US3898149A - Electrolytic diaphragm cell - Google Patents

Electrolytic diaphragm cell Download PDF

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Publication number
US3898149A
US3898149A US411327A US41132773A US3898149A US 3898149 A US3898149 A US 3898149A US 411327 A US411327 A US 411327A US 41132773 A US41132773 A US 41132773A US 3898149 A US3898149 A US 3898149A
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Prior art keywords
cell
anode
plate
cathode
cell body
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US411327A
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Morton S Kircher
Elmer N Macken
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Olin Corp
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Olin Corp
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Priority to US411327A priority Critical patent/US3898149A/en
Priority to CA211,282A priority patent/CA1040135A/en
Priority to ZA00746500A priority patent/ZA746500B/en
Priority to AU74331/74A priority patent/AU489474B2/en
Priority to GB4626574A priority patent/GB1428087A/en
Priority to BR8968/74A priority patent/BR7408968A/en
Priority to JP12531174A priority patent/JPS5328261B2/ja
Priority to ES431521A priority patent/ES431521A1/en
Priority to FR7436275A priority patent/FR2249975B1/fr
Priority to IT53822/74A priority patent/IT1021999B/en
Priority to DE19742451868 priority patent/DE2451868A1/en
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Publication of US3898149A publication Critical patent/US3898149A/en
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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
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/34Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • 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

Definitions

  • ABSTRACT A diaphragm cell for the electrolysis of aqueous salt solutions in which the cylindrical horizontal cell body is supported at one end by the cathode plate and at the opposite end by the anode plate. At least one anode and at least one cathode are attached to their respective plates in a manner which permits brine to encircle and pass between the electrodes.
  • the cell body may be constructed of a light-weight material such as fiber reinforced plastic. Entry to the cell is facilitated by the horizontal arrangement. The resulting diaphragm cell permits a considerable savings in material and construction costs, reduces cell weight while providing improved brine circulation within the cell.
  • Diaphragm-type electrolytic cells are widely used in industry, particularly in the production of chlorine and caustic soda by the electrolysis of sodium chloride brines. Most of these commercial cells consist of a rectangular structure having a top section and a bottom section.
  • the cell bodies are constructed of heavy, loadbearing materials such as cement or concrete with the anode mounted vertically in the bottom section.
  • the anode is attached to metallic conductors and secured by a layer oflead which is in turn covered by a layer of cement.
  • the cathode is mounted in the top section or on a side wall.
  • the cell body has been constructed of a load-bearing material such as concrete.
  • Brine circulation in diaphragm cells of the prior art has been restricted generally to flowing on top of or below and between the electrode sections. Brine has not been free to circulate completely around the electrodes.
  • Another object of the invention is to provide a diaphragm cell having a cathode attached to a conductive end wall and an anode attached to an opposite conducting end wall.
  • a further object of the invention is a diaphragm cell having improved electrolyte circulation.
  • Yet another object of the present invention is to provide a diaphragm cell wherein the cell body is supported by the conductive end walls.
  • An additional object of this invention is to provide a horizontal diaphragm cell having entries to the cell body thru the ends.
  • a still further object of the invention is to provide a horizontal diaphragm cell having a shorter and more direct current path through the cell and between adjacent cells.
  • an electrolytic diaphragm cell comprised of a horizontal cell body having opposite and substantially parallel ends, having a first opening at one end of the cell body and a second opening at the opposite end of the cell body.
  • An electroconductive cathode plate is sealingly attached to the cell body and covers the first opening.
  • the cathode support has at least one cathode attached to the inner surface of the cathode plate.
  • An electroconductivc anode plate is sealingly attached to the cell body and covers the second opening.
  • the anode plate has at least one anode attached to the inner surface of the anode plate.
  • the cathode plate and the anode plate support the cell body.
  • FIGS. 1-6 illustrate the novel cell of the present invention. Corresponding parts have the same numbers in all FIGS.
  • FIG. 1 illustrates a side view of one embodiment of the diaphragm cell of the present invention.
  • FIG. 2 shows a partially sectioned top view of the diaphragm cell of FIG. 1.
  • FIG. 3 depicts an end view of the diaphragm cell of FIG. 1 showing the cathode plate.
  • FIG. 4 is a top view of the cathode section of the diaphragm cell of FIG. 1.
  • FIG. 5 illustrates a top view of the anodesection of the diaphragm cell of FIG. 1.
  • FIG. 6 is a cross sectional view of the diaphragm cell of FIG. 1 taken along lines 6-6.
  • FIGS. l-6 when used to electrolyze aqueous solutions of alkali metal halides form halogen gas, hydrogen gas and an alkali metal hydroxide liquor.
  • halogen gas hydrogen gas
  • alkali metal hydroxide liquor an alkali metal hydroxide liquor
  • FIG. 1 is a side view of one embodiment of the invention illustrating diaphragm cell A having ,a horizontal generally cylindrical cell body I and having flanges 2 and 3 surrounding each opening at the ends of cell body 1.
  • Anode plate 4 is attached to flange 2 at one end of cell body 1 and cathode plate 5 is attached to flange 3 at the other end of cell body 1.
  • Gas kets 6 and 7 seal anode plate 4 to flange 2 and cathode plate 5 to flange 3, respectively.
  • aqueous alkali metal halide solution to be electrolyzed enters thru brine inlet 12 housed in cell body 1.
  • Halogen gas is removed through halogen outlet 10, and hydrogen gas is removed through outlet 11.
  • Electric current is introduced to the cell through conductor 13 attached to anode plate 4.
  • Current is removed from the cell at conductor 14 attached to cathode plate 5.
  • Cathode plate 5 and anode plate 4 support the weight of cell body 1.
  • Anode plate supports 8 bear the weight of anode plate 4 and cathode plate supports 9 uphold cathode plate 5.
  • Anode plate supports 8 and cathode plate supports 9 are bolted or otherwise attached to insulators 23 resting on platforms 24.
  • Drain l5 permits the contents of the cell to be removed. Lugs 16 and 17 aid in the removal of conductive anode plate 4 and conductive cathode plate 5, respectively.
  • FIG. 2 depicts a partially sectioned top view of diaphragm cell A of the present invention.
  • Anodes 21 are attached to anode plate 4 and project across the cell toward cathode plate 5.
  • Cathodes 22 are attached to cathode plate 5 and project across the cell towards anode plate 4.
  • Cathodes 22 support a diaphragm (not shown) of the type described more fully below.
  • Anodes 21 are inserted within the spaces between adjacent cathodes 22.
  • Conductors 13 and 14 have a series of holes permitting these conductors to be attached to conductors on adjacent cells, for example, with bolts.
  • FIG. 3 shows an end view partially sectioned of diaphragm cell A of the present invention.
  • Cathode plate 5 is attached to cell body 1 (not shown) by a series of bolts 25 spaced equidistantly around the periphery.
  • Cathode plate supports 9 provide support for cathode plate 5.
  • Cathodes 22 are attached to and spaced apart from the outer edges of cathode plate 5.
  • Conductor l4 removes current from cathode plate 5.
  • An aqueous alkali metal halide solution is introduced into the cell thru brine inlet 12. Hydrogen gas produced during electrolysis is removed thru hydrogen outlet 11 and the alkali metal hydroxide liquor produced is removed through outlet 20.
  • cathode section 28 of diaphragm cell A A top view of cathode section 28 of diaphragm cell A is depicted in HO. 4.
  • Cathodes 22 are comprised of a conductive element 26 attached to and providing support for the surrounding screen 27. Cathodes 22 are attached to cathode plate 5, being parallel to and separated from each other to form cathode section 28. Cathode section 28 is spaced apart from the perimeter of cathode plate to permit brine to encircle the cathode section.
  • FIG. 5 is a top view of anode section 29 of diaphragm cell A.
  • Anodes 21 are attached to anode plate 4 and are parallel to and separated from each other to form anode section 29.
  • Anode section 29 is spaced apart from the perimeter of anode plate 4 to permit brine to encircle the anode section.
  • FIG. 6 shows a cross-sectional view taken along lines 6-6 of FIG. 1.
  • Anode plate 4 has a plurality of anodes 21 attached to form anode section 29.
  • Cathodes 22, attached to cathode plate 5 (not shown) are arranged so that an anode is inserted between and is substantially equidistant from each adjacent cathode.
  • Anode section 29 is spaced apart from the perimeter of anode plate 4 to permit electrolyte to encircle the anode section.
  • the horizontal cell body of the electrolytic diaphragm cell of the present invention may be of any convenient configuration, for example, it may be rectangular, cylindrical or elliptical. Preferably, it is generally cylindrical or elliptical.
  • the cell body may be constructed of a variety of materials, such as, fiber reinforced plastic, hard rubber, steel, hard rubber-lined steel, titanium, asbestos reinforced plastic or concrete.
  • the cell body comprises a cylindrical shell of fiber reinforced plastic wherein the fiber is, for example, fiberglass and the plasticis, for example, a polyester or epoxy resin.
  • a cell body of this type can be fabricated easily, for example, on a mandrel using filament winding techniques to form a cell body having reduced weight and having high body strength.
  • Additional embodiments may comprise a shell of steel or concrete lined with a protective coating such as rubber, ceramic tile composites, plastics reinforced with asbestos, carbon, silica, or glass flakes, or polyhaloolefin plastics such as polytetrafluoroethylene or polychlorotrifluoroethylene.
  • a protective coating such as rubber, ceramic tile composites, plastics reinforced with asbestos, carbon, silica, or glass flakes, or polyhaloolefin plastics such as polytetrafluoroethylene or polychlorotrifluoroethylene.
  • the cell body may be of any convenient height.
  • a cell body of from about 1 to about 15, and preferably from about 4 to about 12 feet may be employed.
  • the cell body may have a flange surrounding the opening at each end.
  • the anode plate attached to one end of the cell body is wholly or partially constructed of an electroconductive material such as steel, copper, aluminum, titanium or combinations of these materials.
  • an electroconductive material such as steel, copper, aluminum, titanium or combinations of these materials.
  • the electroconductive material can be attacked by the solution or gases in the cell it can be covered, for example, with rubber, a chemically inert plastic such as polytetrafluoroethylene or fiber reinforced plastic or a metal such as titanium or tantalum.
  • the anode plate is composed of steel which is lined with rubber on the inner surface.
  • the steel serves both as an electroconductor and a structural material which has sufficient strength to support the cell body without requiring an excessive mass of material.
  • the anode support plate is attached at one opening of the cell body by any convenient attachment means such as bolts, tie rods or clamps.
  • a series of bolts are used in one embodiment of the present invention to attach the anode plate to the cell body.
  • the bolts placed around the periphery of the plate, facilitate the uniform allignment of anodes when the cell is assembled.
  • the anode plate supports at least one anode.
  • Anodes suitable for use in this invention are composed of graphite, a valve metal such as titanium or tantalum, or a metal, for example, steel, copper or aluminum clad with a valve metal such as tantalum or titanium.
  • the valve metal has a thin coating over a least part of its surface of platinum group metal, platinum group metal oxide, an alloy of a platinum group metal or a mixture thereof.
  • platinum group metal as used in the specification means an element of the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • Anodes can be made in various forms, for example, solid sheets, perforated plates and in the case of conductive metal, as expanded metal or screen.
  • the anodes are attached to the anode support plate by bolting, welding, soldering, or the like.
  • the anodes employed may be any convenient size, for example, from about 1 to about 12, and preferably from about 2 to about 1() feet in height; from about I to about 6, and preferably, from about 2 to about 5 feet in length; and from about 0.05 to about 1.00, and preferably from about 0.l to about 0.8 inches thick.
  • a plurality of anodes are attached to the anode plate, the exact number depending on the size of the anode plate.
  • anodes are attached to the anode plate and constitute the anode section.
  • the anodes are positioned parallel to and separated from each other on the anode plate.
  • the anode section is attached to the anode plate in such a manner that it is spaced apart from the perimeter of the anode plate, as illustrated in FIG. 6. This arrangement permits brine to flow completely around the anode section as well as up through the spaces between the anodes.
  • the cathode plate is composed wholly or partly of an electroconductive material, for example, steel or copper or combinations of these materials. To avoid corrosive damage the cathode plate may be covered, for example, with hard rubber, a plastic such as polytetrafluoroethylene or fiber reinforced plastic.
  • a preferred embodiment is a cathode plate composed of hard rubber lined steel.
  • the steel serves both as an electroconductive metal and a structural material able to support the cell body without requiring an excessive mass of material.
  • the use of steel is economic as it can. if desired, eliminate entirely the requirement for more expensive conductors such as copper.
  • the cathode plate is sealingly attached at one opening of the cell body in anyconvenient manner, for example.
  • the cathode plate is attached to the cell body by a series of bolts spaced around the periphery of the plate. The bolts assure an accurate and simplified alignment of the cathodes when the cell is assembled.
  • a plurality of cathodes are attached to the cathode plate, the exact numer depending on the size of the cathode plate.
  • the diaphragm cell of the present invention for example, from about 2 to about 100 or more and preferably from about 5 to about 50 cathodes constitute the cathode section.
  • the cathodes are positioned parallel to and separated from each other on the cathode plate.
  • the cathodes are foraminous projections extending across the cell body toward the anode support plate.
  • a single cathode comprises a conductive element surrounded by a conductive screen or mesh.
  • the conductive element may be, for example, in the form of a plate or rod with attachment means for the screen or mesh.
  • the conductive element is a steel plate having projections at spaced intervals along the plate.
  • the projections are attached to the cathode screen to provide support and to supply current to the cathode screen.
  • the projections may be made, for example, by punching or stamping the conductive plate.
  • Cathodes are attached to the cathode plate by any suitable means, for example, by welding or bolting.
  • the cathodes may be of any convenient size, for example, from about 1 to about 12, and preferably from about 2 to about feet in height; from about I to about 6 and preferably from about 2 to about 5 feet in length; and from about 0.5 to about 2.0 and preferably from about 0.8 to about 1.5 inches thick.
  • the anode and cathode plates support the weight of the cell body.
  • the anode and cathode plates may support the cell body directly by having a perimeter larger than that of the cell body whereby the weight of the cell rests directly on the anode and cathode plates.
  • the anode and cathode plates are each attached at the lower edge to at least one support, for example, a bracket, brace, or strut.
  • the anode and cathode plate supports are suitably insulated to prevent current loss.
  • any conventional inert diaphragm material is applied or deposited on the cathodes.
  • the diaphragm material which can be used to cover the screen or foraminous portion of the cathode is a fluid-permeable and halogen-resistant material.
  • the material is asbestos fiber deposited on the outer surfaces of the cathode screen by the application of suction to an asbestos fiber slurry.
  • Other diaphragm materials such as polyvinylidene chloride, polypropylene, or polytetrafluoroethylene may also be used.
  • the cathode structure is adapted to permit the use of all types of diaphragms including sheet asbestos, deposited asbestos and synthetics which can be in the form of woven fabrics, for example. polyethylene, polypropylene 0r polytetrafluoroethylene.
  • the cathode section is positioned so that the cathodes project across the cell body in the direction of the anode support plate.
  • the anode section is oppositely positioned such that the anodes project across the cell towards the cathode plate, with the anodes being inserted between adjacent cathodes.
  • the distance between an anode and the adjacent cathode is normally between about one-eighth to about three-eighths of an inch.
  • the diaphragm cell of the present invention may utilize anode and cathode plates of variable height.
  • anode and cathode plates of from about 1 to about 15 and preferably from about 4 to about 12 feet high may be employed.
  • Increasing the height of the diaphragm cell permits a considerable reduction in the floor space required to produce a given quantity of product.
  • an aqueous salt solution for example, an alkali metal chloride such as sodium chloride or potassium chloride
  • the alkali metal chloride solution is introduced into the cell as a brine stream of any desired concentration.
  • the brine level within the cell is brought to a point above the anode and cathode sections within the cell.
  • the hydrostatic head or pressure exerted upon the diaphragm covering the cathodes is varied, thereby varying the flow of electrolyte through the diaphragm into the cathode chamber.
  • the height of the brine above the anode and cathode sections is from about 3 to about 15 or more inches.
  • the anode and cathode sections are spaced apart from the perimeter of their respective plates to provide greatly improved brine circulation within the cell.
  • the anode and cathode sections are centered laterally. They are positioned vertically such that an adequate brine height and gas release space is provided above the anode and cathode section.
  • the space above the electrode sections permits a free release of gas produced in the anode. Without being bound by theory, it is believed that when chlorine gas forms at the anodes and rises, it creates a gas lift action directed vertically along the face of the anodes.
  • This gas lift action draws fresh brine from below the electrode sections, with the fresh brine then flowing upward along the anodes into the region above the anodes, at which point chlorine gas leaves the brine.
  • a diaphragm cell as illustrated in FIGS. l-6, was comprised of a horizontal cylindrical cell body composed of glass fiber reinforced polyester resin and having an outside diameter of about 92 inches. A flange surrounded the openings at each end of the cell body. At one end of the cell a cathode plate was bolted to the flange of the cell body. The cathode plate, composed of mild steel and covered with rubber on the inside face, had an outside diameter of about 96 inches.
  • cathode section was comprised of 27 cathodes, each cathode being welded to the cathode face.
  • a cathode included a steel plate having a series of projections to which a steel screen was attached. Deposited on the screen was an asbestos fiber diaphragm.
  • the cathodes were about 36 inches long, inches high, and 1.125 inches thick and were spaced at a distance of 2.5 inches between centers.
  • the cathode section was spaced at a distance of about 33 inches from the upper and lower perimeters and about 14 inches from the lateral perimeters of the cathode plate.
  • an anode plate was bolted to the flange.
  • the anode plate was about 96 inches in diameter and was composed of mild steel with the inside face being covered with rubber.
  • the anode section had 28 anodes soldered to the anode plate.
  • Each anode was composed of titanium-clad steel and had a portion of its surface coated with a ruthenium oxide.
  • the anodes were about 36 inches long, 30 inches high and 0.18 inch thick and spaced apart 2.5 inches between centers.
  • the anode section was spaced at a distance of about 33 inches from the upper and lower perimeters and about 14 inches from the lateral perimeters of the anode plate.
  • the cathode plate and the anode plate were each externally supported by a steel bracket welded to the plate. The cathode and anode plates supported the weight of the cell body.
  • An aqueous solution containing 300 grams per liter of sodium chloride at a temperature of about 60-70C. was introduced into the cell body thru the brine inlet in the cathode plate.
  • the cell operated at a current of 76 kiloamperes and a voltage of 3.78 to electrolyze the salt solution to produce chlorine, hydrogen and sodium hydroxide.
  • the catholyte liquor obtained had a sodium hydroxide concentration of about 125 grams per liter.
  • the chlorine gas obtained had a hydrogen content of 0.3 percent. Over a period of 106 hours, the cell was operated at a current efficiency of 97 percent, based on chlorine production.
  • An electrolytic diaphragm cell comprised of a. a horizontal cell body having opposite and substantially parallel ends, having a first opening at one end of said cell body and a second opening at the opposite end of said cell body;
  • an electroconductive cathode plate sealingly attached to said cell body and covering said first opening, said cathode plate having at least one cathode attached to the inner surface of said cathode plate;
  • an electroconductive anode plate sealingly attached to said cell body and covering said second opening, said anode plate having at least one anode attached to the inner surface of said anode plate;
  • said cathode plate and said anode plate providing the sole means of support for said cell body.
  • the electrolytic diaphragm cell of claim 4 in which said shell has a lining material selected from the group consisting of fiber reinforced plastic, rubber, asbestos reinforced plastic, ceramic tile composites, polytetrafluoroethylene, or polychlorotrifluoroethylene.
  • said anode is a valve metal selected from the group consisting of titanium or tantalum having at least part of its surface coated with a coating selected from the group consisting of a platinum metal, platinum metal oxide, platinum metal alloy or mixtures thereof.
  • An electrolytic diaphragm cell for the electrolysis of aqueous alkali metal chloride solutions comprised of:
  • an electroconductive cathode plate sealingly attached to said cell body and covering said first opening, said cathode plate having a perimeter greater than that of said cell body, said cathode plate having a cathode section attached to the inner surface of said cathode plate, said cathode section comprising a plurality of cathodes, said cathode section being spaced apart from said perimeter of said cathode plate;
  • an electroconductive anode plate sealingly attached to said cell body and covering said second opening, said anode plate having a perimeter greater than that of said cell body, said anode plate having an anode section attached to the inner surface of said anode plate, said anode section comprising a plurality of anodes, said anode section being spaced apart from said perimeter of said anode plate; and H d. said cathode plate and said anodeplate providing sole means for supporting said cell body.

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Abstract

A diaphragm cell for the electrolysis of aqueous salt solutions in which the cylindrical horizontal cell body is supported at one end by the cathode plate and at the opposite end by the anode plate. At least one anode and at least one cathode are attached to their respective plates in a manner which permits brine to encircle and pass between the electrodes. The cell body may be constructed of a light-weight material such as fiber reinforced plastic. Entry to the cell is facilitated by the horizontal arrangement. The resulting diaphragm cell permits a considerable savings in material and construction costs, reduces cell weight while providing improved brine circulation within the cell.

Description

United States Patent Kircher et al.
Aug. 5, 1975 Assignee:
Filed:
Canada; Elmer N. Macken, Stamford, Conn.
Olin Corporation, New Haven,
Conn.
Oct. 31, 1973 Appl. No.: 411,327
Primary E.\'aminerl-loward S. Williams Assistant Examiner-W. 1. Solomon Attorney, Agent, or Firm.lames B. l-laglind; Donald F. Clements; T. P. ODay [57] ABSTRACT A diaphragm cell for the electrolysis of aqueous salt solutions in which the cylindrical horizontal cell body is supported at one end by the cathode plate and at the opposite end by the anode plate. At least one anode and at least one cathode are attached to their respective plates in a manner which permits brine to encircle and pass between the electrodes.
The cell body may be constructed of a light-weight material such as fiber reinforced plastic. Entry to the cell is facilitated by the horizontal arrangement. The resulting diaphragm cell permits a considerable savings in material and construction costs, reduces cell weight while providing improved brine circulation within the cell.
16 Claims, 6 Drawing Figures [52] US. Cl. 204/252; 204/266; 204/286 [51] Int. Cl B0lk 3/10 [58] Field of Search 204/252, 266, 286
[56] References Cited UNITED STATES PATENTS 3,133,872 5/1964 Miller et a1 204/290 F X 3,477,938 11/1969 Kircher 204/266 3.679.568 7/1972 Westerlund 204/256 X 3,755,108 8/1973 Raetzsch et al.. 204/256 X 3.761.385 9/1973 Ruthel et a1 204/290 F 1 II l SHEET PATENTED 5|975 PATENTEU AUB 51975 SHEET ELECTROLYTIC DIAPHRAGM CELL This invention relates to electrolytic cells for the electrolysis of aqueous salt solutions. More particularly this invention relates to diaphragm type electrolytic cells for the electrolysis of aqueous alkali metal chlo ride solutions.
Diaphragm-type electrolytic cells are widely used in industry, particularly in the production of chlorine and caustic soda by the electrolysis of sodium chloride brines. Most of these commercial cells consist ofa rectangular structure having a top section and a bottom section. The cell bodies are constructed of heavy, loadbearing materials such as cement or concrete with the anode mounted vertically in the bottom section. The anode is attached to metallic conductors and secured by a layer oflead which is in turn covered by a layer of cement. The cathode is mounted in the top section or on a side wall.
In diaphragm cells where the anode has been mounted in a side wall, as for example in US. Pat. Nos. 3,477,938 or 3,247,090, the cell body has been constructed of a load-bearing material such as concrete.
Brine circulation in diaphragm cells of the prior art has been restricted generally to flowing on top of or below and between the electrode sections. Brine has not been free to circulate completely around the electrodes.
Therefore, there is a need for a diaphragm electrolytic cell which can be fabricated from light-weight materials of construction giving significant reduction in cost. In addition, there is need for a diaphragm electrolytic cell having improved electrolyte circulation which permits brine circulation completely around and thru the electrode section.
It is an object of the present invention to provide a diaphragm cell which can be readily fabricated at a reduced cost and having reduced weight.
Another object of the invention is to provide a diaphragm cell having a cathode attached to a conductive end wall and an anode attached to an opposite conducting end wall.
A further object of the invention is a diaphragm cell having improved electrolyte circulation.
Yet another object of the present invention is to provide a diaphragm cell wherein the cell body is supported by the conductive end walls.
An additional object of this invention is to provide a horizontal diaphragm cell having entries to the cell body thru the ends.
A still further object of the invention is to provide a horizontal diaphragm cell having a shorter and more direct current path through the cell and between adjacent cells.
These and other objects of the invention are accomplished in an electrolytic diaphragm cell comprised of a horizontal cell body having opposite and substantially parallel ends, having a first opening at one end of the cell body and a second opening at the opposite end of the cell body. An electroconductive cathode plate is sealingly attached to the cell body and covers the first opening. The cathode support has at least one cathode attached to the inner surface of the cathode plate.
An electroconductivc anode plate is sealingly attached to the cell body and covers the second opening. The anode plate has at least one anode attached to the inner surface of the anode plate. The cathode plate and the anode plate support the cell body.
Accompanying FIGS. 1-6 illustrate the novel cell of the present invention. Corresponding parts have the same numbers in all FIGS.
FIG. 1 illustrates a side view of one embodiment of the diaphragm cell of the present invention.
FIG. 2 shows a partially sectioned top view of the diaphragm cell of FIG. 1.
FIG. 3 depicts an end view of the diaphragm cell of FIG. 1 showing the cathode plate.
FIG. 4 is a top view of the cathode section of the diaphragm cell of FIG. 1.
FIG. 5 illustrates a top view of the anodesection of the diaphragm cell of FIG. 1.
FIG. 6 is a cross sectional view of the diaphragm cell of FIG. 1 taken along lines 6-6.
Apparatus described in FIGS. l-6 when used to electrolyze aqueous solutions of alkali metal halides form halogen gas, hydrogen gas and an alkali metal hydroxide liquor. However, those skilled in the art will recognize that modifications can be made for the use of other starting materials to produce other products.
More in detail, FIG. 1 is a side view of one embodiment of the invention illustrating diaphragm cell A having ,a horizontal generally cylindrical cell body I and having flanges 2 and 3 surrounding each opening at the ends of cell body 1. Anode plate 4 is attached to flange 2 at one end of cell body 1 and cathode plate 5 is attached to flange 3 at the other end of cell body 1. Gas kets 6 and 7 seal anode plate 4 to flange 2 and cathode plate 5 to flange 3, respectively.
An aqueous alkali metal halide solution to be electrolyzed enters thru brine inlet 12 housed in cell body 1. Halogen gas is removed through halogen outlet 10, and hydrogen gas is removed through outlet 11. Electric current is introduced to the cell through conductor 13 attached to anode plate 4. Current is removed from the cell at conductor 14 attached to cathode plate 5.
Cathode plate 5 and anode plate 4 support the weight of cell body 1. Anode plate supports 8 bear the weight of anode plate 4 and cathode plate supports 9 uphold cathode plate 5. Anode plate supports 8 and cathode plate supports 9 are bolted or otherwise attached to insulators 23 resting on platforms 24.
Drain l5 permits the contents of the cell to be removed. Lugs 16 and 17 aid in the removal of conductive anode plate 4 and conductive cathode plate 5, respectively.
FIG. 2 depicts a partially sectioned top view of diaphragm cell A of the present invention. Anodes 21 are attached to anode plate 4 and project across the cell toward cathode plate 5. Cathodes 22 are attached to cathode plate 5 and project across the cell towards anode plate 4. Cathodes 22 support a diaphragm (not shown) of the type described more fully below. Anodes 21 are inserted within the spaces between adjacent cathodes 22. Current enters the cell thru conductor 13 andflows thru anode plate 4, thru anodes 21 attached, thru the electrolyte between anodes 21 and cathodes 22 and thru cathodes 22 to cathode plate 5. Current leaves the -cell thru conductor 14 attached to cathode plate 5. Thus, the current passes thru the cell in a short and direct path. Conductors 13 and 14 have a series of holes permitting these conductors to be attached to conductors on adjacent cells, for example, with bolts.
FIG. 3 shows an end view partially sectioned of diaphragm cell A of the present invention. Cathode plate 5 is attached to cell body 1 (not shown) by a series of bolts 25 spaced equidistantly around the periphery. Cathode plate supports 9 provide support for cathode plate 5. Cathodes 22 are attached to and spaced apart from the outer edges of cathode plate 5. Conductor l4 removes current from cathode plate 5. An aqueous alkali metal halide solution is introduced into the cell thru brine inlet 12. Hydrogen gas produced during electrolysis is removed thru hydrogen outlet 11 and the alkali metal hydroxide liquor produced is removed through outlet 20.
A top view of cathode section 28 of diaphragm cell A is depicted in HO. 4. Cathodes 22 are comprised of a conductive element 26 attached to and providing support for the surrounding screen 27. Cathodes 22 are attached to cathode plate 5, being parallel to and separated from each other to form cathode section 28. Cathode section 28 is spaced apart from the perimeter of cathode plate to permit brine to encircle the cathode section.
FIG. 5 is a top view of anode section 29 of diaphragm cell A. Anodes 21 are attached to anode plate 4 and are parallel to and separated from each other to form anode section 29. Anode section 29 is spaced apart from the perimeter of anode plate 4 to permit brine to encircle the anode section.
FIG. 6 shows a cross-sectional view taken along lines 6-6 of FIG. 1. Anode plate 4 has a plurality of anodes 21 attached to form anode section 29. Cathodes 22, attached to cathode plate 5 (not shown) are arranged so that an anode is inserted between and is substantially equidistant from each adjacent cathode. Anode section 29 is spaced apart from the perimeter of anode plate 4 to permit electrolyte to encircle the anode section.
The horizontal cell body of the electrolytic diaphragm cell of the present invention may be of any convenient configuration, for example, it may be rectangular, cylindrical or elliptical. Preferably, it is generally cylindrical or elliptical. The cell body may be constructed of a variety of materials, such as, fiber reinforced plastic, hard rubber, steel, hard rubber-lined steel, titanium, asbestos reinforced plastic or concrete. In one embodiment the cell body comprises a cylindrical shell of fiber reinforced plastic wherein the fiber is, for example, fiberglass and the plasticis, for example, a polyester or epoxy resin. A cell body of this type can be fabricated easily, for example, on a mandrel using filament winding techniques to form a cell body having reduced weight and having high body strength. Additional embodiments may comprise a shell of steel or concrete lined with a protective coating such as rubber, ceramic tile composites, plastics reinforced with asbestos, carbon, silica, or glass flakes, or polyhaloolefin plastics such as polytetrafluoroethylene or polychlorotrifluoroethylene.
The cell body may be of any convenient height. For example, a cell body of from about 1 to about 15, and preferably from about 4 to about 12 feet may be employed. To facilitate attachment of the electrode plates, the cell body may have a flange surrounding the opening at each end.
The anode plate attached to one end of the cell body, is wholly or partially constructed of an electroconductive material such as steel, copper, aluminum, titanium or combinations of these materials. Where the electroconductive material can be attacked by the solution or gases in the cell it can be covered, for example, with rubber, a chemically inert plastic such as polytetrafluoroethylene or fiber reinforced plastic or a metal such as titanium or tantalum.
In a preferred embodiment, the anode plate is composed of steel which is lined with rubber on the inner surface. The steel serves both as an electroconductor and a structural material which has sufficient strength to support the cell body without requiring an excessive mass of material.
The anode support plate is attached at one opening of the cell body by any convenient attachment means such as bolts, tie rods or clamps.
A series of bolts are used in one embodiment of the present invention to attach the anode plate to the cell body. The bolts, placed around the periphery of the plate, facilitate the uniform allignment of anodes when the cell is assembled. The anode plate supports at least one anode.
Anodes suitable for use in this invention are composed of graphite, a valve metal such as titanium or tantalum, or a metal, for example, steel, copper or aluminum clad with a valve metal such as tantalum or titanium. The valve metal has a thin coating over a least part of its surface of platinum group metal, platinum group metal oxide, an alloy of a platinum group metal or a mixture thereof. The term platinum group metal" as used in the specification means an element of the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum.
Anodes can be made in various forms, for example, solid sheets, perforated plates and in the case of conductive metal, as expanded metal or screen. The anodes are attached to the anode support plate by bolting, welding, soldering, or the like.
The anodes employed may be any convenient size, for example, from about 1 to about 12, and preferably from about 2 to about 1() feet in height; from about I to about 6, and preferably, from about 2 to about 5 feet in length; and from about 0.05 to about 1.00, and preferably from about 0.l to about 0.8 inches thick.
A plurality of anodes are attached to the anode plate, the exact number depending on the size of the anode plate. In the diaphragm cell of the present invention, for example. from about 2 to about or more, and preferably from about 5 to about 50 anodes are attached to the anode plate and constitute the anode section. The anodes are positioned parallel to and separated from each other on the anode plate. The anode section is attached to the anode plate in such a manner that it is spaced apart from the perimeter of the anode plate, as illustrated in FIG. 6. This arrangement permits brine to flow completely around the anode section as well as up through the spaces between the anodes.
The cathode plate is composed wholly or partly of an electroconductive material, for example, steel or copper or combinations of these materials. To avoid corrosive damage the cathode plate may be covered, for example, with hard rubber, a plastic such as polytetrafluoroethylene or fiber reinforced plastic.
A preferred embodiment is a cathode plate composed of hard rubber lined steel. The steel serves both as an electroconductive metal and a structural material able to support the cell body without requiring an excessive mass of material. The use of steel is economic as it can. if desired, eliminate entirely the requirement for more expensive conductors such as copper. The cathode plate is sealingly attached at one opening of the cell body in anyconvenient manner, for example.
by bolts, tie rods or clamps. in one embodiment, the cathode plate is attached to the cell body by a series of bolts spaced around the periphery of the plate. The bolts assure an accurate and simplified alignment of the cathodes when the cell is assembled.
A plurality of cathodes are attached to the cathode plate, the exact numer depending on the size of the cathode plate. In the diaphragm cell of the present invention, for example, from about 2 to about 100 or more and preferably from about 5 to about 50 cathodes constitute the cathode section. The cathodes are positioned parallel to and separated from each other on the cathode plate.
The cathodes are foraminous projections extending across the cell body toward the anode support plate. A single cathode comprises a conductive element surrounded by a conductive screen or mesh. The conductive element may be, for example, in the form of a plate or rod with attachment means for the screen or mesh. In one embodiment of the diaphragm electrolytic cell of the present invention, the conductive element is a steel plate having projections at spaced intervals along the plate. The projections are attached to the cathode screen to provide support and to supply current to the cathode screen. The projections may be made, for example, by punching or stamping the conductive plate. Cathodes are attached to the cathode plate by any suitable means, for example, by welding or bolting.
The cathodes may be of any convenient size, for example, from about 1 to about 12, and preferably from about 2 to about feet in height; from about I to about 6 and preferably from about 2 to about 5 feet in length; and from about 0.5 to about 2.0 and preferably from about 0.8 to about 1.5 inches thick.
In the diaphragm cell of the present invention, the anode and cathode plates support the weight of the cell body. The anode and cathode plates may support the cell body directly by having a perimeter larger than that of the cell body whereby the weight of the cell rests directly on the anode and cathode plates. In another embodiment, the anode and cathode plates are each attached at the lower edge to at least one support, for example, a bracket, brace, or strut. The anode and cathode plate supports are suitably insulated to prevent current loss.
In the use of the present apparatus as a diaphragm cell, any conventional inert diaphragm material is applied or deposited on the cathodes. The diaphragm material which can be used to cover the screen or foraminous portion of the cathode is a fluid-permeable and halogen-resistant material. Preferably the material is asbestos fiber deposited on the outer surfaces of the cathode screen by the application of suction to an asbestos fiber slurry. Other diaphragm materials such as polyvinylidene chloride, polypropylene, or polytetrafluoroethylene may also be used. The cathode structure is adapted to permit the use of all types of diaphragms including sheet asbestos, deposited asbestos and synthetics which can be in the form of woven fabrics, for example. polyethylene, polypropylene 0r polytetrafluoroethylene.
In the assembled diaphragm cell of the present invention. the cathode section is positioned so that the cathodes project across the cell body in the direction of the anode support plate. The anode section is oppositely positioned such that the anodes project across the cell towards the cathode plate, with the anodes being inserted between adjacent cathodes. The distance between an anode and the adjacent cathode is normally between about one-eighth to about three-eighths of an inch.
The diaphragm cell of the present invention may utilize anode and cathode plates of variable height. For example, anode and cathode plates of from about 1 to about 15 and preferably from about 4 to about 12 feet high may be employed. Increasing the height of the diaphragm cell permits a considerable reduction in the floor space required to produce a given quantity of product.
In the operation of the diaphragm cell of the present invention, an aqueous salt solution, for example, an alkali metal chloride such as sodium chloride or potassium chloride, may be employed. The alkali metal chloride solution is introduced into the cell as a brine stream of any desired concentration. The brine level within the cell is brought to a point above the anode and cathode sections within the cell. By adjusting the level within the cell the hydrostatic head or pressure exerted upon the diaphragm covering the cathodes is varied, thereby varying the flow of electrolyte through the diaphragm into the cathode chamber. Under normal operating conditions the height of the brine above the anode and cathode sections is from about 3 to about 15 or more inches.
The anode and cathode sections are spaced apart from the perimeter of their respective plates to provide greatly improved brine circulation within the cell. Preferably the anode and cathode sections are centered laterally. They are positioned vertically such that an adequate brine height and gas release space is provided above the anode and cathode section. In addition to permitting brine to flow completely around the anodes and cathodes, the space above the electrode sections permits a free release of gas produced in the anode. Without being bound by theory, it is believed that when chlorine gas forms at the anodes and rises, it creates a gas lift action directed vertically along the face of the anodes. This gas lift action draws fresh brine from below the electrode sections, with the fresh brine then flowing upward along the anodes into the region above the anodes, at which point chlorine gas leaves the brine. The heavier brine, from which chlorine gas has been partially exhausted, flows laterally above the electrode sections and then downward along the outside edges of the electrode sections.
Current capacities of from about 1,000 to about 300,000 and preferably from about 10,000 to about 200,000 amps, may be employed in electrolyzing aqueous salt solutions in the diaphragm cell of this invention.
The following example is presented to illustrate the invention more fully. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE A diaphragm cell, as illustrated in FIGS. l-6, was comprised of a horizontal cylindrical cell body composed of glass fiber reinforced polyester resin and having an outside diameter of about 92 inches. A flange surrounded the openings at each end of the cell body. At one end of the cell a cathode plate was bolted to the flange of the cell body. The cathode plate, composed of mild steel and covered with rubber on the inside face, had an outside diameter of about 96 inches. The
cathode section was comprised of 27 cathodes, each cathode being welded to the cathode face. A cathode included a steel plate having a series of projections to which a steel screen was attached. Deposited on the screen was an asbestos fiber diaphragm. The cathodes were about 36 inches long, inches high, and 1.125 inches thick and were spaced at a distance of 2.5 inches between centers. The cathode section was spaced at a distance of about 33 inches from the upper and lower perimeters and about 14 inches from the lateral perimeters of the cathode plate.
At the opposite end of the cell body an anode plate was bolted to the flange. The anode plate was about 96 inches in diameter and was composed of mild steel with the inside face being covered with rubber. The anode section had 28 anodes soldered to the anode plate. Each anode was composed of titanium-clad steel and had a portion of its surface coated with a ruthenium oxide. The anodes were about 36 inches long, 30 inches high and 0.18 inch thick and spaced apart 2.5 inches between centers. The anode section was spaced at a distance of about 33 inches from the upper and lower perimeters and about 14 inches from the lateral perimeters of the anode plate. The cathode plate and the anode plate were each externally supported by a steel bracket welded to the plate. The cathode and anode plates supported the weight of the cell body.
An aqueous solution containing 300 grams per liter of sodium chloride at a temperature of about 60-70C. was introduced into the cell body thru the brine inlet in the cathode plate. The cell operated at a current of 76 kiloamperes and a voltage of 3.78 to electrolyze the salt solution to produce chlorine, hydrogen and sodium hydroxide. The catholyte liquor obtained had a sodium hydroxide concentration of about 125 grams per liter. The chlorine gas obtained had a hydrogen content of 0.3 percent. Over a period of 106 hours, the cell was operated at a current efficiency of 97 percent, based on chlorine production.
What is claimed is:
1. An electrolytic diaphragm cell comprised of a. a horizontal cell body having opposite and substantially parallel ends, having a first opening at one end of said cell body and a second opening at the opposite end of said cell body;
b. an electroconductive cathode plate sealingly attached to said cell body and covering said first opening, said cathode plate having at least one cathode attached to the inner surface of said cathode plate;
c. an electroconductive anode plate sealingly attached to said cell body and covering said second opening, said anode plate having at least one anode attached to the inner surface of said anode plate; and
d. said cathode plate and said anode plate providing the sole means of support for said cell body.
2. The electrolytic diaphragm cell of claim 1 in which said cell body is cylindrical in shape.
3. The electrolytic diaphragm cell of claim 2 in which said cell body is comprised of a material of construction selected from the group consisting of steel, concrete, fiber reinforced plastic, hard rubber, asbestos reinforced plastic, or titanium.
4. The electrolytic diaphragm cell of claim 3 in which said cell body is comprised of a shell of a material selected from the group consisting of steel or concrete.
5. The electrolytic diaphragm cell of claim 4 in which said shell has a lining material selected from the group consisting of fiber reinforced plastic, rubber, asbestos reinforced plastic, ceramic tile composites, polytetrafluoroethylene, or polychlorotrifluoroethylene.
6. The electrolytic diaphragm cell of claim 5 in which said cathode plate is a metal selected from the group consisting of steel or copper.
7. The electrolytic diaphragm cell of claim 6 in which said cathode is spaced apart from the perimeter of said cathode plate.
8. The electrolytic diaphragm cell of claim 7 in which said anode plate is a metal selected from the group consisting of steel, copper, aluminum. or titanium.
9. The electrolytic diaphragm cell of claim 8 in which said anode is a valve metal selected from the group consisting of titanium or tantalum having at least part of its surface coated with a coating selected from the group consisting of a platinum metal, platinum metal oxide, platinum metal alloy or mixtures thereof.
10. The electrolytic diaphragm cell of claim 9 in which said anode comprises a metal selected from the group consisting of steel. copper or aluminum, said metal being clad with said valve metal.
11. The electrolytic diaphragm cell of claim 10 in which said anode is spaced apart from the perimeter of said anode plate.
12. The electrolytic diaphragm cell of claim 1 in which a flange surrounds each of said first openings and said second opening.
13. The electrolytic diaphragm cell of claim 1 in which the perimeter of each of said cathode plate and said anode plate is greater than said cell body.
14. The electrolytic diaphragm cell of claim 13 in which said cell body is elliptical in shape.
15. The electrolytic diaphragm cell of claim 1 in which said cathode plate and said anode plate each have at least one support attached to the external side of said plate.
16. An electrolytic diaphragm cell for the electrolysis of aqueous alkali metal chloride solutions comprised of:
a. a cylindrical cell body horizontally arranged having opposite and substantially parallel ends, having a first opening at one end of said cell body and a second opening at the opposite end of said cell body;
b. an electroconductive cathode plate sealingly attached to said cell body and covering said first opening, said cathode plate having a perimeter greater than that of said cell body, said cathode plate having a cathode section attached to the inner surface of said cathode plate, said cathode section comprising a plurality of cathodes, said cathode section being spaced apart from said perimeter of said cathode plate;
c. an electroconductive anode plate sealingly attached to said cell body and covering said second opening, said anode plate having a perimeter greater than that of said cell body, said anode plate having an anode section attached to the inner surface of said anode plate, said anode section comprising a plurality of anodes, said anode section being spaced apart from said perimeter of said anode plate; and H d. said cathode plate and said anodeplate providing sole means for supporting said cell body.

Claims (16)

1. AN ELECTROLYTIC CELL COMPRISED OF A. A HORIZONTAL CELL BODY HAVING OPPOSITE AND SUBSTANTIALLY PARALLEL ENDS, HAVING A FIRST OPENING END OF SAID CELL BODY AND A SECOND OPENING AT THE OPPOSITE END OF THE CELL BODY, B. AN ELECTROCONDUCTIVE CATHODE PLATE SEALINGLY, ATTACHED TO SAID CELL BODY AND COVERING SAID FIRST OPENING, SAID CATHODE PLATE HAVING AT LEAST ONE CATHODE ATTACHED TO THE C. AN ELECTROCONDUCTIVE ANODE PLATE SEALINGLY ATTACHED TO SAID CELL BODY AND COVERING SAID SECOND OPENING, SAID ANODE PLATE HAVING AT LEAST ONE ANODE ATTACHED TO THE INNER SURFACE OF SAID ANODE PLATE, AND D. SAID CATHODE PLATE AND SAID ANODE PLATE PROVIDING THE SOLE MEANS OF SUPPORT FOR SAID CELL BODY.
2. The electrolytic diaphragm cell of claim 1 in which said cell body is cylindrical in shape.
3. The electrolytic diaphragm cell of claim 2 in which said cell body is comprised of a material of construction selected from the group consisting of steel, concrete, fiber reinforced plastic, hard rubber, asbestos reinforced plastic, or titanium.
4. The electrolytic diaphragm cell of claim 3 in which said cell body is comprised of a shell of a material selected from the group consisting of steel or concrete.
5. The electrolytic diaphragm cell of claim 4 in which said shell has a lining material selected from the group consisting of fiber reinforced plastic, rubber, asbestos reinforced plastic, ceramic tile composites, polytetrafluoroethylene, or polychlorotrifluoroethylene.
6. The electrolytic diaphragm cell of claim 5 in which said cathode plate is a metal selected from the group consisting of steel or copper.
7. The electrolytic diaphragm cell of claim 6 in which said cathode is spaced apart from the perimeter of said cathode plate.
8. The electrolytic diaphragm cell of claim 7 in which said anode plate is a metal selected from the group consisting of steel, copper, aluminum, or titanium.
9. The electrolytic diaphragm cell of claim 8 in which said anode is a valve metal selected from the group consisting of titanium or tantalum having at least part of its surface coated with a coating selected from the group consisting of a platinum metal, platinum metal oxide, platinum metal alloy or mixtures thereof.
10. The electrolytic diaphragm cell of claim 9 in which said anode comprises a metal selected from the group consisting of steel, copper or aluminum, said metal being clad with said valve metal.
11. The electrolytic diaphragm cell of claim 10 in which said anode is spaced apart from the perimeter of said anode plate.
12. The electrolytic diaphragm cell of claim 1 in which a flange surrounds each of said first openings and said second opening.
13. The electrolytic diaphragm cell of claim 1 in which the perimeter of each of said cathode plate and said anode plate is greater than said cell body.
14. The electrolytic diaphragm cell of claim 13 in which said cell body is elliptical in shape.
15. The electrolytic diaphragm cell of claim 1 in which said cathode plate and said anode plate each have at least one support attached to the external side of said plate.
16. An electrolytic diaphragm cell for the electrolysis of aqueous alkali metal chloride solutions comprised of: a. a cylindrical cell body horizontally arranged having opposite and substantially parallel ends, having a first opening at one end of said cell body and a second opening at the opposite end of said cell body; b. an electroconductive cathode plate sealingly attached to said cell body and covering said first opening, said cathode plate having a perimeter greater than that of said cell body, said cathode plAte having a cathode section attached to the inner surface of said cathode plate, said cathode section comprising a plurality of cathodes, said cathode section being spaced apart from said perimeter of said cathode plate; c. an electroconductive anode plate sealingly attached to said cell body and covering said second opening, said anode plate having a perimeter greater than that of said cell body, said anode plate having an anode section attached to the inner surface of said anode plate, said anode section comprising a plurality of anodes, said anode section being spaced apart from said perimeter of said anode plate; and d. said cathode plate and said anode plate providing sole means for supporting said cell body.
US411327A 1973-10-31 1973-10-31 Electrolytic diaphragm cell Expired - Lifetime US3898149A (en)

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US411327A US3898149A (en) 1973-10-31 1973-10-31 Electrolytic diaphragm cell
CA211,282A CA1040135A (en) 1973-10-31 1974-10-11 Electrolytic diaphragm cell
ZA00746500A ZA746500B (en) 1973-10-31 1974-10-11 Electrolytic diaphragm cell
AU74331/74A AU489474B2 (en) 1973-10-31 1974-10-15 Electrolytic diaphragm cell
GB4626574A GB1428087A (en) 1973-10-31 1974-10-25 Electrolytic diaphragm cell
BR8968/74A BR7408968A (en) 1973-10-31 1974-10-29 DIAPHRAGM ELECTROLYTIC CELL
JP12531174A JPS5328261B2 (en) 1973-10-31 1974-10-30
ES431521A ES431521A1 (en) 1973-10-31 1974-10-30 Electrolytic diaphragm cell
FR7436275A FR2249975B1 (en) 1973-10-31 1974-10-30
IT53822/74A IT1021999B (en) 1973-10-31 1974-10-30 IMPROVEMENT IN DIAPHRAGM ELECTROLYTIC CELLS
DE19742451868 DE2451868A1 (en) 1973-10-31 1974-10-31 ELECTROLYTIC CELL IN MEMBRANE DESIGN

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US4129495A (en) * 1977-12-30 1978-12-12 Allied Chemical Corporation Support structure for plural cell electrolyzer
US4136004A (en) * 1975-07-15 1979-01-23 Kamarian Georgy M Solid electrode electrolyzer for electrolysis of aqueous solutions
US4322281A (en) * 1980-12-08 1982-03-30 Olin Corporation Method for controlling foaming within gas-liquid separation area
US4339321A (en) * 1980-12-08 1982-07-13 Olin Corporation Method and apparatus of injecting replenished electrolyte fluid into an electrolytic cell
US4340460A (en) * 1980-11-24 1982-07-20 Olin Corporation Internal downcomer for electrolytic recirculation
US4344833A (en) * 1980-12-08 1982-08-17 Olin Corporation Restrictor apparatus for electrolyte flow conduit
US5006215A (en) * 1989-07-27 1991-04-09 The Dow Company Squeezer apparatus
US20090236220A1 (en) * 2006-09-29 2009-09-24 Peter Woltering Electrolysis cell

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US4078987A (en) * 1977-03-30 1978-03-14 Olin Corporation Vacuum assisted assembly method for electrolytic cells and apparatus for utilizing same
US5361921A (en) * 1993-06-29 1994-11-08 Becton Dickinson And Company Combination stopper-shield closure

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US4136004A (en) * 1975-07-15 1979-01-23 Kamarian Georgy M Solid electrode electrolyzer for electrolysis of aqueous solutions
US4129495A (en) * 1977-12-30 1978-12-12 Allied Chemical Corporation Support structure for plural cell electrolyzer
US4340460A (en) * 1980-11-24 1982-07-20 Olin Corporation Internal downcomer for electrolytic recirculation
US4322281A (en) * 1980-12-08 1982-03-30 Olin Corporation Method for controlling foaming within gas-liquid separation area
US4339321A (en) * 1980-12-08 1982-07-13 Olin Corporation Method and apparatus of injecting replenished electrolyte fluid into an electrolytic cell
US4344833A (en) * 1980-12-08 1982-08-17 Olin Corporation Restrictor apparatus for electrolyte flow conduit
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US5006215A (en) * 1989-07-27 1991-04-09 The Dow Company Squeezer apparatus
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IT1021999B (en) 1978-02-20
ES431521A1 (en) 1976-11-01
JPS5074573A (en) 1975-06-19
BR7408968A (en) 1975-11-18
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CA1040135A (en) 1978-10-10
DE2451868A1 (en) 1975-05-07
FR2249975B1 (en) 1978-06-16
GB1428087A (en) 1976-03-17
ZA746500B (en) 1975-10-29
FR2249975A1 (en) 1975-05-30
JPS5328261B2 (en) 1978-08-14

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