US859431A - Apparatus for the electrolytic production of chemical compounds. - Google Patents

Apparatus for the electrolytic production of chemical compounds. Download PDF

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US859431A
US859431A US32098706A US1906320987A US859431A US 859431 A US859431 A US 859431A US 32098706 A US32098706 A US 32098706A US 1906320987 A US1906320987 A US 1906320987A US 859431 A US859431 A US 859431A
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compartment
sodium
lead
pan
cathode
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US32098706A
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Courtland F Carrier Jr
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ELMIRA ELECTROCHEMICAL Co
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ELMIRA ELECTROCHEMICAL Co
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/033Liquid electrodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/30Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof
    • C25B9/303Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof comprising horizontal-type liquid electrode

Definitions

  • the apparatus, and its mode of operation may be best understood by describing it in connection with the production of the oxids of sodium, although its use is not to be understood as being confined to the production of these specific compounds.
  • the oxids of sodium are produced by the oxidation oi previously prepared metallic sodium.
  • Figure 1 represents a longitudinal vertical section through the apparatus;'and Fig. 2, a transverse vertical section of the same on the line a a in Fig. 1.
  • a large pan 1 set in masonry ;2 constitutes the body of the apparatus.
  • This pan isbest made of cast 7 iron and is preferably of rectangular:f6rm'.
  • the opening 4, in Fig. 1, isgshown p9sitioned directly beneath theelectrode-lZ, and Where mor e'than one of these electrodes are employed, the
  • basic material 8 such as magnesia, or other material which will not be attacked by the electrolyte 9 contained therein, or 'by the gases evolved during the process.
  • the .compartment is closed at the top by Specification of Letters Patent. Application filed June 9,1906. Serial no. 320,937.
  • the cathode eompartment consists of a rectangular box 15, preferably of cast iron, which is closed upon all sides except the bottom, being in the form of a rectangular bell.
  • the cathode is a fiat plate of iron or nickel 16, which is supported in the electrolyte17 by x.
  • This cathode compartment is also provided with a charging opening 20 and with a, tap hole 21.
  • This tap hole may be closed by a plug and'the material drawn therefrom intermittently by i the removal of the plug from time to time; or the melted product may be allowed to flow continuously from the hole by way of the channeled lip 22.
  • acirculating device At'the end of the apparatus beyond the cathode .compartment is located acirculating device. This consists of a screw propeller 23, which is rotated in the 1 circular opening 5leading to the compartment 3 by 8!
  • the propeller shaft 25 may be conveniently supported by means of brackets" and 27 secured to, or formed 4 upon, the end of the pan, the propeller being suspended at the proper point in opening 5 by means of a collar 28.
  • “Gasburners 29 are arranged in chambers in the masonry beneath the pan to act as an auxiliary source of heat, and to assist in starting the apparatus, orto tide over an interruption in the electric current. :15
  • the oxids of sodium may be prepared therein as follows: By' means of theburners 29, the furnace is "heated to over 350 C and lead is melted in the pan, or
  • the cathode compartment is filled to the desired depthwith melted sodium hydroxid; A small carbon rod is inserted in one of the graphite anodes in the anode compartment and the anodes are lowered till the rod dips into the lead. When the current is started this rod is heated to bright redness tends to float on the surface, where there is danger of its being consumed by the electrolyte and any gases in solution.
  • the sodium-lead alloy is carried beneath the cathode as it circulates in the manner described.
  • the lead acts as anode.
  • the passage of the current tends to liberate metallic sodium at the cathode and to dissolve sodium from the sodium-lead alloy at the anode. Under proper conditions metallic sodium may be prepared'in this way. If, now, an oxidizing agent is added to the sodium hyd'r'oxid bath, no sodium will be liberated, but sodium oxids will be produced as follows: i i
  • reactions I and II will take place simultaneously, their relative preponderance depending upon the conditions of the operation.
  • the product, as withdrawn from the cathode compartment, will contain both Na O and Na O
  • the Na O may be converted into Na O by heatingin an oxidizing atmosphere, air free from moisture and carbondioxid being most suitable.
  • nitrate is added from time to time in a proportion derived from the above reaction and the number of amperes used.
  • the alloy from which a portion of the sodium has been removed is then returned to the anode compartment in the manner described.
  • An electrolytic apparatus comprising anode and cathode compartments, a bath of molten metal common to both compartments, circulating passages whereby the metal of the bath will be conducted from the anode compartment to the cathode compartment and return, the return paspnrtment remote from the anode compartment to a point in the anode compartment directly beneath an electrode therein and means for producing a circulation of the metal of the bath through said channel whereby an .upheaval of the bath will be caused directly beneath said electrode.
  • An electrolytic apparatus comprising a pan adapted to contain a molten metal bath, anodeand cathode compartments having their bottom ends open and supported above the bottom of the pain 'in position to be sealed by the metal of the bath, a channel formed on the under side of the pan leading from a'point beyond the cathode compartment to a point below an electrode in the anode compartment, openings 'in the bottom of the pan leading to said channel at said points, a screw propeller mounted to.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Description

No. 859,431. PATENTED JULY 9, 1907. 0. F. CARRIER, JR- APPAR TUS FOR THE ELECTROLYTIC PRODUCTION OF CHEMICAL COMPOUNDS.
APPLICATION FILED JUNE 9, 1906.
EH52. g $31? GR L UMQM BY W W 1 7 ATTORN EY prrn s'rn rnsln'rniwr osmcn.
COURTLAND F. CARRIER JR, OF ELMIRA, NEW YORK, ASSIGN'OR TO ELMIR-A ELECTRO- CHEMICAL, COMPANY, OF ELMIRA', NEW YORK.
.ARPARATUS FOR THE ELECTROLYTIC, rnonoo'rron on CHEMICAL COMPOUNDS.
To all whom 'it may concern:
Be it known that I, OoUR'rLANn F, CARRIER, Jr., a
citizen of the United States, residing at Elmira, in the .county of Ohemung and State of New York, have in-- 1 of this character, whereby such compounds may becontinuously produced, and in a manner much'more economical than has hitherto been attained.
The apparatus, and its mode of operation, may be best understood by describing it in connection with the production of the oxids of sodium, although its use is not to be understood as being confined to the production of these specific compounds. As now prepared, the oxids of sodium are produced by the oxidation oi previously prepared metallic sodium. By the use of 2 5 my improved apparatus, however, it is possible to prepare the oxids in a single operation, without using the v expensively prepared metallic sodium in its free form.
I attain my object by constructing the apparatus substantially in the manner illustrated in the accompanying drawings, in which:+ i
Figure 1 represents a longitudinal vertical section through the apparatus;'and Fig. 2, a transverse vertical section of the same on the line a a in Fig. 1. I Like numerals designate like parts in the two views. A large pan 1 set in masonry ;2, constitutes the body of the apparatus. This pan isbest made of cast 7 iron and is preferably of rectangular:f6rm'. On theunder side of the pan, and 09st in one piece with it, is a longitudinal compartment 3,-the purpose of which will /be hereinafter described This compartment communicates with the pan through circular openings formed at 4 and 5.. The opening 4, in Fig. 1, isgshown p9sitioned directly beneath theelectrode-lZ, and Where mor e'than one of these electrodes are employed, the
t chamber 3, at this end, will be so arranged that there will be one ofthese openings beneath each electrode. The remaining portions of the apparatus, are supported within the pan by means of shoulders or lugs formed thereon as indicated at 6. i
A frame 7, preferably of cast iron, open at top and bot- I tom, incloses the anode compartment, this frame being lined with basic material 8, such as magnesia, or other material which will not be attacked by the electrolyte 9 contained therein, or 'by the gases evolved during the process. The .compartment is closed at the top by Specification of Letters Patent. Application filed June 9,1906. Serial no. 320,937.
' Patented July 9, 19(17- cover .10 composed of material simi ar to that of the lin This cover is supplied with feed holes 11 for replenishing the supply of the electrolyte from time to time. Openingsare also provided for the anodes 12 the back of the anode compartment is a port 14, thr0ugh 6 which the gases ,formed during the processare conducted away. i i l The cathode eompartment consists of a rectangular box 15, preferably of cast iron, which is closed upon all sides except the bottom, being in the form of a rectangular bell. The cathode is a fiat plate of iron or nickel 16, which is supported in the electrolyte17 by x. one or more heavy lugs 18 projecting through the bell and insulated therefrom ,by sleeves 19 of any suitable insulating material. This cathode compartment is also provided witha charging opening 20 and with a, tap hole 21. This tap hole may be closed by a plug and'the material drawn therefrom intermittently by i the removal of the plug from time to time; or the melted product may be allowed to flow continuously from the hole by way of the channeled lip 22.
At'the end of the apparatus beyond the cathode .compartment is located acirculating device. This consists of a screw propeller 23, which is rotated in the 1 circular opening 5leading to the compartment 3 by 8! The propeller shaft 25 may be conveniently supported by means of brackets" and 27 secured to, or formed 4 upon, the end of the pan, the propeller being suspended at the proper point in opening 5 by means of a collar 28.
"Gasburners 29 are arranged in chambers in the masonry beneath the pan to act as an auxiliary source of heat, and to assist in starting the apparatus, orto tide over an interruption in the electric current. :15
As an example of the mode of operating this apparams, the oxids of sodium may be prepared therein as follows: By' means of theburners 29, the furnace is "heated to over 350 C and lead is melted in the pan, or
poured in, already melted. Sufficient lead is addedto fill the lower compartment 3 and the pan to a depth sufiicient to form a liquid seal at the bottom of the electrolytic compartments. Tin, cadmium, zinc, orcertainalloys might be used in place or lead, but lead is the cheapest. The cathode compartment is filled to the desired depthwith melted sodium hydroxid; A small carbon rod is inserted in one of the graphite anodes in the anode compartment and the anodes are lowered till the rod dips into the lead. When the current is started this rod is heated to bright redness tends to float on the surface, where there is danger of its being consumed by the electrolyte and any gases in solution. This is prevented by means of a rapid circulation of the lead. The propeller 23 forces the lead down through the opening 5, into and through chamber 3, and thence up through the opening, or openings, 4. The alloy formed in the anode compartment is thus carried on to the cathode compartment as fast as formed, and thus the sodium is prevented fromreuniting with the electrolyte' 9. There is also a special advantage in causingthe-circulation as described. Any impurities in the salt will tend to settle to the bottom and coat over the surface of the lead. This increases the resistance and wastes electrical energy, and also decreases theampere efficiency of the sodium formation. When the lead is forced upward through an opening as shown with sufficient force to form a slight mound, as at 30, this scum will be forced aside by the currents flowing radially from the mound in all directions, thus leaving a clear lead surface directly below the anode for the reception of the liberated sodium. The same result can be accomplished by carrying the opening 4 above the .general level of the lead by means of a pipe, but the force required is greater and the action no more efiicient. The inventor is aware that metallic cathodes have been used, where the return current enters from below, but no application has hitherto been made, to his knowledge, of a circulation so strong that'the results as above described are accomplished for the purpose set forth.
The sodium-lead alloy is carried beneath the cathode as it circulates in the manner described. In this compartment the lead acts as anode. The passage of the current tends to liberate metallic sodium at the cathode and to dissolve sodium from the sodium-lead alloy at the anode. Under proper conditions metallic sodium may be prepared'in this way. If, now, an oxidizing agent is added to the sodium hyd'r'oxid bath, no sodium will be liberated, but sodium oxids will be produced as follows: i i
. Reactions I and II will take place simultaneously, their relative preponderance depending upon the conditions of the operation. The product, as withdrawn from the cathode compartment, will contain both Na O and Na O The Na O may be converted into Na O by heatingin an oxidizing atmosphere, air free from moisture and carbondioxid being most suitable.
The
nitrate is added from time to time in a proportion derived from the above reaction and the number of amperes used. The alloy from which a portion of the sodium has been removed is then returned to the anode compartment in the manner described.
It is to be specially noted that, by the use of this apparatus, it is possible to produce compounds whose production previously involved the use of a free metallic element, without the previous separation of that metal. Also that in this manner it is possible to continuously produce a larger quantity of end product than could be produced if the same number of amperes were to be employed in the previous production of the metal. For example, 'to produce six molecules of Na O by the old method requires l2 atoms of metallic Na. This new apparatus makes it possible to produce the same quantity of No. 0 with a consumption of current equivalent to that required to produce eight atoms of Na.
Having thus described my apparatus and its mode of operation, but without confining it to the production of anyone of the particular class of compounds hereinabove described, nor to the production of such compounds alone, since, by properly arranging the cathode compartment,.a metal in its free state may also be produced and drawn therefrom; what I claim as new and desire to secure by Letters-Patent is:
1. An electrolytic apparatus comprising anode and cathode compartments, a bath of molten metal common to both compartments, circulating passages whereby the metal of the bath will be conducted from the anode compartment to the cathode compartment and return, the return paspnrtment remote from the anode compartment to a point in the anode compartment directly beneath an electrode therein and means for producing a circulation of the metal of the bath through said channel whereby an .upheaval of the bath will be caused directly beneath said electrode.
3. An electrolytic apparatus comprising a pan adapted to contain a molten metal bath, anodeand cathode compartments having their bottom ends open and supported above the bottom of the pain 'in position to be sealed by the metal of the bath, a channel formed on the under side of the pan leading from a'point beyond the cathode compartment to a point below an electrode in the anode compartment, openings 'in the bottom of the pan leading to said channel at said points, a screw propeller mounted to.
COURTLAND F. CARRIER, JR.
' Witnesses:
J. H. O'BRIEN, Lno V. STOELTZLEN,
US32098706A 1906-06-09 1906-06-09 Apparatus for the electrolytic production of chemical compounds. Expired - Lifetime US859431A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3386908A (en) * 1963-12-04 1968-06-04 Pechiney Prod Chimiques Sa Cell for refining aluminum by fusion electrolysis

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3386908A (en) * 1963-12-04 1968-06-04 Pechiney Prod Chimiques Sa Cell for refining aluminum by fusion electrolysis

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