SE200063C1

SE200063C1 -

Info

Publication number: SE200063C1
Authority: SE
Publication date: 1965-01-01

Description

Uppfinnare: K Kordesch Prioritet begiird fran den 30 september 1958 (USA) Foreliggande uppfinning hanfor sig till en cell med hog spanning och hag stromtathet far framstallning av elektricitet genom. kemisk forening ,av vatgas och iklorgas i en syraresistent behallare, inarvid en sadan cell innefattar minst en rarformig vateelektrod av porost aktiverat kolh.altigt material med en vatedissociationskatalysator darpa, en vanlig sur .elektrolyt omgivande ytterytorna hos samtliga elektroder och Tried gastilledning och avledning samt stromuppsamlingsanordningar for elektroderna. Cellen enligt uppfinningen kannetecknas av ,att (a) +elektroderna ha en porositet av 30-%, (b) vatedis.sociationskatalysatorn utgares .av platina, rhodium, palladium, iridium, rutenium eller osmium i en koncentration av 0,25-8 mg per kvadratcentimeter elektrodyta och att (c) tillgänglig yta pa vateelektroden är 5-19 % stone an ytan pa klorelektroden. Inventor: K Kordesch Priority Begiird from September 30, 1958 (USA) The present invention relates to a cell with high voltage and high current density for the production of electricity by. chemical compound, of hydrogen gas and chlorine gas in an acid-resistant container, in which such a cell comprises at least one rare earth electrode of porous activated carbonaceous material with a hydrogen dissociation catalyst darpa, an ordinary acidic electrolyte surrounding the outer surfaces of all electrodes and Tried gas conduction and discharge for the electrodes. The cell of the invention may be characterized in that (a) + the electrodes have a porosity of 30-%, (b) the hydrogen dissociation catalyst is composed of platinum, rhodium, palladium, iridium, ruthenium or osmium in a concentration of 0.25-8 mg per square centimeter of electrode surface and that (c) available surface of the hydrogen electrode is 5-19% stone of the surface of the chlorine electrode.

Pa de bifogade ritningarna visar fig. 1 en vertikal sektion av en cell i enlighet med uppfinningen och fig. 2-6 schematiska vyer, ,som visa olika -arrangemang -av elektroderna i cellen. In the accompanying drawings, Fig. 1 shows a vertical section of a cell in accordance with the invention and Figs. 2-6 are schematic views showing different arrangements of the electrodes in the cell.

Branslecellen enligt foreliggande uppfinning bestar av ett hölje, innehallande porosa vate- och klorelektroder, naldoppade i sur elektrolyt. For att intitiera cellverksamhet far vate resp. klorgas -pass:era genom elektroderna. Vate .diffunderar genom sin elektrod for att ge tva elektroner och tva vatejoner per mol vate. Klorgasen dissosierar till 2 klorjoner med nettoresultatet att dar uppstar en nettostramning av bra. elektroner frau, vatet till klorelektroderna samtidigt med bildandet av klorvate.gas. The fuel cell of the present invention consists of a casing containing porous cotton and chlorine electrodes dipped in acidic electrolyte. In order to initiate cell activity, vate resp. chlorine gas pass: era through the electrodes. Water diffuses through its electrode to give two electrons and two water ions per mole of water. The chlorine gas dissociates into 2 chlorine ions with the net result that there is a net tightening of good. electrons frau, the vat to the chlorine electrodes simultaneously with the formation of chlorvate.gas.

Enligt fig. 1 bestir cellen enligt uppfinndngen .av ett holje 10, lampligen utfort av ett syralaestandigt plastmaterial sasom polysty ren- eller metylmetakrylat- harts, i vilket hOlj e porosa ihaliga aktiverade kolelektroder 12 och 14 aro .monterade, i vilka infOres resp. Tate och klorgas. Dessa gaser inforas medelst tillfOrselledningama 16 och 18, vilka aro fOrbundna :med sina elektroder med kopparbekladda kol-kapor 20 och 22 och som, hallas i lage inuti elektroden medelst en gummiring 24. Liknande rordelar 26, 28 aro fOrbundna med botten av varje elektrod genom kaporna 30, 32 och tjana som gasavloppsledningar. Kaporna 20 och 22 kunna: tjana Isom .stromuppsamlare eller ocksa kunna lampliga sadana av flerpunktstyp Haas in i elektroderna. According to Fig. 1, the cell according to the invention consists of a casing 10, suitably made of an acid-resistant plastic material such as polystyrene or methyl methacrylate resin, in which hollow porous hollow activated carbon electrodes 12 and 14 are mounted, in which are inserted resp. Tate and chlorine gas. These gases are introduced by means of the supply lines 16 and 18, which are connected: with their electrodes with copper-clad carbon caps 20 and 22 and which are held in position inside the electrode by means of a rubber ring 24. Similar rudder parts 26, 28 are connected to the bottom of each electrode by the caps 30, 32 and serve as gas drain lines. The caps 20 and 22 can: serve as current collectors or also be able to light such ones of the multipoint type Haas into the electrodes.

Gummipackningar 34 och 36 vid toppen och botten av behallaren forla.nar styvhet at ko.nstruktionen. Sur elektrolyt infores genom elektrolytappningarna 38. Dessa Oppningar tjana ocksa ■som ett avloppshal for bortforing av klorvategasen, som bildas under cellverksamheten. Om det under cellens verksamhet blir nadva.ndigt att utspana den sura elektrolyten, kan utspadning ske genom tillsattande .av vatten genom oppningen 38. For ytterligare luftning .anordnas HC1-avloppshalen, 39 och 41 i topplattan av cellen. Rubber gaskets 34 and 36 at the top and bottom of the container provide rigidity to the structure. Acidic electrolyte is introduced through the electrolyte openings 38. These openings also serve as a drainage hall for the removal of the chlorine hydrogen gas, which is formed during the cell operation. If it becomes necessary during the operation of the cell to deflate the acidic electrolyte, dilution can take place by adding water through the opening 38. For further aeration, the HCl drainage holes 39 and 41 are arranged in the top plate of the cell.

Kolelektroderna kunna exempelvis framstallas av 100 viktdelar petroleumkoks, kokosnotskol eller lampsvart, 63 viktdelar mjukt beck eller fenolformaldehydharts och 3 viktdelar brannolja. De bildade hEaljena, eller elektrodr&ren brannas sedan vid 1000°C under 6 Unman Vid .att utforande av cellen har tuberna en inre diameter av c:a 12,7 mm och en yttre diameter air c:a 19,0 mm och en porositet i storleksordningen 18-20 %, matt genom vattenmattning. Porositeten hos roren haj es sedan till 25 % genom varmning vid 850°C-950 ° C i en koldioxidatmosfar under flera timmar. 2— — Darefter anbringas katalySatorlosningen; som Sr en 0,1 M losning av Ca(NO3)2 • 6H20 och Al (NO2)3 • 9H20 p. elektroderna och varmesonderdelas- for ,att bilda Co0 • A1202 pa kol- - ytorna. Denna impregneringsbehandling, vii-ken beskrives i till exempel USA-patenten 2 615 932 och 2 669 598 tjanar till att hoja porositeten hos elektroderna till del onskade, slutliga amradet av c:a 30-35 %. The carbon electrodes can be made, for example, from 100 parts by weight of petroleum coke, coconut charcoal or lamp black, 63 parts by weight of soft pitch or phenol formaldehyde resin and 3 parts by weight of fuel oil. The formed helices, or electrodes, are then fired at 1000 ° C for 6 hours. When making the cell, the tubes have an inner diameter of about 12.7 mm and an outer diameter of about 19.0 mm and a porosity in on the order of 18-20%, matt by water matting. The porosity of the tubes is then raised to 25% by heating at 850 ° C-950 ° C in a carbon dioxide atmosphere for several hours. 2— - Then the catalyst solution is applied; as Sr a 0.1 M solution of Ca (NO3) 2 • 6H2O and Al (NO2) 3 • 9H2O on the electrodes and heat sinks, to form Co0 • Al2 O2 on the carbon surfaces. This impregnation treatment, which is described in, for example, U.S. Patents 2,615,932 and 2,669,598 serves to increase the porosity of the electrodes to the desired, final amrade of about 30-35%.

Fiiljande de tidigare skisserade behandlingarna, Overclragas vateelektroderna med en lamplig vatedissosiationskatalysator, sasom platina eller rhodium. Delta kan ske medelst en 10 % vattenlosning air klorplatinasyra eller rhodiumtriklorid, vilken malas ph elektrodytan och song sedan termiskt -sonderdelas i en vatgasatmosfar vid en temperatur i narheten av 400°C med kvarlamnande av endast metallen pa vatgaselektrodens yta. 10 ml air en sadan loaning hstadkognmer ett beraknat ytoverdrag av 2 mg metall per em2 ph en 305 mm (12") vateelektrod. 0,25-8 mg metal] per cm2 ge tillfredsstallande resultat, men optimum air aktivitet uppnas vid en koncentrationsniva av 2 mg per cm2. Forutom platina och rhodium kan andra Overgangsmetaller fran grupp VIII anvandas, inbegripande exempelvis palladium, iridium, rutenium och osMinim, for att paskynda snabb vatejanisation I caller, avsedda att arbeta vid rumstemperatur. Urn, och nickel kumia ocksa anvandas som katalysatorer ftir att paskynda vOtejonisa'Lion, men :dessa arbeta bast vid endast hoga teanperaturer. Following the previously outlined treatments, the hydrogen electrodes are overlaid with a suitable hydrogen dissociation catalyst, such as platinum or rhodium. Delta can be effected by means of a 10% aqueous solution of chloroplatinic acid or rhodium trichloride, which is ground on the electrode surface and then thermally decomposed in a gas atmosphere at a temperature close to 400 ° C leaving only the metal on the surface of the gas electrode. 10 ml of air such a loaning hstadkognmer a calculated surface coating of 2 mg metal per em2 ph a 305 mm (12 ") hydrogen electrode. 0.25-8 mg metal] per cm2 give satisfactory results, but optimum air activity is achieved at a concentration level of 2 In addition to platinum and rhodium, other Group VIII transition metals may be used, including, for example, palladium, iridium, ruthenium and osMinim, to accelerate rapid hydrogenation in callers, intended to operate at room temperature. to speed up vOtejonisa'Lion, but: these work best at only high tea temperatures.

HOgre verkningsgrad av -elektrodarbetet och langre elektrodlivslangd, sarskilt i avseende pa vateelektraden, kan uppnhs- gcnom att iiverdraga elektrodytan med en porOs natriumkarboxymetylcellulosafilm. Higher efficiency of electrode work and longer electrode life, especially with respect to the hydrogen electrode, can be achieved by coating the electrode surface with a porous sodium carboxymethylcellulose film.

Elektroderna enligt foreliggande uppfinning anvandas vanligen i grupper. Anordna.ndet av klor- och vateelektroderna i de namnda grupperna Sr mycket viktigt. Sadana grupperingar av eIektroder visas i figurerna 2-6. Utftiringsformen: enligt fig. 2 bestar ay tva cylindriska elektroder, vate 12 och klor 14, med Parallella axlar. The electrodes of the present invention are commonly used in groups. The arrangement of the chlorine and hydrogen electrodes in the named groups is very important. Such groupings of electrodes are shown in Figures 2-6. The embodiment: according to Fig. 2, there are two cylindrical electrodes, cotton wool 12 and chlorine 14, with parallel shafts.

Utforandet enligt fig. 3 bestar ay ett L-format arrangemang med klorelektrod 14 som bildar pivapunkten. The embodiment according to Fig. 3 consists of an L-shaped arrangement with chlorine electrode 14 which forms the pivot point.

Utforandet enligt fig. 4 bestar av tre elektrader mad parallella axlar och tva vateelektrader p5 varje shin air klorelektroden 14. The embodiment according to Fig. 4 consists of three electrodes with parallel shafts and two hydrogen electrodes p5 each shin air chlorine electrode 14.

Anordningen enligt fig. 5 irmefattar fyra vateelektroder 12, var oak en placerad pa samma avstand frail klorelektroden 14. The device according to Fig. 5 comprises four hydrogen electrodes 12, each also placed at the same distance from the chlorine electrode 14.

Den meat effektiva utforingsformen visas I fig. 6, varvid en elektrod Sr Magma inuti den -andra elektroden. Den centrala elektroden Sr i detta fall klorelektroden. The meat-efficient embodiment is shown in Fig. 6, with one electrode Sr Magma inside the other electrode. The central electrode Sr in this case the chlorine electrode.

FOr basta verksamhet har det befunnits -Onskvart att ha en nagot Ai:are area tillganglig pa vateelektroden an ph klorelektroden. For best operations, it has been found -Unesponsible to have a certain Ai: are area available on the hydrogen electrode than the chlorine electrode.

Numeriskt uttryakt skulle -denna ,differens -Vara av storleksordningen 5-19 %. Ett exegnpet pa ,denna konstruktion Sr ett - koaxiellt arrangemang, i vilket den inre eller mindre elektroden (klor) ligger inuti den yttre och stOrre vateelektroden. Eanellertid kunna lagena air de resp. elektroderna sarntliga air de ovannamnda gestaltningarna vara omvanda ont sa onskas. Numerically speaking, -this, difference -Would be of the order of 5-19%. An example of this construction is a coaxial arrangement in which the inner or smaller electrode (chlorine) lies inside the outer and larger hydrogen electrodes. However, the teams can air de resp. the electrodes especially air the above-mentioned designs be converted evil as desired.

Som forut namnts initieras cellverksamhet genom tillforsel av vate och klorgas till resp. elektroder. Det racker att tillfora gaser till elektroderna med den raangd, som kan producera den onskade stroantatheten. Det Sr med andra ord ej nagot helm air latt tillfora gas I Overskott. Sjalvfallet beror den ,erforderliga rnangden gas pa storleken hos, cellen. En cell innehallande tva kolelektroder c:a 102 mm langa med ybtre och inre diametrar pa c:a 12,7 resp. c:a 19,0 mm erfordrar exempelvis 500 cm3 per timme var av klor och mate for att producera,en ampere vid 1,1 volt. As previously mentioned, cell activity is initiated by supplying cotton and chlorine gas to resp. electrodes. It is sufficient to supply gases to the electrodes with the range that can produce the desired current density. In other words, there is no helm air to supply gas in surplus. Of course, the required amount of gas depends on the size of the cell. A cell containing two carbon electrodes about 102 mm long with outer and inner diameters of about 12.7 resp. about 19.0 mm, for example, requires 500 cm3 per hour each of chlorine and feed to produce, an ampere at 1.1 volts.

Foreliggande cell Sr avsedd aft arbeta vid gastryck fran 1/10 till 10 atinosfarer och vid temperaturer frau 20 °-150°C. Emellertid kan sadana arbetsomraden, alit after onskan, varieras mom vida gra.n-ser for att passa special-la anvandningar am cellen och fortfarande falla inam rumen far -denna uppfinning. The present cell is intended to operate at gas pressures from 1/10 to 10 atmospheres and at temperatures from 20 ° -150 ° C. However, such areas of work, alit as desired, can be varied within wide limits to suit particular applications in the cell and still fall within the scope of this invention.

Pradukten fran den totala cellreaktionen Sr HC1. Enar den maximala losligheten air HCI i vatten vid rumstemperatur ligger i narheten. av 24 % kancentration, arc vissa medel for uppratthallandet ay konstant koncentratian I elektrolyten nodvandiga. Detta hail she enkelt genom -avkaftning av Overskottet av gasformigt HC1 eller genom utspadning air HC1- elektrolyten med vatten, varvid ,det senare Sr att foredraga. The product of the total cell reaction Sr HCl. The maximum solubility of air HCI in water at room temperature is close by. of 24% concentration, arc certain means of maintaining ay constant concentration in the electrolyte necessary. This hail she easily by -crapping off the Excess gaseous HCl or by diluting the air HCl- electrolyte with water, the latter being preferred.

Det Sr inte nodvandigt att demontera hela cellen for att bestamma HC1- koncen.trationen elektrolyten. Konduktiviteten has elektrolyten kan matas ph plats eller ett prom air elektrolyten kan uttagas med en pip ett och analyseras. I vilket fall ,som heist kan cellen fortsatta sin verksamhet utan avbrott. Ogn HC1-innehallet hos elektrolyten Sr- for h8gt far Overskott av HC1 luftas ut genom de visade -utloppen eller tillsattes vatten genom tilled,ningen 38. It is not necessary to disassemble the entire cell to determine the HC1 concentration of the electrolyte. The conductivity of the electrolyte can be fed to a pH site or a prom air electrolyte can be taken out with a spout and analyzed. In any case, as a lift, the cell can continue its operation without interruption. The HCl content of the electrolyte Sr- for high flow Excess HCl is vented through the outlets shown or water is added through the inlet 38.

Den oppna kretsens spanning has del aktuella cellsystemet Sr 1,3 volt i 4N/HCI jam-fort -med ett maximum av appert kretsspanning av 1 volt vid ett vate-syresystem i 12— M KOH. Myeket Men polarisation upptrader under belastning. Vid rumstegriperatur och atmosfartryek erholts 10 ma/ern2 med de tira elektrodformerna vid 1,25 volt, 20 ma/cm2 vid 1,22 volt, 30 ma/cm2 vid 1,20 volt, 50 ma/ can2 yid 1,15 volt och 100 naa/can2 vid 1,10 volt. De sista siffrorna motsvara en stromtathet tic ganger sa h8g som den, som kan erhallas fran vate-syre-bransle-cellsystemet ( — —3 —20 ma/cm) under jamforliga hetingelser. Den :slutna kretsspanrnngen i en. vate-syrebranslecell under dessa betingelser Or alltsa. endast 0,8 volt jainfort med 1,10 volt enligt fbreliggande system. Salunda är del en f8rdel att anvanda branslecellsystemet enligt foreliggande uppfinning for hoga strodustyrkor i de fall, dar krayet p lang livslangd ej Or avgorande:. FOr sadana anvandningsaudamal Or detta system tydlige.n mera lampligt fin. ett vate-syresystem. The open circuit voltage has part current cell system Sr 1.3 volts in 4N / HCl jam-fast -with a maximum of apparent circuit voltage of 1 volt at a hydro-oxygen system in 12-M KOH. Myeket But polarization occurs under load. At room temperature and atmospheric pressure, 10 ma / ern2 is obtained with the three electrode forms at 1.25 volts, 20 ma / cm2 at 1.22 volts, 30 ma / cm2 at 1.20 volts, 50 ma / can2 at 1.15 volts and 100 naa / can2 at 1.10 volts. The last figures correspond to a current density tic times as high as that which can be obtained from the vate-oxygen-fuel cell system (- —3 —20 ma / cm) under comparable conditions. The: closed circuit voltage in one. vate-oxygen fuel cell under these conditions Or so. only 0.8 volts jainfort with 1.10 volts according to the existing system. Thus, it is an advantage to use the fuel cell system of the present invention for high strode strengths in cases where the long life requirement is not critical. FOR SUCH USE AUDIALS OR THIS SYSTEM CLEAR.N MORE LAMPLY NICE a vate-oxygen system.

Claims

1. Patent application: High voltage and high current density fuel cell for the production of electricity by chemical contamination of hydrogen gas or chlorine gas in an acid resistant container, such a cell comprising at least one tubular hydrogen electrode of porous activated carbonaceous material, electrolyte surrounding the outer surfaces of all electrodes and with gas conduction and reading and current collection devices (Or. electrodes, can be characterized in that (a) the electrodes have a porosity of osmium at a concentration of 0.25-8 mg per square centimeter of electrode surface and that (e) available surface area of the hydrogen electrode Or 5-19% stone On the surface of the chlorine electrode Request publications: Patents from France 973217; United Kingdom 521773; Germany 957 491.