DE2213603A1 - METHOD AND DEVICE FOR THE ELECTROLYTIC TREATMENT OF SOLUTIONS CONTAINING HYDROGEN CHLORINE ON GRAPHITE ELECTRODES, KEEPING THE CHLORINE AND HYDROGEN GASES SEPARATED - Google Patents

Description

Dr. Georg Messner

Latemarstrasse 7 - -

aooo Munich go 221360 3

Experience and device for electrolytic treatment of solutions containing chlorine hydrogen on graphite electrodes while keeping the chlorine gases separated and hydrogen.

For many years, hydrochloric acid has been electrolyzed to chlorine and hydrogen hydroxide on uraphite electrodes on an industrial scale, essentially still in apparatus that are mainly built according to the same principles and made of the same materials as at the beginning of a long series of small improvements and, above all, enlargement of the bipolar electrical legs; see Ulimann 3rd edition volume 5, page 3Ü3. Today, a bipolar electric generator for about 10 UDO Amp. Load with 3 - 5U elements working one after the other can be regarded as the standard, which generates about 15,000 kg of chlorine in 50 elements in Zk hours.

The weakest point of all z. Currently existing constructions is the space between the electrodes, especially the diaphragm, which has the task of keeping the two gases produced, chlorine and hydrogen, separate. This diaphragm consists of a fabric made of polyvinyl chloride fibers, which is clamped in a self-supporting manner between its electrodes, which are held by their plastic frames. The supply of HCl takes place through the introduction of hydrochloric acid with a concentration of significantly more than that of the depleted acid with about 10 % HCl and not only serves the purpose of providing the t-iiuktrnlytisch decomposed clay and des verdampt'Lbri HCJ, finrif'urn uuch dt; r removal of the χ-Strumwiirme des Elektrulytiüuri ;. Dii: Liiii ülirunii ernltit in form of 2 separated hydrochloric acid clouds: n, wnvnn the α ine flows through the adjacent space, the other through the cathode space, whereby both lose part of their HCl content, the tinapeiaerate of the hydrochloric acid is measured in such a way that the draining off Hydrochloric acid still contains about 16 % HCl, which corresponds to the maximum conductivity of hydrochloric acid.

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The real benefit of the bisection of the hydrochloric acid fed in is the quickest possible elimination of the chlorine bubbles formed in the anotia space and, on the other hand, the hydrogen bubbles formed in the hathoden space, which increase the electrical conductivity of the electrolyte and thus the cell voltage, all the more so than they do at the usual operating temperature of 7Ü C in addition around 21 UoI. % Water vapor contained.

As long as the diaphragm exterior is undamaged, it is possible to produce practically sufficiently pure chlorine and hydrogen. The purity is 99.7-99.9 Uni λ and above, converted to dry Cl ^ or HL ·.

It is known ,, PWC _1, the chiü compared with other materials, which is still relatively most stable in the BediriQunyen the HCl Eiektroiyne material for the diaphragm is, however, a gradual change by [ 'subject Jachchlorierung that versprühet the fibers, this sodaB the Ultimately, the strength requirements placed on them are no longer sufficient. There are cracks and laughter in the ueuebe and its separating effect on the uase is even at an idle operating temperature of z. ü. 70 C after a few months has often already dropped so far that not only is the purity of the base produced unsatisfactory, but there is also an increasing risk of explosion for the resulting mixture of CIp and H ... There is only one way out to avoid this risk! Up to now oetriebnuntr: breakdown with removal of the damaged and installation of new FVC-üeujebe, üa better ones do not exist, at least not so far.

This cichujierigkGil: practically does not exist, ωεηη mn η arrangements according to the present invention used, uiie si f .; in the following using t: iriii _; fc: examples are described.

A dnr essential Erfindunnrpririzipien is dab. ^1:!, Rlüß my to ^r: iu tensile strength of the HWC FoSern uiir ¹ aniHii't :! ¹ in ϋε: η Dinphrünrnen vuriiitindetcn F; jnerri only st-hr nerinrif; Mni ^ irikirunrien st'.ciit., Ujüc man urfiiiM.jin ί, -ciEimrJU ϊ-.nidiihl by buiillühn häv. ; uu: ti vr; rf; jhri: n: im; Hl i \\ v. M: -. Üniihmr: ii i.:rrt'.i can.

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The basic principle of the structural measures is the renunciation of the so far used self-draining diaphragm as found uiurrie, as a result of the hay making in conventional electrolysers the gas bubbles and the electrolyte significant mechanical stresses exposed, which can be characterized most succinctly with "flutter", an expression that is not only used by flatterbcwegunrjEn occurring mechanical i'.rüfteüpitzen, but also the Permanent bending stress of the more and more atomizing fiber material includes.

One of the principles of procedural measures is the replacement of the two feed acid streams through a single river, which ensures that the diaphragm or the two diaphragms in the special case, * be brought to practically complete contact with solid supports that are permeable to gases and electrolyte; it was found that the diaphragm is mechanically sufficient in the sense mentioned above can relieve it, if you can do it as completely as possible on one more or less rigid, sufficiently permeable for liquids and gases to rest on the substrate.

With the thus given relief of the diaphragm from tensile loads its longer lifespan alone is guaranteed. The remaining features of the present invention provide further improvements, of which the talk will be in other matters of this description.

For decades there have been leakage cells in which the diaphragm rests on a rigid base, for example on iron wire mesh in the case of the diaphragm cells for the electrolytic production of chlorine and caustic soda; However, because of the formation of sodium hydroxide solution, such a cell is so very different that despite a period of more than 3 years of use, ίηγΙιππΙπππϊβ dnr HCl-ElRnlyne the above ijnrianntn kumplnmuntn; L'runci for you: relatively short lifespan tiav Diuphrniinicn urtituunlichBrWsibu biyhur was not known, EudaB already decujEiyen nauh remedy could not be ciinmal ytjuucht; this should be borne in mind when classifying the inventions of the present invention.

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As a material for the diaphragm in the above sense rigid DdBr almost rigid Koste can dig vein braids from durable. '"Material may be Plexiglas etc. uiie Teflon. Allerdinga bjird so necessarily the electrode spacing and the Ghmsche resistance of the cell increases slightly.

In order to avoid that, we searched further and found that a very good base is the one produced and described, for example, as follows is.

The inside of a plane-parallel rectangular graphite plate intended to be used as an electrode is provided parallel to its large outer surfaces and preferably parallel to its short rectangular sides at regular intervals with channels or otherwise incorporated recesses of about 20,000 mm in diameter or a central area, which is preferably one go through the long rectangular side of the graphite plate to the other. Then according to the invention the inner walls of the drill channels with a suitable, z. B. painted cold-curing phenolic resin to avoid erosion of soft graphite by gas and liquid movement during operation. This simple resin coating has proven to be very useful because it allows a cheaper type of graphite to be used without any loss of technical result. j

To the totality of the surface exerts üraphitlamellen electrolytically to get active, to ensure that after attaching the drilling or. Recess channels and before making the saw slots in the graphite, the surface coating with synthetic resin inside the drilling channels and its hardening is awaited.

Awake solidification of the resin paint is, for. U., preferably twisted with a set of circular saw blades, the vrmjcsehene as the electrode surface of the graphite plate coated with a number of among themselves pariilleler, incorporated sägter slots below ¹ JO to the BohrkanalachsEjn from a cDlchen depth ScineblMtter DNSS to tlrjn hrcuzunusstcllcn a few mm in the Aun HarstEllunrjsnründun expedientir | urwfji £ u. previously rjebohrtRn channels penetrate and nn V / f: ibinc1uitijoii / wipe the cavities riur slots and the cavities dta- Uohrkunäie entsbuhon. The iJchlitzu should be about

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1 - 2 mm LJeite and stuia 5 - 20 mm TiEfB and dis between the Slits standing on the graphite lamellae should be 1.5 - 3 mm thick Thick ones. The graphite lamellae are used as electrodes during operation Around parts of the graphite plate, while the slots are mainly to receive the base generated on the lamellae and to derive it serve in the Bahr canals. It should be noted that pipe-like recesses in the interior that are produced in a different way under drilling channels are also used here the graphite electrodes are to be understood.

Fig. 1 shows schematically a unipolar graphite electrode produced according to the present invention, which can be used as a positive vein negative electrode of a cell or as an end electrode of a bipolar electryser in a vertical or horizontal position, after it may be used with a z. B. has been covered on the ridges of the lamellae resting diaphragm, which will be discussed in the following.

Two of the drill channels in Fig. 1 are shown broken away. For cells With the electrode surfaces in a horizontal position, the planes of the slots become Sawn preferably under approx. 9G to the electrode surface. at Cells with a vertical position of the electrode surfaces can be somewhat at an angle deviate from 9U in the sense that the entry of the Lamellas formed rising gas bubbles into the depth of the slots is favored.

In addition to the type of slotting of the graphite surfaces shown schematically in Fig. 1, a modified type can be used, which provides slits with somewhat larger, wide and also somewhat thicker lamellas. But so that the: Uurnriknrunii von MnachwummdiaphraQmen hut ijnlinrjt, before clnr Auüfültruiitj dc; r tififmi Lt-hlit / n according to Fig. 1, a very shallow use, which is cut to the inside, is sawn with only approx the hammers that stand on top of the remaining slats are given a kind of roughening. The finished ElektradenaberflächE this type is shown at a location van Fig. Diagrammatically.

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Both Fig. 1 and Fig. 2 represent a unipolar electrode, as they are used as terminal electrade in bipolar electrification ' can. The diaphragm that normally covers the uraphite lamellae, is omitted in Fig. 1 as well as in Fig. 2 for the sake of clarity.

As shown in Fig. 3 and Fig. U , graphite plates are used as bipolar electrodes, which are provided with slots and lamellas on both sides and accordingly also contain 2 independent sets of drilling channels in their interior, 1 set for chlorine, 1 set for [hydrogen.

As a further invention & in accordance with EK alternative execution example of the slots on the electrode surfaces, we can see the profile of the slots tjE shown schematically in Fig. 7. In this case, the slots do not have a constant depth, but are made as a single group segment of a set of circular saw blades of the same diameter at the point corresponding to each of the Bahrkanal to be cut. The slot fields of the adjacent slot groups of the same electrochemical polarity of an electrode overlap over at least a small distance, so that no part of the active electrode surface remains without slots, which is important for the safe functioning of the cell.

It is particularly advantageous to produce the slots in a continuous manner Process in which the rtrTissägesatz that create the slots as it progresses across the electrical surface, makes garland-like lifting and bending movements, let out all those cannula the one with the relevant electrical panel and its slots in spatial connection come sullen, (ri. h. every second Liohrkanal) be cut. The rjirlanden-like profile of animal slits is made possible It is also the case with bipolar electrodes, all of the flat-edged electrodes of an electrode to arrange in a single plane, which uiierlurum an advantage in the Execution of the cement connection between the electric box and the plastic frame brings on the flanks of their drill channel ends. Another advantage the garland-like profile of the slots suggests that the Inside of each slot is roughly the shape of a flattened funnel has what accompanies the transition dua urzeuyten unuun 'and tier eu

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Fluid from the slit spaces into the Bahrkanal is facilitated and zuiar at every position of the electrodes bzui. the slots. I.

As far as the arrangement of the bahr channels themselves inside the electrade plates is concerned, it can be in a straight row, as shown in Fig. 7, or in a zigzag row, as shown in Fig. K or Fig. 6. However, it can also take place in a straight row in the center line of the graphite plate thickness or, alternatively, in a straight or zigzag line outside the aforementioned center line. According to the invention, the arrangement outside the center line can be used with advantage to make the anodic graphite slots deeper on average than the cathodic ones and thereby give the anadic graphite lamellae a greater useful dimension according to the invention, which leads to a longer service life of the bipolar electrodes and in Fig. 10 'is shown schematically.

According to the present invention, all combinations of position of the Bahrkanal and profile of the slots are possible. The preferred 3 possibilities are the ones shown schematically in Fig. B , Fig. 9 and Fig. 1G, but in the remaining figures, apart from Fig. 21, the zigzag arrangement of the drilling channels and the linear saw slots were used for the graphic simplicity.

Since the drilling channels in cells with vertical electrade surfaces are flooded, ie more or less filled with electrolyte, according to the invention they are divided into 2 preferably unequal parts in their cross-section in the interest of rapid gas discharge by means of an inserted conductive foil made of Teflon, Plexiglas, etc.; the larger part of the cross section is used to ascend the gas bubbles together with the electrolyte, the smaller part to circulate the electrolyte back downwards. A horizontal section with three vertical canals and fluid lines is shown on a natural scale in Fig. B

Eiini · :; iluvch nirii: Lulilfi LIt: ijutüi ΙΛι: π Kannlr; can rn.in z. ü., ü under (jrüßnrnm Üurbrauch von ijraphit, a pair of vnn in a row liücißndon provide drill cannulas, one of which with his Is directly connected to the slot room system, the other channel

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against not. The former acts as a riser for the gas-electrolyte mixture, the twin canal is used for the return circulation of part of the Electrolytes down, uid a local connection of the spaces of the There is twin channels.

According to the present invention, the graphite plates provided with drill channels can be produced not only in the manner described above by stretching the graphite, but alternatively, for. B. also by puttying together sections provided with recesses, as shown in principle and for example in Fig. 6 . The sections with cutouts can be produced directly, for example, on the one hand by extrusion or block pressing, or on the other hand by milling out of corresponding prismatic graphite pieces.

Now let us consider the structure and mode of operation of a bipolar electrical analyzer described, which consists of electrodes of this type in a vertical position of the Llektrodenflächen.

The lecturer consists, for example:

a) from several, e.g. B. ^ D bipolar electrodes in a vertical position;

b) from 1 positive unipolar terminal electrode in a vertical position with Graphite nipples for the positive btromanschlu5;

c) from 1 negative unipolar end electrode in a vertical position with graphite nipples for the negative power connection;

ri) from 1 anodic stiffened end piece üub inside z. D. ebonited

Steel with the collection hood for the chlorine gas and its accompanying ■ electralytes;

e) from 1 cathodic stiffened end piece from inside z. ü. eboniticrtem Steel with the collection hood for the hydrogen gas and its accompanying electralyte;

f) on the steel trimming screws that hold the element package together;

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g) from ΰΒΠ 2 ebonitized horizontal steel girders on which all

ι ^Λ ■

ElsmBnte rest. SiB are mounted on several bases and van separated from them by PnrzBllanisalatars elsctrically ^

h) from the supply pipes for the food acid with the associated Regulating valve and flow meter;

i) from the discharge pipes for chlorine, hydrogen and the HCl-poor cathodic and anodic drainage acids;

k) from a short-circuit switch to switch off the current passage by the tlektralyseur.

For example, each bipolar electrode consists of:

- the graphite electrode with 2 electrolytically effective surfaces; at large electrodes, several uraphite plates are chained together at preferably horizontal joints. Each of the surfaces is with

z. b. approx. 2 mm thick lamellas and approx. 1 - 2 mm between them wide and approx. 5 - 20 mm deep slots. Slats dnd slots run horizontally and form an angle of preferably 9ü;

- the Havegrahmen, which encloses the graphite electrode and in which it is cemented liquid-tight and practically gas-tight.

Fig. 11 shows the vertical section i \ i - N of Fig. 13 through a bipolar electrode. At its upper end, the Havegrahmen shows a number of recesses which, after being assembled with the other frames, form the horizontal outlet channels for chlorine and electrolyte as well as for the first and second fraction. In every horizon tain Ll -hanaisück rftin Kahmcru-j mündnt rl; j; .i ribere Lndt! FiiriBa zuijBhfirigeri vnrLiknluii Bnhrkiiriuln for Ui "and LiEiktrulytuntfiil Bin, in every hnrizuiitiilf! H ,, - hrinuli.itück rluii Wahrnuna mürirJBt the nhart: the end of the accessibility v / urtikalBn Lluhrkanalü door H ,, and tlektrulytanttiil and discharges stjin Hp-üas and the cathodic electrolyte to be repelled into the horizontal channel Bammelhaube for H “leads at one end of the electrical power supply. At the other end of the electrolyzer paint, the mirror image is about

309840/1034 _{BAD 0RIB1NAL}

the same gammel hood for the Cl _n -GaS and the anadic electrolyte component to be repelled.

Man. 12 is the Uertical section GG through Fig. 11.

Fig. 13 is the horizontal section MM of Fig. 11 through several bipolar electrodes, through the negative and positive end electrodes and through the collecting caps for H _n and Ci _n . For the sake of clarity, gaps have been left between the individual components and the diaphragms and the comb-like introduction frames for the food acid have been omitted. According to the invention, the electrode surfaces are provided with closely fitting diaphragms of suitable permeability for liquid and current, which can be either connecting diaphragms or prefabricated diaphragms.

Precoat diaphragms contain loose PVC fibers with any additions from other, also chemically less resistant fibers, such as. B. asbestos, as well as chemically unstable fibers such. B. Rayon, Cotton etc. in addition to small amounts of binders »those in liquid Form or as paste, emulsion etc. can be added.

Prefabricated diaphragms can have the structural character of van Wliesen that contain PVC or other resistant fibers, as well as additives of asbestos fibers, Hcyan fiber, cotton and other not completely resistant Fibers contains ^, as well as gel-like binders that z. B. by impregnation of the nonwoven fabric with diluted z. B. alcoholic phenal resin solution, with alkali silicate solution or alkali cellulose xanthate solutions or mixtures of the latter two or other substances and subsequent treatment with acids, heat, etc. in the diaphragm can be brought in.

Another type of fabricated diaphragms are fabrics, such as the fabrics made from FWC fibers that have already been used. B. the just mentioned can be finished. Between the flange flanges of the elements are chemically determined: seals with a small thickness ninriuLeijt, between the knl.huclincheri and the ciniirlir.chtjn Dinphmiirnn a free / Uiritcintl van ninirfnn mm, zuiBckmüßif. utwa h - 111 mm tilüitiL, di: r vuii LlnktrnlyL fü'l'iillL Uj L unrl dm- Aufiiithrnr; dnr

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Edible acid is used. 9 91 ^ R G S

αθώο ... precoated diaphragms as well as prefabricated diaphragms can also be set up with the help of spray guns, in an analogous way, -like often used in the production of z. B. glass fiber reinforced hunststaff items happens.

The feeding of the food acid to the space between the diaphragms takes place, depending on the dimension of the cells, from 2, 3 or k of the k graphite peripheral sides of the frame, as indicated schematically in Fig. 11 for 3 peripheral bits and in Fig. ΛΗ as a vertical section through the lower HahmEnschenkEl is shown in more detail on a natural scale. Starting from the horizontal feed acid channels located in the 2 side frame legs (see Fig. 11), the acid introduced there is distributed to all elements of the electrolyzer as well as to the end distribution channels on each element frame. From these channels the acid passes through z. B. the indentations carved out in their inner tsil of the comb-like Plexiglas frame between the 2 seals in the space between the diaphragms of each individual electrolytic cell.

Such a comb-like Plexiglas frame is shown as üanzes in Fig. 16 in detail in Fig. 15 and clamped between the Havegflanschen in Fig. 1 **. It goes around the whole hahmenflansch, is only on parts of all EirispGisa & chenkein, for example below, right and left worked out like a comb, while the upper leg remains as a full foil. The plexiglass frame is clamped all around between 2 seals and at the same time imparts pressure on the edges of the two diaphragms via the seal in order to hold them in place. The two diaphragms are indicated in Fig. Along the crests of the braphitlameile as dotted lines and extend as far as the vicinity of the end distributor channels on the Havey frames.

AUb. 1 * 4 shows, in a vertical cross-section, the lowest parts of the vertical cross-section for H. Mori rdnht in jcriurn buhrkanal the lower end rli: r Lt: itfolirj, um rlie lujrum ilur im kleinur

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rising electrnlytstram is diverted to with new I-L gas bubbles and neucgi which has passed over from the diaphragms and urephit slits Electrolytes in the larger part of the cross-section to practice flowing down, ωά the main part of the air bubbles and the newly entered electrolyte content be discharged into the horizontal.H collecting ducts of the frame; see Mbb. 11 and Fig. 13. The same applies to the Cl “drilling channels.

Fig. 17 is the schematic vertical longitudinal section RR of Fig. 13 through a horizontal H collecting duct which is formed from the corresponding parts of the Havegrahmen. The comb-like plastic frames, the seals and the diaphragms, as well as the supports on which the electrolyzer rests, are omitted for the sake of clarity and the individual parts are shown at a distance from one another. Only one of the long screws is shown. You can see the two unipolar end electrodes, 3 bipolar electrodes, the horizontal H "-S? .Miiielkanal, the H _r collecting hood, the Clp collecting hood and the uraphite nipple for the power connections. In addition, the channels for the distribution of the food acid within an element are ancededEutet on the lower frame legs.

Figure 18 is a schematic view of an end face of the electrolyzer. It is shown:

- In the upper part of the view the collection hood with outlet for one of the two gases produced upwards and for the arm electrolyte accompanying it down below;

- h graphite nipple for the direct current connection on the one shown

e;

- The 2 entry points for food acid on the two side thighs the Hüvegrahrnen;

- the long light screws to press together the package of elements and end pieces;

- the steel stiffening ribs at the ends of the long screws attack.

The view of the other end of the electrolyzer is the same as that of Fig. ' KJ is almost identical in appearance.

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Anything that differs slightly from the construction just described is given in the following exemplary embodiment. Only the so-called diaphragm differs from what has already been described. Instead of two fibrous separator layers, whether or Anschiüemmvliese v / arfabrizierte _diaphragms; 2 blinds are installed between anode and cathode in such a way that each blind εη lies against its lectrude, whereas the 2 blinds from each other t: incn distance from each other tiinirjen mm, preferably 5 - θ mm hnbnn. The jalnu elements are placed in such a way that they deflect ascending uzblr-ifjun towards the electrode, blow bubbles that ate from the electrodes and have got into the area between the jalnu elements, are caused by a continuous, sufficiently strong flow of edible acid into the electrode slots and from there pushed into the vertical ear canals, which is favored by the inclination of the louvre foils. The strong flow of food acid used to push the gas bubbles back into the original electrodes does not present any difficulties in terms of the process, since electrolyte must flow through the cells anyway, which serves to dissipate the generated heat and the cooling capacity to be installed by the new process is not noticeable needs to be changed; what increases quantitatively is the difference in the amount of food acid fed in per hour; B. 33 % new acid and recirculated, in noise exchangers somewhat cooled arm acid with about 18 % HCl content, so that the product

,, σ .o. X kg of food acid ^! Cell ~ food acid ^X hour

from a temperature difference t ° _Bila - t ° _{pBlBBaBurB and other} _ Eieitt: the amount X of the hourly | E; led storage acid with constant flow rate; rlßr Llektirrilytinurü y opposite the FnIl with slide

lilix'iii.iniiJii /wi:;nhf.n tlün Lluktrticltjn fiiuh only according to the small Aiiiiurunii iiur LkirkipHnnimt! finds. Diet; Feeding the edible acid into the Closing between the two blinds is best done roughly hori / un Teiler Kichtuntj from the dividing canals in the two lateral roofs the Havegrahmen. The slightly longer current path from anode to

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With regard to the cell voltage, the cathode is compensated for by the possible drop in diaphragms with their inevitable voltage drop The Umlenkleitfalien in the vertical Üohrkanäle can in this ί In this case, the increased dietary acid intake can be omitted Circulation is sufficient for rapid evacuation of gas.

Cells with blinds have the advantage of an even longer average operating time between repair appointments.

Instead of completely replacing diu diaphragms by Jalausian, the diaphi can be replaced by dit ^j . Ueistellung complement of blinds, bras following Unrteile mi L brings:

1. The t-iriBpciEeratß van bpeises ^ urn can be immensely humiliated compared to the filling of the use of only blinds;

2. As supplemented diaphragms, those with very little damping can be used Uliderstand can be used to reduce the gas purity;

3. Even at the end of the service life of the supplemented diaphragm there is a risk of explosive mixtures low and the implementation of the diaphragmatic ilia is not more urgent than in the case of diaphragms alone.

The Blentie / Diaphragmakumbinatian on the anode is particularly advantageous.

In both cases described of cells with vertical electrode surfaces Care must be taken that the electrode and / or Dicphragmenzuiischen spaces uiehre.nri dta uetriebe to its upper end completely with Keep the electrolyte filled to prevent gas mixing. The relevant dumbbell is z. U. by a at the top of a indicator tube for the liquid level attached to the outside of each egg frame happen that always show a visible electrolyte level target.

Dinac An:;:! (! (! I'vihrcliRn hnbun nni.h uiric /i.icittj function, namely as AiifilnO for;] t; ririM: Ιϊ: ΐϋ) ΐ: η; ιη u;>;;, ilit :; inr. fi'mv.m nikü uus ütiiilun Lifiktrn di: iir "iLi! iü ü i! vt ii Lui" I in i ^ n / iiiJ!, s: ht "in room zuiiiiriinai dr; n Uiii [) hrugmnn over-

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and which otherwise accumulate at the upper edge of this room would. The amounts of pleasure that may have leaked are under their own pressure led into an exhaust pipe.

In the event of a business interruption with subsequent emptying of the liquid, in which no renewal of the diaphragms is intended, is approximate in the case of the described electrolyser with a vertical vein vertically standing electrade surfaces ensure that the Liquid, be it electrolyte adsr bs: n.cf! Wssser, Regarding a cell at the same time from the Eleii bradenrauniEn and not from the Gaps between the diaphragms is emptied. The latter does not apply accordingly to the foil of the blinds,

Another inventive tiauari of a lectniysburst, based on the same principles of the invention as they were just presented, has horizontal electrode and digphragm surfaces} an example is described below.

As a result of the horizontal position of the electrical surfaces, the gas tucks held by the upper electrode of a cell, e.g. B. dsr anode go out, by its buoyancy in the electrolyte from the gas of the lower electrode, in this case, the Hsthüce - separated. One must, however, prevent the lias of the lower electrode at the base by a diaphragm and keep it permanently from a tlekt ^ cly "^: not covered the outlet and the outflowing electrolyte are in a horizontal position, the slots and uraphite lamellae on the electrode surfaces also run horizontally and skewed [, crosses / .

The feed acid is fed into each cell continuously into the space between the diaphragms, if both electrodes have such a _# ·, otherwise between the upper electrode and the diaphragm of the lower electrode in the cell. The acid fed in partially flows through the diaphragm of the lower electrode through its slits into the corresponding channels and leaves the customs area together with the lias produced there. The remaining part of the edible acid flows

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optionally by the upper diaphragm of the cell and flows together with the upper electrode formed on the gas by the ■ '' slots in the Bahr channels and leaves the latter by overflow at one end of the channels in the Bahr vertical bammelschächte. In this case, in contrast to cells with vertical electrode surfaces, the ear cannula are not flooded, but are largely filled with gas.

Fig. 19 shows the vertical section ZZ wan Fig. 20 through part of an electrode package parallel to the direction of the use and lamellae of the electrode surfaces. Within a cell, the lower electrode is the cathode; it is covered with a diaphragm, be it the manufactured diaphragm. On the right-hand side of Fig. 19, parts of the frame legs are shown, in which the common vertical feed channel for the feed acid is incorporated at a thickening of the frame leg.

Fig. 20 is the Harizantl section XX of Fig. 19. It shows uiie outside the vertical main supply line of the electrolyser by a calibrated pool a corresponding proportion of food acid is introduced under pressure into the horizontal divider of each element, from ωό the acid is passed through several Small holes or notches in the frame material are distributed approximately evenly over one flank of each element and the element concerned is supplied.

Fig. 21 is a roughly natural scale vertical section through an electrode package, whereby, in contrast to Fig. 19, both electrode and electrode surfaces of each cell are covered by a diaphragm and the food acid is distributed with the help of a chamber-like plastic frame, analogous to Fig. 15 and Fig. 16 for vertical electrodes. A small piece of the comb-like dividing frame is shown in the bottom right-hand corner of the picture.

Dat; Prufil rlnr bü guns int those: ,, üur, uchnn in Fig. 7 above uiui'ilc. The cut vnn AIjLj. 'Ί i:; t. ; ifi dfir ütnllii ciniiii Üt'.hllt7eu rjumncht. Dar in / aLjLi. :. '1 does not exist; / ibutariii / uiiuchiiii üi'iiphitjiliittnn and Havcgrahmen

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309840/1034

• After assembly, let it be largely filled with Havegkitt.

Figure 22 is a top plan view, on a roughly natural scale, of part of a bipolar electrode plate. Since the diaphragm has been omitted for the sake of clarity, the cathodic graphite lamellae and slots and the vertical collecting shafts for the chlorine gas in the Havegrahmen can be seen in places. The collecting shafts for the hydrogen gas are located in the opposite frame leg, not shown. The Bahr channels for Cl "and H" -, as well as an end section of the food acid distributor channel in the frame with some small bores from the channel to the inside of the cell are shown as dashed lines.

The overall system of an exemplary food acid distribution for a single element is shown in Fig. 23 as a horizontal section Y - Y from Fig. The feed acid supply to the vertical distribution channel from the outside takes place either at one point, expediently halfway up the electraylseur, or, if there are a large number of elements in an electrolyzer block, at several points for groups of elements with, for example, 15-20 pieces each.

If the element surfaces are large, it can be advantageous or It may be necessary to install two feeders for food acid on each element frame instead of one, so that the opposite Side of the frame an additional feed device would be of the same type. Outside of the acidity distribution over One element can be seen in Fig. 23, the dashed gas and electrolyte drilling channels for Cl ". These horizontal channels are at one end open and open into elongated vertical Cl "shafts in the Havegrahmen, whereas their other ends are blind. The Hr, -bore tunnels have their analog vertical shafts on the opposite side of the Havegrahmens. In either case, it will be in the vertical The shafts of the Havegrahmen collected gas + run-off electrolyte at the bottom At the end of the electraylseura taken up by a closed collecting channel and discharged to the outside, where the separation into gas and liquid takes place. The other, preferred option is, the process "

309840 / 103A öad original

to collect electrolytes at the bottom, but to let the oase go up and in the corresponding läas collecting hoods at the upper end of the electrolyser to catch.

Instead of the small holes or notches just described, as in Fig. 21, also for the electrolyzer with horizontal electrode surfaces the one inserted between the frame tubes with seals KatnmartigB Werteilerahmche.'n üus plastic can be used, the tlektralyneur with vertical electrode surfaces ^ chon was described, see fig. U, 15, and 16.

The preferred case in terms of the location of the anode and cathode related to a single electrolysis cell is the one with the diaphragm-covered one KathDda below and with the Annae with ahne diaphragm above. In relation to the bipolar graphite electrode plate, it reads the same Case: The cathadiache side of the electrade plate with the diaphragm looks up, the anodic electrode side with or without a diaphragm looks down.

However, it is possible to change the mutual position of the cathode and anode to reverse without that case falling outside of this invention. Even with this reversal, there is always a diaphragm on the electrode located below within the cell, d. H. in this Fall on the anode, while the cathode overlying inside the cell can work with or without a diaphragm. Even in the preferred normal case can either have a diaphragm just lying on it within the cell below Cathode can be used or an additional diaphragm also after .auf the anode lying inside the cell. All these FBlIe are included in the present invention.

According to the invention, the control of the electrolyte level in the individual cells of an electrical lyser can be controlled with the help of the urniobrnchtcn Uurrichtuni] vurnunrimniun with the help of the Uuisf! Iulii "! Do in A> b. 'i!> ills H <ii-izant; ilr.chnitt and in Fig. 2h alo assigned Ueriikalt-chnitt ü - LJ of Fig. 23 is shown. Detiv cell dec Eli.xirclyseuru owns tin bone of'der L'inspeisf lanke 'the furthest in ΐ, for advice Hanman & chonkelflansch εϊηεη hanal with some

8ADORIGiNAL »09840/1034

SAD ORlGiNML ^ _{0 0R} | _G , _NAL

a few connecting holes to the cell interior below the electrolyte level of interest. 1 / starting at each of these handles '' leads a hole through the frame to the outside. From here the connection leads through the intermediary of a flexible hose to a transparent indicator tube which is mounted in a common transparent tube-like vessel. In this closed common transparent KantrnllyefdB connection with one of the produced Cl _? - The gas pressure in the line to be controlled is transferred to the leading vertical shaft of the electrolyser and, according to the invention, the possibly disruptive atmospheric pressure is thereby switched off. It is advisable to keep some of these tapping points at different heights ready for comparative connection, so as not to be able to largely eliminate the influence of the pressure drop in the shaft. The observations on the level indicators in the common control clock serve as criteria for menstruating the supply of acid, for discovering possible damage to individual diaphragms, and for determining the end of the service life of the diaphragms.

As an example, Fig. 35 shows the view of a bipolar electrolyser with several cells with the electrode surfaces in a horizontal position. The two gases Cl _? and H _r are collected and carried away in the collecting hoods of the steel dachshund, which is lined with acid and chlorine resistant inside, whereas the anadic and catholic acid are collected in a collecting channel on the steel floor, which is also lined with che.niüt.: »'· · at'-nidinsm material and is diverted to the outside. In the example in Fig. 25, the feed acid is fed through 2 valves with a flow meter each to the 2 cell groups with 6 cells each. The quantity * regulation of edible acid supply is through the Gchon control device described vnn Fig.? M ntihr urluichtcrt.

By linn lijnijtiii bchi-oubun zürn / uMiinriüMilitiltun tiuv Uiiutnilc; and to the üiuht-

In the meantime, the exercise knit hulbur is only an ijezeiijt. The depending on

Decoiler size '+ or 8 supports and isolators are omitted.

In summary, it should be noted that the illustrated invention The examples described are not exhausted, Sandern that modified forms of application are also based on the invention underlying principles, in particular? 8 40/1 0 3 A

BATH ORIGINAL

- the principle of the diaphragm by resting on a rigid, permeable To give the underlay a longer service life,

- the principle of slots and channels, the so-called Bahr channels composite cavity system inside the electrodes, which allows the or animal diaphragm to rest on a rigid Support allows and it also allows one or both gases keep away from the ElEktrodßn Zwischenraum by the erfindungsctemäSsn HohlraumsystEme jeriei the two gases from its surface adhesion Distribution practices: r his Eli-'ktrariumflüche in sbine Bahrk ^ nülc concentrated, wan each πίε hnllekto * attributed to him for one The surface area of the electrode acts and due to its rahrähnliche Geometric shape (and completely separate for chlorine and hydrogen) connected to its gas collection duct in a technically satisfactory manner can bierden, as well

- the principle of feeding the electrolyte between the diaphragms bzui. between the diaphragm and the counter electrode, al9 in the invention are to be considered included.

With regard to the technological and economic impact of the Invention is to be pointed out in particular:

1. On the much longer life of the diaphragms, mainly on the support of the diaphragms on documents according to the invention based, but without the principle of the electrode cavity systems would not be possible. From increasing the service life of the diaphragms results in savings in the maintenance costs for the diaphragm change and avoidance of product failure, as well as safer avoidability the formation of explosive Cl "- H_ mixtures;

2. The energy savings that result from the practically gas-free resp. lower gas between the electrodes by lowering the cell voltage around 13.1 - 0.1! j volts. This advantage would also be without them Llektrndenhohlr; iumr »ystBm £ j and without the or that on its electrode AuflierjGruiu diaphragm not raw.

BADOR.QINAL. ₃₀₉ 840/1034

3. The fact that one of the described inventive Execution farms, namely in the cells with horizontal Elektror denflächen a considerable saving in floor space compared to the previously used electrolysers, since in this case the Electrolysers according to the present invention are tower-like apparatus, who need üjenio floor space. Since electrolysis systems of this type to be able to work in the open air with judgment and without being uncomfortable cutting into heights is particularly economical.

H. On the fact that the introduction of the sulphate acid made possible by the present invention into the space between the two diaphragms of a cell almost completely excludes mutual contamination of the gases produced, namely in all stages of the age of the diaphragms that are to be exploited, which is also significantly longer, ie an even higher one medium purity of the gases generated can be achieved than before.

309840 / 103A

BATH ORIGINAL

Claims (1)

* f - Dr. Georg Messner OQ Latemarstrasse 7 2213603 'BOOG Munich 9Ü Process and device / u r elecnralytical treatment of solutions containing hydrogen chloride on graphite electrodes with separation of the formed gases chlorine and hydrogen ♦ P ^ benL claims Procedure and device for electrolytic treatment of hydrogen chloride Containing solutions for uraphite electrodes, keeping them separate the formed lots of chlorine and hydrogen characterized, A. that one seeds! each of the two gases produced on site its emergence, also that of every electrode chamber as impoverished Electrolytes to be repelled from the cell out through a coherent cavity system according to the invention inside the graphite electrodeB, consisting of slots, which are sawn into their electrode surface and out into the same Graphite electrode not parallel to the slit direction incorporated, behind the slots and in some places in spatial connection with the slots, standing drill channels or otherwise worked and with the gas outlet from the cell in a sufficiently free connection from flow restriction standing runrarticen recesses inside the Graphite of the electrode, uiobei the bottom is ijChlitzG in graphite either in approximately constant grooving eder in cjirland-like healings v / runs, those that are caused by friction, overlap each other, the üahrkanälun zunt.:nrdnetE:n Eini'tjlschnittaegmenten to be cut uinnn HrHiüsärjfM-jfitzE !! -: zu5inmmHn! iuf..r; t / t Bind, or tut- din f 'urt Lhuf' r.-nden anhtii Ltapurun der, usually the . v. sitiüiit; . Jtr Hn.uGchnnidbddfMi üohrkanäle nnteprechendem Kvthnua fur unu ab gef'ijfirtei * kreis ^ iigeaatttfS are, and MD0RH.NAL 3098 * - / 103 Xl 22136C3 that one or both gases also enter the space between the two electrodes of the cell qby measures prevents such measures applied alone or in combination could be: a) the setting of a diaphragm or an equivalent Uau-partly to a cider to both electrodes of a row, wherein the surface of each diaphragm or component is on the surface of its associated electrode in accordance with the invention Lüeise propped up, b) the installation of blinds or combinations of blinds with thin diaphragms with the proviso that in the room between the blinds bzai. Hambinstionsn a sufficient '"■ a strong stream of food acid is introduced, c) a suitable spatial flow of the electrodes in the Gravitational field, sadcjß die! Gravity bzui. the buoyancy one of the two u & se keeps away from the electrode gap and pushes it into the used and uuhrkanäie of its electrode. 2. V / experience and device according to -, napr characterized, that the graphite lamellas stand between the slots have a thickness of about 1.5-3 mm that the depth of the slits about 1 - 2 mm and the depth of the use is about 5 - 20 mm, the position of the parallel to the outer surface of the Electrode niniicijrbeittitun, uLwu 2Π - 'tu mm wide Uahr or AusLiparungskunaln go Ginijeriugtt?!, Int that Uohrkanaluchsen and Slits crossed crookedly, preferably crossed below about 90 ° run and that the ujerkzeuge generating the slots where slits and channels come closest to each other by crossing, at least as far as they have penetrated into the spaces of the channels, that the resulting spatial cross-sections for the transfer of the generated base together with its from the 309840/1034 BATH ORIGINAL j Schiitzräuraen electrolytes carried in the drill channel spaces ^! are sufficient. - 3. The method and device according to claim 1 and 2 ' characterized, ! da3 the entry of the gas generated at an electrode into the Inside the combined cavity system, the graphite electrode is replaced by a sufficiently resistant, electrically non-conductive, material that is at least all radically wettable by the electrolyte or a mixture of materials, preferably predominantly of polyvinyl chloride or other largely resistontem material with or precoat diaphragm existing without binding agent or prefabricated Diaphragm is established on the combs of the electrodes. forming graphite flakes directly or with a non-conductive, chemically resistant grate or mesh in between and through hydrostatic or hydrostatic plus dynamic overpressure of the electrolyte and gas located outside the diaphragm or by a equivalent negative pressure of the electrolyte or the overlying gas space within the diaphragm to the electrode surface is pressed. 4. The method and device according to claims 1 to 3 characterized, that one or both electrodes of a cell has one on it directly or indirectly supported diaphragm are covered and the introduction of the edible acid in the llaum between the diaphragm and Counter electrode respectively. takes place between the diaphragms. 5. The method and device according to claim 1 to 4 with vertically or inclined electrodes and uiaphragmaflächen characterized, dai.i the vertical or nearly vertical Jiohr- respectively. Recess ungskaη / 1 le are flooded and that for the purpose of acceleration the gas BAD ORiGiNAL 309840/1034 discharge from the drill channels after practicing the free cross-section of a each of the channels cemented by a pinched wire inserted into it flat Dthe curved elongated conductive foil made of sufficiently resistant Material divided into 2, preferably unequal partial cross-sections, where the larger partial cross-section is preferably the assigned one Slitting facing the electrode surface. 6. The method and apparatus according to claim 1 to 5 with vertical or inclined electrode surfaces and flooded vertical or inclined, with the slots of the electrode surface in connection standing drill or recess channels, characterized, that for the purpose of accelerating the Ua saustragung up through the channels mentioned, additional channels worked into the electrode are provided, which facilitate the reverse circulation of a part of the electrolyte serve downwards, but are not themselves in direct connection with the slots, with the proviso that each riser channel with its reverse circulation channel at its upper and lower End through local recess in the graphite or in the frame material in connection, which the passage of the circulating electrolyte allowed from each channel to its twin channel. V. The method and device according to claims 1 to S. characterized, that one or both diaphragms are formed duruh jalousiuartiy Apertures made of enough material: replaced or supplemented with the proviso that a sufficiently increased feed rate of the excess acid between the two diaphragms, between the two Blendc / diaphragm combinations or between orifice / diaphragm combination and diaphragm is adhered to. BATH ORIGINAL 309840/1034 8. The method and device according to claims 1 to 7 characterized, that for the introduction and distribution of the acid in the cell interiors Distribution frames made of sufficiently durable plastic with comb-like jagged recesses in parts of their inner hand and their inner frame area between the flanges the z. B. from Haveg existing Elektrudenrahmen sealed inserted The ipeic acid is preferred for the distributor frames via recesses z. B. Milling of parts of the flange surfaces of the Havecrahmen received zueleiten. 9. The method and apparatus of claim 1 to 6, wherein the unipolar End electrodes are combined with bipolar graphite electrodes, characterized, that each bipolar electrade plate has a coherent cavity system of slots and drilling or recess channels for the jamming and discharge of hydrogen as plus cathodic electrolyte and also contains a cavity system of the same type for chlorine gas plus anodic electrolyte, which the latter with the H, - cavity system has no direct Has connection, with the anodic and cathodic drilling channels in the material of the bipolar graphite electrode plates alternately lying next to each other, with the alternative possibility of symmetrical arrangement of the ear channels in the middle of the thickness of the bipolar uraphite plate to form the anndic slits and ear canals in a mirror-inverted manner about the same as the cathodic or else by asymmetrical arrangement of the Ljahrkanal, ie outside the Mittr. the thickness of the urphite plate, use the anodic without a mat. deepur zu riianhcn e; ls die kathiitJiunhiiii and then L din Um ljr; iuL; liHriimt; n:, inri di; i · riruHlii; chr: n lu'iifjtiitliiniellen im Lnlnvuuiu: cjJlt [u: r liiiheri ^ r: r bt: riiidüUt; r to vtiryruUern. BATH ORIGINAL 309840/1034 10. \>'Ahren rf and apparatus according to claim 1 to 9 characterized, that connection diaphragms are applied to hosts, tissues or braids made of chemically sufficiently resistant and electrically non-conductive material in a suitable layer thickness, which are placed in front of the electrodes as closely as possible, and the mass of the diaphragm is an ulie made of fibers of chemically largely resistant material of uniform vein of different chemical imaturation , preferably made of polyvinyl chloride, represents the fibers and other components of which by at least as much embedded or subsequently introduced binders, ui'B z. B. the evaporation residue from diluted PhennlharzlüEiungen, from alkali silicate by acid treatment regenerated cellulose or mixtures of these bE ^ iden or possibly. analuLsr Litoff ", for the female of colloids, mechanically bound so tightly that the diaphragm is at least as stable as possible ^; This means that they can survive handling the cell without damage to the point where it is complete, and give the diaphragm the desired permeability for electrolyte and electricity. 11. Uerfahren and Uorrichtung according to claim 1 to 1D characterized, the Anschmemmdiaphrsyrneri by sucking in a pulp of fibers and sunstiijen components or by spraying on fibers, other Kompanentun and tlinrieniittel directly on the ridges of the Graphite flakes of the electrodes are applied, uiobp.i the in Claim 113 mentioned other binders alternatively an after-treatment is introduced into the Uiies. BATH ORIGINAL 309840/1034 12. The method and apparatus according to claim 1 to 10 using of prefabricated diaphragms with suitable permeability for electricity and electrolyte characterized, that the prefabricated diaphragms Wüese in connection with Ge ' UHüe are, preferably with Appreticrung by regenerated silica or regenerated cellulose or through dilute phenal resin solutions or by mixtures of these and similar substances. 13. Uerfahren and device according to claim 1 to 10 using of prefabricated diaphragms with suitable permeability for electricity and electrolyte characterized, that the diaphragm is a fleece made of fibers of chemically largely resistant material of uniform or different chemical nature, preferably made of polyvinyl chloride, the long, relatively thick threads of about 0.1 - 1 mm in diameter extending over large parts of the length and width of the diaphragm PVC, Teflon, polyester or other sufficiently resistant materials in ab- ^; stood from multiples of the thread diameter, preferably oriented in 2 directions, and the binder contains regenerated silicic acid, regenerated cellulose, the residue of dilute solutions of phenalhorz, colloids and similar substances alone or in mixtures. 1U. Method and device according to Claims 1 to U and 8 to 13 characterized, that the uraphite electrode surface and the diaphragm surface are horizontal or Hnridherritl horizontal .'jnijeurtinr-it r; .inri. 309840/1034 15. Uerfahren and Uarrichtung according to claim 1 ^ characterized, that at least the electrode UDn lying below within a cell is covered by a diaphragm and the food acid between Diaphragm and the possibly uncovered upper electrode bzuj. is inserted between the two diaphragms. 16. Uerfahren and device according to claim 1 to 15 characterized, that for the purpose of distributing the biscuit acid both on the individual cells and over the surface of each individual cell Herben or holes are provided in those parts of the flange flanges of the Havegrahmen that lie between the row ^{interiors 1} and the distribution channels incorporated in the Hahmenfiansche or flange surfaces. 17. Uerfahren and device according to claim 1 to 16 under control the electrolyte levels in each cell through associated with them transparent indicator tubes characterized, that the transparent indicator tubes in a transparent container are housed, the gas space each with a suitable ausuühl bun place of the Chlnr fnhri.; ntk; n Llektmlyrnjurinnnriräume connected will. 18. The method and device according to claim 1 to 13 and 16 to 17 under ' Checking the electrolyte level in the individual cells of an electrolyzer with vertically arranged electrode surfaces characterized in that from the highest point dBS space between the slide 309840/1034 BATH ORIGINAL phrases of each cell a bond line runs out, which leads into a transparent level indicator, including the open end, the indicator is connected to a common vessel, into which all the level indicator and the one from the display ^; possibly escaping gases and feeds them to an exhaust pipe. 19. The method and device according to claims 1 to 18 characterized, that the drilling channels incorporated into the graphite electrodes for the Gas and electrolyte discharge from the cell before the incorporation of the 5chlitze communicating with them with a coat of acid-resistant and also synthetic resin that is as clear as possible, preferably Phenolic resin provided on their inner walls for the purpose of making it possible the use of a lower and more economical grade of graphite and to protect the graphite of the holes from erosion. 20. Process for the production of unipolar or bipolar uraphite electrodes with integrated cavity systems according to claim 1, 2, 5, 6, 9 and 19 characterized, that the production from plane-parallel braphite plates in the order: a) Incorporation of the Bahrkanal by drilling or milling of the cement to be cemented Share, b) Superficial phenolic resin coating of the inner walls of the Bahrkanaie, c) hardening the resin paint, d) sowing the bchlit / i: at the LlnktrndeimtiRrf ldchnn carries out -in .. _{3eme / 1e34} Blank page