US2688594A - Mercury cell - Google Patents

Mercury cell Download PDF

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Publication number
US2688594A
US2688594A US129073A US12907349A US2688594A US 2688594 A US2688594 A US 2688594A US 129073 A US129073 A US 129073A US 12907349 A US12907349 A US 12907349A US 2688594 A US2688594 A US 2688594A
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United States
Prior art keywords
cell
mercury
cathode
anode
diaphragm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US129073A
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English (en)
Inventor
Oosterman Jan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzona Inc
Original Assignee
American Enka Corp
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Filing date
Publication date
Application filed by American Enka Corp filed Critical American Enka Corp
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Publication of US2688594A publication Critical patent/US2688594A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/36—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in mercury cathode cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/033—Liquid electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/30—Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof
    • C25B9/303—Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof comprising horizontal-type liquid electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells

Definitions

  • This invention relates to an electrolytic cell that is particularly useful in recovering metals and acids from aqueous solution of their salts. More particularly, the invention is directed to an electrolytic cell for electrolyzing aqueous solutions of alkali metal salts according to the amalgam method in order to recover the alkali metal hydroxide and acid from such aqueous solutions.
  • the disadvantage of such an arrangement is that the distance between the anode and the cathode is not uniform 'throughout the cell due to the angular displacement between the anode and cathode, and consequently the current resistance of the electrolyte is higher at the end of the cell where the anode and cathode are the greatest distance from each other, so that in that portion of the cell the current is considerably smaller than at the other end of the cell where the anode and cathode are separated by the least distance. For that reason it is impossible to operate such an electrolytic cell at the maximum current density which it would be possible to employ at the end of the cell where the anode and cathode are separated by the minimum distance, and consequently it is impossible to operate the cell under conditions of maximum einciency.
  • Aten U. S. Patent No. 2,230,023
  • a step-like cathode giving antibiotic to a cascade arrangement in order to avoid too large local differences in current densities.
  • Each step consists of a trough and the supply and discharge-slots of the troughs are arranged in such a way that the cascading iiow or" the mercury takes place in zig-zag fashion.
  • this structure is rather complicated and also at times gives rise to difficulties by permitting dead pockets or elds in the flow of mercury, and where the mercury does not ilow suiciently rapidly it taires too much sodium.
  • the ma- (Cl. 20d-219) M terial over which the mercury flows is made of a non-conductive material, or is covered with such material, which thus renders it somewhat more troublesome in obtaining a good current supply to the mercury cathode.
  • the present invention it has Abeen found surprisingly enough that, contrary to previous expectations, it is possible to carry out in a very eincient manner the electrolysis of aqueous solutions of alkali metal salts in an electrolytic cell having an inclined anode and an inclined diaphragm, by causing mercury to flow over a flat or almost flat metal surface or bottom extending parallel to the anode and diaphragm, the slope of the anode and of the bottom of Sthe cell with respect to the horizontal being between 1:50 and 1:5, and preferably about 1:10.
  • the arrangement of the electrolytic cell according Ito the present invention is such that the metal bottom of the cell is flat or almost flat, and serves as an electrically conductive surface over which the mercury ows, this metal bottom being parallel to the anode, and inclined in the manner indicated in the preceding paragraph.
  • electrolytic cell may include narrow strips of non-conductive, acid-resisting material ldisposed on the bottom of the cell, and extending in longitudinal direction thereover, i. e., in the direction of the now of mercury between the point of supply and the point oi discharge of the mercury, these strips serving to support the diaphragm (and anode) and hence to maintain the desired parallelism between the diaphragm (and anode) and the flowing mercury cathode.
  • Figure 1 illustrates schematically a longitudinal section through the electrolytic cell
  • Figure 2 represents a crosssectional View taken along the line 2--2 of Fiure 1.
  • Figure 3 is an enlarged section of the metal bottom showing the cross grooves.
  • I indicates the slightly inclined rectangular bottom of the cell which is made of iron or other electrically conductive material capable of directly supporting in current-conducting relation the flowing mercury cathode.
  • the slope of the bottom may vary from 1:50 to 1:5, but in the preferred arrangement it is about 1:10.
  • the mercury enters the cathode department of the cell via inlet 2 and, after flowing along the inclined bottom I thereby forming a thin uninterrupted layer 4 serving as the flowing mercury cathode, leaves the cathode compartment via outlet 3.
  • Parallel to the bottom I are disposed a diaphragm 5 and a perforated lead anode 6.
  • Current is supplied to the anode and to the flowing mercury cathode through the iron bottom I in convetnional manner by means not shown.
  • a plurality of strips 'I'I' of a non-conductive, acid-resistant material Disposed longitudinally on the bottom I of the electrolytic cell in the direction of iiow of the mercury cathode are a plurality of strips 'I'I' of a non-conductive, acid-resistant material, these strips by virtue of their longitudinal disposition in the cell forming no hindrance to the even flow of the mercury through the cathode compartment.
  • These strips 1, 'I' serve to support the diaphragm 5 (and anode B) in substantially parallel relation with respect to the iron bottom of the cell and hence with respect to the flowing mercury cathode 4.
  • the upper portion of the electrolytic cell comprises a collecting tank 8 for anolyte, this collecting tank being attached to the bottom I by suitable means such as screws 9, 9. In this way it is possible to replace the diaphragm 5 and the anode 6 when necessary in simple and convenient fashion.
  • the walls of the upper portion of the electrolytic cell may be manufactured from a non-conductive, acid-resisting material I I, or they can be made of a suitable metal such as iron which is covered with such a material. Such portions of the bottom of the cell as are not covered by mercury may also be provided with a non-conductive, acid-resisting covering material I I.
  • the material II, as well as the strips 1, 'I' may be made of ebonite, glass or other acid-resisting, non-conductive material as desired.
  • the diaphragm 5 may be made of porous ebonite, or of acid-resistant asbestos fiber, or a mat of glass fiber held together by an acid-resistant binder, or a ceramic material such as corundum or porous tile, or otherwise as desired.
  • excellent results have been achieved with this electrolytic cell when the diaphragm consists of a fabric impregnated with rubber latex, as disclosed in application Ser. No. 128,911, filed November 22, 1949, by Jan Oosterman, now abandoned.
  • the liquid to be subjetced to electrolysis e. g., an aqueous solution of an alkali metal salt such as sodium sulfate, may be introduced in known manner under the diaphragm 5 at the lower part l2 of the cathode compartment of the cell, and
  • the electrolyte that passes through the diaphragm to the anode collects in the upper portion 8 of the electrolytic cell as acid-enriched anolyte, and overflows from outlet I0.
  • the applied voltages and current densities per se form no part of the present invention. They may be varied over relatively wide ranges, for example as described in the aforesaid Aten patent, or otherwise.
  • cross grooves Ia are provided either over the etnire bottom of the cell or throughout selected portions thereof. rIhese grooves Ia are at right angles to the flow of mercury and, as indicated above, are provided by rough planing or machining the upper surface of the iron bottom of the cell.
  • an aqueous solution of an alkali metal salt e. g., sodium sulfate or a similar salt of a reactive metal
  • enters the cell through the opening I2 passes upwardly along the diaphragm 5 and through the diaphragm into the upper portion of the cell where it contacts the anode 6.
  • sulfuric acid is formed with the evolution of oxygen which escapes through the open top of the electrolytic cell.
  • the acid liquor is discharged through the outlet I9 and the sodium amalgam is drawn off through outlet 3 from whence it is subjected to a process for recovering the alkali metal from the amalgam in known manner.
  • the mercury thus recovered after separation of the sodium or other alkali metal is recirculated through the cathode compartment.
  • the electrolytic cell according to the present invention has the following important advantages, in addition to the substantially uniform anode-cathode spacing throughout the cell as well as the relatively simple structure apparent from the drawings. Because of the provision of the slightly sloping bottom of the cell the fiowing mercury cathode is in the form of a very thin layer, so that the mercury content of the cell is particularly low in comparison with other known types of flowing mercury cathode cells. This represents a substantial saving in investment represented by the relatively expensive mercury, while nevertheless insuring a continuous and uninterrupted flow of mercury. Furthermore, the metal bottom of the cell need not be covered and can be manufactured from any suitable, amalgamable metal.
  • the current supply to the mercury cathode which over its whole area is in electrically conductive relation to the metal bottom, can be arranged for in a very convenient manner simply by connecting the bus-bars for the cathode to the bottom of the cell.
  • an electrolytic cell for removing sodium and sulfuric acid from an aqueous solution of soda sulfate

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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)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
US129073A 1948-12-27 1949-11-23 Mercury cell Expired - Lifetime US2688594A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL144055A NL71709C (nl) 1948-12-27 1948-12-27 Werkwijze voor de electrolyse van alkalizouten volgens de amalgaammethode en cel voor deze electrolyse

Publications (1)

Publication Number Publication Date
US2688594A true US2688594A (en) 1954-09-07

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ID=42272561

Family Applications (1)

Application Number Title Priority Date Filing Date
US129073A Expired - Lifetime US2688594A (en) 1948-12-27 1949-11-23 Mercury cell

Country Status (6)

Country Link
US (1) US2688594A (nl)
BE (1) BE491944A (nl)
DE (1) DE933027C (nl)
FR (1) FR1000268A (nl)
GB (1) GB659565A (nl)
NL (1) NL71709C (nl)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732340A (en) * 1956-01-24 Ozone oxidation reactor
US3002914A (en) * 1956-05-23 1961-10-03 Solvay Preparation of electrodes for electrolysis of aqueous solutions by the mercury process
US3042602A (en) * 1960-10-25 1962-07-03 Oronzio De Nora Impianti Horizontal electrolytic cell
US3109789A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Preparation of phosphine
US3308047A (en) * 1962-10-31 1967-03-07 Oronzio De Nora Impianti Multiple tier inclined mercury cell
US3308043A (en) * 1962-10-31 1967-03-07 Oronzio De Nora Impianti Method of discharging amalgam for inclined plane mercury cells
US3308044A (en) * 1962-10-31 1967-03-07 Oronzio De Nora Impianti Inclined mercury cell and method of operation
US3329595A (en) * 1963-02-27 1967-07-04 Diamond Alkali Co Electrolysis of concentrated sea water
US3337433A (en) * 1959-07-31 1967-08-22 Hooker Chemical Corp Electrolytic process
US3400055A (en) * 1966-05-20 1968-09-03 Oronzio De Nora Impianti Method and apparatus for breaking electric current in flunet conductors
US3972793A (en) * 1975-09-26 1976-08-03 Eli Lilly And Company Continuous flow-through mercury cathode electrolysis cell
WO1993005202A1 (en) * 1991-09-05 1993-03-18 Olin Corporation Cell for direct electrochemical reduction of catholyte
US5209836A (en) * 1991-12-19 1993-05-11 Olin Corporation Baseplate for electrolytic cell with a liquid metal cathode

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR334332A (fr) * 1903-06-25 1903-12-18 Rafael Escriva De Romani Nouveau système pour l'obtention de lessives caustiques concentrées, soude caustique, chlore et ses dérivés, par l'électrolyse du chlorure de sodium
US1109311A (en) * 1912-01-06 1914-09-01 Edward A Allen Method and means for electrolyzing saline solutions.
US1176551A (en) * 1914-03-27 1916-03-21 Karl Heinemann Apparatus for decomposing alkali-chlorid solutions.
GB471912A (en) * 1935-06-27 1937-09-13 Ig Farbenindustrie Ag Improvements in or relating to a process for the electrolysis of sodium sulphate
US2230023A (en) * 1938-03-09 1941-01-28 American Enka Corp Electrolytic cell

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE286011C (nl) *
DE145749C (nl) *
DE869340C (de) * 1950-02-25 1953-03-05 Merck Ag E Verfahren und Vorrichtung zur elektrolytischen Zersetzung waessriger Alkalisulfatloesungen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR334332A (fr) * 1903-06-25 1903-12-18 Rafael Escriva De Romani Nouveau système pour l'obtention de lessives caustiques concentrées, soude caustique, chlore et ses dérivés, par l'électrolyse du chlorure de sodium
US1109311A (en) * 1912-01-06 1914-09-01 Edward A Allen Method and means for electrolyzing saline solutions.
US1176551A (en) * 1914-03-27 1916-03-21 Karl Heinemann Apparatus for decomposing alkali-chlorid solutions.
GB471912A (en) * 1935-06-27 1937-09-13 Ig Farbenindustrie Ag Improvements in or relating to a process for the electrolysis of sodium sulphate
US2230023A (en) * 1938-03-09 1941-01-28 American Enka Corp Electrolytic cell

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732340A (en) * 1956-01-24 Ozone oxidation reactor
US3002914A (en) * 1956-05-23 1961-10-03 Solvay Preparation of electrodes for electrolysis of aqueous solutions by the mercury process
US3337433A (en) * 1959-07-31 1967-08-22 Hooker Chemical Corp Electrolytic process
US3109789A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Preparation of phosphine
US3042602A (en) * 1960-10-25 1962-07-03 Oronzio De Nora Impianti Horizontal electrolytic cell
US3308044A (en) * 1962-10-31 1967-03-07 Oronzio De Nora Impianti Inclined mercury cell and method of operation
US3308043A (en) * 1962-10-31 1967-03-07 Oronzio De Nora Impianti Method of discharging amalgam for inclined plane mercury cells
US3308047A (en) * 1962-10-31 1967-03-07 Oronzio De Nora Impianti Multiple tier inclined mercury cell
US3329595A (en) * 1963-02-27 1967-07-04 Diamond Alkali Co Electrolysis of concentrated sea water
US3400055A (en) * 1966-05-20 1968-09-03 Oronzio De Nora Impianti Method and apparatus for breaking electric current in flunet conductors
US3972793A (en) * 1975-09-26 1976-08-03 Eli Lilly And Company Continuous flow-through mercury cathode electrolysis cell
WO1993005202A1 (en) * 1991-09-05 1993-03-18 Olin Corporation Cell for direct electrochemical reduction of catholyte
US5209836A (en) * 1991-12-19 1993-05-11 Olin Corporation Baseplate for electrolytic cell with a liquid metal cathode
WO1993012270A1 (en) * 1991-12-19 1993-06-24 Olin Corporation Baseplate for eletrolytic cell with metal cathode

Also Published As

Publication number Publication date
BE491944A (nl)
FR1000268A (fr) 1952-02-11
NL71709C (nl) 1952-09-15
DE933027C (de) 1955-09-15
GB659565A (en) 1951-10-24

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