US3819504A - Method of maintaining cathodes of an electrolytic cell free of deposits - Google Patents

Method of maintaining cathodes of an electrolytic cell free of deposits Download PDF

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Publication number
US3819504A
US3819504A US00247326A US24732672A US3819504A US 3819504 A US3819504 A US 3819504A US 00247326 A US00247326 A US 00247326A US 24732672 A US24732672 A US 24732672A US 3819504 A US3819504 A US 3819504A
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United States
Prior art keywords
cell
cathodes
electrodes
deposits
anodes
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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
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US00247326A
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English (en)
Inventor
J Bennett
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
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Diamond Shamrock Corp
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Filing date
Publication date
Application filed by Diamond Shamrock Corp filed Critical Diamond Shamrock Corp
Priority to US00247326A priority Critical patent/US3819504A/en
Priority to AU54197/73A priority patent/AU472998B2/en
Priority to JP48046776A priority patent/JPS5219833B2/ja
Priority to BR3068/73A priority patent/BR7303068D0/pt
Priority to GB2022073A priority patent/GB1384836A/en
Priority to SE7305966A priority patent/SE392295B/xx
Priority to DE2321417A priority patent/DE2321417B2/de
Priority to FR7315332A priority patent/FR2182178B1/fr
Priority to CA169,712A priority patent/CA1019692A/en
Priority to IL42118A priority patent/IL42118A/xx
Priority to IT49700/73A priority patent/IT980373B/it
Priority to DK231873AA priority patent/DK133757B/da
Priority to US435960A priority patent/US3915817A/en
Application granted granted Critical
Publication of US3819504A publication Critical patent/US3819504A/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
Assigned to UNION NATIONAL BANK OF FLORIDA reassignment UNION NATIONAL BANK OF FLORIDA SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: 442 CORPORATION, HURON TECH CORP.
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof

Definitions

  • This invention relates generally to a process for maintaining cathodes positioned in opposed spaced parallel relationship to the anodes in an electrolytic cell free of deposits and in clean condition. More specifically, this invention relates to a method of maintaining such cathodes of an electrolytic cell free of deposits and in clean condition when an electrolyte solution is electrolyzed by passing a direct current between the anodes and cathodes.
  • Another method for cleaning the electrodes is to wash them with a dilute acid, usually'hydrochloric acid.
  • a dilute acid usually'hydrochloric acid.
  • the cell in order to effectively remove deposits by acid treatment, the cell must generally be shut down, the electrolyte drained and the electrode subjected to the acid solution for a period of time sufficient to remove the deposits.
  • the electrodes may be removed from the cell and the acid treatment effected exteriorthe cell. Costs are considerably increased by both the loss in operating production time of the cell and the labor charges.
  • FIG. 1' illustrates diagrammatically in vertical section one of the arrangements of the electrodes for carrying out the method of this invention where the electrodes are foraminous and horizontally disposed.
  • FIG. 2 illustrates another of the electrode arrangements of the method of this invention in which the electrodes are vertically disposed.
  • FIG. 3 illustrates a modification of the arrangement of the electrodes in accordance with the method of this invention wherein the terminal electrodes are integral and both vertically and horizontally disposed.
  • FIG. 4 illustrates an electrode arrangement of this invention similar to that shown in FIG. 3 in which the electrodes are not integral.
  • the invention comprises a method of electrolyzing a solution in a cell having vertical or horizontal electrodes in closely spaced parallel opposed face-toface relation by introducing electrolyte solution to the cell in a manner whereby at least one anode is contacted with said solution prior to contacting a cathode during the introduction of said solution to the cell and contacting at least one anode subsequent to contacting a cathode prior to withdrawal of the solution from the cell.
  • FIG. 1 shows an arrangement of horizontally disposed closely spaced substantially parallel foraminous electrodes in alternating relation with respect to polarity, the external electrodes of the assembly being anodes.
  • the electrolyte solution may flow preferably upwardly through the assembly of the electrodes first contacting the lowermost or bottom terminal electrode, which is an anode, then passing through the entire electrode assembly upwardly and leaving the cell or compartment in which the assembly is disposed by contacting the uppermost or upper terminal electrode of the assembly which is an anode.
  • the flow of the electrolyte solution may obviously be reversed, passing first through the upper most terminal anode and downwardly through the assembly and leaving the cell chamber by contacting the lowermost terminal anode prior to withdrawal from the cell.
  • the electrolyte solution first contacts the anodes of an electrode assembly wherein vertical parallel closely spaced opposed alternating. anodes and cathodes are positioned with each of the anodes extending vertically beyond each of the upper and lower edges of each of the spaced cathodes-The electrodes are genersembly.
  • the flow of the electrolyte solution may be upward upon introduction while leaving the cell at the upper level of the anodes or the flow may be reversed entering the electrode assembly at the uppermost portions of the anodes, flowing through the assembly and subsequent to contacting all other electrodes leaving the cell by lastly contacting the anodes. Referring to FIG.
  • the two terminal electrodes being L-shaped with their long leg extending vertically and the short legs of the L being foraminous and horizontally disposed one above, one below and both perpindicular to the vertical electrodes.
  • the long portions of the terminal electrodes and all the remaining electrodes may be sheet material, the short legs of the L- shaped terminal anodes being foraminous.
  • the electrode arrangement is similar to that in FIG. 3, with the exception that the terminal horizontally disposed anodes, that is, those perpendicular to the plurality of vertically disposed anodes and cathodes in alternate parallel array, are not integral with the terminal vertically disposed anodes, one being spaced above and the other below said vertical array.
  • the process of the invention is useful in a number of electrode arrangements.
  • An important concept of the invention is that upon introduction of an electrolyte solution to a cell the solution must be contacted by an anode prior to contacting the other electrodes and after passage through the electrodes of the cell must be subsequently contacted by an anode prior to withdrawal of the solution from the cell. It will be obvious to one knowledgeable in this art that a large number of electrode assemblies and arrangements may be utilized in conjunction with the application of the process of this invention while maintaining the essential features thereof.
  • the invention has been found applicable in the electrolysis of saline solutions including salted water, brackish water and synthetic sea water, the latter being made in conformance to known, established formulas for such synthetic solution.
  • the electrolysis of the saline solution has been carried out in diaphragm-less cells for production of sodium hypochlorite wherein sodium hydroxide and hydrogen have been formed at the cathode and chlorine at the anode with the chemical reaction of the electrolytic products in situ to provide the sodium hypochlorite.
  • This process has been found to operate for long periods of time with satisfac-' tory current efficiency and with the cathodes remaining in clean condition free of deposits and without plugging.
  • the cathodes By comparison in cells for sodium hypochlorite production wherein the electrodes have been contacted simultaneously or indiscriminately by electrolyte solution upon its introduction and withdrawal from the cell, the cathodes have been found to operate for limited periods of time before deposits and precipitates form on the cathodes and reduce the cell efficiency. While the reasons for the results obtained in the practice of the process of this invention are not completely understood the invention is not intended to be limited by any theory of operation.
  • EXAMPLE 1 An electrolytic cell including a horizontally disposed electrode assemblyas shown in FIG. I was continuously operated for the production of sodium hypochlorite.
  • Aqueous sodium chloride solution containing about g/l sodium chloride was continuously introduced into the cell chamber by charging a predetermined amount of tap water and saturated brine solution into the chamber in separate streams.
  • the aqueous sodium chloride solution was continuously electrolyzed to form sodium hypochlorite by passing a direct current from the anodes to the cathodes.
  • the temperature of the electrolyte solution ranged from about 10C. to about C. with water flowing through an electrically insulated cooling coil immersed in the solution.
  • the hard tap water feed was found by chemical analysis to have a calcium content of about parts per million.
  • the mixed water feed and saturated brine solution were introduced to the cell beneath the lowermost electrode,'a terminal anode, of the electrode assembly.
  • the cell was operated continuously for a period of three months without formation on the electrodes of deposits which detrimentally affect operation of the cell.
  • the surfaces of the cell chamber, cooling coils and all other equipment arranged within the cell, with the exception of the electrodes, were covered by a heavy calcium carbonate deposit.
  • EXAMPLE 2 The same type of electrolytic cell and assembly of electrodes-used in Example I was employed for the continuous production of sodium hypochlorite.
  • the feed solution in this case was sea water and the cell was operated at 0.75 amps/sq.in.
  • the cell was operated for a 10 day period without the formation on the electrodes of deposits which detrimentally affect cell operation.
  • the cell was then operated in the same manner with the exception that the terminal anodes previously used were replaced by terminal cathodes. After 12 hours, deposits which formed on the electrodes substantially plugged the openings and prevented flow of the electrolyte solution. The cell was incapable of operating and had to be shutdown.
  • An improvement in an electrolytic cell including a cell chamber having side, bottom, and end walls, means for introducing solution to and removing solution from said cell, and a plurality of vertically disposed anodes and cathodes in alternate parallel array, which improvement comprises terminal vertical anodes in said array and terminal, horizontal, foraminous anodes disposed above and below and perpendicular to said array.
  • each of said horizontal terminal anodes is integral with one of said vertical terminal anodes, thereby forming two L- shaped terminal anodes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
US00247326A 1972-04-28 1972-04-28 Method of maintaining cathodes of an electrolytic cell free of deposits Expired - Lifetime US3819504A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US00247326A US3819504A (en) 1972-04-28 1972-04-28 Method of maintaining cathodes of an electrolytic cell free of deposits
AU54197/73A AU472998B2 (en) 1972-04-28 1973-04-06 Method of maintaining cathodes ofan electrolytic cell free of deposits
JP48046776A JPS5219833B2 (enrdf_load_stackoverflow) 1972-04-28 1973-04-26
IL42118A IL42118A (en) 1972-04-28 1973-04-27 Method of maintaining cathodes of an electrolytic cell free of deposits and cell for use in this method
SE7305966A SE392295B (sv) 1972-04-28 1973-04-27 Forfarande for att forhindra katodavstettningar vid elektrolys av en natriumkloridlosning i en elektrolyscell
DE2321417A DE2321417B2 (de) 1972-04-28 1973-04-27 Elektrolysezelle
FR7315332A FR2182178B1 (enrdf_load_stackoverflow) 1972-04-28 1973-04-27
CA169,712A CA1019692A (en) 1972-04-28 1973-04-27 Method of maintaining cathodes of an electrolytic cell free of deposits
BR3068/73A BR7303068D0 (pt) 1972-04-28 1973-04-27 Aperfeicoamentos em processo para a eletrolise de solucoes eletroliticas e em celula eletrolitica
IT49700/73A IT980373B (it) 1972-04-28 1973-04-27 Cella elettrolitica e relativo procedimento di impiego con man tenimento del catodo privo di depositi durante la elettrolisi
DK231873AA DK133757B (da) 1972-04-28 1973-04-27 Fremgangsmåde ved elektrolyse af saltopløsninger i en elektrolytisk celle.
GB2022073A GB1384836A (en) 1972-04-28 1973-04-27 Electrolytic processes
US435960A US3915817A (en) 1972-04-28 1974-01-23 Method of maintaining cathodes of an electrolytic cell free of deposits

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00247326A US3819504A (en) 1972-04-28 1972-04-28 Method of maintaining cathodes of an electrolytic cell free of deposits

Publications (1)

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US3819504A true US3819504A (en) 1974-06-25

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US00247326A Expired - Lifetime US3819504A (en) 1972-04-28 1972-04-28 Method of maintaining cathodes of an electrolytic cell free of deposits

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US (1) US3819504A (enrdf_load_stackoverflow)
JP (1) JPS5219833B2 (enrdf_load_stackoverflow)
AU (1) AU472998B2 (enrdf_load_stackoverflow)
BR (1) BR7303068D0 (enrdf_load_stackoverflow)
CA (1) CA1019692A (enrdf_load_stackoverflow)
DE (1) DE2321417B2 (enrdf_load_stackoverflow)
DK (1) DK133757B (enrdf_load_stackoverflow)
FR (1) FR2182178B1 (enrdf_load_stackoverflow)
GB (1) GB1384836A (enrdf_load_stackoverflow)
IL (1) IL42118A (enrdf_load_stackoverflow)
IT (1) IT980373B (enrdf_load_stackoverflow)
SE (1) SE392295B (enrdf_load_stackoverflow)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014767A (en) * 1974-10-18 1977-03-29 Ametek, Inc. Self-contained waste disposal system including self-cleaning filter
US4142959A (en) * 1974-11-21 1979-03-06 Electro-Chlor Corporation Electrode assembly
US4151052A (en) * 1977-02-18 1979-04-24 Chlorine Engineers Corp., Ltd. Process for producing sodium hypochlorite
US4179347A (en) * 1978-02-28 1979-12-18 Omnipure, Inc. System for electrocatalytic treatment of waste water streams
FR2432057A1 (fr) * 1978-07-18 1980-02-22 Chlorine Eng Corp Ltd Cellule electrolytique pour l'electrolyse de l'eau de mer
US4193858A (en) * 1978-11-03 1980-03-18 Diamond Shamrock Corporation Stack pack electrolytic cell
US4461692A (en) * 1982-05-26 1984-07-24 Ppg Industries, Inc. Electrolytic cell
US5728287A (en) * 1996-10-31 1998-03-17 H2 O Technologies, Ltd. Method and apparatus for generating oxygenated water
US5911870A (en) * 1997-04-11 1999-06-15 H20 Technologies, Ltd. Housing and method that provide extended resident time for dissolving generated oxygen into water
US6171469B1 (en) 1996-10-31 2001-01-09 H2O Technologies, Ltd. Method and apparatus for increasing the oxygen content of water
US6296756B1 (en) 1999-09-09 2001-10-02 H20 Technologies, Ltd. Hand portable water purification system
US6358395B1 (en) 2000-08-11 2002-03-19 H20 Technologies Ltd. Under the counter water treatment system
US20020168418A1 (en) * 2000-08-04 2002-11-14 H20 Technologies, Ltd. Method and apparatus for treating water for use in improving the intestinal flora of livestock and poultry
US20130074655A1 (en) * 2011-09-27 2013-03-28 Nichromet Extraction Inc. Method and a system for gold extraction with halogens
US9206492B2 (en) 2014-03-12 2015-12-08 Dundee Sustainable Technologies Inc. Closed loop method for gold and silver extraction by halogens

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH038753U (enrdf_load_stackoverflow) * 1989-06-13 1991-01-28
JP2013253270A (ja) * 2012-06-05 2013-12-19 Sharp Corp 二酸化炭素還元装置
JP2013253269A (ja) * 2012-06-05 2013-12-19 Sharp Corp 二酸化炭素還元装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US756328A (en) * 1901-05-20 1904-04-05 Samuel B Christy Recovery of gold and silver from cyanid solutions.
US883170A (en) * 1906-03-10 1908-03-31 Samuel B Christy Electrode for the recovery of metals from solutions by electrolysis.
US1392524A (en) * 1917-11-24 1921-10-04 Puiggari Miguel Process for the purifying and clarifying of water
US2367811A (en) * 1941-04-19 1945-01-23 Stephen F Urban Pickling solution
US3117066A (en) * 1960-11-01 1964-01-07 Ionics Electrolytic process for producing halogen gases and the apparatus therefor
US3616356A (en) * 1967-09-18 1971-10-26 Clarence H Roy Electrolysis in a particulate carbon packing

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US756328A (en) * 1901-05-20 1904-04-05 Samuel B Christy Recovery of gold and silver from cyanid solutions.
US883170A (en) * 1906-03-10 1908-03-31 Samuel B Christy Electrode for the recovery of metals from solutions by electrolysis.
US1392524A (en) * 1917-11-24 1921-10-04 Puiggari Miguel Process for the purifying and clarifying of water
US2367811A (en) * 1941-04-19 1945-01-23 Stephen F Urban Pickling solution
US3117066A (en) * 1960-11-01 1964-01-07 Ionics Electrolytic process for producing halogen gases and the apparatus therefor
US3616356A (en) * 1967-09-18 1971-10-26 Clarence H Roy Electrolysis in a particulate carbon packing

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014767A (en) * 1974-10-18 1977-03-29 Ametek, Inc. Self-contained waste disposal system including self-cleaning filter
US4142959A (en) * 1974-11-21 1979-03-06 Electro-Chlor Corporation Electrode assembly
US4151052A (en) * 1977-02-18 1979-04-24 Chlorine Engineers Corp., Ltd. Process for producing sodium hypochlorite
US4179347A (en) * 1978-02-28 1979-12-18 Omnipure, Inc. System for electrocatalytic treatment of waste water streams
FR2432057A1 (fr) * 1978-07-18 1980-02-22 Chlorine Eng Corp Ltd Cellule electrolytique pour l'electrolyse de l'eau de mer
US4193858A (en) * 1978-11-03 1980-03-18 Diamond Shamrock Corporation Stack pack electrolytic cell
US4461692A (en) * 1982-05-26 1984-07-24 Ppg Industries, Inc. Electrolytic cell
US6171469B1 (en) 1996-10-31 2001-01-09 H2O Technologies, Ltd. Method and apparatus for increasing the oxygen content of water
US5728287A (en) * 1996-10-31 1998-03-17 H2 O Technologies, Ltd. Method and apparatus for generating oxygenated water
US6478949B1 (en) 1996-10-31 2002-11-12 H2O Technologies, Ltd. Method and apparatus for increasing the oxygen content of water
US5911870A (en) * 1997-04-11 1999-06-15 H20 Technologies, Ltd. Housing and method that provide extended resident time for dissolving generated oxygen into water
US6110353A (en) * 1997-04-11 2000-08-29 H20 Technologies, Ltd. Housing and method that provide extended resident time for dissolving generated oxygen into water
US20040222106A1 (en) * 1997-04-11 2004-11-11 H2O Technologies, Ltd. Housing and method that provide extended resident time for dissolving generated oxygen into water
US6296756B1 (en) 1999-09-09 2001-10-02 H20 Technologies, Ltd. Hand portable water purification system
US20020168418A1 (en) * 2000-08-04 2002-11-14 H20 Technologies, Ltd. Method and apparatus for treating water for use in improving the intestinal flora of livestock and poultry
US6358395B1 (en) 2000-08-11 2002-03-19 H20 Technologies Ltd. Under the counter water treatment system
US20130074655A1 (en) * 2011-09-27 2013-03-28 Nichromet Extraction Inc. Method and a system for gold extraction with halogens
US9051626B2 (en) * 2011-09-27 2015-06-09 Dundee, Technologies Durables Inc. Method and a system for gold extraction with halogens
US9206492B2 (en) 2014-03-12 2015-12-08 Dundee Sustainable Technologies Inc. Closed loop method for gold and silver extraction by halogens

Also Published As

Publication number Publication date
DK133757B (da) 1976-07-12
BR7303068D0 (pt) 1974-07-11
AU472998B2 (en) 1976-06-10
IT980373B (it) 1974-09-30
FR2182178A1 (enrdf_load_stackoverflow) 1973-12-07
JPS5219833B2 (enrdf_load_stackoverflow) 1977-05-31
GB1384836A (en) 1975-02-26
IL42118A (en) 1975-12-31
DE2321417A1 (de) 1973-11-15
CA1019692A (en) 1977-10-25
FR2182178B1 (enrdf_load_stackoverflow) 1977-12-30
IL42118A0 (en) 1973-06-29
JPS4947264A (enrdf_load_stackoverflow) 1974-05-07
SE392295B (sv) 1977-03-21
DK133757C (enrdf_load_stackoverflow) 1976-11-29
AU5419773A (en) 1974-10-10
DE2321417B2 (de) 1980-04-24

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AS Assignment

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

AS Assignment

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

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Effective date: 19841024

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Owner name: UNION NATIONAL BANK OF FLORIDA, FLORIDA

Free format text: SECURITY INTEREST;ASSIGNORS:HURON TECH CORP.;442 CORPORATION;REEL/FRAME:006209/0776

Effective date: 19920814