US3902985A - Alakali metal chlorate cell having metal bipolar electrodes - Google Patents

Alakali metal chlorate cell having metal bipolar electrodes Download PDF

Info

Publication number
US3902985A
US3902985A US420743A US42074373A US3902985A US 3902985 A US3902985 A US 3902985A US 420743 A US420743 A US 420743A US 42074373 A US42074373 A US 42074373A US 3902985 A US3902985 A US 3902985A
Authority
US
United States
Prior art keywords
bipolar
individual
pair
insulating means
insulating
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
US420743A
Inventor
Carl W Raetzsch
Hugh Cunningham
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.)
PPG Industries Inc
Original Assignee
PPG Industries Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by PPG Industries Inc filed Critical PPG Industries Inc
Priority to US420743A priority Critical patent/US3902985A/en
Priority to CA212,727A priority patent/CA1036540A/en
Priority to NO744250A priority patent/NO145988C/en
Priority to SE7415010A priority patent/SE410869B/en
Application granted granted Critical
Publication of US3902985A publication Critical patent/US3902985A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C25B9/17Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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

Definitions

  • ABSTRACT Disclosed is a bipolar electrolytic cell for the evolution of alkali metal halates.
  • the electrolytic cell has a plurality of bipolar units, each of the bipolar units having individual conducting means with anodes mounted on one side and cathodes mounted on the opposite side. Between each pair of individual conducting means are individual insulating means.
  • the assembly of conducting means including the anodes and cathodes mounted on each individual conducting means, and the insulating means, are held together by compressive means imposing a compressive force on the insulators and conductors.
  • the bipolar units are offset from the prior and subsequent bipolar units so that the electrodes are interleaved and so that an individual insulator of one bipolar unit serves to provide an interelectrode gap between the electrodes of that unit and the electrodes of the-adjacent bipolar unit.
  • Alkali metal halates such as sodium chlorate, may be prepared electrolytically.
  • alkali metal halide is fed to an electrolytic cell.
  • alkali metal chloride is fed to the cell.
  • Hydrogen is evolved at the cathode and alkali metal hydroxide is produced adjacent to the cathode. Chlorine and hydroxyl ion come into contact within the electrolyte chamber and react according to equation (i),
  • hypochlorite ion in which the chlorine has a valence of +1 may be self-oxidized to a chlorite ion, in which the chlorine has a valence of +3, and a chloride ion, in which the chlorine has a valence of l according to reaction (ii).
  • the chlorite ion is oxidized by hypochlorite ion to chlorate ion in which the chlorine has a valence of +5, as shown in reaction (iii).
  • the starting point of the electrolytic alkali metal halate process is the alkali metal halide, e.g., sodium chloride, in which the halogen has a valence of l.
  • the halogen in the alkali metal halate has a valence of +5. Therefore, the valence change necessary for the production of alkali metal halate is from l to +5, a total of +6. In this way, 6 Faradays are required for the production of 1 equivalent of the alkali metal halate.
  • hypohalite solution In the electrolysis of an acidic solution of an alkali metal halide, a hypohalite solution is first produced containing little free hypohalous acid. However, in the presence of a mineral acid such as chromic acid or sulfuric acid, the concentration of hypohalous acid is increased, and the oxidation of the hypohalous acid by hypohalite ions produces halate ion, halogen, and hydrogen. Hydrogen ions then react to form more hypohalous ion and the process continues with the formation of halate ion in all parts of the electrolyte.
  • a mineral acid such as chromic acid or sulfuric acid
  • halate ion takes place throughout the entire cell, and in fact throughout the system wherever halite ion and hypohalite ion are present.
  • the cell liquor is recovered from the cell it is clarified, e.g., by filtration, and then fed to an evaporator for concentration. Afterward, separation occurs and crystallized sodium chloride is recovered. The cell liquor may then be returned to saturating means for adjustment to desired brine strength and returned to the cell.
  • the cell liquor is cooled to crystallize the sodium chlorate then returned to the cell.
  • bipolar halate cells having compact electrolysis volumes, but permitting the use of large cell bodies, i.e., cell bodies characterized by large electrolyte volumes. In this way, a small volume is utilized for electrolysis while a large volume is provided for the chemical formation of halate ion. Because of the increased electrolyte tempera ture of the electrolyte, due to the higher current densities obtained with metal electrodes, the solubility of alkali metal halates in cell liquor is increased. The large cell volume relative to electrode volume provides a longer cell residence time. The combination of higher temperature, higher halate solubility, and longer residence time provides higher concentrations of halate in the cell liquor. The longer residence times allows more of the halate to be formed by chemical reaction rather than by electrolysis, thereby providing a higher current efficiency. The higher temperature allows a brine feed to be utilized rather than solid salt feed.
  • a bipolar alkali metal halate cell having a plurality of individual bipolar units electrically in series.
  • Each bipolar unit has a number of individual conductor elements.
  • An individual conductor element contains a metal mounted on one side and a metal cathode mounted on the opposite side.
  • Individual insulators correspond to each pair of individual conductors and are interposed between a pair of individual conductors. In this way, an individual insulator is interposed between a pair of adjacent, individual conductors, and an individual conductor is interposed betweena pair of adjacent, individual insulators.
  • Each individual bipolar unit further includes compressive means, imposing a compressive force upon a combination of alternating insulators and conductors. In this way'a rigid bipolar unit is provided.
  • the bipolar units are arrayed in bipolar configuration with the anodes of one bipolar unit interleaved between a pair of cathodes of a subsequent bipolar unit.
  • the anodes of a bipolar unit and cathodes of the subsequent bipolar unit are separated from each other by the insulators, referred to above, of both of the bipolar units.
  • the cathodes of a bipolar unit are interleaved between a pair of anodes of a prior bipolar unit, withthe cathodes of the bipolar unit, and the anodes of the prior bipolar unit being separated from each other by the insulating means of the pair of bipolar units.
  • FIG. 1 is a partial cutaway perspective view anode
  • FIG. 2 is a perspective, partially-exploded view of a segment of a pair of adjacent bipolar units of the electrolytic cell of this invention.
  • FIG. 3 is a plan view of three'bipolar units of the electrolytic cell of this invention.
  • FlG. 4 is a side elevation of a bipolar unit of the electrolytic cell of this invention.
  • the bipolar electrolyzer 1 of this invention contains a plurality of bipolar units 21 through 24 in series with the subsequent and adjacent bipolar units in the electrolyzer, thereby defining a plurality of adjacent individual bipolar cells 11 through 14.
  • Bipolar configuration may be understood by considering the current flow. Electrical current travels from an anode 51 of one cell 11 attached to the first bipolar unit 21 of that cell 11 to the cathode 61 of the cell. The cathode 61 is attached to the second bipolar unit 22 of the cell 11. The current then passes from the cathode 61 through the conducting means 30 of the bipolar unit 22 to the anode 51 connected to the bipolar unit 22 which is in turn the anode 51 of the next adjacent cell 12 in the electrolyzer 1.
  • the anodes 51 of the bipolar unit 22 are interleaved between the cathodes 61 of the next adjacent bipolar unit 23.
  • the cathodes 61 of the bipolar unit 23 are interleaved between the anodes 51 of the immediately preceding bipolar unit 22. Direct short circuits between the anodes 51 and cathodes 61 of adjacent bipolar units 21 and 22 are prevented by the insulating means 40 as will be more fully described hereinafter.
  • An individual bipolar unit 21 contains a plurality of individual conducting means 30.
  • the individual conducting means 30 are interposed between the cathodes 61 of one cell 11 on one side of the bipolar unit 21 and the anodes 51 of the next adjacent cell 12 on the opposite side of the bipolar unit 21. Current travels from the cathode 61 of the prior cell 11 through the conducting means 30 of the bipolar unit 21 to the anode 51 of the next adjacent cell 12.
  • the iii dividual conducting means 30 includes an electroeonductive, first metal member 32 having an anode 51 connected to one side thereof, an alkali resistant, electroeonductive, second metal member 34 having cathodes 61 connected to the opposite side thereof, and a third metal member 36 between, and mechanically and electrically connected to first 32 and second 34 metal members.
  • the first metal member 32 i.e., the acid resistant, electroeonductive metal member having the anode 51 connected thereto, is fabricated of a material that is resistant to anodic products while retaining its electroconductivity.
  • the acid resistant metal member is fabricated of a valve metal.
  • the valve metals are those metals which form an oxide film when exposed to acidic media or to electroeonductive media under anodic conditions.
  • the valve metals include titanium, zirconium, hafnium, vanadium, columbium, tantalum, and tungsten. Titanium, tantalum, or tungsten, are the most commonly used valve metal for electrolytic cell structural members because of their lower cost and ready availability. Titanium is the preferred material for this service because of its lowest cost relative to the other valve metals.
  • the first metal member or acid resistant, electrocon ductive metal member 32 is shown in rectangular form. This is because of the ready availability of rectangular stock, the conformity to insulating means 40 as will be described more fully hereinafter. and ease of rigidly connecting the anodes 51 substantially parallel to each other to the metal member. However, it should be understood that the first metal member may be cylindrical or of other shape.
  • the alkali resistant, electroeonductive, second metal member 34 is fabricated of a material that is resistant to cathode products such as hydroxyl ion while retaining its electroconductivity.
  • Such materials include iron, steel, cobalt, nickel, and the like. Most commonly, iron or steel is used.
  • the second metal member 34 is shown rectangular in form, it is to be understood that it may be of cylindrical or other shape. However, a rectangular form is preferred because of the availability of rectangular stock, the conformity to the insulating means 40 as will be described more fully hereinafter, and the ease of welding the cathodes 61 thereto so as to provide substantially parallel, spaced cathode fingers 61.
  • a third metal member 36 is interposed between, and mechanically and electrically connected to said first metal member 32 and said second metal member 34.
  • the third metal member 36 is typically fabricated of a material that is electroeonductive, and substantially impermeable to the flow of hydrogen. Such materials include copper, aluminum, and lead. Most frequently copper is used.
  • the third member 36 provides electrical conductivity between the cathodes 61 of one cell 11 and the anodes 51 of the next adjacent cell 12. Additionally, the copper member prevents the flow of nascent hydrogen from the cathode 61 through the conducting means 40 to the anode 51 of the next adjacent cell.
  • the copper member 36 may be bonded to the first metal member or acid resistant metal member 32 by welding, friction welding, soldering, bolting, or the like.
  • the copper member 36 may also be bonded to the alkali resistant or second metal member 34 by welding, friction welding, soldering, bolting or the like.
  • the copper member 36 is shown in rectangular form because of the ready availability of rectangular stock. However, it is to be understood that the copper member 36 may be of cylindrical stock.
  • Electrodes 51 and 61 are mounted on the opposite surfaces of the conductor 30.
  • Anodes 51 are connected to one side of the first metal member 32.
  • the anodes 51 are substantially parallel to each other and extend from the first metal member 32.
  • the anodes 51 themselves are fabricated of an electroeonductive, corrosion resistant metal.
  • the metal will be a valve metal as described hereinbefore, with titanium being the preferred valve metal.
  • the anodes may be in the form of a sheet or plate, or perforate sheet or a foraminous material such as expanded metal mesh.
  • the anodes 51 are coated with an electroeonductive material, having low chlorine overvoltage.
  • Typical materials useful for coating metal anodes for use in elec trolytic cells include the platinum group metals, ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • the coating compound may be an oxide of a platinum group metal such as ruthenium dioxide, rhodium trioxide. palladium dioxide, osmium dioxide, iridium trioxide. or platinum dioxide.
  • the coating compound may be an oxygen containing compound of a platinum group metal such as calcium ruthenate, calcium rhodate, calcium ruthenite, calcium rhodite, the delafossites such as platinum cobaltate or palladium cobaltate, or a pyrochlore such as bismuth rathenate, or bismuth rhodate.
  • the coating material on the surface of the anode may be lead dioxide or other non-precious metal containing oxygen compounds.
  • the cathodes 61 are connected to the opposite side of the second metal member 34.
  • the cathodes 61 are fabricated of an alkali resistant, hydroxyl ion resistant, electroconductive metal.
  • the cathodes 61 may be fab ricated of iron, steel, cobalt, nickel, iron, manganese, or the like. Most commonly, they are fabricated or iron, or steel, because of the ready availability thereof.
  • the cathodes may be in the form of a sheet, plate, perforate sheet or plate, or foraminous or expanded metal mesh. Most commonly, they are fabricated of iron, or steel, because of the ready availability thereof.
  • the cathodes may be in the form of a sheet, plate, perforate sheet or plate, or foraminous or expanded metal mesh. Most commonly they have an open area from about 35 to about 85 percent and preferably from about 65 to about 75 percent.
  • insulating means i.e., insulators 40 surround the individual conducting means, i.e., the conductors 30 providing separation between adjacent individual conductors 30.
  • the insulators 4O correspond to the individual conductors 30 and are complimentary in shape to the individual conductors 30 so as to totally cover and fit flush against the copper portion 36. In this way the insulators 40 bear against the copper members 36 and provide a tight fit therebetween, preventing contact of the copper members 36 by the electrolyte.
  • the insulators 40 are interposed between a pair of individual conductors 30 and are arranged sequentially in an individual bipolar unit in such a way that an insulator 40 is interposed between a pair of adjacent individual conductors 30 and an individual conductor 30 is interposed between a pair of adjacent individual insulators 40.
  • the insulators 40 include means for maintaining an interelectrode gap between the pair of electrodes 51 adjacent thereto and the pair of electrodes 61 of a subsequent bipolar unit.
  • the insulators also include means for maintaining an inter-electrode gap between the pair of electrodes of opposite charge adjacent thereto 61, and a pair of electrodes 51 of the prior bipolar unit.
  • the interelectrode gap may be provided by means within the insulators such as a non-conductive structure for engaging the electrodes of the prior bipolar unit, i.e., anodes 51, parallel to and spaced from the oppositely charged electrodes, i.e., the cathodes 61, of the bipolar unit.
  • the insulators 40 also include structure for engaging the electrodes of the subsequent bipolar unit, i.e., cathodes 61,. and maintaining them in a spaced relationship, i.e., parallel to and spaced from the oppositely charged electrodes 31, i.e., the anodes, of the bipolar unit.
  • the structural means for accomplishing this may include spaced slot means, grooves, notches, or channels within the insulator.
  • the means for maintaining inter-electrode may include spaced wedges, extended frames, an extended edge, or fin means, such as the extended edge 46 shown in FIGS. 2, 3, and 4.
  • the individual insulating means include compressible, electrolyte resistant electrically non-conductive,
  • the compressible means may be rubber, polyethylene, Kynar, Teflon, or the like.
  • the substantially incompressible means 44 may be H frames, channel frames, or other shapes.
  • the substantially incompressible electrolyte resistant means 44 include the means 46 for maintaining alignment of electrodes of adjacent bipolar units as shown withparticularity in FIGS. 2 and 3.
  • the individual bipolar units include compressive means providing rigid bipolar structural units.
  • the compressive means include an electrically insulative bolt means 70 extending through the individual insulating means 40 and the individual conducting means 30 of the individual bipolar unit.
  • the electrically insulative bolt means 70 includes a core 71 of a structural material of high tensile strength, e.g., iron or steel or other structural metal, and may include a sheathing or coating thereon 73 of an electrically non-conductive material.
  • the compressive means include iron or steel rod member 71 and a surface 73 of Kynar, Teflon, or the like-At the opposite extreme ends of the compressive means, are bearing surface means 75 which are substantially co-extensive with and bearing upon an external pair of insulating means 46 at the ex treme ends of the bipolar unit, and nuts 77.
  • the individual bipolar units 21 through 24 are assembled into a plurality of individual cells 11 through 14 within a cell body 1.
  • the bipolar units 21 through 24 may be mounted on base structures 81 through 84 within the cell body 1. This gives electrolyte volume under the electrodes, thereby allowing alkali metal halate formation under the bipolar units 21 through 24 and above the bipolar units 21 through 24.
  • the bipolar units are shown generally at FIG. 1 and with specific detail in FIGS. 2, 3, and 4. As there shown, the bipolar units are arrayed in series with subsequent and adjacent bipolar units of the electrolytic cell.
  • the cell body 1 can be rubber-lined metal such as ethylenepropylene-diene lined steel, neoprene lined steel, or the like. Additionally, the cell body 1 can be a concrete body.
  • the cell body 1 is closed at the top and includes means for feeding brine to the cell and recovering the alkali metal chlorate and hydrogen gas therefrom.
  • the cell liquor contains from about 650 to about 750 grams per liter of sodium chlorate, from about 60 to about grams per liter of sodium chloride, approximately 2 grams per liter of sodium dichromate added to improve the electrolytical efficiency of the cell, and trace amounts of sodium hypochlorites.
  • the current density is from about 200 to about 600 amperes per square foot.
  • a residence time within the cell of from about 40 to about 250 milliliters per ampere is provided and preferably from about 65 to about 200 milliliters per ampere.
  • the pH of the cell liquor within the cell is from about pH 5.6 to about pH 6.9 and preferably from about pH 6 to about pH 6.8. Under these conditions the temperature of the electrolyte is from about 50C. to about 100C., frequently in excess of 80C. and as high as 95C. or 98C. or even 100C.
  • feed may either be parallel feed, i.e., a plurality of individual feeds substantially corresponding to each of the individual cells, or the feed may be series feed, wherein the brine is fed at one end of the cell and the alkali metal chlorate is recovered at the opposite end of the cell.
  • series feed is preferred,- as the feed to the first cell is low in hypochlorite ion concentration, thereby providing a high degree of chemical formation of chlorate ion and a high current efficiency.
  • a bipolar electrolytic cell for the evolution of alkali metal chlorates comprising:
  • each of said bipolar units comprising:
  • a plurality of individual conducting means having metal anode means mounted on one end thereof and cathode means mounted on the other end thereof, said individual conducting means comprising an acid resistant, electroconductive metal member having the said metal anode means connected thereto; an alkali resistant, electroconductive metal member having the said cathode means connected thereto; and a high electroconductivity, low hydrogen permeability metal member between and mechanically and electrically connected to said metal members.
  • bipolar units being arrayed in a bipolar configuration wherein:
  • the anodes of a bipolar unit are interleaved between a pair of cathodes of a subsequent bipolar unit and separated therefrom by the insulating means of both of said bipolar units;
  • the cathodes of a bipolar unit are interleaved between a pair of anodes of a prior bipolar unit and separated therefrom by the insulating means of both of said bipolar units.
  • the bipolar electrolytic cell of claim 1 wherein the acid resistant metal is chosen from the group consisting of titanium. zirconium, hafnium, vanadium, columbium, tantalum, and tungsten.
  • bipolar electrolytic cell of claim 1 wherein said insulating means include means for maintaining an interelectrode gap between a pair of electrodes adjacent thereto and a pair of electrodes of an adjacent bipolar unit in series therewith.
  • the bipolar electrolytic cell of claim 4 wherein the means for maintaining an interelectrode gap comprise means for mechanically engaging the electrodes of the prior and subsequent bipolar units.
  • bearing surface means substantially coextensive with and bearing upon an external pair of said insulating means at the extreme end of the bipolar unit.
  • a bipolar electrolytic cell for the evolution of alkali metal chlorates comprising:
  • each of said bipolar units comprising:
  • a plurality of individual conducting means having metal anode means mounted on one end thereof and cathode means mounted on the other end thereof, said individual conducting means comprising an acid resistant, electroconductive metal member having the said metal anode means connected thereto; an alkali resistant, electroconductive metal member having the said cathode means connected thereto; and a copper member between and mechanically and electrically connected to said metal members;
  • individual insulating means corresponding to and interposed between a pair of said individual conducting means, whereby an individual insulating means is interposed between a pair of adjacent, individual conducting means, and an individual conducting means is interposed between a pair of adjacent, individual insulating means, said individual insulating means comprising a compressible, electrolyte resistant, electrolyte impermeable, insulating means on facing surfaces of said copper members and substantially coextensive therewith thereby to prevent contact of the copper by electrolyte; and
  • the anodes of a bipolar unit are interleaved beducting means whereby to Provide a rigid bipolar tween a pair of cathodes of a subsequent bipolar unit, said compressive means comprising: electrically insulative bolt means extending through I means of both of said bipolar units; and Sald Individual m-sulatmg means and conduc-tmg 2 the cathodes of a bipolar unit are interleaved bemeans; and bearing surface means substantially coextensive i and bearing upon an external tween a pair of anodes of a prior bipolar unit and pair of said insulating means at the extreme end Separated theleffom y he nsulating means of of the bipolar unit; and 0 both of said bipolar units.
  • bipolar units being arrayed in a bipolar configunit and separated therefrom by the insulating

Abstract

Disclosed is a bipolar electrolytic cell for the evolution of alkali metal halates. The electrolytic cell has a plurality of bipolar units, each of the bipolar units having individual conducting means with anodes mounted on one side and cathodes mounted on the opposite side. Between each pair of individual conducting means are individual insulating means. The assembly of conducting means, including the anodes and cathodes mounted on each individual conducting means, and the insulating means, are held together by compressive means imposing a compressive force on the insulators and conductors. The bipolar units are offset from the prior and subsequent bipolar units so that the electrodes are interleaved and so that an individual insulator of one bipolar unit serves to provide an inter-electrode gap between the electrodes of that unit and the electrodes of the adjacent bipolar unit.

Description

United States Patent [1 1 Raetzsch et al.
[ 51 Sept. 2, 1975 ALAKALI METAL CHLORATE CELL HAVING METAL BIPOLAR ELECTRODES [75] Inventors: Carl W. Raetzsch; Hugh Cunningham, both of Corpus Christi, Tex.
[73] Assignee: PPG Industries, Inc., Pittsburgh, Pa.
[22] Filed: Nov. 30, 1973 [21] Appl. No.: 420,743
[52] US. Cl. 204/268; 204/95; 204/270;
[51] Int. Cl B0lk 3/00 [58] Field of Search 204/95, 254, 255, 256, 204/268, 270, 286
[56] References Cited UNlTED STATES PATENTS 3,759,813 9/1973 Raetzsch ct al 204/268 X 3,759,815 9/1973 Larsson 204/268 3,791,947 2/1974 Loftficld 204/95 Primary Examiner-John H. Mack Assistant E.\'aminer-W. l. Solomon Attorney, Agent, or Firm-Richard M. Goldman [57 ABSTRACT Disclosed is a bipolar electrolytic cell for the evolution of alkali metal halates. The electrolytic cell has a plurality of bipolar units, each of the bipolar units having individual conducting means with anodes mounted on one side and cathodes mounted on the opposite side. Between each pair of individual conducting means are individual insulating means. The assembly of conducting means, including the anodes and cathodes mounted on each individual conducting means, and the insulating means, are held together by compressive means imposing a compressive force on the insulators and conductors. The bipolar units are offset from the prior and subsequent bipolar units so that the electrodes are interleaved and so that an individual insulator of one bipolar unit serves to provide an interelectrode gap between the electrodes of that unit and the electrodes of the-adjacent bipolar unit.
10 Claims, 4 Drawing Figures PATENTEU SEP 2 I975 SHEET 1 UF 2 ALAKALI METAL CHLORATE CELL HAVING METAL BIPOLAR ELECTRODES BACKGROUND OF THE INVENTION Alkali metal halates, such as sodium chlorate, may be prepared electrolytically. In the electrolytic preparation of alkali metal halates, alkali metal halide is fed to an electrolytic cell. For example, in the case of a chlorate cell, alkali metal chloride is fed to the cell. Hydrogen is evolved at the cathode and alkali metal hydroxide is produced adjacent to the cathode. Chlorine and hydroxyl ion come into contact within the electrolyte chamber and react according to equation (i),
thereby forming hypochlorite ion. The hypochlorite ion, in which the chlorine has a valence of +1 may be self-oxidized to a chlorite ion, in which the chlorine has a valence of +3, and a chloride ion, in which the chlorine has a valence of l according to reaction (ii).
The chlorite ion, in turn, is oxidized by hypochlorite ion to chlorate ion in which the chlorine has a valence of +5, as shown in reaction (iii).
(iii) The starting point of the electrolytic alkali metal halate process is the alkali metal halide, e.g., sodium chloride, in which the halogen has a valence of l. The halogen in the alkali metal halate has a valence of +5. Therefore, the valence change necessary for the production of alkali metal halate is from l to +5, a total of +6. In this way, 6 Faradays are required for the production of 1 equivalent of the alkali metal halate.
In the electrolysis of an acidic solution of an alkali metal halide, a hypohalite solution is first produced containing little free hypohalous acid. However, in the presence of a mineral acid such as chromic acid or sulfuric acid, the concentration of hypohalous acid is increased, and the oxidation of the hypohalous acid by hypohalite ions produces halate ion, halogen, and hydrogen. Hydrogen ions then react to form more hypohalous ion and the process continues with the formation of halate ion in all parts of the electrolyte. Side reactions, e.g., the evolution of oxygen at the cathode, and the reaction of nascent hydrogen with oxygen containing ions, may be reduced by the addition of chromate ion, i.e., sodium chromate into the electrolyte thereby favoring the evolution of halite ion.
The chemical formation of halate ion takes place throughout the entire cell, and in fact throughout the system wherever halite ion and hypohalite ion are present.
In the operation of sodium chlorate cells of the prior art, the combination of thick electrodes and low current densities, e.g., less than about 100 amperes per square foot, provided a cell operating temperature of about 50 to about 65C. In such cells solid sodium chloride had to be substantially continuously added to the cell.
In a batch chlorate cell operation, after the cell liquor is recovered from the cell it is clarified, e.g., by filtration, and then fed to an evaporator for concentration. Afterward, separation occurs and crystallized sodium chloride is recovered. The cell liquor may then be returned to saturating means for adjustment to desired brine strength and returned to the cell. In a continuous chlorate cell process, without evaporation or removal of sodium chloride, the cell liquor is cooled to crystallize the sodium chlorate then returned to the cell.
SUMMARY OF THE INVENTION According to this invention, bipolar halate cells are provided having compact electrolysis volumes, but permitting the use of large cell bodies, i.e., cell bodies characterized by large electrolyte volumes. In this way, a small volume is utilized for electrolysis while a large volume is provided for the chemical formation of halate ion. Because of the increased electrolyte tempera ture of the electrolyte, due to the higher current densities obtained with metal electrodes, the solubility of alkali metal halates in cell liquor is increased. The large cell volume relative to electrode volume provides a longer cell residence time. The combination of higher temperature, higher halate solubility, and longer residence time provides higher concentrations of halate in the cell liquor. The longer residence times allows more of the halate to be formed by chemical reaction rather than by electrolysis, thereby providing a higher current efficiency. The higher temperature allows a brine feed to be utilized rather than solid salt feed.
According to this invention, a bipolar alkali metal halate cell is provided having a plurality of individual bipolar units electrically in series. Each bipolar unit has a number of individual conductor elements. An individual conductor element contains a metal mounted on one side and a metal cathode mounted on the opposite side. Individual insulators correspond to each pair of individual conductors and are interposed between a pair of individual conductors. In this way, an individual insulator is interposed between a pair of adjacent, individual conductors, and an individual conductor is interposed betweena pair of adjacent, individual insulators. Each individual bipolar unit further includes compressive means, imposing a compressive force upon a combination of alternating insulators and conductors. In this way'a rigid bipolar unit is provided.
The bipolar units are arrayed in bipolar configuration with the anodes of one bipolar unit interleaved between a pair of cathodes of a subsequent bipolar unit. The anodes of a bipolar unit and cathodes of the subsequent bipolar unit are separated from each other by the insulators, referred to above, of both of the bipolar units. In the same way, the cathodes of a bipolar unit are interleaved between a pair of anodes of a prior bipolar unit, withthe cathodes of the bipolar unit, and the anodes of the prior bipolar unit being separated from each other by the insulating means of the pair of bipolar units. I
DETAILED DESCRIPTION The invention may be understood reference to the appended Figures. In the Figures:
FIG. 1 is a partial cutaway perspective view anode FIG. 2 is a perspective, partially-exploded view of a segment of a pair of adjacent bipolar units of the electrolytic cell of this invention.
FIG. 3 is a plan view of three'bipolar units of the electrolytic cell of this invention. FlG. 4 is a side elevation of a bipolar unit of the electrolytic cell of this invention.
The bipolar electrolyzer 1 of this invention contains a plurality of bipolar units 21 through 24 in series with the subsequent and adjacent bipolar units in the electrolyzer, thereby defining a plurality of adjacent individual bipolar cells 11 through 14. Bipolar configuration may be understood by considering the current flow. Electrical current travels from an anode 51 of one cell 11 attached to the first bipolar unit 21 of that cell 11 to the cathode 61 of the cell. The cathode 61 is attached to the second bipolar unit 22 of the cell 11. The current then passes from the cathode 61 through the conducting means 30 of the bipolar unit 22 to the anode 51 connected to the bipolar unit 22 which is in turn the anode 51 of the next adjacent cell 12 in the electrolyzer 1.
The anodes 51 of the bipolar unit 22 are interleaved between the cathodes 61 of the next adjacent bipolar unit 23. The cathodes 61 of the bipolar unit 23 are interleaved between the anodes 51 of the immediately preceding bipolar unit 22. Direct short circuits between the anodes 51 and cathodes 61 of adjacent bipolar units 21 and 22 are prevented by the insulating means 40 as will be more fully described hereinafter.
An individual bipolar unit 21 contains a plurality of individual conducting means 30. The individual conducting means 30 are interposed between the cathodes 61 of one cell 11 on one side of the bipolar unit 21 and the anodes 51 of the next adjacent cell 12 on the opposite side of the bipolar unit 21. Current travels from the cathode 61 of the prior cell 11 through the conducting means 30 of the bipolar unit 21 to the anode 51 of the next adjacent cell 12. The iii dividual conducting means 30 includes an electroeonductive, first metal member 32 having an anode 51 connected to one side thereof, an alkali resistant, electroeonductive, second metal member 34 having cathodes 61 connected to the opposite side thereof, and a third metal member 36 between, and mechanically and electrically connected to first 32 and second 34 metal members.
The first metal member 32, i.e., the acid resistant, electroeonductive metal member having the anode 51 connected thereto, is fabricated of a material that is resistant to anodic products while retaining its electroconductivity. Most commonly, the acid resistant metal member is fabricated of a valve metal. The valve metals are those metals which form an oxide film when exposed to acidic media or to electroeonductive media under anodic conditions. The valve metals include titanium, zirconium, hafnium, vanadium, columbium, tantalum, and tungsten. Titanium, tantalum, or tungsten, are the most commonly used valve metal for electrolytic cell structural members because of their lower cost and ready availability. Titanium is the preferred material for this service because of its lowest cost relative to the other valve metals.
- The first metal member or acid resistant, electrocon ductive metal member 32 is shown in rectangular form. This is because of the ready availability of rectangular stock, the conformity to insulating means 40 as will be described more fully hereinafter. and ease of rigidly connecting the anodes 51 substantially parallel to each other to the metal member. However, it should be understood that the first metal member may be cylindrical or of other shape.
On the opposite side of the conductor 30 is an alkali resistant, electroeonductive metal member 34 having cathode fingers 61 connected thereto. Preferably, the alkali resistant, electroeonductive, second metal member 34 is fabricated of a material that is resistant to cathode products such as hydroxyl ion while retaining its electroconductivity. Such materials include iron, steel, cobalt, nickel, and the like. Most commonly, iron or steel is used.
While the second metal member 34 is shown rectangular in form, it is to be understood that it may be of cylindrical or other shape. However, a rectangular form is preferred because of the availability of rectangular stock, the conformity to the insulating means 40 as will be described more fully hereinafter, and the ease of welding the cathodes 61 thereto so as to provide substantially parallel, spaced cathode fingers 61.
A third metal member 36 is interposed between, and mechanically and electrically connected to said first metal member 32 and said second metal member 34. The third metal member 36 is typically fabricated of a material that is electroeonductive, and substantially impermeable to the flow of hydrogen. Such materials include copper, aluminum, and lead. Most frequently copper is used. The third member 36 provides electrical conductivity between the cathodes 61 of one cell 11 and the anodes 51 of the next adjacent cell 12. Additionally, the copper member prevents the flow of nascent hydrogen from the cathode 61 through the conducting means 40 to the anode 51 of the next adjacent cell.
The copper member 36 may be bonded to the first metal member or acid resistant metal member 32 by welding, friction welding, soldering, bolting, or the like.
The copper member 36 may also be bonded to the alkali resistant or second metal member 34 by welding, friction welding, soldering, bolting or the like.
The copper member 36 is shown in rectangular form because of the ready availability of rectangular stock. However, it is to be understood that the copper member 36 may be of cylindrical stock.
Electrodes 51 and 61 are mounted on the opposite surfaces of the conductor 30. Anodes 51 are connected to one side of the first metal member 32. The anodes 51 are substantially parallel to each other and extend from the first metal member 32. The anodes 51 themselves are fabricated of an electroeonductive, corrosion resistant metal. Most commonly, the metal will be a valve metal as described hereinbefore, with titanium being the preferred valve metal. The anodes may be in the form of a sheet or plate, or perforate sheet or a foraminous material such as expanded metal mesh.
The anodes 51 are coated with an electroeonductive material, having low chlorine overvoltage. Typical materials useful for coating metal anodes for use in elec trolytic cells include the platinum group metals, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Alternatively, the coating compound may be an oxide of a platinum group metal such as ruthenium dioxide, rhodium trioxide. palladium dioxide, osmium dioxide, iridium trioxide. or platinum dioxide. Alternatively, the coating compound may be an oxygen containing compound of a platinum group metal such as calcium ruthenate, calcium rhodate, calcium ruthenite, calcium rhodite, the delafossites such as platinum cobaltate or palladium cobaltate, or a pyrochlore such as bismuth rathenate, or bismuth rhodate. Alternatively, the coating material on the surface of the anode may be lead dioxide or other non-precious metal containing oxygen compounds.
The cathodes 61 are connected to the opposite side of the second metal member 34. The cathodes 61 are fabricated of an alkali resistant, hydroxyl ion resistant, electroconductive metal. The cathodes 61 may be fab ricated of iron, steel, cobalt, nickel, iron, manganese, or the like. Most commonly, they are fabricated or iron, or steel, because of the ready availability thereof. The cathodes may be in the form of a sheet, plate, perforate sheet or plate, or foraminous or expanded metal mesh. Most commonly, they are fabricated of iron, or steel, because of the ready availability thereof. The cathodes may be in the form of a sheet, plate, perforate sheet or plate, or foraminous or expanded metal mesh. Most commonly they have an open area from about 35 to about 85 percent and preferably from about 65 to about 75 percent.
As shown with particularity in FIGS. 2 and 3, insulating means, i.e., insulators 40 surround the individual conducting means, i.e., the conductors 30 providing separation between adjacent individual conductors 30.
The insulators 4O correspond to the individual conductors 30 and are complimentary in shape to the individual conductors 30 so as to totally cover and fit flush against the copper portion 36. In this way the insulators 40 bear against the copper members 36 and provide a tight fit therebetween, preventing contact of the copper members 36 by the electrolyte.
The insulators 40 are interposed between a pair of individual conductors 30 and are arranged sequentially in an individual bipolar unit in such a way that an insulator 40 is interposed between a pair of adjacent individual conductors 30 and an individual conductor 30 is interposed between a pair of adjacent individual insulators 40.
The insulators 40 include means for maintaining an interelectrode gap between the pair of electrodes 51 adjacent thereto and the pair of electrodes 61 of a subsequent bipolar unit. The insulators also include means for maintaining an inter-electrode gap between the pair of electrodes of opposite charge adjacent thereto 61, and a pair of electrodes 51 of the prior bipolar unit. The interelectrode gap may be provided by means within the insulators such as a non-conductive structure for engaging the electrodes of the prior bipolar unit, i.e., anodes 51, parallel to and spaced from the oppositely charged electrodes, i.e., the cathodes 61, of the bipolar unit. The insulators 40 also include structure for engaging the electrodes of the subsequent bipolar unit, i.e., cathodes 61,. and maintaining them in a spaced relationship, i.e., parallel to and spaced from the oppositely charged electrodes 31, i.e., the anodes, of the bipolar unit. The structural means for accomplishing this may include spaced slot means, grooves, notches, or channels within the insulator. Alternatively, the means for maintaining inter-electrode may include spaced wedges, extended frames, an extended edge, or fin means, such as the extended edge 46 shown in FIGS. 2, 3, and 4.
The individual insulating means include compressible, electrolyte resistant electrically non-conductive,
i.e., electrically insulative, means 42 on facing surfaces corresponding to facing surfaces of adjacent conducting means 30. The compressible means may be rubber, polyethylene, Kynar, Teflon, or the like.
lnterposed between a pair of the compressible, insulative means 42 is a substantially incompressible, electrolyte resistant, electrically non-conductive, electrically insulating means 44. The substantially incompressible means 44 may be H frames, channel frames, or other shapes. The substantially incompressible electrolyte resistant means 44 include the means 46 for maintaining alignment of electrodes of adjacent bipolar units as shown withparticularity in FIGS. 2 and 3.
The individual bipolar units include compressive means providing rigid bipolar structural units. As shown in FIGS. 2 and 3, the compressive means include an electrically insulative bolt means 70 extending through the individual insulating means 40 and the individual conducting means 30 of the individual bipolar unit. The electrically insulative bolt means 70 includes a core 71 of a structural material of high tensile strength, e.g., iron or steel or other structural metal, and may include a sheathing or coating thereon 73 of an electrically non-conductive material. According to one exemplification,,the compressive means include iron or steel rod member 71 and a surface 73 of Kynar, Teflon, or the like-At the opposite extreme ends of the compressive means, are bearing surface means 75 which are substantially co-extensive with and bearing upon an external pair of insulating means 46 at the ex treme ends of the bipolar unit, and nuts 77.
The individual bipolar units 21 through 24 are assembled into a plurality of individual cells 11 through 14 within a cell body 1.
The bipolar units 21 through 24 may be mounted on base structures 81 through 84 within the cell body 1. This gives electrolyte volume under the electrodes, thereby allowing alkali metal halate formation under the bipolar units 21 through 24 and above the bipolar units 21 through 24.
The bipolar units are shown generally at FIG. 1 and with specific detail in FIGS. 2, 3, and 4. As there shown, the bipolar units are arrayed in series with subsequent and adjacent bipolar units of the electrolytic cell.
The cell body 1 can be rubber-lined metal such as ethylenepropylene-diene lined steel, neoprene lined steel, or the like. Additionally, the cell body 1 can be a concrete body.
The cell body 1 is closed at the top and includes means for feeding brine to the cell and recovering the alkali metal chlorate and hydrogen gas therefrom.
Under normal operating conditions, with a sodium chloride feed, the cell liquor contains from about 650 to about 750 grams per liter of sodium chlorate, from about 60 to about grams per liter of sodium chloride, approximately 2 grams per liter of sodium dichromate added to improve the electrolytical efficiency of the cell, and trace amounts of sodium hypochlorites. In the operation of the cell, the current density is from about 200 to about 600 amperes per square foot. A residence time within the cell of from about 40 to about 250 milliliters per ampere is provided and preferably from about 65 to about 200 milliliters per ampere. The pH of the cell liquor within the cell is from about pH 5.6 to about pH 6.9 and preferably from about pH 6 to about pH 6.8. Under these conditions the temperature of the electrolyte is from about 50C. to about 100C., frequently in excess of 80C. and as high as 95C. or 98C. or even 100C.
In the operation of the bipolar electrolytic cell, feed may either be parallel feed, i.e., a plurality of individual feeds substantially corresponding to each of the individual cells, or the feed may be series feed, wherein the brine is fed at one end of the cell and the alkali metal chlorate is recovered at the opposite end of the cell. Generally, series feed is preferred,- as the feed to the first cell is low in hypochlorite ion concentration, thereby providing a high degree of chemical formation of chlorate ion and a high current efficiency.
While the cell has been described with reference to the production of sodium chlorate from sodium chloride, it is to be understood that the cell as herein described above may also be used for the production of sodium bromate from sodium bromide brine, potassium chlorate from potassium chloride brine, and potassium bromate from potassium bromide brine. Although 'the invention has been described with reference to particular specific details and certain preferred exemplifications, it is not intended to thereby limit the scope of this invention except insofar as the details are recited in the appended claims.
We claim:
l. A bipolar electrolytic cell for the evolution of alkali metal chlorates comprising:
A. a plurality of bipolar units, each of said bipolar units comprising:
1. a plurality of individual conducting means having metal anode means mounted on one end thereof and cathode means mounted on the other end thereof, said individual conducting means comprising an acid resistant, electroconductive metal member having the said metal anode means connected thereto; an alkali resistant, electroconductive metal member having the said cathode means connected thereto; and a high electroconductivity, low hydrogen permeability metal member between and mechanically and electrically connected to said metal members.
2. individual insulating means corresponding to and interposed between a pair of said individual conducting means, whereby an individual insulating means is interposed between a pair of adj acent, individual conducting means, and an individual conducting means is interposed between a pair of adjacent, individual insulating means; and
3. compressive means imposing a compressive force upon said insulating means and said conducting means whereby to provide a rigid bipolar unit;
B. said bipolar units being arrayed in a bipolar configuration wherein:
l. the anodes of a bipolar unit are interleaved between a pair of cathodes of a subsequent bipolar unit and separated therefrom by the insulating means of both of said bipolar units; and
2. the cathodes of a bipolar unit are interleaved between a pair of anodes of a prior bipolar unit and separated therefrom by the insulating means of both of said bipolar units.
2. The bipolar electrolyte cell of claim 1 wherein the high electroconductivity, low hydrogen permeability metal member is a copper member.
3. The bipolar electrolytic cell of claim 1 wherein the acid resistant metal is chosen from the group consisting of titanium. zirconium, hafnium, vanadium, columbium, tantalum, and tungsten.
4. The bipolar electrolytic cell of claim 1 wherein said insulating means include means for maintaining an interelectrode gap between a pair of electrodes adjacent thereto and a pair of electrodes of an adjacent bipolar unit in series therewith.
5. The bipolar electrolytic cell of claim 4 wherein the means for maintaining an interelectrode gap comprise means for mechanically engaging the electrodes of the prior and subsequent bipolar units.
6. The bipolar electrolytic cell of claim 1 wherein said individual insulating means comprise compressible, electrolyte resistant, insulating means on facing surfaces of adjacent individual conducting means.
7. The bipolar electrolytic cell of claim 6 wherein said individual insulating means comprise substantially incompressible, electrolyte resistant, insulating means interposed between a pair of compressible insulating means.
8. The bipolar electrolytic cell of claim 1 wherein said compressive means comprise:
electrically insulative bolt means extending through said individual insulating means and conducting means; and
bearing surface means substantially coextensive with and bearing upon an external pair of said insulating means at the extreme end of the bipolar unit.
9. The bipolar electrolytic cell of claim 1 wherein said individual insulating means comprise:
compressible, electrolyte resistant, electrolyte impermeable, insulating means on facing surfaces of said copper members and substantially coextensive therewith thereby to prevent contact of the high electroconductivity low hydrogen permeability metal member by electrolyte.
10. A bipolar electrolytic cell for the evolution of alkali metal chlorates comprising:
A. a plurality of bipolar units, each of said bipolar units comprising:
1. a plurality of individual conducting means having metal anode means mounted on one end thereof and cathode means mounted on the other end thereof, said individual conducting means comprising an acid resistant, electroconductive metal member having the said metal anode means connected thereto; an alkali resistant, electroconductive metal member having the said cathode means connected thereto; and a copper member between and mechanically and electrically connected to said metal members;
2. individual insulating means corresponding to and interposed between a pair of said individual conducting means, whereby an individual insulating means is interposed between a pair of adjacent, individual conducting means, and an individual conducting means is interposed between a pair of adjacent, individual insulating means, said individual insulating means comprising a compressible, electrolyte resistant, electrolyte impermeable, insulating means on facing surfaces of said copper members and substantially coextensive therewith thereby to prevent contact of the copper by electrolyte; and
3. compressive means imposing a compressive uration wherein:
force p Said insulating means and Said 1. the anodes of a bipolar unit are interleaved beducting means whereby to Provide a rigid bipolar tween a pair of cathodes of a subsequent bipolar unit, said compressive means comprising: electrically insulative bolt means extending through I means of both of said bipolar units; and Sald Individual m-sulatmg means and conduc-tmg 2 the cathodes of a bipolar unit are interleaved bemeans; and bearing surface means substantially coextensive i and bearing upon an external tween a pair of anodes of a prior bipolar unit and pair of said insulating means at the extreme end Separated theleffom y he nsulating means of of the bipolar unit; and 0 both of said bipolar units.
B. said bipolar units being arrayed in a bipolar configunit and separated therefrom by the insulating

Claims (25)

1. THE ANODES OF A BIPOLAR UNIT ARE INTERLEAVED BETWEEN A PAIR OF CATHODES OF A SUBSEQUENT BIPOLAR UNIT AND SEPARATED THEREFROM BY THE INSULATING MEANS OF BOTH OF SAID BIPOLAR UNITS, AND
1. A PLURALITY OF INDIVIDUAL CONDUCTING MEANS HAVING METAL ANODE MEANS MOUNTED ON ONE END THEREOF AND CATHODE MEANS MOUNTED ON THE OTHER END THEREOF, SAID INDIVIDUAL CONDUCTING MEANS COMPRISING AN ACID RESISTANT, ELECTROCONDUCTIVE METAL MEMBER HAVING THE SAID METAL ANODE MEANS CONNECTED THERETO, AN ALAKALI RESISTANT, ELECTROCONDUCTIVE METAL MEMBER HAVING THE SAID CATHODE MEANS CONNECTED THERETO, AND COPPER MEMBER BETWEEN AND MECHANICALLY AND ELECTRICALLY CONNECTED TO SAID METAL MEMBERS,
1. A bipolar electrolytic cell for the evolution of alkali metal chlorates comprising: A. a plurality of bipolar units, each of said bipolar units comprising:
1. a plurality of individual conducting means having metal anode means mounted on one end thereof and cathode means mounted on the other end thereof, said individual conducting means comprising an acid resistant, electroconductive metal member having the said metal anode means connected thereto; an alkali resistant, electroconductive metal member having the said cathode means connected thereto; and a high electroconductivity, low hydrogen permeability metal member between and mechanically and electrically connected to said metal members.
1. the anodes of a bipolar unit are interleaved between a pair of cathodes of a subsequent bipolar unit and separated therefrom by the insulating means of both of said bipolar units; and
1. a plurality of individual conducting means having metal anode means mounted on one end thereof and cathode means mounted on the other end thereof, said individual conducting means comprising an acid resistant, electroconductive metal member having the said metal anode means connected thereto; an alkali resistant, electroconductive metal member having the said cathode means connected thereto; and a copper member between and mechanically and electrically connected to said metal members;
1. the anodes of a bipolar unit are interleaved between a pair of cathodes of a subsequent bipolar unit and separated therefrom by the insulating means of both of said bipolar units; and
2. the cathodes of a bipolar unit are interleaved between a pair of anodes of a prior bipolar unit and separated therefrom by the insulating means of both of said bipolar units.
2. the cathodes of a bipolar unit are interleaved between a pair of anodes of a prior bipolar unit and separated therefrom by the insulating means of both of said bipolar units.
2. individual insulating means corresponding to and interposed between a pair of said individual conducting means, whereby an individual insulating means is interposed between a pair of adjacent, individual conducting means, and an individual conducting means is interposed Between a pair of adjacent, individual insulating means, said individual insulating means comprising a compressible, electrolyte resistant, electrolyte impermeable, insulating means on facing surfaces of said copper members and substantially coextensive therewith thereby to prevent contact of the copper by electrolyte; and
2. The bipolar electrolyte cell of claim 1 wherein the high electroconductivity, low hydrogen permeability metal member is a copper member.
2. individual insulating means corresponding to and interposed between a pair of said individual conducting means, whereby an individual insulating means is interposed between a pair of adjacent, individual conducting means, and an individual conducting means is interposed between a pair of adjacent, individual insulating means; and
2. INDIVIDUAL INSULTATING MEANS CORRESPONDING TO AND INTERPOSED BETWEEN A PAIR OF SAID INDIVIDUAL CONDUCTING MEANS, WHEREBY AN INDIVIDUAL INSULATING MEANS IS INTERPOSED BETWEEN A PAIR OF ADJACENT, INDIVIDUAL CONDUCTING MEANS AND AN INDIVIDUAL CONDUCTING MEANS IS INTERPOSED BETWEEN A PAIR OF ADJACENT, INDIVIDUAL INSULATING MEANS, SAID INDIVIDUAL INSULATING MEANS COMPRISING A COMPRESSIBLE, ELECTROLYTE RESISTANT, ELECTROLYTE IMPERMEABLE, INSULATING MEANS ON FACING SURFACES OF SAID COPPER MEMBERS AND SUBSTANTIALLY COEXTENSIVE THEREWITH TTHEREBY TO PREVENT CONTACT OF THE COPPER BY ELECTROLYTE, AND
2. THE CATHODES OF A BIPOLAR UNIT ARE INTERLEAVED BETWEEN A PAIR OF ANODES OF A PRIOR BIPOLAR UNIT AND SEPARATED THEREFROM BY THE INSULATING MEANS OF BOTH OF SAID BIPOLAR UNITS.
3. COMPRESSIVE MEANS IMPOSING A COMPRESSIVE FORCE UPON SAID INSULATING MEANS AND SAID CONDUCTING MEANS WHEREBY TO PROVIDE A RIGID BIPOLAR UNIT, SAID COMPRESSIVE MEANS COMPRISING: ELECTRICALLY INSULATIVE BOLT MEANS EXTENDING THROUGH SAID INDIVIDUAL INSULATING MEANS SUBSTANTIALLY COEXTENSIVE WITH AND BEARING UPON MEANS AN EXTERNAL PAIR OF SAID INSULATING MEANS AT THE EXTREME END OF THE BPOLAR UNIT, AND B. SAID BIPOLAR UNITS BEING ARRAYED IN A BIPOLAR CONFIGURATION WHEREIN:
3. compressive means imposing a compressive force upon said insulating means and said conducting means whereby to provide a rigid bipolar unit; B. said bipolar units being arrayed in a bipolar configuration wherein:
3. The bipolar electrolytic cell of claim 1 wherein the acid resistant metal is chosen from the group consisting of titanium, zirconium, hafnium, vanadium, columbium, tantalum, and tungsten.
3. compressive means imposing a compressive force upon said insulating means and said conducting means whereby to provide a rigid bipolar unit, said compressive means comprising: electrically insulative bolt means extending through said individual insulating means and conducting means; and bearing surface means substantially coextensive with and bearing upon an external pair of said insulating means at the extreme end of the bipolar unit; and B. said bipolar units being arrayed in a bipolar configuration wherein:
4. The bipolar electrolytic cell of claim 1 wherein said insulating means include means for maintaining an interelectrode gap between a pair of electrodes adjacent thereto and a pair of electrodes of an adjacent bipolar unit in series therewith.
5. The bipolar electrolytic cell of claim 4 wherein the means for maintaining an interelectrode gap comprise means for mechanically engaging the electrodes of the prior and subsequent bipolar units.
6. The bipolar electrolytic cell of claim 1 wherein said individual insulating means comprise compressible, electrolyte resistant, insulating means on facing surfaces of adjacent individual conducting means.
7. The bipolar electrolytic cell of claim 6 wherein said individual insulating means comprise substantially incompressible, electrolyte resistant, insulating means interposed between a pair of compressible insulating means.
8. The bipolar electrolytic cell of claim 1 wherein said compressive means comprise: electrically insulative bolt means extending through said individual insulating means and conducting means; and bearing surface means substantially coextensive with and bearing upon an external pair of said insulating means at the extreme end of the bipolar unit.
9. The bipolar electrolytic cell of claim 1 wherein said individual insulating means comprise: compressible, electrolyte resistant, electrolyte impermeable, insulating means on facing surfaces of said copper members and substantially coextensive therewith thereby to prevent contact of the high electroconductivity low hydrogen permeability metal member by electrolyte.
10. A BIPOLAR ELECTROLYTIC CELL FOR THE EVOLUTION OF ALKALI METAL CHLORATES COMPRISING: A. PLURALITY OF BIPOLAR UNITS, EACH OF SAID BIPOLAR UNITS COMPRISING:
US420743A 1973-11-30 1973-11-30 Alakali metal chlorate cell having metal bipolar electrodes Expired - Lifetime US3902985A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US420743A US3902985A (en) 1973-11-30 1973-11-30 Alakali metal chlorate cell having metal bipolar electrodes
CA212,727A CA1036540A (en) 1973-11-30 1974-10-31 Alkali metal chlorate cell having metal bipolar electrodes
NO744250A NO145988C (en) 1973-11-30 1974-11-26 BIPOLAR ELECTROLYCLE CELL FOR THE PREPARATION OF ALKALIMETAL CHLORATE
SE7415010A SE410869B (en) 1973-11-30 1974-11-29 BIPOLES ELECTROLYSIS CELL FOR THE PRODUCTION OF ALKALIMETAL CHLORATES

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US420743A US3902985A (en) 1973-11-30 1973-11-30 Alakali metal chlorate cell having metal bipolar electrodes

Publications (1)

Publication Number Publication Date
US3902985A true US3902985A (en) 1975-09-02

Family

ID=23667664

Family Applications (1)

Application Number Title Priority Date Filing Date
US420743A Expired - Lifetime US3902985A (en) 1973-11-30 1973-11-30 Alakali metal chlorate cell having metal bipolar electrodes

Country Status (4)

Country Link
US (1) US3902985A (en)
CA (1) CA1036540A (en)
NO (1) NO145988C (en)
SE (1) SE410869B (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2474534A1 (en) * 1980-01-28 1981-07-31 Pennwalt Corp APPARATUS FOR PRODUCING SODIUM HYPOCHLORITE
US4285786A (en) * 1980-05-09 1981-08-25 Allied Chemical Corporation Apparatus and method of monitoring temperature in a multi-cell electrolyzer
US4302610A (en) * 1980-05-27 1981-11-24 Allied Corporation Vanadium containing niobates and tantalates
US4332659A (en) * 1979-12-17 1982-06-01 Hooker Chemicals & Plastics Corp. Electrolytic apparatus for the manufacture of alkali metal halate
US4332648A (en) * 1979-12-17 1982-06-01 Hooker Chemicals & Plastics Corp. Electrolytic apparatus for the manufacture of alkali metal halate
US4448663A (en) * 1982-07-06 1984-05-15 The Dow Chemical Company Double L-shaped electrode for brine electrolysis cell
US4461692A (en) * 1982-05-26 1984-07-24 Ppg Industries, Inc. Electrolytic cell
EP0144621A2 (en) * 1983-11-24 1985-06-19 Uhde GmbH Electrolytic cell for the electrolysis of an aqueous halogenide electrolyte
US4530742A (en) * 1983-01-26 1985-07-23 Ppg Industries, Inc. Electrode and method of preparing same
US6805787B2 (en) 2001-09-07 2004-10-19 Severn Trent Services-Water Purification Solutions, Inc. Method and system for generating hypochlorite
WO2009010737A2 (en) * 2007-07-18 2009-01-22 Green Metals Limited Calcium ruthenate electrode materials
WO2023150554A3 (en) * 2022-02-01 2023-10-05 Verdagy, Inc. Electrolyzer cell

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225061A (en) * 1991-05-24 1993-07-06 Westerlund Goethe O Bipolar electrode module

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3759813A (en) * 1970-07-17 1973-09-18 Ppg Industries Inc Electrolytic cell
US3759815A (en) * 1970-11-26 1973-09-18 Kema Nord Ab Electrode assembly
US3791947A (en) * 1972-01-26 1974-02-12 Diamond Shamrock Corp Electrolytic cell assemblies and methods of chemical production

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3759813A (en) * 1970-07-17 1973-09-18 Ppg Industries Inc Electrolytic cell
US3759815A (en) * 1970-11-26 1973-09-18 Kema Nord Ab Electrode assembly
US3791947A (en) * 1972-01-26 1974-02-12 Diamond Shamrock Corp Electrolytic cell assemblies and methods of chemical production

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332659A (en) * 1979-12-17 1982-06-01 Hooker Chemicals & Plastics Corp. Electrolytic apparatus for the manufacture of alkali metal halate
US4332648A (en) * 1979-12-17 1982-06-01 Hooker Chemicals & Plastics Corp. Electrolytic apparatus for the manufacture of alkali metal halate
FR2474534A1 (en) * 1980-01-28 1981-07-31 Pennwalt Corp APPARATUS FOR PRODUCING SODIUM HYPOCHLORITE
US4285786A (en) * 1980-05-09 1981-08-25 Allied Chemical Corporation Apparatus and method of monitoring temperature in a multi-cell electrolyzer
US4302610A (en) * 1980-05-27 1981-11-24 Allied Corporation Vanadium containing niobates and tantalates
US4461692A (en) * 1982-05-26 1984-07-24 Ppg Industries, Inc. Electrolytic cell
US4448663A (en) * 1982-07-06 1984-05-15 The Dow Chemical Company Double L-shaped electrode for brine electrolysis cell
US4530742A (en) * 1983-01-26 1985-07-23 Ppg Industries, Inc. Electrode and method of preparing same
EP0144621A3 (en) * 1983-11-24 1985-07-10 Uhde GmbH Electrolytic cell for the electrolysis of an aqueous halogenide electrolyte
EP0144621A2 (en) * 1983-11-24 1985-06-19 Uhde GmbH Electrolytic cell for the electrolysis of an aqueous halogenide electrolyte
US6805787B2 (en) 2001-09-07 2004-10-19 Severn Trent Services-Water Purification Solutions, Inc. Method and system for generating hypochlorite
WO2009010737A2 (en) * 2007-07-18 2009-01-22 Green Metals Limited Calcium ruthenate electrode materials
WO2009010737A3 (en) * 2007-07-18 2009-04-02 Green Metals Ltd Calcium ruthenate electrode materials
US20100282602A1 (en) * 2007-07-18 2010-11-11 Green Metals Limited Electrode materials
US8313624B2 (en) * 2007-07-18 2012-11-20 Green Metals Limited Electrode materials
WO2023150554A3 (en) * 2022-02-01 2023-10-05 Verdagy, Inc. Electrolyzer cell

Also Published As

Publication number Publication date
CA1036540A (en) 1978-08-15
NO145988C (en) 1982-07-07
NO145988B (en) 1982-03-29
NO744250L (en) 1975-06-23
SE7415010L (en) 1975-06-02
SE410869B (en) 1979-11-12

Similar Documents

Publication Publication Date Title
US3976549A (en) Electrolysis method
US3902985A (en) Alakali metal chlorate cell having metal bipolar electrodes
US4210501A (en) Generation of halogens by electrolysis of hydrogen halides in a cell having catalytic electrodes bonded to a solid polymer electrolyte
EP2870277B1 (en) Apparatus and method of producing metal in a nasicon electrolytic cell
US3836448A (en) Frames for electrolytic cells of the filter-press type
EP0507862A4 (en) Electrochemical chlorine dioxide generator
DE2656110A1 (en) BIPOLAR ELECTRODE FOR FILTER PRESS ELECTROLYSIS CELLS AND PROCESS FOR THEIR PRODUCTION
JPS5949318B2 (en) Electrolytic production method of alkali metal hypohalite salt
GB2054651A (en) Electrolytic cell
US3791947A (en) Electrolytic cell assemblies and methods of chemical production
US4464243A (en) Electrode for use in electrolytic cell
US3948750A (en) Hollow bipolar electrode
US4853096A (en) Production of chlorine dioxide in an electrolytic cell
US4311567A (en) Treatment of permionic membrane
US4059495A (en) Method of electrolyte feeding and recirculation in an electrolysis cell
US3930980A (en) Electrolysis cell
US3884791A (en) Electrolytic cell having metal electrodes
JPH03199387A (en) Manufacture of alkali metal chlorate or perchlorate
US5225061A (en) Bipolar electrode module
GB1572646A (en) Preventing or substantially reducing corrosion of cell parts in electrolysis
US4088551A (en) Electrolytic cell and method of electrolysis
US3984304A (en) Electrode unit
US4269675A (en) Electrolyte series flow in electrolytic chlor-alkali cells
US4161438A (en) Electrolysis cell
EP0328818B1 (en) Production of chlorine dioxide in an electrolytic cell