US20120138477A1 - Bipolar electrodes with high energy efficiency, and use thereof for synthesising sodium chlorate - Google Patents

Bipolar electrodes with high energy efficiency, and use thereof for synthesising sodium chlorate Download PDF

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Publication number
US20120138477A1
US20120138477A1 US13/382,664 US201013382664A US2012138477A1 US 20120138477 A1 US20120138477 A1 US 20120138477A1 US 201013382664 A US201013382664 A US 201013382664A US 2012138477 A1 US2012138477 A1 US 2012138477A1
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United States
Prior art keywords
electrodes
bipolar
coating
electrode
titanium
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.)
Abandoned
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US13/382,664
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English (en)
Inventor
Robert Schulz
Sylvio Savoie
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Hydro Quebec
Meeir Technologie Inc
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Hydro Quebec
Meeir Technologie Inc
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Assigned to HYDRO-QUEBEC, MEEIR TECHNOLOGIE INC. reassignment HYDRO-QUEBEC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHULZ, ROBERT, SAVOIE, SYLVIO
Publication of US20120138477A1 publication Critical patent/US20120138477A1/en
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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
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C25B1/265—Chlorates
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

Definitions

  • the present invention relates to novel bipolar electrodes with a cathodic coating on a part of it and an anodic coating on another part of it. It also relates to the usage of these novel electrodes for the synthesis of sodium chlorate.
  • FIGS. 1 a and 1 b are schematic views of mono-polar electrodes
  • FIGS. 2 a and 2 b are schematic views of bipolar electrodes
  • FIG. 3 is an illustration of an adhesion test of a coating of iron aluminide on steel 1020;
  • FIG. 4 is an illustration of an adhesion test of a coating of iron aluminide on titanium
  • FIG. 5 is a scheme illustrating the assembly of traction dowels used for the adhesion tests
  • FIG. 6 is an illustration of a corrosion test in a chlorate solution of a DSA electrode and of a coating of the type Fe 3 ⁇ x Al 1+x M y T z on a substrate of titanium;
  • FIG. 7 is a schematic view of a bipolar electrode in accordance with the invention.
  • FIGS. 8 a , 8 b are schematic views of bipolar modules in accordance with the invention.
  • FIGS. 9 a , 9 b and 9 c are photographs of bipolar electrodes fabricated in such a manner that a part of these electrodes is covered by a coating of the DSA type and another part by a coating of the type Fe 3 ⁇ x Al 1+x M y T z .
  • NaClO 3 sodium chlorate
  • the process is very energy-consuming and requires between 5000 and 5500 kW of electricity per ton of sodium chlorate.
  • the electrolysis cells in which a high continuous current circulates customarily comprises anodes that are dimensionally stable (DSA) and uncoated cathodes of steel or of titanium.
  • DSA anodes are well-known in the art of electrolysis cells, see, for example: WO4101852, WO4094698, U.S. Pat. No. 6,071,570, U.S. Pat. No. 4,528,084, U.S. Pat. No. 5,989,396, U.S. Pat. No. 6,572,758, U.S. Pat. No. 4,233,340; U.S. Pat. No. 5,419,824; U.S. Pat. No. 5,593,556 and U.S. Pat. No. 5,672,394.
  • DSA anodes typically comprise a substrate of titanium on which a coating of ruthenium oxide is applied possibly with other oxides or compounds such as iridium oxide.
  • ruthenium oxide is applied possibly with other oxides or compounds such as iridium oxide.
  • the energy losses on the anodic side are low. This is reflected by a low anodic overvoltage several tens of millivolts. However, it is not the same on the cathodic side.
  • the cathodic overvoltage on the surface of a steel plate is approximately 900 mV whereas on the surface of a plate of titanium it is approximately 1200 mV.
  • the energy losses on the cathodic side thus represent the main source of energy losses in the process. It is for this reason that in the course of recent years the inventors of the present invention attempted to find performing cathode coatings that allow the overpotential on these electrodes to be lowered.
  • WO/2008/138148 which also originates from the inventors of the present invention, gives an example of such cathode coatings. It describes alloys of the type Fe 3 ⁇ x Al 1+x M y T z that are applied on the surface of an electrode for making a coated cathode that is very performing in regards to energy.
  • FIG. 1 shows schematic views of mono-polar electrodes.
  • each electrode only plays one role, that of anode or of cathode. Consequently, there is no ambiguity about the type of coating to be applied if one wishes to improve the energy efficiency of such cells.
  • a substrate of titanium will be selected and a coating of ruthenium oxide will be applied in order to make a DSA and for the cathode a steel plate could be selected and a coating of the type Fe 3 ⁇ x Al 1+x M y T z could be applied in order to make a cathode with high energy performance.
  • FIG. 2 shows schematic views of bipolar electrodes.
  • an electrode or a module of electrodes simultaneously plays the role of anode and that of cathode.
  • the negative face of the bipolar electrode is cathodic while the positive face is anodic.
  • the electrodes in the left part of the bipolar module (negative sign) are cathodic while the electrodes on the right side (positive sign) are anodic.
  • a bipolar module of electrodes such as the one shown at the bottom of FIG. 2 presents an additional problem.
  • the electrodes on the anodic side (right side of the module) are customarily DSAs on substrates of titanium whereas the electrodes on the cathodic side (left side of the module) are steel plates. Now, it is very difficult to weld titanium to steel. Such a module therefore presents a difficulty in the assembly.
  • the present invention has the goal of solving these problems associated with bipolar electrodes.
  • the invention therefore has, as first subject matter, a bipolar electrode with high energy efficiency, which electrode has a part provided with a cathodic coating and another part that is distinct from the first one and that is provided with an anodic coating.
  • the anodic coating is of the DSA type
  • the cathodic coating consists of an alloy with the formula:
  • M represents one or several catalytic species selected from Ru, Ir, Pd, Pt, Rh, Os, Re, Ag and Ni;
  • T represents one or several elements from Mo, Co, Cr, V, Cu, Zn, Nb, W, Zr, Y;
  • x is a number greater than ⁇ 1 and lower than or equal to +1;
  • y is a number greater than 0 and lower than or equal to +1;
  • z is a number between 0 and +1.
  • the substrate on which the coatings are applied can be a substrate of steel or a substrate of titanium.
  • the invention also has as subject matter a bipolar module of electrodes containing several electrodes such as those described above.
  • the invention also has as subject matter the use of the bipolar electrode or of the bipolar module in accordance with the invention for the electrosynthesis of sodium chlorate.
  • FIG. 3 shows an adhesion test of the coating of the type Fe 3 Al on a substrate of steel 1020 according to ASTM C633.
  • the fracture took place at a stress of 11,922 psi, that is quite close to the fracture limit of the glue serving for the mounting of the dowels (see the scheme of FIG. 5 ).
  • the adhesion of a coating of iron aluminide on a steel substrate is excellent.
  • FIG. 4 shows a similar test for the adhesion of the coating of the same type on a substrate of titanium.
  • the fracture took place at a stress of 10,604 psi, that is, a value almost as high as the previously measured one. Consequently, the adhesion of the coating is just as good on a substrate of titanium as on a substrate of steel.
  • a substrate of steel preferably a stainless steel of the ferritic type not containing Ni.
  • a layer of Ti is preferably applied on one side by a method such as “cold spray” before applying the DSA coating on the same side and on the layer of Ti.
  • a coating of the type Fe 3 ⁇ x Al 1+x M y T z is applied on the other side as previously but this time on steel.
  • FIG. 6 shows the “current-voltage” curves in a chlorate solution at 22° C. measured relative to a reference electrode Ag/AgCl by sweeping the potential 5 mV/sec for a DSA electrode and a coating of the type Fe 3 ⁇ x Al 1+x M y T z on a substrate of titanium.
  • the corrosion threshold is approximately 1.2 V. The galvanic couple between these dissimilar materials is thus reduced by an appropriate selection of the chemical composition of the coating based on iron aluminide.
  • FIG. 7 shows schematic views of bipolar electrodes in accordance with the invention.
  • first electrode one face has an anodic coating while the other face has a cathodic coating.
  • second bipolar electrode one end of the electrode is covered on two sides by a cathodic coating whereas the other end is covered by an anodic coating.
  • FIG. 8 shows schematic views of bipolar modules constituted by an assembly of bipolar electrodes represented in FIG. 7 .
  • FIGS. 9 a and 9 b show photographs of bipolar electrodes such as those represented schematically in FIG. 7
  • FIG. 9 c shows the appearance of a bipolar electrode in accordance with the invention after an immersion of 69 hours in a chlorate solution at 22° C. A beginning of pitting corrosion is observed on the cathodic part but the structural integrity of the coating is still excellent.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
US13/382,664 2009-07-08 2010-04-08 Bipolar electrodes with high energy efficiency, and use thereof for synthesising sodium chlorate Abandoned US20120138477A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CA2,671,211 2009-07-08
CA2671211A CA2671211A1 (fr) 2009-07-08 2009-07-08 Electrodes bipolaires a haute efficacite energetique et usage de celles-ci pour la synthese du chlorate de sodium
PCT/CA2010/000531 WO2011003173A1 (fr) 2009-07-08 2010-04-08 Electrodes bipolaires à haute efficacité énergétique et usage de celles-ci pour la synthèse du chlorate de sodium

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US20120138477A1 true US20120138477A1 (en) 2012-06-07

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US (1) US20120138477A1 (fr)
EP (1) EP2451995A4 (fr)
CN (1) CN102859041B (fr)
BR (1) BR112012000318A2 (fr)
CA (2) CA2671211A1 (fr)
WO (1) WO2011003173A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107034483A (zh) * 2017-04-10 2017-08-11 广东卓信环境科技股份有限公司 一种氯酸钠发生器电极的制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013159219A1 (fr) * 2012-04-23 2013-10-31 Chemetics Inc. Cathode en acier inoxydable modifiée en surface destinée à un électrolyseur
ITMI20120873A1 (it) * 2012-05-21 2013-11-22 Industrie De Nora Spa Elettrodo per evoluzione di prodotti gassosi e metodo per il suo ottenimento
US9050482B1 (en) * 2013-04-01 2015-06-09 Jeffry L. VanElverdinghe Trampoline with elongate spring mount and bed with integral spring cover
US9278241B2 (en) * 2013-04-01 2016-03-08 Jeffry L. VanElverdinghe Trampoline with elongate spring mount and bed with integral spring cover

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3826732A (en) * 1973-05-25 1974-07-30 Hooker Chemical Corp Bipolar electrode
US5225061A (en) * 1991-05-24 1993-07-06 Westerlund Goethe O Bipolar electrode module
US5868913A (en) * 1993-08-13 1999-02-09 Imperial Chemical Industries Plc Electrode and preparation thereof
US6235167B1 (en) * 1999-12-10 2001-05-22 John E. Stauffer Electrolyzer for the production of sodium chlorate
US20060079943A1 (en) * 2004-08-31 2006-04-13 Narciso Hugh L Jr Devices and methods for gynecologic hormone modulation in mammals
WO2008138148A1 (fr) * 2007-05-15 2008-11-20 HYDRO-QUéBEC Alliages nanocristallins du type fe3al(ru) et usage de ceux-ci sous forme nanocristalline ou non pour la fabrication d'électrodes pour la synthèse du chlorate de sodium

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075070A (en) * 1976-06-09 1978-02-21 Ppg Industries, Inc. Electrode material
US4422917A (en) * 1980-09-10 1983-12-27 Imi Marston Limited Electrode material, electrode and electrochemical cell
US4530742A (en) * 1983-01-26 1985-07-23 Ppg Industries, Inc. Electrode and method of preparing same
CA2154428C (fr) * 1995-07-21 2005-03-22 Robert Schulz Alliages a base de ti, ru, fe et o et usage de ceux-ci pour la fabrication de cathodes pour la synthese electrochimique du chlorate de sodium
BRPI0515969A (pt) * 2004-10-12 2008-08-12 Canexus Chemicals Canada Ltd células de clorato eletrolìticas não divididas com catodos revestidos
CA2612543C (fr) * 2005-06-30 2011-09-20 Akzo Nobel N.V. Procede chimique

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3826732A (en) * 1973-05-25 1974-07-30 Hooker Chemical Corp Bipolar electrode
US5225061A (en) * 1991-05-24 1993-07-06 Westerlund Goethe O Bipolar electrode module
US5868913A (en) * 1993-08-13 1999-02-09 Imperial Chemical Industries Plc Electrode and preparation thereof
US6235167B1 (en) * 1999-12-10 2001-05-22 John E. Stauffer Electrolyzer for the production of sodium chlorate
US20060079943A1 (en) * 2004-08-31 2006-04-13 Narciso Hugh L Jr Devices and methods for gynecologic hormone modulation in mammals
WO2008138148A1 (fr) * 2007-05-15 2008-11-20 HYDRO-QUéBEC Alliages nanocristallins du type fe3al(ru) et usage de ceux-ci sous forme nanocristalline ou non pour la fabrication d'électrodes pour la synthèse du chlorate de sodium
US20100159152A1 (en) * 2007-05-15 2010-06-24 Hydro-Quebec Nanocrystalline alloys of the fe3al(ru) type and use thereof optionally in nanocrystalline form for making electrodes for sodium chlorate synthesis

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107034483A (zh) * 2017-04-10 2017-08-11 广东卓信环境科技股份有限公司 一种氯酸钠发生器电极的制备方法

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CN102859041B (zh) 2015-06-17
EP2451995A4 (fr) 2016-11-16
CN102859041A (zh) 2013-01-02
WO2011003173A8 (fr) 2011-04-14
BR112012000318A2 (pt) 2019-06-04
EP2451995A1 (fr) 2012-05-16
CA2767434A1 (fr) 2011-01-13
WO2011003173A1 (fr) 2011-01-13
CA2671211A1 (fr) 2011-01-08

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