EP0088461B1 - Electrode pour la production de gaz par électrolyse et cellule d'électrolyse à membrane à perméabilité sélective - Google Patents
Electrode pour la production de gaz par électrolyse et cellule d'électrolyse à membrane à perméabilité sélective Download PDFInfo
- Publication number
- EP0088461B1 EP0088461B1 EP83200233A EP83200233A EP0088461B1 EP 0088461 B1 EP0088461 B1 EP 0088461B1 EP 83200233 A EP83200233 A EP 83200233A EP 83200233 A EP83200233 A EP 83200233A EP 0088461 B1 EP0088461 B1 EP 0088461B1
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- Prior art keywords
- electrolysis
- plate
- zone
- electrode
- electrolyte
- 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.)
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 127
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 title claims description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 43
- 238000005192 partition Methods 0.000 claims description 17
- 230000002093 peripheral effect Effects 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000007789 gas Substances 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 20
- 229910052801 chlorine Inorganic materials 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000004891 communication Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000012267 brine Substances 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000001174 ascending effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001198 elastomeric copolymer Polymers 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920003935 Flemion® Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007930 Oxalis acetosella Species 0.000 description 1
- 235000008098 Oxalis acetosella Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
-
- 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
- C25B9/70—Assemblies comprising two or more cells
Definitions
- the present invention relates to an electrode for the production of gas by electrolysis, as well as to a membrane electrolysis cell, with selective permeability, equipped with such an electrode.
- Membrane electrolysis cells with selective permeability are well known in the art, where they are used in particular for the production of hydrogen and a halogen by electrolysis of an aqueous solution of alkali metal halide, for example for the production of hydrogen, chlorine and an aqueous solution of sodium hydroxide by electrolysis of sodium chloride brine. They are generally formed by an alternation of anodes and vertical cathodes, between which membranes with selective permeability are interposed so as to delimit electrolysis chambers which are alternately anodic and cathodic and are in communication with supply conduits electrolytes and enclosures for the recovery of electrolysis products.
- the anode chambers are in communication with a conduit for the supply of a concentrated aqueous solution of chloride of sodium and with an enclosure for the recovery of chlorine and a dilute solution of sodium chloride and the cathode chambers are in communication with a supply conduit serving for the introduction of water or a dilute solution of sodium hydroxide and with an enclosure for the recovery of hydrogen and a concentrated solution of sodium hydroxide.
- this known electrolysis cell thus has the disadvantage of requiring a large footprint on the ground and imposing high investment costs.
- the invention overcomes the disadvantages of known electrolysis cells, by providing an electrode of new design, which greatly improves the efficiency of electrolysis cells, especially cells with selective permeability membrane, while allowing productivity high, high energy efficiency and reduced footprint.
- the invention relates to an electrode for the production of gas by electrolysis, comprising a vertical plate pierced with openings which connect one face of the plate, comprising at least two stepped electrolysis zones separated by an inactive zone, at the 'other face where are arranged supply and discharge conduits for gas and electrolyte; according to the invention conduits are arranged along the plate parallel to the latter and the openings are distributed on the plate so that, on the one hand, each of the electrolysis zones is free of opening, between a lower opening connected to an electrolyte supply conduit and an upper opening connected to a gas and electrolyte evacuation conduit and, on the other hand, the inactive zone is located between the lower opening of the upper electrolysis zone and the upper opening of the lower electrolysis zone.
- the electrolysis zones are surface zones of the plate, which effectively participate in the electrolysis and on which the gas is generated.
- a plate made of a film-forming material chosen from titanium, tantalum, is advantageously used, tungsten, niobium, zirconium and the alloys of these metals, carrying, in its electrolysis zones a conductive coating of an anode active material chosen from platinum, iridium, osmium, palladium, rhodium, ruthenium, the alloys of these metals and the compounds, for example the oxides, of these metals.
- the coating of the anode may advantageously comprise one of the active anode materials described in patents BE-A 769677, BE-A 769680, BE-A 784255 and BE-A 785 605 (Solvay & Cie ).
- the plate can be in mild steel or nickel, optionally covered, in its electrolysis zones, with an active conductive coating chosen from oxidized compounds of the spinel type, for example magnetite, or obtained by thermal decomposition of a thermodecomposable compound of a metal chosen from cobalt, iron, manganese and nickel, as suggested in patents FR-A 2434213 and FR-A 2 460 343 (Solvay & Cie).
- the inactive area is a surface area of the plate, which does not participate in electrolysis during normal use of the electrode.
- the electrolysis zones of the electrode are free of opening and each arranged between a lower opening and an upper opening which are respectively in communication with an electrolyte supply conduit and with a conduit evacuation of the electrolyte and of the gas generated on the electrolysis zone; these conduits are arranged along the rear face of the plate.
- the lower opening and the upper opening of each electrolysis zone may each consist of a single opening of large section or of a plurality of orifices. It is advantageous for the openings to extend as far as possible over the horizontal width of the electrolysis zones. For this purpose, they can for example consist of a very elongated rectangle, horizontal or slightly inclined, or in a horizontal or slightly inclined row of several orifices such as circular, oval, square or rectangular perforations.
- the overall section of the upper opening is chosen as a function of that of the lower opening and of the height of the said electrolysis zone, so as to ensure a permanent regular flow of water. electrolyte and gas along the electrolysis zone.
- the height of the electrolysis zones is generally limited so as to ensure their regular upward flow of the electrolyte by gas siphon and to achieve an acceptable current density over its entire surface.
- the choice of the optimum height is conditioned by the search for an acceptable compromise between a maximum electrolysis energy yield, favored by a low height, and maximum productivity for a minimum investment, favored by a large height.
- the choice of the optimum height of the electrolysis zone depends on the nature of the gas to be produced, the electrolyte used and the current density chosen.
- the electrode according to the invention has the advantageous characteristic of having each electrolysis zone supplied with an electrolyte free of gas, from its lower part, the gas produced being discharged with the electrolyte at the upper part of the zone electrolysis.
- the arrangement of the conduits serving for the supply of the electrolyte and for the evacuation of the gas and the electrolyte on the rear face of the plate makes it possible to provide thereon several stepped electrolysis zones, each delimited between a lower opening and an upper opening. This feature of the invention makes it possible to produce very high electrodes having several stepped electrolysis zones of reduced height, thereby ensuring high productivity with maximum energy efficiency.
- the discharge conduit for each electrolysis zone comprises a chimney common to all the electrolysis zones, delimited between the plate, a vertical partition arranged opposite -vis of it and a peripheral frame joining the plate to the partition.
- This embodiment of the invention has the advantage of ensuring rapid and easy evacuation of the gas produced and of causing a rapid upward flow of the electrolyte along the active areas of the plate, by gazosiphon. All other things remaining, cheerful, this ascending flow is all the more rapid as the plate and the chimney are high and the number of electrolysis zones is large.
- electrodes according to the invention comprising from three to five stepped electrolysis zones, each having a height of between 8 and 15 cm.
- Electrodes of greater height for example two meters high or more, having from eight to twelve or more stepped electrolysis zones, the height of which is fixed between 5 and 15 cm.
- the choice of very high electrodes comprising a large number of electrolysis zones makes it possible to reduce the width of the electrodes. This results in the advantage of a reduction in current losses by the Joule effect through the electrodes, in the case of electrolysis cells where the electrodes are supplied with current along a vertical lateral edge.
- the electrolyte supply conduit of each electrolysis zone advantageously consists of a horizontal tubular conduit, attached to the plate, at the inside the chimney, and open opposite the lower opening of said electrolysis zone.
- the electrode is a unipolar electrode, in which the aforementioned partition is pierced with openings and comprises, on its face external to the chimney, on the one hand, at least two stepped electrolysis zones, free of openings between an upper opening in communication with the chimney and a lower opening in communication with a tubular conduit for the supply of electrolyte, housed in the chimney, parallel to the partition, and, d on the other hand, an inactive zone between the lower opening of the upper electrolysis zone and the upper opening of the lower electrolysis zone.
- the electrode according to the invention finds a particularly advantageous application as an anode or cathode for the production of a gas in an electrolysis cell with a membrane with selective permeability.
- the invention therefore also relates to an electrolysis cell comprising a membrane with selective permeability interposed between a pair of vertical electrodes, at least one of which is the seat of a gas emission during the electrolysis of a electrolyte, conforms to the electrode described above; the cell comprises at least one electrolysis chamber delimited by the membrane, an electrode as described above, comprising, on its face facing the membrane, at least two stepped electrolysis zones, separated by an inactive zone, and a peripheral seal which is interposed between the membrane and the electrode and which comprises a transverse band interposed between the membrane and the inactive area of the electrode.
- membrane with selective permeability is understood to mean a thin, non-porous membrane comprising an ion-exchange material.
- the choice of the material constituting the membrane and of its ion exchange material will depend on the nature of the electrolytes subjected to the electrolysis and on the products which it is sought to obtain.
- the material of the membrane is chosen from those which are capable of withstanding the thermal and chemical conditions normally prevailing in the cell during electrolysis, the ion-exchange material being chosen from anion-exchange materials or materials cation exchangers, depending on the electrolysis operations for which the cell is intended.
- membranes which are well suited are cationic polymer membranes fluorinated, preferably perfluorinated, containing cationic functional groups derived from sulfonic acids, carboxylic acids or phosphonic acids or mixtures of such functional groups.
- membranes of this type are those described in patents GB-A 1 497 748 and GB-A 1497749 (Asahi Kasei Kogyo KK), GB-A 1 518387, GB-A 1 522877 and US-A4126588 (Asahi Glass Company Ltd) and GB-A 1 402 920 (Diamond Shamrock Corp).
- Membranes particularly suitable for this application of the cell according to the invention are those known under the brands "Nafion” O (du Pont de Nemours & Co) and "Flemion” lm (Asahi Glass Company Ltd).
- the seal can be made of any elastic and inert material capable of withstanding the chemical and thermal environment normally prevailing in the cell during its operation; its mechanical strength and elasticity must be sufficient for it to withstand the internal pressure of the electrolysis chamber and ensure an effective seal thereof.
- a synthetic rubber such as an elastomeric copolymer of ethylene and propylene known under the brand "Dutral” O (Montedison) or an elastomeric copolymer of vinylidene fluoride and of hexafluorpropylene, known under the brand “Viton” e (EI du Pont de Nemours & Co).
- the electrodes according to the invention can be of the monopolar type or of the bipolar type.
- the peripheral frame of the electrode may be made of metal and connected directly to the electrical conductors; alternatively, these can be coupled to a lateral extension of the electrode plates in which case the frame can be either of metal or of a material which is not electrically conductive.
- bipo electrode cell laires these are each formed of a pair of plates as described above, one of which is an anode plate and the other, a cathode plate, the two plates being assembled on both sides other of a peripheral frame and isolated by a hermetic vertical wall inside the frame.
- the electrical connection between the two plates can be ensured by the frame, which is then made of metal, or by electrical conductors joining the plates to one another, through the wall.
- the intermediate transverse strip of the seal divides the electrolysis chamber into two superimposed parts each corresponding to an individual electrolysis zone of the plate of the electrode.
- each of the abovementioned parts of the electrolysis chamber is individually supplied with electrolyte at its lower part, via the lower opening of the corresponding electrolysis zone, the electrolyte undergoes an upward movement therein by gasosiphon, by the gas generated by electrolysis and is evacuated with it by the upper opening of said electrolysis zone.
- the cell shown in Figures 1 to 6 is intended for the production of chlorine, hydrogen and an aqueous solution of sodium hydroxide, by electrolysis of a sodium chloride brine. It is of the filter press type and comprises a vertical end anode 1 and a vertical end cathode 2, between which alternate vertical anodes 3, membranes 4 with selective permeability and cathodes 5.
- Membranes 4 are membranes cationic agents such as those known under the names “NAFION” (from Pont de Nemours & Co) or “Flemion” (Asahi Glass Co) which have been explained above.
- the seals 6 are made of an elastic material, waterproof, non-conductive of electricity and able to resist chlorine, for example in an elastomeric copolymer of ethylene and propylene known under the brand "Dutral" (Montedison). They include an intermediate horizontal strip 9 which divides the anode 7 and cathode 8 chambers into two superimposed parts.
- the anode end 1 shown in detail in Figures 2 to 4, is box-shaped and formed of a vertical plate 10 of titanium and a vertical partition 11 of titanium connected together by a rigid peripheral frame 12 in titanium.
- the plate 10 On its face oriented towards the membrane 4, the plate 10 comprises a lower electrolysis zone 33, an upper electrolysis zone 34 and an inactive intermediate zone 35.
- the electrolysis zones 33 and 34 each extend between a slot lower horizontal 13 and an upper horizontal slot 14; between these slots, the electrolysis zones 33 and 34 are free of openings.
- the electrolysis zones 33 and 34 are intended to participate in the production of chlorine by electrolysis of an aqueous solution of sodium chloride and for this purpose they carry a conductive coating formed from a mixture of ruthenium oxide and dioxide titanium.
- the intermediate zone 35 is defined as being an inactive zone, since it does not have the main function of being the site of production of chlorine during the electrolysis. It is intended to receive the horizontal strip 9 of the seal 6, to isolate the two parts of the electrolysis chamber.
- the plate 10 also has a vertical marginal strip 36 beyond the slots 13 and 14, the role of which will be explained below.
- the inactive zone 35 and the vertical lateral strip 36 can be free of active conductive coating or wear one, like the electrolysis zones 33 and 34.
- the upper slots 14 of the electrolysis zones 33 and 34 both open into a common chimney 15 delimited between the plate 10, the partition 11, the frame 12 and a vertical transverse panel 16.
- the lower slots 13 each open into a conduit of individual tubular supply 17 secured to the rear face of the plate 10, inside the chimney 15.
- the tubular conduits 17 are closed at 18 and open through the panel 16, into a common cavity 19 delimited between the panel 16, the frame 12, the partition 11 and the vertical strip 36 of the plate 10.
- the cavity 19 is in communication with a chamber 20 (FIG. 4), via orifices 21 formed in a vertical spar of the frame 12.
- a tube 22 connects the chamber 20 to a general adductor of a concentrated aqueous solution of sodium chloride, not shown.
- Holes 23 formed in the upper horizontal beam 42 of the frame 12 provide communication between the chimney 15 and the upper zone 24 of the chamber 20, which is open at 25 and is surmounted by an enclosure 26 of large horizontal section, serving for the recovery of the chlorine produced at the anode during the electrolysis and for the separation of the anolyte entrained with it.
- a tube 27 opening into the bottom of the chamber 20 serves for the evacuation of at least a fraction of the anolyte separated from the gas which escapes through a tube 46 at the top of the chamber 26.
- Metal plates 28, for example copper, are welded to a vertical spar of the frame 12, to allow its coupling to a source of electric current, not shown.
- the intermediate anode 3 (Fig. 1 and 5) differs from the anode 1, only in that the partition 11 is replaced there by a plate 29 identical to the plate 10 and pierced by two horizontal slots 14 both opening in the chimney 15 and two horizontal slots 13 each opening into an individual tubular conduit 17.
- the plate 29 thus also has two active electrolysis zones 33 and 34 and an inactive zone 35 intended to receive the intermediate strip 9 of a seal 6.
- Cathodes 2 and 5 are of a construction similar to that of anodes 1 and 3, except that they are made of steel or nickel.
- the constituent elements of cathodes 2 and 5 bear the same reference numbers as their counterparts of anodes 1 and 3, with a prime index to differentiate them.
- the tubing 22 ' is connected to a general adductor for admitting water or a dilute solution of sodium hydroxide (containing for example 10% by weight of sodium hydroxide), the tubing 27' is used to withdraw from the chamber 20 'a concentrated aqueous solution of sodium hydroxide (containing for example of the order of 25 to 40% by weight of sodium hydroxide) and the tube 46' is used for the evacuation of the 'hydrogen.
- the anodes 1 and 3 are arranged head to tail relative to the cathodes 2 and 5, so that the chambers 26 ' of the cathodes are arranged opposite the corresponding chambers 26 of the anodes.
- This arrangement has various advantages: on the one hand, it accommodates enclosures 26 and 26 'of large width, which is favorable for good separation of gases and electrolytes; on the other hand, all the anode dishes 28 are located on the same side of the cell and all the cathode dishes 28 'are located on the opposite side, which simplifies their connection in bypass to a source of direct current.
- This arrangement of the anodes and cathodes of the cell according to the invention also facilitates the coupling of the pipes 22, 22 ′, 27 and 27 ′ to four general conduits for the admission and evacuation of the electrolytes.
- the dishes 28 of the anodes are coupled in bypass to the positive terminal of a direct current source and the dishes 28 'of the cathodes are coupled in bypass to the negative terminal of this Power source.
- a concentrated brine of sodium chloride is introduced through the pipes 22 into the chambers 20 of the anodes 1 and 3, from where it passes into the tubular conduits 17, via the openings 21 and the cavity 19. From the conduits 17, the brine penetrates in the anode chambers 7 through the slots 13, where it is electrolysed in contact with the electrolysis zones 33 and 34 of the anode plates 10 and 29.
- the chlorine generated in this way in the anode chambers 7 causes the anolyte to move there ascending, by gazosiphon and is evacuated with it by the upper slots 14. From the chimney 15, the chlorine and the anolyte pass into the chamber 24 then the enclosure 26 where the sudden variation in section causes the separation of the chlorine and anolyte.
- the chlorine escapes through the tubing 46 and the anolyte descends into the chamber 20; a fraction is drawn off through the tubing 27 and the remaining fraction is recycled in the tubular conduits 17 with the brine coming from the tubing 22.
- water or a dilute solution of sodium hydroxide is admitted into the chambers 20 'of the cathodes 2 and 5 through the tubing 22', from where it passes into the cathode chambers 8 via the tubular conduits 17 'and the slots 13 'of the cathode plates 10' and 29 '.
- the hydrogen generated by electrolysis in the cathode chambers 8 moves there from bottom to top and is evacuated therewith with the catholyte through the slots 14 '; it passes successively in the chimney 15 'of the cathodes, then in their enclosure 26' where the hydrogen is separated from the catholyte and evacuated by the tube 46 '.
- the catholyte separated in the enclosure 26 ' descends into the chamber 20'; a fraction is drawn off through the tubing 27 'while the remaining fraction is recycled into the cavity 19' and the tubular conduits 17 ' , with the water or the diluted solution admitted by the tubing 22'.
- the natural draft of the chimneys 15 and 15 ′ is generally sufficient to ensure the upward flow of the electrolytes in the anode chambers 7 and cathode chambers 8. If necessary, to further accelerate this flow and increase the productivity of the cell, a fan can be provided in a general manifold, not shown, common to the nozzles 46 (46 ').
- tubular conduits 17 and 17 ′ are pierced with a row of holes 30 in their upper part, to degas the electrolyte circulating in these conduits.
- spacers are arranged between the membranes 4 and the electrode plates 10, 29, 10 ', 29', these spacers consisting of vertical rods 31 or obliques 32 (Fig. 3), which are fixed parallel to these plates by engagement of their free ends in holes made in the plates.
- These rods can for example be made of titanium in the case of anodes and of steel or nickel in the case of cathodes. They can also be made of a polymeric material, for example polytetrafluoroethylene.
- the spacing rods 31 and 32 are replaced by narrow strips, vertical or oblique, seals 6.
- FIG. 7 shows a modified embodiment of the end anode 1 of the cell of FIG. 1.
- the plate 10 comprises four stepped electrolysis zones 33, 34, 37 and 38, separated by three inactive zones 35 and each pierced with a pair of openings 13 and 14 which will be described in detail later.
- two vertical transverse panels 16 join the plate 10 to the partition 11 and thus separate the chimney 15 from two marginal cavities 19 connected together by four horizontal tubular conduits 17 applied against the plate 10 opposite the openings 13.
- the openings 13 are used for the admission of the electrolyte to the electrolysis zones 33, 34, 37 and 38 and include a horizontal slot opposite the tubular conduits 17 and extensions 39 in the vertical marginal strips 36 of the plate 10 , opposite the cavities 19.
- the openings 14 are used for the evacuation of chlorine and the anolyte and consist of horizontal slots facing the chimney 15, as in the embodiment of Figures 2 to 5. These slots 14 stop below the marginal bands 36, so that they do not communicate with the cavities 19.
- the seal 6 comprises three intermediate transverse bands 9 which each comprise a horizontal element 40 engaged between a pair of slots 13 and 14 and two inclined end elements 41 whose role will be explained below.
- the extensions 39 of the slots 13 are preferably inclined in the same direction as the elements 41 of the seal 6.
- the upper horizontal beam 42 of the frame 12 is pierced with a central orifice 23 facing the chimney 15 and a pair of orifices 21 facing the two cavities 19.
- the orifices 21 and 23 open into a large common room section, not shown, surmounting the frame 12 and similar to the chambers 26 of the cell of FIGS. 1 to 6, said chamber being in communication, at its upper part, with a chlorine evacuation orifice and, at its lower part, near of the spar 42 of the frame 12, with a tube for the supply of a concentrated aqueous solution of sodium chloride.
- the plate 10 is further extended, beyond the frame 12, by a vertical marginal strip 45, intended to connect it to a direct current source.
- the frame 12 can be either of metal, for example titanium, or of a material which is not electrically conductive, for example of polytetrafluoroethylene.
- the two cavities 19 and the tubular conduits 17 are permanently filled with a concentrated aqueous solution of sodium chloride introduced continuously through the orifices 21.
- the solution passes through the slots 13 and their extensions 39 and is driven from bottom to top along the electrolysis zones 33, 34, 37 and 38 of the plate 10, under the effect of the gazosiphon generated by the chlorine generated therein.
- the chlorine and the anolyte are evacuated from the electrolysis zones 33, 34, 37 and 38 in the chimney 15, via the slots 14.
- the inclined elements 41 of the bands 9 of the seal 6 serve as a deflector for channeling the chlorine and the anolyte to the slots 14.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83200233T ATE20543T1 (de) | 1982-02-26 | 1983-02-15 | Elektrode zur elektrolytischen gasherstellung und elektrolysezelle mit selektiv-durchlaessiger membran. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8203374 | 1982-02-26 | ||
FR8203374A FR2522338A1 (fr) | 1982-02-26 | 1982-02-26 | Electrode pour la production de gaz par electrolyse et cellule d'electrolyse a membrane a permeabilite selective |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0088461A1 EP0088461A1 (fr) | 1983-09-14 |
EP0088461B1 true EP0088461B1 (fr) | 1986-06-25 |
Family
ID=9271465
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83200233A Expired EP0088461B1 (fr) | 1982-02-26 | 1983-02-15 | Electrode pour la production de gaz par électrolyse et cellule d'électrolyse à membrane à perméabilité sélective |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0088461B1 (enrdf_load_stackoverflow) |
AT (1) | ATE20543T1 (enrdf_load_stackoverflow) |
DE (1) | DE3364228D1 (enrdf_load_stackoverflow) |
FR (1) | FR2522338A1 (enrdf_load_stackoverflow) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4927509A (en) * | 1986-06-04 | 1990-05-22 | H-D Tech Inc. | Bipolar electrolyzer |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL156233B (nl) * | 1949-10-24 | Societe Anonyme, Societe Industrielle Pour La Diffusion D'equipement Et De Materiel "Sidemat", Parijs. | Aansluitinrichting voor apparatuur op een brandstofhouder. | |
CH288156A (de) * | 1949-11-03 | 1953-01-15 | Montedison Spa | Elektrodensystem für Bipolarelektrolyseure. |
JPS51119681A (en) * | 1975-04-15 | 1976-10-20 | Asahi Glass Co Ltd | A cell frame for an electrolizer |
-
1982
- 1982-02-26 FR FR8203374A patent/FR2522338A1/fr active Granted
-
1983
- 1983-02-15 AT AT83200233T patent/ATE20543T1/de not_active IP Right Cessation
- 1983-02-15 EP EP83200233A patent/EP0088461B1/fr not_active Expired
- 1983-02-15 DE DE8383200233T patent/DE3364228D1/de not_active Expired
Also Published As
Publication number | Publication date |
---|---|
FR2522338B1 (enrdf_load_stackoverflow) | 1984-04-27 |
EP0088461A1 (fr) | 1983-09-14 |
DE3364228D1 (en) | 1986-07-31 |
ATE20543T1 (de) | 1986-07-15 |
FR2522338A1 (fr) | 1983-09-02 |
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