US809085A

US809085A - Electrolytic apparatus.

Info

Publication number: US809085A
Application number: US16656603A
Authority: US
Inventors: Henry Spencer Blackmore
Original assignee: Individual
Current assignee: Individual
Priority date: 1903-07-22
Filing date: 1903-07-22
Publication date: 1906-01-02
Anticipated expiration: 1923-01-02

Description

PATENTED JAN. 2, 1906.

H. S. BLAGKMORE. ELECTROLYTIC APPARATUS" APPLICATION FILED JULY 22. 1903.

UNITED STATES PATENT OFFICE.

ELECTROLYTIC APPARATUS- Specification of Letters Patent.

Patented. Jan. 2, 1906.

Application filed July 22, 1903. Serial N0. 166,566-

fication.

cathode.

This apparatus is especially intended for the production of a lead -sodium alloy or a mercury-sodium amalgam and the recovery of the sodium therefrom as hydrate or oxid.

Referring to the accompanying drawings, Figure 1 is a transverse vertical section of an apparatus employing a molten electrolyte and Fig. 2 is a transverse vertical section of an apparatus employing an aqueous solution of an electrolyte and a cathode of mercury, and Fig. 3 is a transverse vertical section of a modified apparatus.

The apparatus of Fig. 1 consists of the following parts: An iron vessel 1 is set within a furnace-casing 2, of fire-brick, and supported therein in part by an annular flange .3, ex'

tending outwardly from the upper edge of the vessel and resting upon the fire-brick, and in part by pier 4, rising centrally from the bottom of the furnace-chamber into supporting contact with the bottom of the vessel. The contents of the vessel are brought into a molten condition by any suitable means, that shown, being a burner 5, extending through an opening 6 in the side wall of the furnace. The electrolyte and cathode may be subsequently maintained in a molten condition by the electrolyzing-current. From the flange of the vessel a cathode-terminal 7 extends to a binding-post 8. The vessel has an iron'cover 9, supported by but insulated from the vessel by an insulating-packing 10, preferably of magnesia. The cover has a side opening 11, with closure 12, to permit the introduction of lead, and a large central opening 13, within which is arranged the anode-chamber 14. This anode-chamber consists of a tubular casing 15, of iron, having an inwardly-extending flange 16 at its lower open end, a cover 17, with central opening for the anode-terminal, and a non-conducting lining 18, preferably of magnesia, which at the upper end of the chamber extends out between a flange at the upper end of the casing and a corresponding flange on the cover'to provide an insulating-packing. The anode-chamber has a lateral neck 19, with tight-fitting cover 20, for the introduction of sodium chlorid or other material to be eleotrolyzed. The flange 16 at the lower end of the anode-chamber supports a disk 21 of foraminous material, preferably iron-wire gauze, which disk is overlaid by a diaphragm 22. This diaphragm preferably consists of loose granular material of greater specific gravity than the molten electrolyte and less specific gravity than the molten cathode arranged upon support 21 in a layer of considerable depth. The material which I have found especially suitable for such diaphragm when molten sodium chlorid is to be electrolyzed is magnetite broken into angular fragments of such size as to pass through a'sieve having a mesh of fifty to the inch. The molten lead 23, acting as a cathode, preferably rises to such height in vessel 1 that the entire mass of loose material 22 constituting the diaphragm floats upon the surface of the lead, the diaphragm thereby remaining in close contact with the cathode notwithstanding considerable change in the surface-level of the molten lead. The wire-gauze 21 is merelya safety device to prevent the material of the diaphragm from dropping out of the anode-chamber in case the molten lead falls to any abnormal low level and is not necessary to the proper working of the apparatus. The anode 24:, which may be a rod or rods of graphitized carbon, is carried by an adjustable rod 25, which may be of metal protected with porcelain and extends through a stufling-box 26 in cover 17. From one side of the anode-chamber extends an outlet-pipe 27 to draw ofl chlorin or other gaseous products, the removal of this chlorin being perfectly assisted by the action of an airinjeotor 28 in pipe 27, which serves to maintain a slight vacuum in the anode-chamber. The lead-sodium alloy produced by electrolysis of the molten sodium chlorid being lighter than lead is continuously displaced as formed from the surface of the cathode beneath the diaphragm and rises to the surface of the oathode around the anode-chamber, this being at a higher level than below the diaphragm. The alloy may be thence drawn off. It is preferable, however, to continuously remove the sodium from the alloy and convert it into its hydrate or oxid, the remaining lead being returned by gravity to the bottom of vessel 1 beneath the diaphragm to receive further additions of sodium. This result may be accomplished invarious ways, but preferably by the following means: WVithin and some distance below the surface of the molten lead cathode is an annular pipe 29, arranged around and concentric with the anode-chamber. This pipe has two rows of downwardly and outwardly opening perforations 30. Connecting with pipe 29 is a pipe 31, having valve 32, which serves for the introduction of molten sodium hydrate. This sodium hydrate, injected in a plurality of flue streams into the molten lead-sodium alloy, is reduced by the sodium to sodium oxid with evolution of hydrogen, which rises and passes off from the electrolytic cell through pipe 33. Sodium oxid rises and floats on the surface of the cathode and, remaining in a molten condition, is continuously drawn off as it rises above a certain level by an inverted siphon 34, extending from the side of vessel 1 and delivering into a vessel 35, situated in an adjoining chamber in the brickwork of the furnace. To facilitate the oxidation of the sodium, a layer of loose granular conducting material is arranged at or near the surface of the cathode around the anode-chamber. This material may consist of small angular fragments of iron, magnetite, of ferrosilicon. The material should be at least in part beneath the surface of the cathode, and this arrangement may be effected either by employing a floating layer of such depth that its weight causes the lower particles to be submerged or by flxing a horizontal ring of wire-gauze between the anode-chamber 13 and the outer wall of the vessel at or below the surface of the cathode. This loose granular. material serves to distribute the streams of sodium hydrate rising from pipe 29 and bring them into thor-- ough and intimate contact with the sodium in the alloy. The oxidizing reaction is facilitated by the innumerable local couples due to the contact of the sodium and the relatively negative particles of iron, 82:0. The sharp corners of the particles also increase the speed of the reaction. The oxidation of the sodium may also be effected by successively introducing oxygen and hydrogen or air and natural gas through pipe 29, the oxygen serving to convert the lead-sodium alloy into sodium plumbate, which is then reduced to metallic lead by the hydrogen with production of sodium hydrate.

The sodium oxid received in vessel 35 is maintained in a molten condition by any suit able means, as by the waste products escaping from the main furnace-chamber through a side passage 36, sweeping around the vessel and passing out through openings 37 in the supporting-flange of the vessel. Vessel 35 has a cover 36, through which passes the stem of a float level-indicator 40. The sodium oxid may be withdrawn, if desired, through valved outlet 38. It is preferred, however, to continuously convert this oxid into hydrate. For this purpose a pipe 41 leads up ward from beneath the level of the molten oxid in vessel 35 past a steam-injector 42, which serves both to introduce the water necessary for hydration and to carry the old material upward to a vessel 43. The upper end of pipe 41 is bent and extends downward into vessel 43 to open beneath the surface of the molten sodium hydrate therein. A springclosed air-inlet valve is arranged in the bend to prevent any siphoning of hydrate back through pipe 41. Vessel 43 is heated by a burner 45 and has a valved outlet 46 for the finished product. The cover of vessel 43 also carries a level-indicator 47. Such amount of sodium hyhrate as is required to oxidize the sodium taken up by the lead cathode continuously passes off from vessel 43 through a trapped outlet 48,communicating with pipe 31.

The modification shown in Fig. 2 is similar in most respects to the apparatus already described, with the exception that a mercury cathode is employed, while the electrolyte is an aqueous solution, no external heat being therefore required. The anode-chamber 14 is preferably constructed of glass or porcelain without lining. Theoxidation of the sodium taken up by the cathode 23 may be effected in the usual manner by placing a layer of water 49 on the surface of the cathode around the anode-chamber, into which depend carbon electrodes 50, short-circuited to the oathode by connections 51 to the metallic cover of the metal containing vessel. 1 preferably employ, however, for this purpose a perforated annulus of pipe 29 like that heretofore described, by which water or a dilute solution of sodium hydrate is injected into the body of the mercury sodium amalgam, the resulting strong sodium hydrate solution being withdrawn through side outlet 34. The resulting solution may be further strengthened by recirculating it through the amalgam, with or without previous additions of water. The floating diaphragm 22 employed in this modification may be of broken magnetite, as heretofore, or of broken glass or silica sand. A layer 60 of conducting particles on and beneath the surface of the cathode around the anode-chamber may be employed to facilitate oxidation of the sodium, as heretofore described.

l/Vhen sodium or other easily-oxidizable metal is deposited into the mercury, the re sulting amalgam, being lighter than the mercury, rises around the anode-chamber to a level Where the sodium is oxidized and removed, the depleted mercury again returning to its position beneath the diaphragm.

The term alloy as used in the claims is intended to also cover an amalgam or alloy containing mercury.

Various modifications may be made in the apparatus shown and described within the scope of the generic claims. The partition which divides the containing vessel into an electrolyzing and an oxidizing compartment may be of other form and arrangement than the tubular anode-chamber shown. The diaphragm and superposed electrolyte may be placed outside of the tubular partition and the oxidizing agent introduced within it, or a straight depending partition may be employed to partially separate the two chambers.

By the term depending partition as used in the claims is meant any partition which has a passage or passages at its lower portion. If the diaphragm is a rigid sheet, both it and the partition may be arranged in an inclined position. In some cases the diaphragm may be entirely omitted if care is taken to maintain the bodies of electrolyte, liquid metal, and products of oxidation at uniform levels.

The height of the column of electrolyte required to counterbalance the liquid-metal cathode outside the anode-chamber may be decreased by slightly increasing the normal atmospheric pressure on the surface of the electrolyte. This may be easily effected by restricting the outflow of chlorin by regulatlug-valve or choking device 27 in the outletpipe 27 and dispensing with the injector 28. The weight of this column resting on the oathode is advantageous, in that it serves to bring the electrolyte and liquid metal into close contact.

The arrangement shown in Fig. 3 is similar to those already described, with the exception that the electrolyzing-current is passed in a reverse directionthat is, from the liquid metal through the electrolyte. In this figure, 52 represents a vessel having a partition 53, both of non-conductive material, and a horizontal diaphragm 54:. The body 55, of molten lead, extends beneath the diaphragm and to a higher level at one side of the partition. Electrolyte 56, fused sodium chlorid, floats upon the lead and contains the cathode 59. Upon the other surface of the molten lead is a body of molten lead chlorid 57, communicating with which is the anode 58. The electrolytic current decomposes the sodium chlorid, liberating the sodium, which may be skimmed off or, if the temperature is sufliciently high, removed as a vapor. The chlorin combines with the lead, and the lead chlorid flows up into the body of lead chlorid, which is simultaneously electrolyzed, liberating chlorin and returning the lead to receive further addition of chlorin. By depressing the anode 58 into the lead lead may be continuously produced and drawn off, further additions of metallic lead being then required.

Having now described my invention, what I claim as new, and desire to secure by Letters Patent, is

1. An apparatus for electrolyzing lightmetal compounds, comprising an electrolytic vessel having a means for producing a heavy and light metal alloy by the electrolysis of the light-metal compounds, in combination with means for displacing the heavy and light metal alloy by gravity, means for associating the heavy and light metal alloy with a metal hydroxid, means for removing the light-metal oxid thus produced, means for converting the light-metal oxid into light-metal hydroxid, and means for returning a portion of the lightmetal hyd roxid to the chamber containing the heavy and light metal alloy.

2. An apparatus for electrolyzing lightmetal compounds, comprising an electrolytic vessel ha ing a means for producing a lead and light-metal alloy by the electrolysis of the light-metal compounds, in' combination with .means for displacing the lead and light-metal alloy by gravity, means for associating the lead and light-metal alloy with a metal hydroxid, means for removing the light-metal oxid thus produced, means for converting the light-metal oxid into light-metal hydroxid,

ing light-metal oxid to the action of steam, .and means for returning a portion of the light-metal hydroxid thus produced to the chamber containing the lead and light-metal alloy.

4:. An apparatus for electrolyzing alkalimetal compounds, comprising an electrolytic 'vessel having means for producing a heavymetal and alkali-metal alloy by the electrolysis of the alkali-metal compound, in combination with means for displacing the heavymetal and alkali-metal alloy by gravity, means for associating the heavy-metal and alkalimetal alloy with a metal hydroxid, means for removing the alkali-metal oxid thus produced, means for converting the alkali-metal oxid into alkali-metal hydroxid, and means for returninga portion of the alkalirmetal hydroxid to the chamber containing the heavy-metal and alkali-metal alloy.

5. An apparatus for electrolyzing alkalimetal compounds, comprising an electrolytic vessel having means for producing lead and alkali-metal alloy by the electrolysis of the alkali-metal compound, in combination with means for displacing the lead and alkali-metal alloy by gravity, means for associating the lead and alkali-metal alloy with a metal hydroxid, means for removing the alkal-metal oxid thus produced, means for converting the alkali-metal oxid into alkali-metal hydroxid, and means for returning a portion of the alkali-metal hydroxid to the chamber containing the lead and alkali-metal alloy.

6. An apparatusior electrolyzing alkali- &

metal compounds, comprising an electrolytic metal hydroxid thus produced to the cham-.

ber containing the lead and alkali-metal alloy.

7. An apparatus for electrolyzing sodium compounds, comprising an electrolytic vessel having means for producing a heavy-metal and sodium alloy by the electrolysis of the sodium compound, in combination with means for displacing the heavy-metal and sodium alloy by gravity, means for associating the heavy-metal and sodium alloy with a metal hydroxid, means for removing the sodium oxid thus produced, means for converting the sodium oxid into sodiumhydroxid, and means for returning a portion of the sodium hydroxid to the chamber containing the heavy-metal and sodium alloy.

8. An apparatus for electrolyzing sodium compounds, comprising an electrolytic vessel having means for producing lead and sodium alloy by electrolysis of the sodium compound, in combination with means for displacing the lead and sodium alloy by gravity, means for associating the lead and sodium alloy with a metal hydroxid, means for removing the sodium oxid thus produced, means for converting the sodium oXid into sodium hydroxid, and means for returning a portion of the sodium hydroxid to the chamber containing the lead and sodium alloy.

9. An apparatus for electrolyzing sodium compounds, comprising an electrolytic vessel having means for producing lead and sodium alloy by the electrolysis of the sodium compound, in combination with means for displacing the lead and sodium alloy by gravity, means for associating the lead and sodium alloy with a metal hydroxid, means for removing the sodium oxid thus produced, means for exposing the sodium oxid to the action of steam, and means for returning a portion of v the sodium hydroxid thus produced to the chamber containing the lead and sodium alloy.

10. An apparatus for electrolyzing sodium chlorid, comprising an electrolytic vessel having means for producing a heavy-metal and sodium alloy by the electrolysis of sodium chlorid, in combination with means for displacing the heavy-metal and sodium alloy by gravity, means for associating the heavy-metal and sodium alloy with a metal hydroxid, means for removing the sodium oxid thus produced, means for converting the sodium oxid into sodium hydroxid, and means for returning a portion of the sodium hydroxid to the chamblclr containing the heavy-metal and sodium a 0y.

11. An apparatus for electrolyzing sodium chlorid, comprising an electrolytic vessel having means for producing lead-sodium alloy by the electrolysis of sodium chlorid, in combination with means for displacing the lead-sodium alloy by gravity, means for associating the lead-sodium alloy with a metal hydroxid, means for removing the sodium oxid thus produced, means for converting the sodium oxid into sodium hydroxid, and means for returning a portion of the sodium hydroxid to the chamber containing the lead and sodium alloy.

12. An apparatus for electrolyzing sodium chlorid, comprising an electrolytic vessel having means for producing lead-sodium alloy by the electrolysis of sodium chlorid, in combination with means for displacing the lead-sodium alloy by gravity, means for associating the lead-sodium alloy with a metal hydroxid, means for removing the sodium oxid thus produced, means for exposing the sodium oxid to the action of steam, and means for returning a portion of the sodium hydroxid thus produced to the chamber containing the lead and sodium alloy.

In testimony whereof I have signed my name to this specification in the presence of two subscribing witnesses.

HENRY SPENCER BLACKMORE.

Witnesses:

(J. O. WRIGHT, H. N. JENKINS.