBKTpOfla HBJíaeTCSl TO, OK IlOKPUTHe COflepiKHT OKHCJIU HPHAHH H pyTOIIHH IIΡΗ MOJIbHOM COOTIIOUieilHH (0.75-3) = 1.

AonOJIHHTeAblIUM OTAHHHTeAblIUM ΠΡΗ3Ι1ΒΚΟΜ ΠΡθΑϋΙΟΙΜβΙΐηΟΓΟ ΒΑβΚΤρΟΑβ SIBJISIOTCÍI TO. A ΠΟΚρΜΤΗΟ coAepwHT okhcjiu THTaiia b KojiHMecTBe 50-75 moji. *. 271 058 2 npaKTHMecKoe HcnojiiraoBaiiHe npeajiaraeMoro ojiexTpoaa h ero npeHMyuiecTBa nepea η3βοι, * τημμajiexTpoaoM b ycjiOBHHX 3JiexTpojiH3a βολιιμχ uct op

IlEHMSEL ·.

Ha THTaiioBye ociiooy saexTpoaa. npeaBapHTeabHO npouieauiyn necxocTpyHiiyio oapaetmcy, aeeawHpoDaime h rpatuieriHe. nanocHT ποκροβιιμη pacTBop - CMemaiiHUH βολιιμΗ pacTBop IrCH, TICH h Ru OIICI3. ΠΟΚΡΟΒΙΙΜΗ paCTBOp ΓΟΤΟΒΛΤ H3 HCXOaHUX paCTBOpCIB Η ΟΗΠΟΗβΙΙΤΟΒ: paCTBOpa ΓΗΛΡΟΟΚΟΗΧΛΟΡΗΛΒpyTGHHSi (RUOIICI3) b Boae c KOiiueiiTpaiiHefi 150 * 5 γ / ji; paCTBOpa 'leTupexxaopHCToro THTaHa (TICH) b aoae c KoiHTpauHen 220 * 5 γ / λ <b nepecseTe on TIO2): ccjjth TpexxjiopncToro ηρηληη (I.rCl3) CaoeaBJiXioT □ cMeuiamu pacTBop RuQIICla -TICH b BHae κρηοτλλλοβ).

AxTHBlloe noxpuTHe 3ΛβχτρθΛβ Η3ΓΟΤββλπκ> τ μηογοολοΗιιμμ. KawauH cjioh HaHocsiT no cjiejiymueiíTexHOJiorwv pacxoa CMeuiaimoro paCTBOpa 11 and οληιι cjioh - 25 mji / m2. ίτο cooTBeTCTByeT aaK.naaKtaKTHBHOH Maccu 1-2 γ / μ2; j j ece ama ama ama ama ama M M M M M M M M M M M M M M M M M TeMnepaType150 ° C. 3aTBH ocDKiirauT πρη TeMnepaType 350 ° C b Teneime 20 MHiiyT nepeue 2-3 cjioh. nocaeayioiiiHecjioh npoKaJiHBawT πρη TeMnepaType 450-500 ° C b τβ'ΐεκΗβ 20-40 MHHyr.

Bcero tsuJio ηογοτοβλθηο 9 sjíexTpoaoe, H3 hhx aea - OTBenaJiH no cocTaey HseecTiioMyojiexTpojty (oepauiiM 1 h 0) [21. aaa - οτββίολη no cocTaey H3BecTiioMy oJiexTpoay (oepa3tu> i 4,5,6,7). Aiληιι oe> pa3eu (oepaaeu 9) HaaiocTpHpyeT ajiexTpoa c ποχρμτηθμ H3 cmech okhcjiob THTaiia, py H pyTeilHH. ΠΡΗΜΘΜ ΟΟΛβρίΚβΙΙΗβ OKHCH THTaHa B CMCCH COCTHBJIHeT ΜβΙΙΗβ 50 ΜΟΛ.%.

Oepaaeu No.l cocoTBercTByeT oeiuenpHUHTOMy b iipoMMuuieiitiocTH OKHCHOMy pyTeiiHeeo-THTanoBOMyanoay (OPTn-saperHCTpHpoBaHHuun τοργοβμη 3Hax). H3MepeHHH noTeimHajia ANOA προβοληλη b ycnonasix xjiopiioro aaeKTpojiHaa: KoímeiiTpauHHpaCTBOpa χλορηαβ uaTpHH 280 γ / λ, Texiiepa peck-90 ° C, PLI "3.0 to 3.5, njioTiiocTb Toxa - 1000, 2000.4000, 6000, 10000 H Λ / m2 HB ycjiciBasix χλορλτιιογο 3jieKTpojiH3a: 400 r / l aC 03-100 g / l NaCl. PLL-7 iiJioTliocTb Toxa 1000-3000 Λ / μ2: ToxnepaTypa 80 ° C CToňXOCTb 3ΛΘΚΤΡΟΛΟΒ OUeHHBaAaCb well lieCKOJILKHM yCKOPBHlIUM ΗΒΤΟΛΗΚΒΜ H3Y * ieHHHH3HOCOCToftxocTH ΟΛβκτροΛΟΒΐ well HeToay nepeMeimoH noanpiiocTH h aMajiaraHaUHH, πρκ sJíexTpuJiHae bpacTBope NaOll. h b ycjioiixax AJiHTeabHoro ajiBKTpcuiHaa.

CyuiHOCTi, e nepeMeimoH nojiHpnocTH η aMaJibraMauHH 3axjno'iaeTCH b ejieayioiiieM = HcnuTMBaeMUH oepaaeu npn ojiotiiocth Toxa 1 Λ / cm2. TeMnepaType 60 ° C pacTBope xnopmia iiarpmi cKonueiiTpauHeti 300 r / .π noaBepraioT nepeMeimoH atioanoH η κβτοΛίιοΗ ποληρη3βιιηη b Teneime 40MHiiyT. 3aTeM nyβκτροΛ cnycxaioT at 30 cexyne u aMa urany ιιβτρηπ c xonuetiTpauHeH ηβτρηη 0.2% noMacce. IlocJie othx HCiiMTaimH ojiexTpoa npoMUBa »T b ληοτηλληροβ8ΗΗοΗ eoae. cyuiaT h onpeaejinioTποτθρη Beca. M3HOCOCToHKOCTb 3ΛβΚΤρθΛΟΒ ΠΡΗ 3ΛβΚΤρθΛΗ3β paCTBOpOB NaOll. H3y * alDT B CJieaylOlUHX yL-χ: 200 r / l pacTBop NaOll. TeMiiepaTypa 90 ° C, njioTHOCTb Toxa 2 Λ / cm2 h onpeaeJiHioT πατορ »eecao« pa3ua h epeHH α 3anHpatmH and Hoaa.

PeayjibTaTU HcnuTaimH npHBeaenu b TaeJiHue.

Kax Hίιο H3 pesyjibTaTOB. npHBeaeHiiux b Taejmue. aHyaTaTaTaTa (oepaauu 4.5.6.7) noTynaTeTaTyAaYaXTpoYa (oepauuu 1.8) noBiomimie aiioanoro noTenuHaaa b ycjioBHMxXJlOPHOrOH XJIOpaTHOrO3JISXTPOJI3a. 3,271,039

TaejiHUa o b p a 3 n u 12 3 4

HaHMenoaatiHe

noKaaaTejteH

CrjoTfiouieHHe okhcjiobb aKTHBioon wacce. % MY. T102 70 88.66 78.95 70.8 Ir02 - 3.91 7.25 12.5 Ru02 30 7.43 13.8 16.7 τιθ2 = <irOz + RuOa) 2.33: 1 7.8 = 1 3.75 = 1 2.44 = 1 :2: RuOa - 0.528: 1 0.525 = 1 0.75 = 1 (loTeHiiHaji aiiojta byCJIOBHflX XJIOpHOrO3jOctHyA3a. B.flpH nJIOTHOCTH TOKa <ft / M2) = 1000 1.3 1.45 1.32 1.30 2000 1.33 1.50 1.34 1.32 4000 1.35 1.55 1.36 1.35 6000 1.37 1.60 1.38 1.36 10000 1.40 1.62 1.39 1.37 noTeiitmaJi anoaa b ycJiOBHsix XJiopaTnoro 3JieKTpoJiH3a. B, (HB3). npH njioTiiocTH TOKa (fl / M2> = 1000 1.40 2000 1.43 3000 1.49 5 6 7 8 9 70.0 70.0 75.0 50.0 45 15.0 20.0 18.7 30.0 22 15.0 10.0 6.3 20.0 33 2.33 = 1 2.33 = 1 3 = 1 1 = 1 0.82 = 1 1 = 1 2 = 1 3 = 1 1.5 = 1 0.67 = 1,271,059 4 npoAOJimeHHe TaejiHuu 1.30 1.30 1.31 1.32 1.31 1.31 1.31 1.32 1.33 1.34 1.35 1.36 1.36 1.36 1.35 1.36 1.37 1.37 1.37 1.361.41 1.401.44 1.43

O B P Λ 3 II U

RaHMenosaiiHe __ noKa3aTejieR 1 2 3 4 CTCiHKOCTb aJieKTpoaa ΠΟ ΜβΤΟΛΨ ΠβΡβΜβΗ-

Ho naJlSipilOCTH H aMajibraMauHH, ηγ / cm2 0.2 0.4 0.3 0.15

BOTToqAanpH 3JieKTpjlH3e BpacTBope 200 γ / jiNoOll noTepH aKTHBiBiMMaccu <nr) ot BpeMeiiH3jieKTpojH3a. Mac: 5 Mac 0.4 10 Mac 0.9 15 Mac 1.2 20 Mac 1.7 25 Mac 2.1 30 Mac 40 Mac 45 Mac 50 Mac 55 Mac 60 Mac 70 Mac 0.3 0.6 0.3 0.6 0.8 0.4 0.9 1.2 0.6 1.4 1.5 0.8 1.8 2.0 0.9 2.4 2.5 1.7 3.7 1.9 2.8 4.0 4.6 4.8

BpeMfl npoeera and BMXOAa 83 'CTPOS1 yesaa. Mac. 23 30 40 60 (lpesoiiaMaJibHaíi 3aKJiaaKa βκτηβ ~ nofi Maccu. ΜΓ 5.6 5.5 5.8 5.4 5,271,059

npojiojDKeHHe TaejiHHW 0.07 0.05 0.08 0. 17 0.5 0.1 0.2 0.1 0.3 0.4 0.2 0.3 0.2 0.5 0.7 0.3 0.5 0.4 0.9 0.9 0.7 0.6 0.5 1.7 1.5 1.1 0.8 0.9 2.5 2. 1 2.5 1.8 1.2 3.1 2.7 3.0 2.7 2.5 3.8 3.3 3.6 3.6 2.9 4.5 4.7 5.0 4.2 3.3 5.2 5.3 5.0 3.6 5.5 5.3 4.3 5.8 5.4 5.1 70 70 70 50 45 5.8 5.5 5.2 5.6 5.7 271 059 6

Bo BCeH 3aHBJieHHOM HHTepBajie MOJItHOrO COQTHOlUeHHX OKHCJIOB HPHAHH Η ΡΥΤΘΗΗϋ B ΠΟΚΡΜΤΗΗ. aHMeiiiio <0.75-3): 1, ctoííkoctb npejuiomeinioro ajieKTpoaa. oueiiHBaeMaa on ποτβρβ βκτΗΒΗοϋ Macau.Kax iiph HcnuTaiiHSix on Meiw nepeMeimoň hojisiphocth h aMajiBraMauHH. «κ h b CH CH CH CH CH CH CH CH CH CH CH CH CH CH CH CH CH CH CH O O O O O O O O,,,,,,,,,,,,,,,,,,,,,,. πρΗΜθριιο b 1.5-2 pa3a. Πρη coAepmatiHM okhch THTana β ποκρητηη eojiee 75 moji. % h πρη myo cooTnouienHH okhcjiobOKHCJIOB HpHJIHH H pyTeilHH ΒΗΘ 3aXBJieHIIOrO HIITepBajia CTOilKOCTb 3JieKTpO.ua iinme, mkm ynpeJuioweHitora (cM.oepaanu 2 u 3). CjieayeT οτμθτητβ * ito πρη cofleputaiWH okhch THTana bποκρητηη Meiiee 50 my.% Aawe b npenejiax 3asiB.neHHoro HHTepeajia Mojiaiioro cooTiiouieiiHsi okhcjiobhphahh h pyTeHHH ctoUkoctb oJieKTpOfla najineTcx HeyaoBJíeTBopHTejiBHoň (cM.oepaaeu 9). 271 059 • OPHYJIA Η30ΕΡΕΤΕΙΙΗ »1. 'JjieKTpCMi juih 3jieKTPOJiH3a boahux pacTBoprjB xaophaob iubaomhux HeTaJiJioB, coAepmauiHH □ ciiOBy H3 BeiiTHJibHoro MfíTajiJia c HaiiecemiUM Ha nee ποκρμτηθη H3 cmoch okhcjiob THTana. hphahíih pyTeHHH, eoaepixaHHe okhch THTana and cMecH cocTaojisieT eojiee 50 moa.%. hto. c ueJibio nrjBUiueHHX ctoBkocth 3JieKTpo «a. ποκρΗΤΜβ coaepwHTOKHCJ1U HPHAHII H pyTeilHH IlpH MOJIBHOM COOTHOUieHHH <0.75-3) = 1. 2. 3ΑβκτροΑ no n.l. o τ x h la lanutH fi c h Ten, ίτο πακρωτΗβ coaepmHT okhcjiu thtíiiiíib KOJiHMecTBe 50-75 mo.ji.%. HCTOMIIHKH HH «OPHaUHH. ΠΡΗΗίΙΤΗθ BO BIIHHaHHe ΠΡΗ 3ΚΟΠβρΤΗ3β: l.US, Λ. 3940751. 2.SU. ň. I 271 059 8

P E · E P A T

3ΛΕΚΤΡΟΛ AJIH 3ΛΕΚΤΙΌΙΙΗ3Λ ΒΟΛΙ114Χ PftCTBOPOB XJlOPHflOB UEJIOHIIUX METAJLHOB

HacxspeTeiiHe otiiochtch k oejiacTH aJieKTpoxHMMnecKHX προη ^ βολοτβ. καιικρθτιιο. κ ajiexTPoaaMajisi 3JieKTpoJiH3a boahmx pacTBOpaB xjkjphaob uieJioMiiux MBTajiJioB c najiyneimeM xjiapa h KaycTH * iecKoňCOflU. XJIOpaTOB h rHHOxjiopHTOB. npejuiometi bjibktpoa juia aJieKTpojiwaa boahmx pacTBopoe xjiophaob uteJioMHUx MeraJinoB.coAepmaiUHií ocnosy H3 ajieKTponpoBoanoro MaTepHaJia c naHeceiiHUM on nee ηκτηβηνη ποκρμτηθμ ηίchbch okhcjiob THTaiia, HpHaHíi H pyTeHHSi, npn'ieH HiirpeAHeiiTU bbíitu npx cjiejiymmeM cooTiiouieiiHH for MOJinpiiux%.

TlOa: <IrCte + Rutte> - <1-ί · 3>: 1 H Irtte: Ru02- <0.75-33): 1 npeannomoHiiuft ojieKTpoa oeeciieMHuaeT cTaeHJibiiocTi · yesaiioro noTemmaJia bo upkmh 3.πθκραπΗ3β πρβκτΗΜβοκκ λο nojitioro cpaeaTMBaHHfl βκτηβηογο noKpuTHsi. noBuuieHHe ctoRkocthBJieKTpoAa npH 3aiuejiaHHBaHHH aHOJiHTa h noBuuiemiux coaepHtaHHax KHcjiopoaa b aHOAHux raaax hnoBNiuetiMe euxoaa no Toxy xjiopa.

MsoepeTeiiHB HOHffiT <suTb Hcnojib3OBaHO and TexiiojiorHH xjiopHoro. rjiopaTHoro η γηποχλορητηογοnpOH3BOACTBa 3JieKTpOXHMH'ieCKHMH ΗβΤΟΛάΗΗ.

Claims (2)

271 OS9 OBJECT OF THE INVENTION An electrode for the electrolysis of aqueous solutions of alkali metal chlorides containing a base of an electroconductive metal coated with a mixture of titanium oxides. Iridium and rutene. wherein the titanium content of the mixture is more. more than 50 mole, characterized in that the aim of increasing the resistance of the electrode comprises a coating of Iridium oxide and ruthenium at a molar ratio of 0.75 to 3 -1. 2. The electrode according to item 1, characterized by it. wherein the coating comprises titanium oxide in an amount of 50 to 75 mole%