US3928166A - Dimensionally adjustable anode-dimensionally stable diaphragm combination for electrolytic cells - Google Patents

Dimensionally adjustable anode-dimensionally stable diaphragm combination for electrolytic cells Download PDF

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Publication number
US3928166A
US3928166A US447215A US44721574A US3928166A US 3928166 A US3928166 A US 3928166A US 447215 A US447215 A US 447215A US 44721574 A US44721574 A US 44721574A US 3928166 A US3928166 A US 3928166A
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US
United States
Prior art keywords
anode
diaphragm
dimensionally
cell
asbestos
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
US447215A
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English (en)
Inventor
Kevin J O'leary
Charles P Tomba
Iii Robert W Fenn
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.)
Diamond Shamrock Chemicals Co
Eltech Systems Corp
Diamond Shamrock Corp
Original Assignee
Diamond Shamrock Corp
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 Diamond Shamrock Corp filed Critical Diamond Shamrock Corp
Priority to US447215A priority Critical patent/US3928166A/en
Priority to PH16852A priority patent/PH11079A/en
Priority to EG96/75A priority patent/EG11615A/xx
Priority to TR18616A priority patent/TR18616A/xx
Priority to YU491/75A priority patent/YU39936B/xx
Priority to NO750676A priority patent/NO145249C/no
Priority to LU71938*A priority patent/LU71938A1/xx
Priority to DK80575*#A priority patent/DK80575A/da
Priority to IE434/75A priority patent/IE41351B1/xx
Application granted granted Critical
Publication of US3928166A publication Critical patent/US3928166A/en
Assigned to DIAMOND SHAMROCK CHEMICALS COMPANY reassignment DIAMOND SHAMROCK CHEMICALS COMPANY CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). (SEE DOCUMENT FOR DETAILS), EFFECTIVE 9-1-83 AND 10-26-83 Assignors: DIAMOND SHAMROCK CORPORATION CHANGED TO DIAMOND CHEMICALS COMPANY
Assigned to ELTECH SYSTEMS CORPORATION reassignment ELTECH SYSTEMS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: DIAMOND SHAMROCK CORPORATION, 717 N. HARWOOD STREET, DALLAS, TX 75201
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material

Definitions

  • ABSTRACT A diaphragm cell for the electrolytic production of chlorine and alkali metal hydroxide, in other respects conventional, is improved by the provision of a dimen- 3 Claims, No Drawings DIMENSIONALLY ADJUSTABLE ANODE-DIMENSIONALLY STABLE DIAPHRAGM A large portion of the worlds production of chlorine and caustic by the'electrolysis of brine takes place in diaphragm type cells. In such cells, the adjacent anodes and cathodes are separated by hydraulically permeable diaphragms, generally of asbestos fibers.
  • these asbestos diaphragms are formed by direct deposition of the fibers from a slurry onto the cathode, generally a woven steel mesh.
  • This diaphragm-coated cathode is employed spaced a fixed'distance from the adjacent anode, the latter now being in most instances a dimensionally stable anode, e.g., titanium sheet or expanded metal bearing an electrically conductive, electrocatalytically active coating, often based on a platinum group metal.
  • a dimensionally stable, thermoplastic polymer-modified, asbestos diaphragm a dimensionally stable, thermoplastic polymer-modified, asbestos diaphragm.
  • Such a cell operates at a low voltage and a high current efficiency for extended periods of time and is easy to assemble and service when necessary.
  • the entire cathode assembly and cover of an existing diaphragm cell may be employed, the only cell modifications necessary being those required to accommodate the metal anodes.
  • any diaphgram cell for the electrolysis of alkali metal halide solutions, especially sodium and potassium chlorides, may be improved by incorporation of the diaphragm and anode combination of this invention.
  • new designs, such as bipolar cells may be improved by rendering the anode, the cathode, or both, dimensionally adjustable, that is, by providing for movement of one or both electrodes from the partition separating adjacent cell units toward the adjacent electrode, the diaphragm being disposed therebetween.
  • dimensionally adjustable anode or electrode refers to those electrodes wherein it is possible on assembly of the cell to move the active anode surface closer to the diaphragm-coated cathode on assembly.
  • such electrodes will comprise an active anode sheet or face connected to a riser or other primary electrical conductor by a means capable of causing the desired movement while maintaining electrical integrity.
  • the anode face is a metal sheet, continuous or foraminous, generally at least partially coated with an electrically conductive, electrocatalytically active material.
  • the anode face will be expanded titanium metal, to allow for gas release and electrolyte circulation, coated with a platinum group metal oxide or related material.
  • the riser or other conductor serves to convey current from the cell base or a source external the cell to the operating anode face. Conveniently, this may take the form of a metal pillar, such as copper-cored titanium, extending through the cell base. See, for example, US. Pat. No; 3,591,483, incorporated herein by reference.
  • the anode face is then connected to this conductor by a moveable, conductive, connecting means such as a flexible titanium sheet.
  • Dimensionally adjustable electrodes of a type useful as the anodes of this invention are described in more detail in US. Pat. No. 3,674,676, the teachings of which as to electrode configuration, alternatives, and advantages are incorporated herein by reference. Other designs may suggest themselves to one skilled in the art, it only being essential that the requisite capacity to move the active anode sheet toward the opposed diaphragm-coated cathode on cell assembly be present.
  • a dimensionally stable, polymer-modified, asbestos diaphragm Combined with the dimensionally adjustable anode is a dimensionally stable, polymer-modified, asbestos diaphragm.
  • Dimensional stability with respect to the diaphragm refers to resistance to swelling in the aqueous electrolyte as well as resistance to chemical and mechanical attrition.
  • These desirable properties are achieved by treating conventional (usually chrysotile) asbestos fibers with various chemically and mechanically resistant thermoplastic polymers.
  • various polyfluorocarbons such as poly(vinyl fluoride), poly(vinylidene fluoride), polytetrafluoroethylene, polyperfluoroethylene propylene, and the like.
  • chlorinated resins such as poly(vinylidene chloride) and the chloro-fluoro materials such as polychlorotrifluoroethylene and polychlorotrifluoroethylene polyethylene copolymers.
  • chlorinated resins such as poly(vinylidene chloride)
  • chloro-fluoro materials such as polychlorotrifluoroethylene and polychlorotrifluoroethylene polyethylene copolymers.
  • These polymers may be incorporated into the asbestos diaphragm by preforming the asbestos fibers as a diaphragm or sheet and subsequently soaking same in a solution of the appropriate monomers, followed by in situ polymerization. In this fashion, however, a continuous polymer coating on the asbestos fibers is obtained and the advantageous ion exchange properties of the asbestos are thereby lost.
  • the polymers will be incorporated in the asbestos as such, by either dissolving or suspending same in an appropriate media followed by soaking the preformed asbestos sheet or diaphragm therein or drawing the polymer into the asbestos, for example, by vacuum. Subsequently, the treated asbestos structure is dried and cured, i.e., raised to the temperature at which the thermoplastic polymer melts, thereby locking together adjacent asbestos fibers on cooling and imparting the desired dimensional stability.
  • a preferred method of obtaining the desired dimensionally'stable diaphragm is by deposition from a slurry of asbestos fibers and thermoplastic polymer particles in the form of polymer granules or fibers. This uniform slurry is then drawn onto the cathode screen or other sheet-forming support, followed by drying and curing at the appropriate elevated temperature to obtain a discontinuous but coherent polymer coat. This method and the results obtained thereby are described more fully in copending US. Ser. No. 324,508, filed Jan. 17, 1973.
  • the object is to obtain a dimensionally stable diaphragm comprising an asbestos fiber lattice stabilized with a thermoplastic polymer that has been subjected to fusion to bind adjacent asbestos fibers together and, preferably, provide a discontinuous polymer coating on said fibers.
  • the dimensionally stable diaphragm will have been applied directly onto the cathode surface, usually a wire screen. If this is the case, then the diaphragm-coated cathode assembly may be positioned over the array of dimensionally adjustable anodes to provide the desired alternating anode-cathode arrangement, following which the anodes may be allowed or caused to expand, thus reducing the interelectrode gap.
  • the cell may then be operated conventionally but with the above-described advantages.
  • An improvement in a cell for the electrolysis of aqueous alkali metal chloride solutions comprising a container divided into anode-containing and cathodecontaining compartments by a hydraulically permeable diaphragm, which improvement comprises, in combination:
  • a dimensionally adjustable electrode comprising an anode-working face, an anode riser, and a moveable means for connecting the anode working face and anoderiser with electrical integrity
  • a diaphragm a dimensionally stable, heat-fused, polyfluorocarbon-asbesto's diaphragm, said diaphragm having a discontinuous polyfluorocarbon coating binding the asbestos together.
  • a cell as in claim 1 wherein said polyfluorocarbon is polytetrafluoroethylene.
  • An improvement in a cell for the electrolysis of aqueous alkali metal chloride solutions comprising a container divided into anode-containing and cathodecontaining compartments by a hydraulically permeable diaphragm, which improvement comprises, in combination:
  • a dimensionally adjustable electrode comprising an anode-working face, an anode riser, and a moveable means for connecting the anode working face and anode riser with electrical integrity
  • said diaphragm a dimensionally stable, heatfused, polymer-asbestos diaphragm, said polymer being selected from the group consisting of poly(- vinylfluoride), poly(vinylidene fluoride), polytetrafluoroethylene, polyperfluoroethylene propylene, and polychlorotrifluoroethylene-polyethylene, said diaphragm having a discontinuous polymer coating binding the asbestos together.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US447215A 1974-03-01 1974-03-01 Dimensionally adjustable anode-dimensionally stable diaphragm combination for electrolytic cells Expired - Lifetime US3928166A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US447215A US3928166A (en) 1974-03-01 1974-03-01 Dimensionally adjustable anode-dimensionally stable diaphragm combination for electrolytic cells
PH16852A PH11079A (en) 1974-03-01 1975-02-24 Dimensionally adjustable anode-dimensionally stable diaphragm combination for electrolytic cell
EG96/75A EG11615A (en) 1974-03-01 1975-02-25 Modified diaphragm electrolytic cell
TR18616A TR18616A (tr) 1974-03-01 1975-02-27 Diyaframi tadil edilmis elektrolit huecresi
NO750676A NO145249C (no) 1974-03-01 1975-02-28 Celle for elektrolyse av vandige alkalimetallkloridopploesninger
LU71938*A LU71938A1 (en, 2012) 1974-03-01 1975-02-28
YU491/75A YU39936B (en) 1974-03-01 1975-02-28 Cell for the electrolysis of alkali metal chlorides
DK80575*#A DK80575A (en, 2012) 1974-03-01 1975-02-28
IE434/75A IE41351B1 (en) 1974-03-01 1975-02-28 Modified diaphragm electrolytic cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US447215A US3928166A (en) 1974-03-01 1974-03-01 Dimensionally adjustable anode-dimensionally stable diaphragm combination for electrolytic cells

Publications (1)

Publication Number Publication Date
US3928166A true US3928166A (en) 1975-12-23

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ID=23775449

Family Applications (1)

Application Number Title Priority Date Filing Date
US447215A Expired - Lifetime US3928166A (en) 1974-03-01 1974-03-01 Dimensionally adjustable anode-dimensionally stable diaphragm combination for electrolytic cells

Country Status (9)

Country Link
US (1) US3928166A (en, 2012)
DK (1) DK80575A (en, 2012)
EG (1) EG11615A (en, 2012)
IE (1) IE41351B1 (en, 2012)
LU (1) LU71938A1 (en, 2012)
NO (1) NO145249C (en, 2012)
PH (1) PH11079A (en, 2012)
TR (1) TR18616A (en, 2012)
YU (1) YU39936B (en, 2012)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032423A (en) * 1976-06-09 1977-06-28 Ppg Industries, Inc. Method of assembling a bipolar electrolyzer
US4036729A (en) * 1975-04-10 1977-07-19 Patil Arvind S Diaphragms from discrete thermoplastic fibers requiring no bonding or cementing
US4036728A (en) * 1976-05-21 1977-07-19 Diamond Shamrock Corporation Converting a diaphragm electrolytic cell to a membrane electrolytic cell
US4093533A (en) * 1975-12-12 1978-06-06 The Dow Chemical Company Bonded asbestos diaphragms
FR2371529A1 (fr) * 1976-11-18 1978-06-16 Basf Wyandotte Corp Diaphragme pour l'electrolyse des halogenures de metaux alcalins et procede pour sa fabrication
DE2841148A1 (de) * 1977-09-22 1979-04-12 Kanegafuchi Chemical Ind Vorrichtung zur elektrolyse von alkalimetallchloriden
US4182670A (en) * 1976-06-11 1980-01-08 Basf Wyandotte Corporation Combined cathode and diaphragm unit for electrolytic cells
DE2930609A1 (de) * 1978-07-27 1980-02-14 Oronzio De Nora Impianti Verfahren zur elektrolytischen erzeugung von halogenen und dafuer geeignete elektrolysezelle
US4210515A (en) * 1975-02-10 1980-07-01 Basf Wyandotte Corporation Thermoplastic fibers as separator or diaphragm in electrochemical cells
US4238303A (en) * 1978-08-14 1980-12-09 E. I. Du Pont De Nemours And Company Diaphragm modifier for chlor-alkali cell
US4444640A (en) * 1980-09-22 1984-04-24 Diamond Shamrock Corporation Dimensionally stable asbestos-polytetrafluoroethylene diaphragms for chloralkali electrolytic cells
US4563260A (en) * 1983-01-27 1986-01-07 Eltech Systems Corporation Modified liquid permeable asbestos diaphragms with improved dimensional stability
US4666573A (en) * 1985-09-05 1987-05-19 Ppg Industries, Inc. Synthetic diaphragm and process of use thereof
EP0627501A3 (en) * 1993-05-28 1995-04-19 Nora Permelec Brasil Improved chlorine-alkali electrolysis process, which is carried out with porous asbestos diaphragms.

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3721125A (en) * 1971-06-23 1973-03-20 Singer Co Thermal actuator for a meter temperature compensating mechanism

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674676A (en) * 1970-02-26 1972-07-04 Diamond Shamrock Corp Expandable electrodes
US3694281A (en) * 1969-04-28 1972-09-26 Pullman Inc Process for forming a diaphragm for use in an electrolytic cell
US3803016A (en) * 1972-02-09 1974-04-09 Fmc Corp Electrolytic cell having adjustable anode sections
US3853721A (en) * 1971-09-09 1974-12-10 Ppg Industries Inc Process for electrolysing brine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3694281A (en) * 1969-04-28 1972-09-26 Pullman Inc Process for forming a diaphragm for use in an electrolytic cell
US3674676A (en) * 1970-02-26 1972-07-04 Diamond Shamrock Corp Expandable electrodes
US3853721A (en) * 1971-09-09 1974-12-10 Ppg Industries Inc Process for electrolysing brine
US3803016A (en) * 1972-02-09 1974-04-09 Fmc Corp Electrolytic cell having adjustable anode sections

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4210515A (en) * 1975-02-10 1980-07-01 Basf Wyandotte Corporation Thermoplastic fibers as separator or diaphragm in electrochemical cells
US4154666A (en) * 1975-04-10 1979-05-15 Basf Wyandotte Corporation Method of making fiber diaphragms
US4036729A (en) * 1975-04-10 1977-07-19 Patil Arvind S Diaphragms from discrete thermoplastic fibers requiring no bonding or cementing
US4138314A (en) * 1975-04-10 1979-02-06 Basf Wyandotte Corporation Method of forming diaphragms from discrete thermoplastic fibers requiring no bonding or cementing
US4093533A (en) * 1975-12-12 1978-06-06 The Dow Chemical Company Bonded asbestos diaphragms
US4036728A (en) * 1976-05-21 1977-07-19 Diamond Shamrock Corporation Converting a diaphragm electrolytic cell to a membrane electrolytic cell
US4112149A (en) * 1976-05-21 1978-09-05 Diamond Shamrock Corporation Converting a diaphragm electrolytic cell to a membrane electrolytic cell
US4032423A (en) * 1976-06-09 1977-06-28 Ppg Industries, Inc. Method of assembling a bipolar electrolyzer
US4182670A (en) * 1976-06-11 1980-01-08 Basf Wyandotte Corporation Combined cathode and diaphragm unit for electrolytic cells
FR2371529A1 (fr) * 1976-11-18 1978-06-16 Basf Wyandotte Corp Diaphragme pour l'electrolyse des halogenures de metaux alcalins et procede pour sa fabrication
US4126535A (en) * 1976-11-18 1978-11-21 Basf Wyandotte Corporation Chlorotrifluoroethylene containing polymer diaphragm
DE2841148A1 (de) * 1977-09-22 1979-04-12 Kanegafuchi Chemical Ind Vorrichtung zur elektrolyse von alkalimetallchloriden
DE2930609A1 (de) * 1978-07-27 1980-02-14 Oronzio De Nora Impianti Verfahren zur elektrolytischen erzeugung von halogenen und dafuer geeignete elektrolysezelle
US4789443A (en) * 1978-07-27 1988-12-06 Oronzio Denora Impianti Elettrochimici S.P.A. Novel electrolysis cell
US4238303A (en) * 1978-08-14 1980-12-09 E. I. Du Pont De Nemours And Company Diaphragm modifier for chlor-alkali cell
US4444640A (en) * 1980-09-22 1984-04-24 Diamond Shamrock Corporation Dimensionally stable asbestos-polytetrafluoroethylene diaphragms for chloralkali electrolytic cells
US4563260A (en) * 1983-01-27 1986-01-07 Eltech Systems Corporation Modified liquid permeable asbestos diaphragms with improved dimensional stability
US4666573A (en) * 1985-09-05 1987-05-19 Ppg Industries, Inc. Synthetic diaphragm and process of use thereof
EP0627501A3 (en) * 1993-05-28 1995-04-19 Nora Permelec Brasil Improved chlorine-alkali electrolysis process, which is carried out with porous asbestos diaphragms.

Also Published As

Publication number Publication date
NO750676L (en, 2012) 1975-09-02
YU39936B (en) 1985-06-30
EG11615A (en) 1977-08-15
LU71938A1 (en, 2012) 1975-12-09
IE41351L (en) 1975-09-01
NO145249B (no) 1981-11-02
TR18616A (tr) 1977-06-22
DK80575A (en, 2012) 1975-09-02
PH11079A (en) 1977-10-25
YU49175A (en) 1982-06-30
IE41351B1 (en) 1979-12-19
NO145249C (no) 1982-02-10

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STCF Information on status: patent grant

Free format text: PATENTED FILE - (OLD CASE ADDED FOR FILE TRACKING PURPOSES)

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Owner name: DIAMOND SHAMROCK CHEMICALS COMPANY

Free format text: CHANGE OF NAME;ASSIGNOR:DIAMOND SHAMROCK CORPORATION CHANGED TO DIAMOND CHEMICALS COMPANY;REEL/FRAME:004197/0130

PS Patent suit(s) filed
AS Assignment

Owner name: ELTECH SYSTEMS CORPORATION, 6100 GLADES ROAD, BOCA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:DIAMOND SHAMROCK CORPORATION, 717 N. HARWOOD STREET, DALLAS, TX 75201;REEL/FRAME:004357/0479

Effective date: 19841024