US586729A - Office - Google Patents

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(No Model.) 4 SheetsSheet 1.

O. KELLNER. METHOD or AND APPARATUS FOR EFFEGTING ELEGTRO'LYSIS. No. 586,729. Patented July 20, 1897.

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(170 Model.) 4 Sheets-Sheet 2.

. G. KELLNBR. METHOD OF AND APPARATUS FOR EFFEGTING BLEGTROLYSIS. No. 586,729. Patented July 20,1897.

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4 Sheets-Sheet 3.

(No Model.)

uKELLN'ER. METHOD OF AND APPARATUS FOR EFPEGTING ELEGTROLYSIS.

Patented July 20, 1897.

Int/Te 712% Car? 16 Zlnpr m wvm (No Model.) 4 Sheets-Sheet 4. O. KELLNER. METHOD OF AND APPARATUS FOR EFFEGTING ELBGTROLYSIS. No. 586,729. Patented July 20, 1897.

f I I s\\\\\\\\\\\\\'\\ ////////////////A//////////A siding at provemen ts in the Method of RED STATES PATENT OF ICE;

CARL KELLNER, or VIENNA, AUSTRIA-HUNGARY.

Marl-loner ANDAP-PARATUTS FOR EFFE'CTING ELE'CTROILYSIS.

SPECIFICATION forming part of LettersPatent No. 586,729, dated J uly 20, 1897.

Application filed February 24,1896. serial No- 580,569.

in Belgium December 15, 1894, No. 113,221;

(No model.) Patented in France December 15, 1894, Ho- 243,672 in Italy December 31, 1894, XXIX, 37,828,

and LIXIV, 179 1 in Aultria Jmiuaryll, 1896, No. /208; in Hungary February 28, 1895 I0. 2,265; in Bwitzerh'miiduly 4, 1895,1lo. 10,658, and

in Norway July 16, 1895, No. 4,439.

To all whom it may concern Be it known that I, CARE KELLNER, a subject of the Emperor of Austria-Hungary, re-

Vienna, in the Province of Lower Austria, in the Empire of Austria-llungary, have invented certain new and useful 1mand Apparatus for Eifecting Electrolysis, (for which patents have-been obtained in the following countries, to wit: Austria, dated January 17, 18 95, No. 45/208; Hungary, dated February 28,

.1895, No. 2,255; France, dated December 15, 1894, No. 243,672; Belgium, dated December 15, 1894, No. 113,221; Italy, dated December 31, 1894, XXIX, 37,82S, and LXXIV, 170; switzerland dated July 4 1895, No. 10,558; and Norway, dated July 16, 1805, No. 4,439,) andI do hereby declare the following to be a full, clear,and exact description of the invention, such as will enable others skilled in the art to which it appertains to make and use the same, reference being bad to the accompanying drawings, and to letters of reference marked thereon, which form a part of this specification.

As is well known, the vertical arrangement of electrolytic apparatus is for many reasons to be preferred to the horizontal arrangement. This is especially the case with apparatus in which mercury is employed as an electrode, because, first, it is diflicult to place and maintain large and heavy apparatus horizontal with such accuracy as to cause thebott-om to be everywhere uniformly covered with a thin layer of this expensive metal; second, it is difiicult to act electrolytically upon large horizontal surfaces uniformly,and experience shows that an amalgam of an alkali metal decomposes the water of the electrolyte at the places of small current density, which in the case of the electrolysis of the chlorids of the alkali metals causes the formation of hypochlorites; third, the output capacity. of horizontal apparatus is restricted by difliculties in respect of construction and material,

.many contacts, large space, and numerous ties of mercury in constant uniform movement. 7

' It has heretofore been proposed to employ mercury in a vertical or inclined formas a cathode, for instance-by causing itto trickle in thin sheets'or streams down over vertical equivalent of energy by means of verticallyarranged, extremely simple, durable, and 1c liably-working apparatus without the use of a porous diaphragm or partition.

'According'to this invention the mercury cathode is employed in the form of narrowstrips, which are formed by a system of channels and are compelled to circulate in a helical or zigzag path or paths about 'the anode or anodes while they are being continuously freed in a cell separated from the decomposin g-chamber-from the cation they have taken up in their course Byemploying this method it has also been rendered possible to construct apparatus of any desiredoutput capacity.

The quantity of mercury required is small in consequence of the'high current density that is attainable therewith, and the raising apparatus or operation is simple because it is suflicient-,in the case of an apparatus however large, to raise up to the initial convolution of the helical path only that quantity of mercury which is requisite for a single convolution of the helix. In carrying this method into prac- 'tice the apparatus illustrated byway of example in a number of modified forms in the accompanying drawings may be employed.

Figure 1 illustrates in vertical section, Fig.

2 partly in plan and partly in horizontal section, an apparatusconstructed of cylindrical shape. Figs. 3 to 5 are respectively aperspective vicw,'a part vertical section, and a part horizontal section showing a cylinder providcd with helical channels for guiding the mercury strip or stream. Figs. 6, Z, and 8 are respectively an elevation partly in section, a vertical section, and ahorizontal section illustrating another construction of apparatus of flat shape adapted to be inserted into exist-- ing electrolytic apparatus in place of a diaphragm. Figs. 9 and 10 show, respectively, in horizontal an'dvertical section another arrangement of apparatus in which the striplikc layer of mercury, in contradistinctiou to the two forms-of apparatus shown inFi'gs. 1 to 8, is subjected to action or influence on both sides, (as irradiated from both sides,) and is consequently adapted to work with a large current density. Fig. 11 shows partly in elevation andtpartly in section a portion of the channel used in the apparatus shown in Figs. 9 and 10. I 3

In the apparatus illustrated in Figs. lgto 5 A is a cylinder, composed of material such as poncelain or stoneware, provided with. nu-

I merous helical channels a a a. b b b, (of

which only a few-are shown for the sake of c1earness,) through which the mercury flows in the form of a stream, the parts of the mercury stream in the several channels consti-' tuting strips. The'cha'nnels are arranged on the cylinder A, Fig, 3, in such a manner that the first, third, fifth, and so on convolutions that is to say, the channels forming the oddnumbered convolution of the helix-are situated on the inner surface of the cylinder, while the channels forming the second,fou-rth, sixth, and so on, or even-numbered convolution', are situated on the outer surface of the cylinder. The internal channels situated in the decomposing-cell communicate with the external channels situated in the forming-cell each by means of an opening or slit 0, formed in the wall of the cylinder.

In the cylinder A, to the uppermost channel act which the'mercury is'supplied through a pipe q, there is inserted a suitable anode (or anodes) B,prefcrably of cylindrical shape,

which is filled with the solid salt to be decom:-

posed, so that this salt cannot enter into the mercury-channels, but by passing from below the anode into the electrolyte around the same will become dissolved therein and so maintain The whole is arranged the strength thereof. in a vessel 0, which contains the substance (water or other fluid reagent) with which the separated cation is to be combined and is closed by a cover d.

r is the inlet-pipe for the liquid reagent, and 'r' and 'r are gas-exit pipes.

The anode B is connected tothe positive pole of an electric generator and the mercury is connected with the negative pole thereof.

As the resistance of the long stream of mercury, with the considerable current consumption, would be very appreciable, it is advisable to connect the stream of mercury at various points in its length with the negative pole of the electric generator. For this purpose the vessel 0 is made of metal-for example, iron-and is connected electrically at various points with the mercury by means of the wires n, the vessel itself being connected to a wire n, as shown on the left-hand side of Fig. 1, by which it is placed in electrical con nection with the negative pole of the electric generator; but if electricity produced by the combination of the cation dissolved in the mercury cathode with the liquid reagent in the vessel 0 is to be utilized then, as shown on the right-hand side of Fig. 1, the wires on are connected to form another common return-lead n to the negative pole of the electhe vessel 0. The mercury in the external channels and the vessel form in this case the electrodes of asecondary element which can be advantageously used for supplying current to another electrolytic apparatus or for relieving the mainsource of current-supply.

' If it is mainly desired to etfecta decomposition of the mercury amalgam that shallbe capable of regulation,-all the mercury strips are again connected bya lead with the negative pole of the "dynamo-machine,.and into this lead there is included a resistance W, Fig. 9, and beyond the latter a connection is made with the conducting vesselC. In this way there is formed a short-circuited element which promotes the formation of caustic soda. The efliciency of this element-that is to say, the speed of the decomposition of the amalgam -may be regulated by varying the resistance. I

The mode of operation of the apparatus is as follows: Assuming, for example, that common salt is to be decomposed with the object of producing simultaneously by electrolysis caustic soda and chlorin gas, then a solution of common salt is placed in the decomposing vessel A and water in the combining vessel G, and mercury is poured into the topmost inner channel a. As soon as the electric circuit is completed sodium will be separated from the solution of common salt contained in the decomposing vessel and will unite with the mercury cathode, but during the passage of the mercury amalgam through the second of the vessel A, the above-mentioned sodium will combine with the water inthe combin and liberation of hydrogen. The mercury freed from the sodium then passes at once into the next inner helical convolution a, again amalgamates with sodium, carries the same into the outer helical convolution b in the combining vessel, where it yields up the sodium as before, and so on, passing finally out of the apparatus in a pure condition by a pipe q to a pump 12 or other suitable raisthe pipe q, and thus to the topmost inner channel a for reuse.

The concentrated solution of caustic soda is drawn off from the vessel 0 through a pipe 12. If instead of water a solution of sodium ,tric generator, another lead m extending from helical convolution b,"situated on the outside ing vessel, with formation of caustic soda ing device, by which it is again delivered to nitrate be used in the combining vessel, ammonia-gas will be liberated instead of hydrogen. The hydrogen or ammonia, as the case may be, escapes through the pipe 1-, while the chlorin escapes through the pipe T the gases being conducted by these pipes to the place where they are to be utilized.

The hereinbefore-described arrangement of vessel A with mercury-channels serves to provide a fluid-tight divisi'onbetween the interiors of the decomposing and combining vessels; but incases where no-value willbe attached to this arrangement there may be employed in place of the cylinder A an insulatin g-wall A for se'paratin g the two spaces, as shown in Figs. 6, 7, and S. This wall is provided on both sides with the oppositelyinclined channels a a b b, that are co'nnected together by means of slots 0, so that the mercury flows along a flattened helical or zigzag path extending alternately through the decomposing-space and the combining-spaces. This arrangement'is especially suitable for use in existing electrolytic apparatus which work with diaphragms, because it is merely necessary to insert the wall A with channel in place of the diaphragm.

In the case of very large apparatus it will be advantageous to employ the construction of apparatus shown in Figs. 9, 10, and 11. I11 this arrangement the channel portions 0, a and b b are arranged, respectively, in separate decomposing and combining vessels, the said channel port-ions being connected together by means of bent pipes f, situated outside of and between the said vessels.

Of course it will be' understood that the channels a a, &c., and b '1), &c., are connected to form a continuous coil-like structo re, the channels (0 11 leading into channels a b, the latter into channels a" b", and so on throughout the series, as shown inpart in Figs. 9 and 10, in which last-named figure two of the channels connected by pipe fare shown connected with the last two channels of the series that lead to exit-pipe g, which may be connected by a pump or other rais- 1 ing apparatus with the supply-pipe g1.

In the construction described the mercury entering at q flows continuously, or substantially so, and alternately from the decom posing vessel to the combining vessel from top downward and out at Such mercury as it flows through the open channels or portions a be. b, &c., of the channeled conduit comes in contact with the electrolyte and the solvent in said decomposing and combining vessels, respectively, in the presence in the former vessel of two electrodes of opposite polarity arranged in the decomposing vessel on opposite sides and intermediate of the conduit convolutions, as shown, so that the mercury is caused to flow between electrodes of opposite polarity, and is in this manner subjected to the action of the electric current from opposite sides, (irradiated,) whereby but one-half the quantity of mercury neecssary in the apparatuses hereinbefore referred to will be required, while the output will be the same.

I claim- 1. In a process for the electrolytic-decomposition of salts of metals capable 0t combining with mercury, passing an electric current through a solution of such salt, to a mercury cathode flowing uninterruptedly from a higher to a lower level and before reaching such lower level flowing alternately and repcatedl y out of contact with the salt solution into contact with an agent capable of decomposing the compound or amalgam formed, for the purpose set forth.

- 2. In a process for the electrolytic decomposition of salts of metals capable of combining with mercury, passing an electric current through asolution of such salt to -a mercury cathode flowing uninterruptedly from a higher to a lower level and before reachin such lower level and while under the inflhence of the electric current flowing alternately and repeatedly out of contact with the salt solution into contact with an agent capable of decomposing the compound or amalgam formed while under the influence of such electric current, for the purpose set forth.

3. In a proccssfor the electrolytic decomposition ol salts of metals capable of combining with mercury, passing an electric current through a solution of such salt to a mercury cathode flowing uninterruptedly from a higher to a lower level and before reaching such lower level and while under the influence of the electric current flowing alternately and repeatedlyout of contact with the salt solution into contact with an agent capable of decomposing the compound or amalgam formed while under the influence of such electric current, for the purpose set forth.

4. In a process for the electrolytic decomposition of salts of metals capable of combining with mercury, passing an electric current through a solution of such salt to a mercury cathode flowing in a contracted or ribbonlike streamlet uninterruptedly from a; higher to a lower level and before reaching such lower level flowing repeatedly out of contact with the salt solution into contact with an agent capable of decomposing the compound or amalgam formed, for the purpose set forth.

5. In a process for the electrolytic decomposition of salts of metals capable of combining with mercury, passing an electric current through a solution ofsuch salt to a mercury cathode flowing in a contracted or ribbonlike streamlet uninterruptedly from ahigher to a lower level and before reaching such lower level, flowing while under the influence of the electric current alternately and repeatedly out of contact with the salt solution into contact with an agent capable of decomposing the com pou ml or amalgam formed, for the purpose set forth.

6. In a process for the electrolytic decomposition of salts of metals capable of combinin g with mercury, passing an electriccurrent through a solution of such salt to a body of mercury included in the electric circuit,-and moving a plurality of contracted or ribbonlike streamlets of said mercury alternately and repeatedly through said solution and through an agent capable ofdecornposing the compound or amalgam formed, for the purpose set forth;

7. In a process for the electrolytic decomposition of salts of metals capable of combining with mercury, passing an electric current through a solution of such salt to a-mercury cathode flowing uninterruptedly from a higher to a lower level and before reaching such lower level flowing alternately and repeatedly out of contact with said solution into contact with an oxidant and solvent of the cation in the compound or' amalgam formed and using the mercury of said compound or amalgam as an electrode for a primary element, for the purpose set forth.

8." In a process 'for the electrolytic decomposition of salts of metals capable of combining with mercury, passing an electric current through'a solution of such salt, to a body of mercuryincluded-in the electric circuit, moving a plurality of contracted or ribbon-like streamlets of said merc'urysimultaneously and alternately through an oxidant and solvent of the cation in the compound or amalgam formed, and using the mercury in said compound or amalgam as an electrode for a primary element, for the purpose set forth.

9. In a process for the electrolytic decomposition of salts of metals capable of combining with mercury, passing an electric current through a solution of such salt toa mercury cathode flowing in a contracted or ribbon like streamlet in a zigzag direction from a higher to a lower level and before reaching such lower level flowing alternately and repeatedly out of contact with said solution into contact with an agent capable of decomposing the compoundor amalgam formed, for the purpose set forth.

10. An electrolytic apparatus comprising two compartments, a fixed anode in one of them, a mercury cathode, and means for causing said cathode to uninterruptedly flow from a higher to a lower level alternately and repeatedly from one compartment to the other before reaching such lower level.

11. A partition for electrolytic apparatus provided on both faces with a series of superposed channels, those on one face being inclined in a direction opposite to that of the channels on the other face, and openings inof said compartments, a'second electrode for both compartments formed of mercury, in combination with means for continuously moving the mercury in a downward direction alternately and repeatedly from/one compartment to the other, and electrical connections connecting the mercury in one of' the compartments to the fixed electrode for said compartment,.for the purpose set forth.

13. An electrolytic apparatus comprising two concentrically-arranged vessels, the inner vesselprovided on both faces with downwardly-inclined channels connected in series to form a continuous channel from the upper to the lower end of said vessel,a pump whose force and suction pipes are respectively connected with the initial and terminal of said channel, a body of mercury adapted to circulate through said channel and a cylindrical fixed electrode extending nearly to the bot- .tom of the inner vessel; in combination with electric connections respectively connecting the mercury in the channel portions in the outer face of the inner vessel, and the fixed electrode in said inner vessel with opposite poles of a source of electricity, substantially asand for the purpose set forth.

14. An electrolytic apparatus comprising two compartments each provided with downwardly-inclined and interconnected channelsections forming a continuous channel leading alternately from one compartment to the other, a body of mercury in said channel, and a pump whose force and suction pipes are respectively connected with the initial and terminal of said channel, whereby the mercury therein is caused to continuously flow in a downward direction through the channel, and alternately from one compartment to the other; in combination with a fixed electrode in one of said compartments connected with one pole of a source of electricity, electrical conductors connecting the mercury in the channel-sections of the other compartment with the other pole of said source of electricity, and a resistance interposed in the last-named connections, for the purpose set forth.

15. In a process for the electrolytic decomposition of salts of metals capable of combining with mercury, passing an electric current throngha solution of such salt to a mercury cathode flowing from a higher to a lower level altern atcly and repeatedly out of contact with said solution into contact with an agent capable of decomposing the compound or amalgam formed, and short-circuiting the amalgam when brought into contact with said decomposing agent with a suitable cathode, for the purpose set forth.

. In testimony whereof I afiix my signature in presence of two witnesses.

CARL KELLNER.

Witnesses:

DEAN B. MAsoN, HARRY BELMONT.

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