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WO2008138945A2 - Electrode for membrane electrolysis cells - Google Patents

Electrode for membrane electrolysis cells Download PDF

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Publication number
WO2008138945A2
WO2008138945A2 PCT/EP2008/055887 EP2008055887W WO2008138945A2 WO 2008138945 A2 WO2008138945 A2 WO 2008138945A2 EP 2008055887 W EP2008055887 W EP 2008055887W WO 2008138945 A2 WO2008138945 A2 WO 2008138945A2
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WO
WIPO (PCT)
Prior art keywords
electrode
grooves
electrode according
membrane
electrolysis
Prior art date
Application number
PCT/EP2008/055887
Other languages
French (fr)
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WO2008138945A3 (en
Inventor
Angelo Ottaviani
Leonello Carrettin
Dino Floriano Di Franco
Corrado Mojana
Michele Perego
Original Assignee
Industrie De Nora S.P.A.
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
Priority to AT08759575T priority Critical patent/ATE490354T1/en
Priority to JP2010507912A priority patent/JP5193287B2/en
Priority to AU2008249990A priority patent/AU2008249990B2/en
Priority to CA002687319A priority patent/CA2687319A1/en
Priority to MX2009012314A priority patent/MX2009012314A/en
Priority to EP08759575A priority patent/EP2147133B1/en
Priority to BRPI0811852-3A2A priority patent/BRPI0811852A2/en
Priority to PL08759575T priority patent/PL2147133T3/en
Priority to DE602008003789T priority patent/DE602008003789D1/en
Application filed by Industrie De Nora S.P.A. filed Critical Industrie De Nora S.P.A.
Priority to CN2008800158766A priority patent/CN101707932B/en
Priority to DK08759575.7T priority patent/DK2147133T3/en
Publication of WO2008138945A2 publication Critical patent/WO2008138945A2/en
Publication of WO2008138945A3 publication Critical patent/WO2008138945A3/en
Priority to IL201541A priority patent/IL201541A/en
Priority to EG2009111668A priority patent/EG25970A/en
Priority to US12/617,773 priority patent/US20100059389A1/en
Priority to HK10110136.2A priority patent/HK1143615A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C25B1/14Alkali metal compounds
    • C25B1/16Hydroxides
    • 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
    • C25B1/24Halogens or compounds thereof
    • C25B1/26Chlorine; Compounds thereof
    • 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making

Definitions

  • the invention relates to an electrode for electrochemical applications, in particular to an electrode for membrane electrolysis cells made on a metal support. Electrolytic processes carried out in cells separated by ion-exchange membranes are among the most relevant industrial electrochemical applications. Some examples of such applications are the electrolysis of alkali chloride brines (chlor-alkali electrolysis), with particular reference to the electrolysis of sodium chloride brine for the production of chlorine and caustic soda, and the electrolysis of hydrochloric acid solutions.
  • the anodic compartment of the electrolysis cell is separated from the cathodic compartment by means of an ion-exchange membrane.
  • the anodic compartment of the cell is fed with a sodium chloride brine, for instance at a concentration of about 300 g/l; chlorine evolution takes place on the anode surface, at a current density usually not above 4 kA/m 2 , while brine is consequently depleted down to an outlet concentration usually comprised between 200 and 220 g/l.
  • Sodium ions are transported by the electric field across the membrane to the cathodic compartment, where the caustic product is generated at a concentration usually not higher than 33% by weight. The caustic product is then extracted and concentrated by evaporation outside the cell.
  • the product gas has the tendency to build-up between the membrane and the electrode surfaces facing the same, increasing the ohmic drop in the contact zone and locally depleting the chloride-ion concentration due to poor electrolyte renewal. Brine dilution favours the local evolution of oxygen with consequent acidification.
  • chlorine build-up, oxygen build-up, depletion of trapped brine, acidification accounts for the early deterioration of the membranes, particularly in form of blister generation especially in correspondence of interstitial zones between anode and membrane, leading to voltage increase and electrolysis efficiency decrease.
  • a similar deterioration may also take place in the interstitial zones between membrane and cathode: in this case, liquid stagnation leads to an increase in the caustic product concentration, which may reach a value up to 40- 45%.
  • Such a high alkalinity can damage the membrane chemical structure, with consequent voltage increase going along with the onset of localised blistering, as described for the anode side.
  • US 4,608,144 disclosed an anode surface equipped with vertical parallel channels alternatively directed to brine feed and withdrawal, and further equipped with horizontal channels of lower section reciprocally connecting the feed and withdrawal channels. In this way a forced brine circulation is achieved, somehow preventing the adhesion of chlorine bubbles.
  • US 5,1 14,547 discloses an anode aimed at promoting brine circulation at the membrane-anode interface in order to obviate the increase in the electrical resistance associated with the depletion of stagnating brine at the interface by means of a structure consisting of vertical channels connected with slanted secondary channels disposed in a herringbone pattern.
  • US 2006/0042935 addresses the same problem by providing an irregular anode surface obtained by sandblasting or acid etching in order to improve the brine supply to the anode. While all of the proposed measures might contribute to some extent to prevent deterioration of ion-exchange membranes in the usual process conditions, they fail to guarantee an optimal functioning in the exasperated process conditions needed to meet the current market requirements aimed at a higher cell productivity.
  • One embodiment provides an electrode obtained on a metal substrate having a multiplicity of locally parallel grooves with a depth of 0.005 to 0.02 mm and a pitch - defined as the distance between adjacent grooves - of 0.01 to 0.5 mm.
  • locally parallel grooves it is hereby intended a multiplicity of grooves, of open or closed shape, running in parallel at least in part of their length; the path of the locally parallel grooves may assume a generally parallel trend across the whole electrode structure, in straight lines or with curvatures of any type.
  • the electrode surface presents locally parallel grooves having a closed shape and intersecting one another reciprocally.
  • the electrode as hereinbefore defined can be advantageous in any electrolytic application, especially for working in direct contact with an ion-exchange membrane; in the case of chlor-alkali electrolysis, the above electrode can be assembled with its grooved surface in direct contact with the membrane, with surprisingly advantageous results both used as the anode and/or as the cathode.
  • the metal substrate may be made of different materials, including but not limited to titanium and titanium alloys for anode application and nickel, nickel alloys and stainless steels for cathode application.
  • the substrate geometry can be of any type: as a non limiting example, the grooved surface can be provided on punched or expanded sheets, meshes and structures comprised of parallel strips optionally rotated along the horizontal axis, also called louvered electrodes.
  • the electrode substrate can be provided with a known catalytic coating on its grooved surface: for instance, when use as anode for chlorine evolution in chlor-alkali cells is intended, the electrode substrate may be provided with a coating based on noble metals or oxides thereof. Electrodes obtained on the substrate as hereinbefore defined can be particularly useful in chlor-alkali electrolysis cells, both as anodes for chlorine evolution and as cathodes for hydrogen evolution, especially when assembled with the grooved surface in direct contact with the membrane. In case of straight grooves running parallel across the whole structure, orienting the grooves in the vertical direction can provide an improved circulation of electrolyte and gas- bubble release from the surface.
  • Life-tests were also carried out with excellent results at anolyte concentrations below 200 g/l (in particular down to 150 g/l), with caustic product concentrations above 33% (in particular up to 37%) and maintaining pressure differentials across the two compartments higher than 3000 Pa (in particular up to 10000 Pa), conditions which normally led to a quick deterioration of the membranes when prior art electrodes were employed.
  • the electrode obtained on a grooved substrate as defined allows a particularly efficient release of the gas bubbles, also in comparison with grooved electrodes of the prior art, possibly because the densely packed and shallow grooves favour capillary transport phenomena as opposed to an electrolyte circulation.
  • the electrode as defined can be obtained by simple and cheap methods such as a superficial erosion carried out by means of abrasive paper or fabric - optionally in a continuous rolling process - lamellar grinding wheels or grindstones; other techniques include the use of draw-benches or rolling mills, besides more sophisticated technologies such as laser etching or lithographic techniques, according to the selected geometry.
  • the erosion by grindstone for instance can be suitable for obtaining locally parallel grooves of closed shape and intersecting one another, while a lamellar grinding wheel, a draw-bench or a rolling mill can be more suitable for obtaining generally parallel grooves along the whole surface.
  • An electrode obtained with the above mentioned techniques can allow a sensible cost reduction compared to other grooved electrodes known in the art and characterised by a much higher groove depth, which cannot be obtained by simple abrasion.
  • All samples prepared in the previous example were cut into 150 mm x 200 mm wide pieces and characterised, coupled in various combinations, in a multiple bench for chlor-alkali electrolysis accelerated lifetime tests.
  • Each station of the multiple bench was equipped with one membrane electrolysis cell suitable for accommodating one anode and one cathode of 1 mm thickness in direct contact with a reference sulphonic/carboxylic double layer membrane (Nafion ® 982 produced by DuPont, U.S.A.).
  • the electrode samples of tables 1 and 2 were assembled with vertically oriented grooves.
  • the lifetime test was carried out simultaneously starting-up all cells with the various combinations of anodes and cathodes at process conditions much more severe than the common industrial practice, determining the time of ion- exchange membrane decay, defined as the time required for the cell voltage to increase by 0.5 V with respect to the initial value at the process current density.
  • An electrolysis cell as in example 2, equipped with an anode sample A4 and a cathode sample C2, and a second analogous electrolysis cell equipped with a non- grooved anode sample AO and a non-grooved cathode sample CO were subjected to a lifetime test at process conditions sensibly more severe than the common industrial practice.
  • the cell equipped with electrode samples AO and CO had to be shut down because the progressive deterioration of the membrane had caused a strong increase in the cell voltage, which attained high values strongly fluctuating in time.
  • the cell disassembly evidenced a general formation of blisters on the surface, with a higher population in correspondence of the brine exhaust outlet nozzle, where an incipient local delamination of the two layers of the membrane could also be observed.
  • the cell equipped with anode A4 and cathode C2 was dismantled after 2400 hours of continuous testing at practically constant voltage. Upon disassembling the cell, no particular phenomenon of membrane deterioration was observed.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to an electrode for membrane electrolysis cells comprising a grooved metal support favouring the gas release and the electrolyte renewal on its surface. The grooved geometry of the support may be obtained by erosion of a metal sheet with abrasive media in a continuous process.

Description

ELECTRODE FOR MEMBRANE ELECTROLYSIS CELLS
BACKGROUND
The invention relates to an electrode for electrochemical applications, in particular to an electrode for membrane electrolysis cells made on a metal support. Electrolytic processes carried out in cells separated by ion-exchange membranes are among the most relevant industrial electrochemical applications. Some examples of such applications are the electrolysis of alkali chloride brines (chlor-alkali electrolysis), with particular reference to the electrolysis of sodium chloride brine for the production of chlorine and caustic soda, and the electrolysis of hydrochloric acid solutions.
In the following description, reference will be made to sodium chloride electrolysis as the most representative example in terms of overall production, but the present invention shall not be understood as limited to such application.
In membrane chlor-alkali electrolysis, the anodic compartment of the electrolysis cell is separated from the cathodic compartment by means of an ion-exchange membrane. The anodic compartment of the cell is fed with a sodium chloride brine, for instance at a concentration of about 300 g/l; chlorine evolution takes place on the anode surface, at a current density usually not above 4 kA/m2, while brine is consequently depleted down to an outlet concentration usually comprised between 200 and 220 g/l. Sodium ions are transported by the electric field across the membrane to the cathodic compartment, where the caustic product is generated at a concentration usually not higher than 33% by weight. The caustic product is then extracted and concentrated by evaporation outside the cell. Hydrogen evolution also takes place on the cathode surface. The need of decreasing the capital investment has led to the design of plants operating at higher current density: in fact, while older plants usually work at 3 kA/m2, those of newer construction operate at about 5 kA/m2. The current trend in plant design is to further increase such values up to 6 kA/m2 or more. The evolution of gas in form of bubbles, whose flow-rate increases at increasing current densities, may cause pressure fluctuations potentially dangerous for the mechanical integrity of the membrane: for this reason, the pressure differential across the two compartments is usually controlled in an accurate fashion and maintained below 3000 Pa, which complicates the cell operation. Moreover, the product gas has the tendency to build-up between the membrane and the electrode surfaces facing the same, increasing the ohmic drop in the contact zone and locally depleting the chloride-ion concentration due to poor electrolyte renewal. Brine dilution favours the local evolution of oxygen with consequent acidification. The combination of these different aspects (chlorine build-up, oxygen build-up, depletion of trapped brine, acidification) accounts for the early deterioration of the membranes, particularly in form of blister generation especially in correspondence of interstitial zones between anode and membrane, leading to voltage increase and electrolysis efficiency decrease. A similar deterioration may also take place in the interstitial zones between membrane and cathode: in this case, liquid stagnation leads to an increase in the caustic product concentration, which may reach a value up to 40- 45%. Such a high alkalinity can damage the membrane chemical structure, with consequent voltage increase going along with the onset of localised blistering, as described for the anode side.
A few measures have been proposed to improve brine circulation near the electrode surface in order to mitigate the problems associated with gas bubble stagnation: US 4,608,144 disclosed an anode surface equipped with vertical parallel channels alternatively directed to brine feed and withdrawal, and further equipped with horizontal channels of lower section reciprocally connecting the feed and withdrawal channels. In this way a forced brine circulation is achieved, somehow preventing the adhesion of chlorine bubbles. US 5,1 14,547 discloses an anode aimed at promoting brine circulation at the membrane-anode interface in order to obviate the increase in the electrical resistance associated with the depletion of stagnating brine at the interface by means of a structure consisting of vertical channels connected with slanted secondary channels disposed in a herringbone pattern. US 2006/0042935 addresses the same problem by providing an irregular anode surface obtained by sandblasting or acid etching in order to improve the brine supply to the anode. While all of the proposed measures might contribute to some extent to prevent deterioration of ion-exchange membranes in the usual process conditions, they fail to guarantee an optimal functioning in the exasperated process conditions needed to meet the current market requirements aimed at a higher cell productivity.
It would therefore be desirable to have an electrode for membrane electrolytic cells overcoming the limitations of the prior art, particularly as regards the possibility to operate a membrane electrolysis cell with higher performances in terms of parameters such as membrane lifetime, higher applicable current density, operative voltage, concentration of the caustic product obtained in the cell, degree of brine utilisation or maximum applicable pressure differential.
SUMMARY
Various aspects of the invention are set out in the accompanying claims.
One embodiment provides an electrode obtained on a metal substrate having a multiplicity of locally parallel grooves with a depth of 0.005 to 0.02 mm and a pitch - defined as the distance between adjacent grooves - of 0.01 to 0.5 mm.
By locally parallel grooves it is hereby intended a multiplicity of grooves, of open or closed shape, running in parallel at least in part of their length; the path of the locally parallel grooves may assume a generally parallel trend across the whole electrode structure, in straight lines or with curvatures of any type. In one embodiment, the electrode surface presents locally parallel grooves having a closed shape and intersecting one another reciprocally.
The electrode as hereinbefore defined can be advantageous in any electrolytic application, especially for working in direct contact with an ion-exchange membrane; in the case of chlor-alkali electrolysis, the above electrode can be assembled with its grooved surface in direct contact with the membrane, with surprisingly advantageous results both used as the anode and/or as the cathode. The metal substrate may be made of different materials, including but not limited to titanium and titanium alloys for anode application and nickel, nickel alloys and stainless steels for cathode application. The substrate geometry can be of any type: as a non limiting example, the grooved surface can be provided on punched or expanded sheets, meshes and structures comprised of parallel strips optionally rotated along the horizontal axis, also called louvered electrodes.
The electrode substrate can be provided with a known catalytic coating on its grooved surface: for instance, when use as anode for chlorine evolution in chlor-alkali cells is intended, the electrode substrate may be provided with a coating based on noble metals or oxides thereof. Electrodes obtained on the substrate as hereinbefore defined can be particularly useful in chlor-alkali electrolysis cells, both as anodes for chlorine evolution and as cathodes for hydrogen evolution, especially when assembled with the grooved surface in direct contact with the membrane. In case of straight grooves running parallel across the whole structure, orienting the grooves in the vertical direction can provide an improved circulation of electrolyte and gas- bubble release from the surface. In the case of cells assembled according to the configuration known in the art as zero-gap, wherein both electrodes are in direct contact with the membrane, the inventors observed that manufacturing both the anode and the cathode on grooved substrates as defined made possible to operate at current densities largely exceeding 6 kA/m2, up to 10 kA/m2, with totally acceptable cell voltages. Life-tests were also carried out with excellent results at anolyte concentrations below 200 g/l (in particular down to 150 g/l), with caustic product concentrations above 33% (in particular up to 37%) and maintaining pressure differentials across the two compartments higher than 3000 Pa (in particular up to 10000 Pa), conditions which normally led to a quick deterioration of the membranes when prior art electrodes were employed.
Without wishing to be limited by any particular theory, it might be supposed that the electrode obtained on a grooved substrate as defined allows a particularly efficient release of the gas bubbles, also in comparison with grooved electrodes of the prior art, possibly because the densely packed and shallow grooves favour capillary transport phenomena as opposed to an electrolyte circulation.
The electrode as defined can be obtained by simple and cheap methods such as a superficial erosion carried out by means of abrasive paper or fabric - optionally in a continuous rolling process - lamellar grinding wheels or grindstones; other techniques include the use of draw-benches or rolling mills, besides more sophisticated technologies such as laser etching or lithographic techniques, according to the selected geometry. The erosion by grindstone for instance can be suitable for obtaining locally parallel grooves of closed shape and intersecting one another, while a lamellar grinding wheel, a draw-bench or a rolling mill can be more suitable for obtaining generally parallel grooves along the whole surface.
An electrode obtained with the above mentioned techniques can allow a sensible cost reduction compared to other grooved electrodes known in the art and characterised by a much higher groove depth, which cannot be obtained by simple abrasion.
EXAMPLE 1
Six 1 mm thick and 600 mm x 800 mm wide sheets of titanium grade 1 were degreased and subjected to an erosion treatment with a lamellar grinding wheel, obtaining grooves of 0.2 mm pitch on all samples at various depths; the sheets were expanded according to a known technique, obtaining a rhomboidal-mesh geometry of 10 mm x 5 mm diagonals and 1 .6 mm displacement step. Upon completion of the expansion procedure, the grooves measured with a profilometer displayed average depths as reported in table 1 : TABLE 1
Figure imgf000007_0001
Similarly, three 1 mm thick and 600 mm x 800 mm wide sheets of nickel were degreased and subjected to the same erosion treatment and subsequent expansion, so as to obtain an identical geometry. Upon completion of the expansion procedure, the grooves measured with a profilometer displayed average depths as reported in table 2:
TABLE 2
Figure imgf000007_0002
One sheet of titanium and one of nickel, having the same size as the previous samples, identified as AO and CO respectively, were subjected to the same expansion treatment as the above samples, after sandblasting with corundum and subsequent etching in HCI as known in the art; no additional abrasive treatment was effected on these samples.
All titanium samples were subsequently coated with a ruthenium and titanium oxide- based catalyst for anodic evolution of chlorine, with an overall catalyst loading of 12 g/m2. A new check of the groove depth did not show any significant variation introduced by the coating step. EXAMPLE 2
All samples prepared in the previous example were cut into 150 mm x 200 mm wide pieces and characterised, coupled in various combinations, in a multiple bench for chlor-alkali electrolysis accelerated lifetime tests. Each station of the multiple bench was equipped with one membrane electrolysis cell suitable for accommodating one anode and one cathode of 1 mm thickness in direct contact with a reference sulphonic/carboxylic double layer membrane (Nafion® 982 produced by DuPont, U.S.A.). The electrode samples of tables 1 and 2 were assembled with vertically oriented grooves. The lifetime test was carried out simultaneously starting-up all cells with the various combinations of anodes and cathodes at process conditions much more severe than the common industrial practice, determining the time of ion- exchange membrane decay, defined as the time required for the cell voltage to increase by 0.5 V with respect to the initial value at the process current density.
Process conditions were set as follows:
- brine concentration at the anodic compartment outlet: 150 g/l - concentration by weight of product caustic soda: 37%
- pressure differential across the two compartments: 5000 Pa
- current density: 12 kA/m2
The results obtained are reported in table 3:
TABLE 3
Figure imgf000009_0001
EXAMPLE 3
An electrolysis cell as in example 2, equipped with an anode sample A4 and a cathode sample C2, and a second analogous electrolysis cell equipped with a non- grooved anode sample AO and a non-grooved cathode sample CO were subjected to a lifetime test at process conditions sensibly more severe than the common industrial practice.
Process conditions were set as follows:
- brine concentration at the anodic compartment outlet: 180 g/l
- concentration by weight of product caustic soda: 35%
- pressure differential across the two compartments: 4000 Pa - current density: 10 kA/m2
After about 900 hours of testing, the cell equipped with electrode samples AO and CO had to be shut down because the progressive deterioration of the membrane had caused a strong increase in the cell voltage, which attained high values strongly fluctuating in time. The cell disassembly evidenced a general formation of blisters on the surface, with a higher population in correspondence of the brine exhaust outlet nozzle, where an incipient local delamination of the two layers of the membrane could also be observed.
The cell equipped with anode A4 and cathode C2 was dismantled after 2400 hours of continuous testing at practically constant voltage. Upon disassembling the cell, no particular phenomenon of membrane deterioration was observed.
The previous description shall not be intended as limiting the invention, which may be practised according to different embodiments without departing from the scopes thereof, and whose extent is solely defined by the appended claims. Throughout the description and claims of the present application, the term "comprise" and variations thereof such as "comprising" and "comprises" are not intended to exclude the presence of other elements or additives.
The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention before the priority date of each claim of this application.

Claims

1 . Electrode for membrane electrolysis cells comprising a metal substrate having at least one surface equipped with a multiplicity of locally parallel grooves, the depth of said grooves ranging from 0.001 to 0.1 mm and the distance between adjacent grooves ranging from 0.1 to 0.5 mm.
2. The electrode according to claim 1 wherein said depth of said grooves ranges from 0.005 to 0.02 mm.
3. The electrode according to claim 1 or 2 wherein said grooves are generally parallel along the whole surface.
4. The electrode according to claim 1 or 2 wherein said locally parallel grooves are intersecting one another.
5. The electrode according to any one of the preceding claims wherein the material of said substrate is selected from the group consisting of titanium and alloys thereof, nickel and alloys thereof, stainless steel.
6. The electrode according to any one of the preceding claims wherein said substrate has a geometry selected from the group consisting of punched or expanded sheets, meshes and louvered structures.
7. The electrode according to any one of the preceding claims further comprising a catalytic coating applied to said surface provided with grooves.
8. The electrode according to claim 7 wherein said catalytic coating comprises noble metals or oxides thereof.
9. Electrolysis cell comprising at least one electrode according to the preceding claims in direct contact with an ion-exchange membrane.
10. Cell according to claim 9 wherein said at least one electrode is assembled with said grooves generally parallel along the whole surface oriented in a mostly vertical direction.
1 1 . Method for manufacturing an electrode according to any one of claims 1 to 8 comprising the step of forming said multiplicity of grooves on said metal substrate by continuous erosion.
12. The method according to claim 9 wherein said erosion is carried out continuously by means of at least one device selected from the group of rollers of abrasive paper or fabric, grindstones and lamellar grinding wheels.
13. The method according to claim 9 wherein said erosion is carried out by means of a draw-bench or a rolling mill.
14. Process of electrolysis of an alkali chloride brine carried out by applying direct electric current in a membrane electrolysis cell comprising the step of evolving a gaseous product on the surface of one electrode according to any one of claims 1 to 8.
15. The process according to claim 14 wherein said gaseous product is anodically-evolved chlorine or cathodically-evolved hydrogen.
16. The process according to any one of claims 14 to 15 wherein the density of said direct electric current is at least 5 kA/m2.
17. The process according to any one of claims 14 to 16 wherein the pressure differential across the membrane of the electrolysis cell is at least 3000 Pa.
18. The process according to any one of claims 14 to 17 wherein the concentration of said brine at the anodic compartment outlet is at most 200 g/l.
19. The process according to any one of claims 14 to 18 wherein a caustic solution at a weight concentration of at least 33% is produced at the cathodic compartment.
20. Electrode for membrane electrolysis cells substantially as hereinbefore described with reference to the examples and the drawings.
PCT/EP2008/055887 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells WO2008138945A2 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
DE602008003789T DE602008003789D1 (en) 2007-05-15 2008-05-14 ELECTRODE FOR MEMBRANE ELECTROLYSIS CELLS
AU2008249990A AU2008249990B2 (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells
CA002687319A CA2687319A1 (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells
MX2009012314A MX2009012314A (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells.
EP08759575A EP2147133B1 (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells
BRPI0811852-3A2A BRPI0811852A2 (en) 2007-05-15 2008-05-14 ELECTRODES FOR MEMBRANE ELECTROLYSIS CELLS.
PL08759575T PL2147133T3 (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells
AT08759575T ATE490354T1 (en) 2007-05-15 2008-05-14 ELECTRODE FOR MEMBRANE ELECTROLYSIS CELLS
CN2008800158766A CN101707932B (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells
JP2010507912A JP5193287B2 (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cell
DK08759575.7T DK2147133T3 (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells
IL201541A IL201541A (en) 2007-05-15 2009-10-15 Electrode for membrane electrolysis cells
EG2009111668A EG25970A (en) 2007-05-15 2009-11-11 Electrode for membrane electrolysis cells
US12/617,773 US20100059389A1 (en) 2007-05-15 2009-11-13 Electrode for Membrane Electrolysis Cells
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US20100059389A1 (en) 2010-03-11
CL2008001402A1 (en) 2008-08-22
JP2010526938A (en) 2010-08-05
KR20100023873A (en) 2010-03-04
DE602008003789D1 (en) 2011-01-13
AU2008249990B2 (en) 2012-02-02
BRPI0811852A2 (en) 2014-11-18
EP2147133A2 (en) 2010-01-27
CA2687319A1 (en) 2008-11-20
DK2147133T3 (en) 2011-02-28
AR066579A1 (en) 2009-08-26
RU2436871C2 (en) 2011-12-20
IL201541A (en) 2013-03-24
PT2147133E (en) 2011-02-24
JP5193287B2 (en) 2013-05-08
MX2009012314A (en) 2009-12-03
EG25970A (en) 2012-11-13
ES2357080T3 (en) 2011-04-18
TW200902767A (en) 2009-01-16
CN101707932B (en) 2011-07-27
IL201541A0 (en) 2010-05-31
WO2008138945A3 (en) 2009-01-15
RU2009146284A (en) 2011-06-20
PL2147133T3 (en) 2011-05-31
CN101707932A (en) 2010-05-12
ITMI20070980A1 (en) 2008-11-16
ATE490354T1 (en) 2010-12-15
EP2147133B1 (en) 2010-12-01
HK1143615A1 (en) 2011-01-07
AU2008249990A1 (en) 2008-11-20

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