US3676325A - Anode assembly for electrolytic cells - Google Patents

Anode assembly for electrolytic cells Download PDF

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Publication number
US3676325A
US3676325A US44044A US3676325DA US3676325A US 3676325 A US3676325 A US 3676325A US 44044 A US44044 A US 44044A US 3676325D A US3676325D A US 3676325DA US 3676325 A US3676325 A US 3676325A
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Prior art keywords
titanium
anode assembly
web portion
assembly according
foraminate
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Expired - Lifetime
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US44044A
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English (en)
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Frank Smith
John Hubert Entwisle
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous

Definitions

  • An anode assembly for electrolytic cells comprising: a downwardly-facing, openended, horizontally-elongated [52] US. Cl ..204/288, 204/219, 204/250, titanium channel member having a web portion and two de- 204/284, 204/286, 204/290 F pending flange portions integral with the web portion; a titani- [51] Int. Cl alone
  • the present invention relates to an anode assembly for electrolytic cells. More particularly it relates to an anode assembly which is particularly suitable for use in cells where gas is evolved at the anode.
  • anodes particularly in cells electrolyzing aqueous alkali metal chloride solutions, structures in which a layer of a platinum group metal or metals and/or the oxides thereof constitutes the working anode surface and is carried on a support made of a film-forming metal, usually titanium.
  • the anode conductor leading the current to the anode within the cell may also be constructed of titanium since this metal is resistant to electrochemical attack under the severe anodic conditions ruling in the cell, but in order to reduce capital expenditure and running costs it is desirable to use as far as possible a cheaper and better conducting metal.
  • the present invention overcomes these problems by providing a friction-welded joint between an aluminum current leadin and a titanium member which supports the anode structure proper.
  • Other advantageous features of the invention will appear hereinafter.
  • anode assembly for electrolytic cells which comprises a titanium tube having a flat titanium closure attached in fluid-tight manner across one end, an aluminum current lead-in at least partially within the tube and coaxial therewith having one end frictionwelded to the titanium closure, and a foraminate titanium structure carrying on at least a part of its surface a coating comprising an operative electrode material, the said foraminate titanium structure lying in a plane parallel to the said titanium closure and being electrically connected thereto by titanium members which together with the said closure define an inverted channel shape.
  • titanium we mean titanium alone or an alloy based on titanium and having anodic polarization properties comparable to those of titanium.
  • the operative electrode material may be any material which is active in transferring electrons from an electrolyte to the underlying titanium structure of the anode assembly and which is resistant to electrochemical attack under the conditions ruling in the cell where the anode is to be used.
  • the operative electrode material may suitably consist of one or more platinum group metals i.e.
  • platinum platinum, rhodium, iridium, ruthenium, osmium and palladium, and/or oxides thereof, or another metal or a compound which will function as an anode and which is resistant to electrochemical dissolution in the cell, for instance rhenium, rhenium trioxide, magnetite, titanium nitride, the borides, phosphides or silicides of the platinum group metals, or an oxidic semiconducting compound.
  • rhenium, rhenium trioxide, magnetite, titanium nitride, the borides, phosphides or silicides of the platinum group metals, or an oxidic semiconducting compound for instance rhenium, rhenium trioxide, magnetite, titanium nitride, the borides, phosphides or silicides of the platinum group metals, or an oxidic semiconducting compound.
  • coating comprising an operative electrode material may also contain electronically non-conducting oxides, particularly oxides of the film-forming metals such as titanium, as is known in the art, to anchor the operative electrode material more securely to the supporting titanium structure and to increase its resistance to dissolution in the working cell.
  • a preferred coating comprising an operative electrode material for anodes that are to be used in mercury-cathode cells electrolyzing alkali metal chloride solutions consists of at least one oxide of at least one platinum group metal, particularly ruthenium dioxide, as the operative electrode material, and titanium dioxide.
  • the titanium tube passes through sealing means in thecell casing, for instance the cover of the cell, so that the aluminum current lead-in rod is protected from contact with the cell contents.
  • the aluminum current lead-in rod is made of sufficient length to protrude from the titanium tube for easy connection of an electrical bus-bar to the end of the rod outside the cell.
  • the titanium closure and the titanium members together defining an inverted channel shape are fabricated from one integral piece of titanium metal.
  • the inverted channel shape may extend both laterallyand longitudinally well beyond the limits defined by the cross-section of the end of the titanium tube to which the base of the channel forms a closure, and usually will so extend, in order to support a coated foraminate titanium structure of sufficient area to provide the desired working anode area when installed in the cell.
  • Such embodiments are illustrated in the accompanying drawings FlG. 1-7, which are not to scale and in which like parts are numbered alike.
  • FIG. 1 and FIG. 2 show vertical sections at right angles to each other through the center of an electrode assembly.
  • the center part of an inverted titanium channel 1 forms a fluid-tight closure across the lower end of titanium tube 2 by virtue of a peripheral weld around the end of the tube indicated as 3.
  • An aluminum current lead-in rod 4 has its lower end attached to the center of the channel 1 by a friction weld indicated at 5.
  • the edges of the channel 1 are welded at intervals as indicated at 6 to a horizontally-disposed foraminate titanium structure 7 which carries on at least a part of its surface a coating (not shown) comprising an operative electrode material as defined hereinbefore.
  • the foraminate titanium structure 7 may suitably be a multi-holed titanium sheet, for instance a sheet of expanded titanium metal.
  • the foraminate structure may be built up from longitudinally-extended titanium members spaced apart with their long axes parallel to each other, each one being welded to both bottom edges of the inverted channel. These members may be for instance flat strips. rods, hemicylindrical channels which are convex upwards or convex downwards or channels of U-shaped or inverted U- shaped, the closed end of the U being optionally flattened.
  • an arrangement approximating to the said built-up structure of longitudinally-extending members spaced apart with their long axes parallel to each other may be produced by pressing from a titanium sheet by means of a slotting and forming tool, whereby a structure with pressed-out louvres is obtained.
  • The. louvre slats so obtained may suitably be turned at right angles to the original plane of the titanium sheet or they mayhave each of their edges rolled round to form approximately hemicylindrical members which alternate with the slots from which the metal forming them has been pressed out.
  • FIG. 3 shows an anode assembly in which the foraminate titanium structure is built up from parallel-spaced titanium strips 8, which each have one long edge welded to both bottom edges of the inverted titanium channel 1 as again indicated at 6.
  • the other parts of FIG. 3 correspond to those of FIG. 2.
  • at least half of the coating thereon comprising an operative electrode material may suitably be carried on the faces of the strips 8 (the vertical surfaces in the configuration in the drawing), as taught for instance in British Patent Specification No. 1,076,973 for coatings of the platinum group metals on anode surfaces formed from titanium ribs.
  • the titanium tube which surrounds the aluminum current lead-in may be provided with a flange at its lower end, the fluid-tight joint between the titanium tube and the inverted titanium channel then being made by welding the flange to the channel.
  • each of the sides of the inverted channel may be terminated by a flange, the foraminate titanium structure carrying the coating comprising an operative electrode material then being welded to these flanges.
  • An anode assembly incorporating these optional features is illustrated in FIG. 4, with the flange 8 and weld 9 replacing the weld 3 of FIG. 1 and the flanges l and welds ll replacing the welds 6 of FIG. 1.
  • the aluminum current lead-in rod 4 is shown substantially filling the cross-section of titanium tube 2.
  • this arrangement in which only sufficient clearance is provided between the rod and the tube for easy assembly of these parts, so as to obtain the lowest electrical resistance in the aluminum rod commensurate with the diameter of the tube employed. It is not, however, essential for the rod to be a close fit within the tube and a wider gap may be provided between these two members if desired.
  • An anode assembly according to the invention is very suitable for use in a cell wherein gas is evolved at the anode, with the working anode structure of coated foraminate titanium arranged parallel to a substantially horizontal cathode, e.g. a flowing mercury cathode, since gas evolved beneath the current lead-in can pass freely upwards through the foraminate structure into the space beneath the inverted titanium channel.
  • the gas may be allowed to flow out from under the ends of the inverted channel or, if desired, one or more openings to assist the escape of gas may be provided in the top of the channel between the centrally disposed titanium tube and each end of the channel. Suitable arrangements of opening are shown in FIG.
  • FIG. 5 which are plan views showing only the titanium channel-shaped member 1 and the current lead in 4 with its surrounding titanium tube 2.
  • FIG. 5 there is one large opening 12 provided towards each end of the channel.
  • FIG. 6 there is a plurality of small openings 13 towards each end of the channel and in the arrangement of FIG. 7 the channel is cut away at each end in approximately a V-shape 14 to assist the escape of gas.
  • An anode assembly for electrolytic cells which comprises a titanium tube having a fiat titanium closure attached in fluidtight manner across one end, an aluminum current lead-in rod at least partially within the tube and coaxial therewith having one end friction-welded to the titanium closure, and a foraminate titanium structure carrying on at least a part of its surface a coating comprising an operative electrode material, the said foraminate titanium structure lying in a plane parallel to the said titanium closure and being electrically connected thereto by titanium members which together with the said closure define an inverted channel shape.
  • the foraminate titanium structure comprises a titanium sheet having a plurality of louvre slats pressed out so as to form a plurality of corresponding slots, the slats having rolled edges so as to form a series of approximately hemicylindrical members which alternate with the slots.
  • anode assembly according to claim 1, wherein the coating comprising an operative electrode material consists of at least one oxide of at least one platinum group metal as the operative electrode material and titanium dioxide.
  • An anode assembly for electrolytic cells comprising:
  • a downwardly-facing, open-ended, horizontally-elongated titanium channel member having a web portion and two depending flange portions integral with the web portion;
  • a titanium tube secured at one end to said web portion in a fluid-tight manner so that said web portion closes said end, said web portion having at least one gas escape opening therethrough located intermediate said tube and each end of said channel;
  • a foraminate titanium structure lying in a plane parallel to said web portion and electrically connected to the lower edges of the flange portions, said foraminate structure carrying on at least a part of its surface a coating comprising an operative electrode material.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
US44044A 1969-06-27 1970-06-08 Anode assembly for electrolytic cells Expired - Lifetime US3676325A (en)

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GB3254469 1969-06-27

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US (1) US3676325A (US07902200-20110308-C00004.png)
JP (1) JPS4815146B1 (US07902200-20110308-C00004.png)
BE (1) BE752433A (US07902200-20110308-C00004.png)
FI (1) FI57446C (US07902200-20110308-C00004.png)
FR (1) FR2063122B1 (US07902200-20110308-C00004.png)
GB (1) GB1304518A (US07902200-20110308-C00004.png)
ZA (1) ZA703781B (US07902200-20110308-C00004.png)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2408392A1 (de) * 1973-02-21 1974-08-22 Ici Ltd Anoden fuer elektro-chemische verfahren
US3900384A (en) * 1972-11-24 1975-08-19 Ppg Industries Inc Method of assembling a bipolar electrode having friction welded conductor/connector means and bipolar electrode formed thereby
US3912616A (en) * 1973-05-31 1975-10-14 Olin Corp Metal anode assembly
US3951767A (en) * 1973-05-29 1976-04-20 Metallgesellschaft Aktiengesellschaft Method and apparatus for the electrolysis of alkali metal chlorides
US3953316A (en) * 1973-11-05 1976-04-27 Olin Corporation Metal anode assembly
US3981788A (en) * 1974-08-23 1976-09-21 Kureha Kagaku Kogyo Kabushiki Kaisha Caustic alkali producing multiple vertical diaphragm type electrolytic cell admitting of easy assembly
US3988220A (en) * 1974-01-04 1976-10-26 Ppg Industries, Inc. Process for electrolyzing brine in a bipolar electrolytic diaphragm cell having friction welded conductor connector means
US4013525A (en) * 1973-09-24 1977-03-22 Imperial Chemical Industries Limited Electrolytic cells
US4022679A (en) * 1973-05-10 1977-05-10 C. Conradty Coated titanium anode for amalgam heavy duty cells
US4069130A (en) * 1975-01-29 1978-01-17 Kerr-Mcgee Chemical Corporation Bipolar electrode and method for constructing same
US4085016A (en) * 1976-07-20 1978-04-18 Noranda Mines Limited Method and apparatus for the oxidation of organic material present in concentrated sulfuric acid
US4323438A (en) * 1979-04-10 1982-04-06 Bayer Aktiengesellschaft Anode for alkali metal chloride electrolysis
US4391695A (en) * 1981-02-03 1983-07-05 Conradty Gmbh Metallelektroden Kg Coated metal anode or the electrolytic recovery of metals
US4457811A (en) * 1982-12-20 1984-07-03 Aluminum Company Of America Process for producing elements from a fused bath using a metal strap and ceramic electrode body nonconsumable electrode assembly
USRE32561E (en) * 1981-02-03 1987-12-15 Conradty Gmbh & Co. Metallelektroden Kg Coated metal anode for the electrolytic recovery of metals
US4784735A (en) * 1986-11-25 1988-11-15 The Dow Chemical Company Concentric tube membrane electrolytic cell with an internal recycle device
EP0686455A1 (de) * 1994-06-06 1995-12-13 Heraeus Elektrochemie Gmbh Verfahren zur Verbindung zwischen einer Elektrode für elektrolytische Zwecke und einem Stromzuführungsbolzen und Verbindingsanordnung
US5584975A (en) * 1995-06-15 1996-12-17 Eltech Systems Corporation Tubular electrode with removable conductive core
WO1998024490A1 (en) * 1996-12-05 1998-06-11 Entremed, Inc. Improved electrodes and method of use
US20030059945A1 (en) * 2001-02-21 2003-03-27 Dzekunov Sergey M. Apparatus and method for flow electroporation of biological samples
US20030073238A1 (en) * 2001-08-22 2003-04-17 Dzekunov Sergey M. Apparatus and method for electroporation of biological samples
US20030119685A1 (en) * 2001-09-26 2003-06-26 The Procter & Gamble Company Personal cleansing compositions comprising silicone resin-containing adhesives
US20040115784A1 (en) * 2002-09-30 2004-06-17 Maxcyte, Inc. Apparatus and method for streaming electroporation
US6773669B1 (en) 1995-03-10 2004-08-10 Maxcyte, Inc. Flow electroporation chamber and method
US20050282200A1 (en) * 2004-05-12 2005-12-22 Maxcyte, Inc. Methods and devices related to a regulated flow electroporation chamber
CN109183135A (zh) * 2018-09-14 2019-01-11 华晶精密制造股份有限公司 一种用于生产电镀金刚石切割线的阳极装置

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5418086Y2 (US07902200-20110308-C00004.png) * 1973-05-28 1979-07-10
JPS52115848U (US07902200-20110308-C00004.png) * 1976-02-29 1977-09-02
DE2949495C2 (de) * 1979-12-08 1983-05-11 Heraeus-Elektroden Gmbh, 6450 Hanau Elektrode für Elektrolysezellen
US4657652A (en) * 1986-02-28 1987-04-14 Pennwalt Corporation Electrolytic cell and anode for brine electrolytes

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE453750C (de) * 1927-12-14 I G Farbenindustrie Akt Ges Elektrolysierzelle
GB668618A (en) * 1949-10-24 1952-03-19 Oerlikon Maschf Improvements in or relating to a plate-type electrode for electrolysers
US3271289A (en) * 1959-07-22 1966-09-06 Oronzio De Nora Impianti Mercury cathode electrolytic cell having an anode with high corrosionresistance and high electrical and heat conductivity
US3297561A (en) * 1961-05-08 1967-01-10 Ici Ltd Anode and supporting structure therefor
US3318792A (en) * 1957-12-17 1967-05-09 Ici Ltd Mercury cathode cell with noble metaltitanium anode as cover means
US3409533A (en) * 1964-03-23 1968-11-05 Asahi Chemical Ind Mercury-method cell for alkali chloride electrolysis
US3437579A (en) * 1965-04-20 1969-04-08 Ici Ltd Anode assembly
US3455810A (en) * 1965-02-04 1969-07-15 Uddeholms Ab Fastening means for an electrode in a so-called horizontal electrolytic cell
US3458423A (en) * 1965-12-07 1969-07-29 Basf Ag Mercury cathode alkali-chlorine cell containing a porous titanium or tantalum layered anode
US3511766A (en) * 1967-10-02 1970-05-12 Dow Chemical Co Current lead-in pin

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE453750C (de) * 1927-12-14 I G Farbenindustrie Akt Ges Elektrolysierzelle
GB668618A (en) * 1949-10-24 1952-03-19 Oerlikon Maschf Improvements in or relating to a plate-type electrode for electrolysers
US3318792A (en) * 1957-12-17 1967-05-09 Ici Ltd Mercury cathode cell with noble metaltitanium anode as cover means
US3271289A (en) * 1959-07-22 1966-09-06 Oronzio De Nora Impianti Mercury cathode electrolytic cell having an anode with high corrosionresistance and high electrical and heat conductivity
US3297561A (en) * 1961-05-08 1967-01-10 Ici Ltd Anode and supporting structure therefor
US3409533A (en) * 1964-03-23 1968-11-05 Asahi Chemical Ind Mercury-method cell for alkali chloride electrolysis
US3455810A (en) * 1965-02-04 1969-07-15 Uddeholms Ab Fastening means for an electrode in a so-called horizontal electrolytic cell
US3437579A (en) * 1965-04-20 1969-04-08 Ici Ltd Anode assembly
US3458423A (en) * 1965-12-07 1969-07-29 Basf Ag Mercury cathode alkali-chlorine cell containing a porous titanium or tantalum layered anode
US3511766A (en) * 1967-10-02 1970-05-12 Dow Chemical Co Current lead-in pin

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900384A (en) * 1972-11-24 1975-08-19 Ppg Industries Inc Method of assembling a bipolar electrode having friction welded conductor/connector means and bipolar electrode formed thereby
DE2408392A1 (de) * 1973-02-21 1974-08-22 Ici Ltd Anoden fuer elektro-chemische verfahren
US4022679A (en) * 1973-05-10 1977-05-10 C. Conradty Coated titanium anode for amalgam heavy duty cells
US3951767A (en) * 1973-05-29 1976-04-20 Metallgesellschaft Aktiengesellschaft Method and apparatus for the electrolysis of alkali metal chlorides
US3912616A (en) * 1973-05-31 1975-10-14 Olin Corp Metal anode assembly
US4013525A (en) * 1973-09-24 1977-03-22 Imperial Chemical Industries Limited Electrolytic cells
US3953316A (en) * 1973-11-05 1976-04-27 Olin Corporation Metal anode assembly
US3988220A (en) * 1974-01-04 1976-10-26 Ppg Industries, Inc. Process for electrolyzing brine in a bipolar electrolytic diaphragm cell having friction welded conductor connector means
US3981788A (en) * 1974-08-23 1976-09-21 Kureha Kagaku Kogyo Kabushiki Kaisha Caustic alkali producing multiple vertical diaphragm type electrolytic cell admitting of easy assembly
US4069130A (en) * 1975-01-29 1978-01-17 Kerr-Mcgee Chemical Corporation Bipolar electrode and method for constructing same
US4085016A (en) * 1976-07-20 1978-04-18 Noranda Mines Limited Method and apparatus for the oxidation of organic material present in concentrated sulfuric acid
US4323438A (en) * 1979-04-10 1982-04-06 Bayer Aktiengesellschaft Anode for alkali metal chloride electrolysis
US4391695A (en) * 1981-02-03 1983-07-05 Conradty Gmbh Metallelektroden Kg Coated metal anode or the electrolytic recovery of metals
USRE32561E (en) * 1981-02-03 1987-12-15 Conradty Gmbh & Co. Metallelektroden Kg Coated metal anode for the electrolytic recovery of metals
US4457811A (en) * 1982-12-20 1984-07-03 Aluminum Company Of America Process for producing elements from a fused bath using a metal strap and ceramic electrode body nonconsumable electrode assembly
US4784735A (en) * 1986-11-25 1988-11-15 The Dow Chemical Company Concentric tube membrane electrolytic cell with an internal recycle device
EP0686455A1 (de) * 1994-06-06 1995-12-13 Heraeus Elektrochemie Gmbh Verfahren zur Verbindung zwischen einer Elektrode für elektrolytische Zwecke und einem Stromzuführungsbolzen und Verbindingsanordnung
US6773669B1 (en) 1995-03-10 2004-08-10 Maxcyte, Inc. Flow electroporation chamber and method
US20050019311A1 (en) * 1995-03-10 2005-01-27 Holaday John W. Flow electroporation chamber and method
US5584975A (en) * 1995-06-15 1996-12-17 Eltech Systems Corporation Tubular electrode with removable conductive core
WO1998024490A1 (en) * 1996-12-05 1998-06-11 Entremed, Inc. Improved electrodes and method of use
US6090617A (en) * 1996-12-05 2000-07-18 Entremed, Inc. Flow electroporation chamber with electrodes having a crystalline metal nitride coating
US6485961B1 (en) 1996-12-05 2002-11-26 Maxcyte, Inc. Electrodes having a continuous, crystalline metal nitride coating and method of use
US20030059945A1 (en) * 2001-02-21 2003-03-27 Dzekunov Sergey M. Apparatus and method for flow electroporation of biological samples
US7029916B2 (en) 2001-02-21 2006-04-18 Maxcyte, Inc. Apparatus and method for flow electroporation of biological samples
US20030073238A1 (en) * 2001-08-22 2003-04-17 Dzekunov Sergey M. Apparatus and method for electroporation of biological samples
US7141425B2 (en) 2001-08-22 2006-11-28 Maxcyte, Inc. Apparatus and method for electroporation of biological samples
US7186559B2 (en) 2001-08-22 2007-03-06 Maxcyte, Inc. Apparatus and method for electroporation of biological samples
US20030119685A1 (en) * 2001-09-26 2003-06-26 The Procter & Gamble Company Personal cleansing compositions comprising silicone resin-containing adhesives
US20040115784A1 (en) * 2002-09-30 2004-06-17 Maxcyte, Inc. Apparatus and method for streaming electroporation
US20050282200A1 (en) * 2004-05-12 2005-12-22 Maxcyte, Inc. Methods and devices related to a regulated flow electroporation chamber
US7771984B2 (en) 2004-05-12 2010-08-10 Maxcyte, Inc. Methods and devices related to a regulated flow electroporation chamber
US9546350B2 (en) 2004-05-12 2017-01-17 Maxcyte, Inc. Methods and devices related to a regulated flow electroporation chamber
CN109183135A (zh) * 2018-09-14 2019-01-11 华晶精密制造股份有限公司 一种用于生产电镀金刚石切割线的阳极装置

Also Published As

Publication number Publication date
GB1304518A (US07902200-20110308-C00004.png) 1973-01-24
ZA703781B (en) 1972-01-26
FR2063122A1 (US07902200-20110308-C00004.png) 1971-07-09
FI57446B (fi) 1980-04-30
BE752433A (fr) 1970-12-24
FR2063122B1 (US07902200-20110308-C00004.png) 1973-01-12
JPS4815146B1 (US07902200-20110308-C00004.png) 1973-05-12
FI57446C (fi) 1980-08-11

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