US1431602A - Art of electrolysis - Google Patents

Description

C. G. SPENCER.

ART OF ELECTROLYSIS.

APPLICATION FILED JAN.15, 1921.

1A3 LEW. Patented Oct. w, 1922.

3 SHEETS-SHEET I.

C. G. SPENCER.

Patented Oct. 10, 1922..

3 SHEETSSHEET 2.

0. G. SPENCER.

ART OF ELECTROLYSIS.

APPLICATION FILED JAN. 15, 1921. 1A1 my Patented 0015.10, 1922 3 SHEETS-SHEET 3.

CLARENCE G. SPENCER, OF NEW YORK, N. Y.

ART OF ELECTROLYSIS.

Application filed January 15, 1921. Serial No. 437,4L97.

To all whom it may concern:

Be it known that I, CLARENCE Gr. SPENCER, a citizen of the United States, residing at New York, county of New York, and State of New York, have invented certain new and useful Improvements in the Art of Electrolysis; and I 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.

This invention relates to art of electrolysis; and has to do more particularly with the electrolytic generation of oxygen and hydrogen from water.

In generating oxygen and hydrogen by electrolytic decomposition of an aqueous electrol to, such as a solution of an acid or an alka i, and especially where the operation is conducted at comparatively high current densities with necessarily ensuing rapid and copious evolution of the gases, some difficulty is experienced in thoroughly freeing the en- 'erated gases. from the entrained electro e to the extent necessary to render said gases fit for use .in certain industrial operations."

Une object of the present invention is therefore to provide for thoroughly washing the generated gases by subdividing said gases into such minute bubbles that all portions thereof may be thoroughly exposed to the action of a washing liquid and eflicient cleansing of the gases thus effected.

The invention also has for an object the provision of means whereby structurally separate single-cell or multi-cell units of a generating battery or electrolyzer may be quickly and easily removed from its place in the series of units, or replaced after such removal. 7

"With the foregoing objects in view, as well as others that will become apparent as the description proceeds, the invention comprises the novel combinations of parts hereinafter described in connection with a practical typical embodiment of the invention, and then more particularly pointed out in the claims. Such typical embodiment is illustrated in the accompanying drawings wherein- Fig. 1 is a side elevation ofelectrolytic apparatus embodying the princlples of the invention, certain parts being shown broken awa and in section;

Fig. 2 is an'end elevation of the apparatus shown in Fig. 1, viewed from the left;

Fig. 3 is a plan of the apparatus, with the upper part of the framework removed to disclose parts beneath;

Fig. 4 1s a view of one of the gas washing and cooling devices on a larger scale, partly broken away and in section;

F1gs. 5 and 6 are plan views of details, partly in section on the lines 5-5 and 66, respectively, of Fig.4; and

Fig. 7 is a fragmentary sectional detail of means for holding the adjustable overflow control rod in position.

Referrin to the drawings, the apparatus shown in igs. 1, 2 and 3 is of a type generally similar to that disclosed in my prior co-pending application Serial No. 354,015. filed January 26, 1920; and while the novel features hereinafter claimed are capable of employment in types of apparatus differing from that disclosed herein and in said prior application, this type is here chosen as convenient to illustrate an embodiment of the invention in a desirable practical construction.

In the construction here illustrated, 10 designates generally'a cell group or battery unit, of which groups or units any suitable number may be electrically connected in series by removable jumpers 10*, each group or unit comprising a plurality of cells, six for example, constructed and arranged in series in any appropriate manner, but in the present instance more particularly in the manner fully set forth and claimed in my co-pending application aforesaid. As a detailed description of the specific construction and arrangement of the individual cells COIllprised in each of the units 10 is not essential to an understanding of the present invention, such description is omitted here. Each of said units 10 is removably suspended individually by suitable means such as straininsulator suspension devices 11 fromhoverhead longitudinal angles 12, which are carried in closely spaced pairs by a framework comprising uprights 13, cross pieces 14, and stringers 14, all suitably connected together to provide rigid supporting means which may be insulated from ground in any effective manner unnecessary to illustrate here. Suspended from a beam 15 carried on the upper part of the framework, is a double track 16 extending longitudinallv of the apparatus, upon Which track are arranged to run the rollers 17 of a rigid carrier device having a depending eye 18 to which may be attached suitable tackle or hoist means for raising and lowering any one of the several cell units or groups into or out of position in the series, this novel arrangement greatly fa.- cilitating the assembling of the units or the replacement of any one of them as may be necessary from time to time in practical operation. Suitable means are provided for separately leading off the gaseous products, hydrogen and oxygen in this instance, from the several cathode and anode chambers of each unit; and means are also provided for supplying electrolyte to the respective anode and cathode chambers of the cells and for leading electrolyte therefrom in systematic circulation. In this instance 19 and 20 are the main oiftakes for the oxygen and hydrogen, respectively. Manifold offtake headers 21, one for each unit or group 10 of cells are connected respect vely by risers 22 to the oxygen main ofl'take 19, as shown in Fig. 1; and each header 21'is connected by suitable individual olfta-kes 23 to all of the anode compartments of the corresponding unit or cell group 10. An exactly similar arrangement is provided for connecting the cathode compartments of each unit or cell group to thehydrogen main ofi'take 20.

The hydrogen and oxygen offtake mains 19 and 20 lead respectively into the upper portions of separate electrolyte and gas-separating chambers or tanks 24 and 25 for separation of gas and electrolyte. In going to the anolyte and oxygen tank 24, the offt-ake 19 enters the upper end of a trap 26 which is in the form of a large pipe section mounted on the top of said tank and Opening downward thereinto, said pipe 19 being bent downwardly and discharging into the trap at some little distance below the point at 'which the lateral branch 27 extends horizontally from the upper part of the trap. Similarly, the hydrogen main offtake 20 discharges into the upper part of a trap 28 arranged above the catholyte and hydrogen tank 25, and discharges below the level of the lateral branch pipe 29 extending horizontally therefrom. The purpose of this arrangement will appear more fully hereinafter.

The electrolyte chambers or tanks 24 and 25. may be structurally seperate tanks having an equalizing connection; or, as in the present instance, said chambers may be formed in what is in effect one tank divided by appropriate baflie or partition means into said chambers 24 and 25 which are non-coinmu'nicating except at a level well below the minimum level at which electrolyte stands therein. The electrolyte level is so maintained in the system that there is always a space in the upper part of each tank for separation of gas and electrolyte carried over into the tank from the cells through olftake 19 or 20, as the case may be, most of the electrolyte that goes over with the gas being caught in trap 26 or trap 28, and the gases, oxygen and hydrogen, largely freed from electrolyte, passing off through the lateral branches 27 and 28, respectively.

In the type of apparatus here illustrated, electrolyte is systematically circulated through the cells and the electrolyte tanks 24 and 25, the circulation of anolyte and catholyte being maintained distinct throughout that part of the system where the electrolyte carries substantial proportions of the generated gases. The circulation is induced partly by the thermal head due to generation of heat within the cells, and also to an even greater extent by the gas lift effect due to rapid evolution of the generated gases within the cells and the restricted diameter of the oxygen and hydrogen olftakes going to the mains 19 and 20. This latter effect is especially pronounced where high current densities are employed in operation, say more than one ampere per square inch of projected electrode area, for which type of operation the present apparatus is well adapted.

As here shown, anolyte leaves each cell of a group or battery unit 10 through individual offtake. 29, the anolyte olftakes of each group entering an oiftake manifold 30 for that group, which manifold is connected by a valved pipe 31 to anolyte ofltake header 32, discharging into the upper part of anolyte chamber 24. The catholyte leaving the cathode compartments of each cell group 10 is conducted through individual catholyte offtakes 33 into catholyte manifolds (not shown, but similar to manifolds 30), oil which one is provided for each cell group and which are connected to catholyte olftake header 34 which discharges into catholyte tank 25. As before stated, the lower portions of said chambers 24 and 25 are in communication, so that after sufficient opportunity has been given for complete separation of the evolved gases, the substantially gasfree anolyte and catholyte may mingle and pass through outlet pipe 35 into T-pipe 36, of which one branch leads to the anolyte intake main 37, while the other leads to catholyte intake main 38. The anolyte intake main is connected by individual pipes 39 to anolyte intake manifolds 40, one for each cell group, which latter are connected by individual anolyte intakes (not shown) to the respective anode compartments of the several cells of each unit or group, in a manner already described in the case of the anolyte ofl'takes 29. Theconnections of the catholyte intake main 38 to intake manifolds or headers for the several cell groups, andthe connections of these headers to the several cathode chambers of the cells, are not here illustrated but are the same as already described for the corresponding parts of the anolyte circulation system. The pipe 35 has a valved connection 36 which may be employed to. drain the system of electrolyte, or to supply fresh electrolyte thereto. The electrolyte ordinarily employed is asolution of caustic soda in water, although employment of other electrolytes is not excluded.

One of the most important features of the present invention is the provision of es pecially efficient combined means for cooling and washin and controlfing the back pressure thereo and visually indicating the flow of gases from the system. In the arrangement here disclosed for efiecting this, the oxygen and hydrogen leaving the traps through pipes 27 and 29 respectively, are led through separating, washing and cooling systems which are designated generally in the drawings by the reference characters W and W for oxygen and hydrogen, respectively. Since these systems are substantially identical in the present example, it will suflice to describe only one of them, namely, that for oxygen. The pipe 27, after leaving the trap 26, bends downwardly and enters a vertical pipe 41 through a T-coupling 42. The pipe 41 is suitably connected by said coupling to an opening in the bottom of a gas washer and cooler tank indicated generally at 43. As is best shown in Fig. 4, this tank consists of a glass cylinder 44 mounted between a base 45 and a cover 46, said base and cover being flanged as shown and the assemblage being firmly clamped together by means of tension rods 47 and nuts 48. Flanged insulating bushings 48 serve to insulate the rods 47 and nuts 48 from the castings 45 and 46, the gas outlet pipe 68 being therefore insulated from potential-carrying parts such as pipe 41 which is connected metallically and through the hot caustic solution of low resistance to the source of electrical potential. In the present instance, the base is provided with an integral bracket 49 whereby the device may be bolted or otherwise secured to the apparatus frame as shown in Fig. 1. On its upper side the base 45 is provided with an annular shoulder 50 between which and the lower edge of the cylinder 44 is placed suitable packing 51. A disc 52 of porous material, of such character as successfully to resistthe action of alkali, also rests on the packing 51, the joint between the disc and the cylinder 44 being caulked with asbestos 53 or other suitable material. While the invention in its broader aspects is not limited to the employment of a particular porous material for the disc 52, T have found that porous stone-like mineral matter, such as pure silica in the form of a coherent porous plate or slab, and especially the form obtainable commercially as filtros, offers special advantages for the purposesin VlW;' and the employment of porous siliceous material of this character is therefore recommended.

the evolved gases, regulatin tilt Filtros is especially suitable because of the extreme fineness of its porosities and its generally satisfactory characteristics, especially as regards inertness and long life in service.

The disc 52 is centrally apertured to receive a tube or pipe 54, composed of glass in this instance, which is held stationary in able overflow tube 56 telescopically dis posed therein and provided with bearing or centering rings 57, of rubber or the like, which fit closely around the tube 56 and engage the inner walls of said tube 54 snugly. The tube 56 is open at both ends,

andshould be of such length that when adjusted to its highest position, its'lower end will be somewhat below the point at which the pipe 27 enters pipe 41. Suitable means are provided for enabling adjustment of the telescopic overflow tube 56--54 from the exterior of the washer chamber 43. In this instance, the adjustment may be effected by means of a rod 58 which is suitably secured to the upper end of pipe 56 and which extends through the gas outlet 59 leading from the top of the washer chamber andthrough the T-coupling 60, said rod being held in position in the coupling by means of a threaded plug or gland member 61 which screws into said couplingand forms therewith a stuffing box, through which said rod 58 may be slidably moved up or down and by which it is held in any adjustable position. Any suitable means may be employed for securing rod 58 to said pipe 56,. but in the present instance the means for this purpose comprise a yoke or fork. 62 fastened by strap 63 and pin 64 to the lower end of the rod, the, arms of said yoke carrying secured thereto a clamp device composed of two straps 65 which are clamped to the arms and to the pipe 56 by appropriate. means such as bolts 66 or the like. In normal operation, cooling and washing water is fed into the washing chamber through inlet pipe 67 continuously; while washed and cooled gas is conducted away from the washer through pipe 68 leading from coupling 60 of the gas outlet. A thermometer well 69 tO' h01d a thermometer 70 maybe provided in the cover 46.

The pipe 41, as here shown, extends downward some distance below' the junction of the pipe- 27 therewith, and then bends upward again, to provide a Urshaped water sea-l indicated generally at 71, said seal having an outlet or spout 72 discharging valve 78 in the water supply pipe 79. When into funnel shaped upper end 73 of a waste pipe 74, the upper end of the waste pipe being spaced some little distance below the outlet pipe 72 as a means of insulating the latter from the ground.

The apparatus here shown also comprises means for automatically maintaining the level of the electrolyte in the system at a predetermined point, and for supplying water'to the system as fast as it is used up. Such means comprises in this instance a float 75 mounted in a tank 76, which latter is connected by a pipe 77 to the electrolyte supply system at a point intermediate the chambers 24 and 25 and in communication with both. The liquid level in float tank 76, which corresponds to the highest desired level in the electrolyte circulating system, determines the position of the float 75 and in the position here shown, the float is at its highest point and closes the electrolyte level falls and the float sinks, the valve opens and makeup water enters tank 76. Pipe 79 conducts any temporary overflow from the discharge valve into the open upper end of stand pipe 80, which communicates with that portion of the electrolyte supply system intermediate chambers 24 and 25.

The mode of operating the apparatus above described is sufficiently apparent; and,

except for the operation of the gas washing, cooling and regulatin system, the operation has already been ully described in, my prior application aforesaid. The evolved gas, either hydrogen or oxygen as the case may be, after having been freed in the separating chambers 24, 25, of most of the moisture mechanically carried over from the cells, passes into the vertical pipe 41-, and thence upwardly through the annular space around the guide sleeve 54, entering the space between the base 45 of the washer and the porous plate or disc 52. The gas being under moderate pressure passes rapidly upward through the porosities of disc 52 and emerges into the body of wash water 81 on the upper side "thereof, being subdivided into very fine bubbles by its passage through the minutev pores of the disc and being therefore in a condition adapting it to be thoroughly freed from alkali and cooled by the wash water. The wash Water, which is fed in continuously through inlet 67 at the necessary rate to effect efiicient washing and cooling of the gas, continuously overflows the upper end of the adjustable outlet pipe 56 when the, washer is in operation, passing downwardly through said ipe and thence. into the water seal 71, l rOm which it is discharged through 72 into pipe 74. The rings 57 fit sufficiently well both the tube 56 and the inside of sleeve 54 to prevent escape of any substantial quantity of water through the annular space between these members. Fig. 4 shows the upper surface of the body of wash water 81 considerably below the upper end of outflow pipe 56; but it is to be understood that the drawing represents a quiescent condition at a moment when gas is not passing through the washer. \Vhen gas is passing normally, the wash water is very much increased in volume by the enormous number of fine gas bubbles, so that under such conditions its level is very much higher than is shown in the drawing.

What I claim is:

1. Electrolytic apparatus comprising the combination, with an electrolyzer, of gas washing means operatively connected thereto, said gas washing means comprising a container havin an intake connected to said electrolyzer and an outlet, and a body of porUs mineral matter interposed between said intake and outlet.

2. Electrolytic apparatus comprising the combination, with an electrolyzer, of gas washing means operatively connected thereto, said gas washing means comprising a. container having in its lower portion a gas intake connected to said electrolyzer, a partition of porous mineral matter adjacent said intake, a water intake and a water overflow above said partition, and a gas outlet also above said partition.

3. Electrolytic apparatus comprising the combination, with an electrolyzer, of gas washing means operatively connected thereto, said gas washing means comprising a container having an intake connected to said electrolyzer and an outlet, and a body of filtros interposed between said intake and outlet.

4. Electrolytic apparatus comprising the combination, with an electrolyzer, of gas washing means operatively connected thereto, said gas washing means comprising a container having in its lower portion a gas intake connected to said electrolyzer, a. partition of filtros adjacent said intake, av water intake and a water overflow above said partition, and a gas outlet also, above said partition.

5. A gas washer comprising a container, a partition of orous mineral matter, such as filtros, dividing said container into upper and lower parts, a gas intake entering such lower part, a gas outlet leading from the upper part, a water intake entering said upper part, and an adjustable water overflow leadingfrom said upper part.

6. A gas washer comprising a container having a gas intake entering its lower part, a partition of filtros or the like arranged above said intake, an overflow pipe extending though said partition and into said gas intake, a smaller pipe telescoping inside of the first pipe and extending therealmve.

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individually removable from and insertable 10 in its place in the assemblage indepemlently of the others, and a traveling hoist also carried by said supporting means in operative relation to said units.

In testimony whereof I hereunto aflix my 15 signature.

CLARE-i l (E (l. SPENCER.

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