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WO1993011281A2 - Cellule electrochimique - Google Patents

Cellule electrochimique Download PDF

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Publication number
WO1993011281A2
WO1993011281A2 PCT/GB1992/002157 GB9202157W WO9311281A2 WO 1993011281 A2 WO1993011281 A2 WO 1993011281A2 GB 9202157 W GB9202157 W GB 9202157W WO 9311281 A2 WO9311281 A2 WO 9311281A2
Authority
WO
WIPO (PCT)
Prior art keywords
cell
anode
electrode
surface area
electrolyte
Prior art date
Application number
PCT/GB1992/002157
Other languages
English (en)
Other versions
WO1993011281A3 (fr
Inventor
Shaun Bullen
Original Assignee
Imperial Chemical Industries Plc
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
Application filed by Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to FI942600A priority Critical patent/FI942600L/fi
Priority to EP92923892A priority patent/EP0611401A1/fr
Priority to AU29503/92A priority patent/AU665037B2/en
Priority to JP5509920A priority patent/JPH07501852A/ja
Publication of WO1993011281A2 publication Critical patent/WO1993011281A2/fr
Publication of WO1993011281A3 publication Critical patent/WO1993011281A3/fr
Priority to NO942059A priority patent/NO942059L/no

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C25B1/13—Ozone
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46155—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/78—Details relating to ozone treatment devices
    • C02F2201/782—Ozone generators

Definitions

  • This . invention relates to an electrolytic cell.
  • the invention relates in particular to an electrolytic cell in which ozone is to be produced.
  • Electrolytic cells are known in which water is dissociated into its respective elemental species, i.e. O2 and H2 which are liberated at the anode and cathode respectively. Under appropriate conditions O3 is also produced at the anode.
  • Electrolytic cells are also known for the production of ozone which comprise air cathodes and in which the cathode reaction which takes place is the reduction of ambient air to water in an acidic electrolyte, the water then being oxidised at the anode to oxygen and ozone. Consequently since hydrogen is not produced at the cathode surface, the cell voltage is substantially reduced. Furthermore the construction of the cell is less complex than cells which comprise hydrogen evolving cathodes, for example a separator between the anode and cathode is not required since hydrogen is not evolved at the cathode, and control of the overall process is simpler, namely the need for periodic additions of water is reduced. Thus, in US Patent No.
  • an electrolytic cell for the production of ozone which comprises a tubular anode structure, the outer surface of which functions as an anode within a tubular air cathode structure, the inner surface of which functions as a cathode.
  • the current density at the anode surface is greater than that at the cathode surface, in particular that the current density at the anode surface is at least about twice that of the cathode surface in order that the power consumption due to polarisation losses at the cathode surface may be reduced, thereby avoiding hydrogen evolutior and increasing air cathode lifetime.
  • anode surface is cooled.
  • Use of a cooled anode surface substantially improves the current efficiency of the process. It is known for example that where the temperature of the anode is reduced from 25°C to 0°C, a fourfold improvement in the current efficiency may be obtained. Furthermore, use of a cooled anode in electrolytic cells for the production of ozone often increases the lifetime of the anode.
  • the anode is typically cooled by the flow of a refrigerant fluid within the anode. It is therefore important that the surface area of the anode is as large as possible in order that effective heat exchange with the electrolyte may take place thereby ensuring efficient cooling of the anode. On the other hand a low anode surface area relative to that of the cathode is desirable in order that the anode current density may be high.
  • the internal radius of the cathode will be 4 cm. i.e. the inter-electrode gap will be 2 cm. This large
  • inter-electrode gap leads to a high electrical resistance tc the flow of current through the cell and an undesirable increase in the voltage of the cell.
  • air cathodes are difficult to fabricate in a tubular form and they lead to mechanical problems during manufacture of the electrolytic cell, for example sealing within the cell.
  • an electrolytic cell comprising first and second electrode structures, at least the first electrode structure having a surface area in heat exchange relation with the electrolyte and part only of said surface area being electrolytically active.
  • each of the first and second electrode structures has a surface area which is in heat transfer relation with the electrolyte, a part only of said surface area of the first electrode structure being electrolytically active and the active surface area of said second electrode
  • the first electrode structure is an anode structure and the second electrode structure is a cathode structure, the
  • the active surface areas of the anode and cathode structures will usually be of such an extent that in operation the current density established at the surface of the anode structure is at least 20Z greater than that established at the surface of the cathode structure.
  • the current density established at the surface of the anode structure is at least 502, especially at least 802 greater than that established at the surface of the cathode structure.
  • the anode structure may have high surface area in heat exchange relation with the electrolyte, thus facilitating efficient heat exchange, yet only a part of that surface area is electrolytically active thus ensuring relatively high anode current densities, relative to the cathode current density.
  • electrolytically active anode surface there is meant that part of the anode surface at which the electrolytic process takes place, that is that part of the anode surface with which the cathode surface has substantial electrical interaction, i.e. current in the form of a flow o ions through the electrolyte takes place between the active anode surface and the active cathode surface.
  • the anode structure may be constructed from different materials; for example one part of the anode structure may be constructed from a suitable anode material which presents said electrolytically active anode surface, and a second part may be constructed from a material which is not capable of functioning as an electrolytically active anode surface.
  • the anode surface includes both the surface which is constructed from a suitable anode material and the surface which is not so constructed, although the surface which functions as an active anode surface is only that surface which is constructed from a suitable anode material.
  • At least that part of the anode structure which has a surface area exposed for contact with the electrolyte in operation of the cell is made completely from a material which is suitable for use as an anode and that a portion of the exposed anode surface is prevented from functioning as an active anode surface by suppressing the electrolytic interaction between that portion and the cathode structure, for example by providing means for masking that portion of the anode surface from the cathode surface.
  • an electrolytic cell comprising first and second electrode structures, part only of the surface area of at least the first electrode structure being electrolytically active, and means for masking the remaining part of the surface area of the first electrode structure in such a way as to render said remaining part of the surface area substantially electrolytically inactive.
  • the masking means may comprise for example, a coating, cover, insert or any other suitable part, such that there is substantially no ozone producing electrolytic interaction between the masked portion(s) of the anode surface and the cathode surface.
  • the masking means may take any suitable shape and form provided that it suppresses the electrolytic interaction between the masked portion of the anode surface and the cathode surface.
  • the material used for effecting masking is typically therefore an electrically insulating material.
  • the material should also be inert to the electrolyte, which may be highly corrosive. Suitable materials include inert polymeric materials such as polyvinyl chloride or polyfluorinated polymers, for example polytetrafluoroethylene which are electrical insulators and which have resistance to oxidising gases and excellent resistance to highly acidic and corrosive solutions.
  • the extent of the masking should be such as to achieve the desired current density difference between the active anode surface and the cathode surface.
  • the unmasked anode surface area which functions as an active anode surface should be less than about 802 of the area of the cathode surface, preferably less than about 602 of the cathode surface.
  • the anode structure may have any suitable form, for example it may be in the form of a tube or or it may be a planar anode.
  • the electrolytically active and inactive surface areas of the anode structure may be distributed around the periphery of the anode structure.
  • the anode structure may have an elongate configuration and the active and inactive surfaces may extend longitudinally of the elongate anode structure.
  • the electrolytic cell preferably further comprises means for circulating a coolant fluid in heat transfer relation with the anode structure in such a way that heat exchange is secured between the coolant and the electrolyte through the active and inactive surface areas of the anode structure.
  • a particularly preferred form of the anode by which such coolant circulation may be achieved is a tubular anode, the lumen of which provides a path for the flow of a coolant fluid.
  • the coolant fluid may flow through the lumen of the anode or the lumen may be provided with a member extending within the lumen, for example a hollow finger through which the coolant fluid is caused to flow.
  • the cold finger may be constructed, for example, of copper.
  • the surface area of the tubular anode structure which is exposed for contact with the electrolyte may be the outer surface or periphery of the tubular structure, and the electrolytically active and inactive parts of this surface area may therefore be distributed peripherally around, and extending longitudinally of, the tubular structure.
  • the electrolytic cell preferably comprises means for routing the electrolyte along a path in which it is in heat exchange relation wit:, a substantially electrolytically inactive part of the surface area of the anode structure.
  • the routing means preferably provides at least one flow path extending longitudinally of the anode structure.
  • the active and inactive surfaces of the anode structure may extend generally co-extensively with one another longitudinally of the anode structure.
  • the cell preferably comprises means for preventing the flow of electrolyte peripherally of the anode structure from a region where the electrolyte is in communication with an active surface of the anode structure to a region where the inactive surface area is located.
  • the cathode structure may take any suitable form although we generally prefer to use a planar or tubular structure.
  • the inner surface of the tube may be the electrolytically active cathode surface and the radius of the inner surface of the cathode structure may be reduced compared to that hereinbefore described with reference to US Patent 4,541,989 thus reducing the inter electrode gap but maintaining the differential current density between the electrolytically active anode surface and the cathode surface .
  • the cathode structure is of a planar configuration since we prefer to employ an air cathode (as described hereafter).
  • Air cathodes of planar configuration are readily manufactured and are easily installed in the electrolytic cell.
  • an electrolytic cell comprising at least one tubular anode and at least one planar cathode allows both simple scaling of the cell to much larger sizes as hereinafter described, and facilitates the achievement of the current density difference between the active anode surface and the cathode surface defined according to the first aspect of the invention.
  • the cathodic structure is of planar configuration
  • two of said cathode structures of planar configuration are present in the cell and that the anode structure is located between, and in spaced relation with, said cathode structures and that the anode structure has separate electrolytically active surfaces in confronting relation with the cathode structures.
  • the anode structures may then have electrolytically inactive surface areas located between the said separate active surface areas.
  • the anode structures may be arranged between the two planar cathode structures in a direction parallel to said cathode structures.
  • an electrolytic cell for the production of ozone comprising at least one tubular structure the outer surface of which functions as an anode surface and at least one planar cathode structure.
  • a cell in accordance with this third aspect of the invention may incorporate (severally or collectively, or any combination thereof, as the context admits) those features of said first and second aspects of the invention as discussed hereinbefore.
  • the cell comprises at least two planar cathodes between which are located one or more tubular anodes, preferably at least two tubular anodes.
  • the number of tubular anodes which are employed depends at least to some extent upon the desired rate of production of ozone from the cell, the dimensions, in particular the length and diameter of the tubular anodes and the current density at the electrolytically active anode surfaces during operation of the cell.
  • the cell may comprise up to about 12 tubular anodes where ozone production in the order of 100 g/hour i c desired. The ease with which the cell may be scaled up in order to increase the rate of production of ozone, simply bv the provision of further tubular anodes between the air
  • the cell may comprise more than two planar cathode structures, with one or more tubular anode
  • each pair of cathode structures such that the cell may comprise a row of tubular anodes between each pair of opposingly faced planar cathodes.
  • the cell comprises means masking the remaining part of the surface area of the anode structure in such a way as to render it substantially
  • Active and inactive portions of the anode surface area may be defined by providing in the cell a first boundary means for bounding together with the cathode structure and a part only of the surface area of the anode structure a 25 chamber for enclosure of an electrolyte whereby said part only of the anode surface area constitutes an electrol tically active surface area of the anode structure and second boundary means for bounding together with a further part or parts of the surface area of said anode 30 structure at least one channel in fluid communication with said chamber to provide for flow of electrolyte over said further part(s) of the surface area of the anode structure, n said further parts constituting a substantially electrolytically inactive surface area of the anode % 35 structure.
  • the first and second boundary means may further constitute a masking means as hereinbefore described, and may, for example be provided by an insulating body or bodies extending between the anode surface and the cathode surface.
  • The, or each insulating body may be in the form of, for example, a wedge-shaped member or truncated cone, with its narrow end in contact with and extending from the cathode surface to its wide end in contact with the outer surface of one or more anode structures whereby to mask that portion of the surface area of the anode structure which is not in confronting relation with the cathode surfaces, from the cathode surfaces.
  • the first and second boundary means for example one or more insulating bodies may be provided as separate inserts for provision within the cell.
  • the or each insulating body is formed as part of a cell body in which the anode and cathode structures are supported.
  • the cell body may be so configured that it masks the surfaces of the anode which are not in confronting relation with the cathode surfaces.
  • the active anode surface will in this case be the surface of the anode adjacent the cathode surface and the mean distance between the active anode surface and the cathode surface is preferably less than 10mm, more preferably less than 5mm and especially less than 4mm.
  • the wedge may be shaped such that the wedge only comes into contact with a small area of the anode surface to be masked.
  • the wedge may be cut away to form circulation channels, at the portion of the wedge which is adjacent the anode surface to be masked so that electrolyte may circulate over the anode surface between the masking wedge member and the anode surface.
  • the electrolyte may flow freely over substantially all or a section of the masked and electrolytically inactive portion of the anode structure, providing an increased total surface area for heat exchange and thus cooling of the active anode surface.
  • a further advantage of the provision of, for example, re-circulation channels adjacent the masked and electrolytically inactive anode portion(s) is that a recirculating flow of electrolyte may be achieved over the active anode surface which serves to remove bubbles of 15 gaseous products which may form on the active anode surface and which may, if not removed, lead to an increase in the cell voltage.
  • This flow of electrolyte is achieved because substantially no electrolysis takes place within the recirculation channels so that the electrolyte in the 20 channels tends to be ungasified, whereas the formation of gaseous products of electrolysis takes place in the electrolyte chambers thus producing a gasified electrolyte.
  • a recirculating flow of electrolyte is thereby generated by the density difference between the gasified and ungasified 25 electrolyte .
  • Fluid-tight seals should be maintained between the electrolyte chambers and the re-circulation channels in order to prevent current leakage from electrolyte between the active anode and cathode surfaces to the electrolyte 30 flowing within the recirculation channels.
  • an electrolytic cell for the production of ozone comprising an anode structure, a cathode structure and a chamber for containing electrolyte within which , j electrolysis occurs and which further comprises at least one re-circulation channel in fluid communication with the electrolyte but within which electrolysis does not occur.
  • the recirculation channels may be provided within the cell itself or they may be provided externally of the ceil.
  • Cell head spaces which may serve as both disentrainment areas for product gases and reservoirs for electrolyte may be provided within the cell, into and from which electrolyte from and into both the electrolyte chambers between the active anode and cathode surfaces, and recirculation channels may flow, and from which product gases may be collected.
  • Air cathodes which are commercially available components, are typically composed of polytetrafluoroethylene-bonded-carbon containing small amounts of catalytic materials, for example platinum.
  • the materials used as the anode surface in the electrolytic cell of the present invention may be conventional anode materials as described more fully in, for example, European Patent 0 041 365.
  • the anode surface may be constructed from platinum or lead dioxide, particularly lead dioxide in the beta crystalline form.
  • a special form of carbon, specifically vitreous or glassy carbon is particularly preferred for use as the anode surface material since it has a high oxygen overpotential and thus a high efficiency for ozone production, it is stable in strong acid electrolytes and is stable to oxidising conditions generated in the cell.
  • glassy carbon is a material which possesses poor electrical conductivity so that where current is fed to the anode structure through a conducting memeber provided adjacent only the electrolytically active surfaces of.
  • the electrolyte used in the electrolytic cell is typically a known electrolyte, for example, an aqueous solution of a highly electronegative anion (and associated cation) such as are, for example, described in European Patent 0 041 365.
  • the electronegative anion used is preferably as electronegative as possible, and more preferably is a fluoro-anion.
  • the fluoro-anion may be the fluoro-anion of a Group V-B element of the Periodic Table, for example phosphorous and arsenic which form hexa-fluoro anions.
  • Non-metallic elements such as Si and Sb also form hexa-fluoro-anions .
  • suitable fluoro-anions may be mentioned, inter alia PO2F2", HTiFg", NbF7 2 ⁇ , TaF7 2 ", NiF 6 2 -, ZrF 5 2 ", GeF 6 2 -, FeF 6 2 ⁇ .
  • the phosphorous, arsenic, boron and silicon fluoro-anions are the preferred anions for addition to the aqueous electrolyte and in particular polyhalogenated boranes. We especially prefer to employ the tetrafluoroborate anion.
  • the fluoro-anions may be added to the aqueous electrolyte solution in the form of their respective acids or as water-soluble salts.
  • the acid-form of the fluoro-anions may be preferred because of their higher solubilities in water
  • the fluoro-anion salts for example sodium or potassium, offer the advantage that their aqueou ⁇ solutions have higher pH ' s than do the solutions of their respective acid forms, and they therefore are less corrosive towards the cathodes.
  • an increase in the anion concentration also increases the corrosivity of the electrolyte towards the cathodes. Suitable anion concentrations may be readily determined by routine experimentation.
  • the construction of the electrolytic cell may, apart from its construction according to the various aspects of the invention as hereinbefore defined, follow conventional technology taking into consideration the corrosive nature of the fluoro-anion electrolytes and the high oxidising power of the ozone gases.
  • the parts of the cell in contact with the corrosive electrolyte and oxidising products of electrolysis are preferably constructed of materisl which are inert both to the highly corrosive electrolyte and the oxidising gases.
  • the cell body may therefore be constructed from, or coated with, an inert material, for example an inert polymeric material such as polyvinyl chloride or polyfluorinated polymers, for example polytetrafluoroethylene which have resistance to oxidising gases and excellent resistance to highly acid and corrosive solutions .
  • an inert material for example an inert polymeric material such as polyvinyl chloride or polyfluorinated polymers, for example polytetrafluoroethylene which have resistance to oxidising gases and excellent resistance to highly acid and corrosive solutions .
  • the anode and cathode compartments of the cell should be separated such that the hydrogen evolved at the cathode is not in fluid-flow contact with the gases evolved at the anode.
  • separators are well known ir. the art. Conventionally they are prepared from a perfluorinated polymeric cation exchange material, for example "Na ion" (registered Trademark of E.I.Du Pont). Such a separator i ⁇ not needed in the preferred embodiments of the invention where an air cathode is used and where hydrogen is not generated by the cathode process.
  • the anode and cathode structures are disposed within the electrolytic cell with electrical leads leading to the exterior of the cell. Electrical potential may be applied to the anode by contact with part only of a surface of the anode structure which corresponds to the electrolytically active surface area of the anode structure, for example by means of a conducting member, constructed from, for example, copper, which is provided along the anode adjacent the active anode surface in order that current is fed predominantly to the active anode surface and not to that anode surface which is masked from the cathode.
  • a conducting member constructed from, for example, copper
  • the conducting member is preferably provided on a surface of the anode which is not in direct contact with the electrolyte, for example where the anode is in the form of a hollow tube the conducting member may be provided within the lumen of the tube, in order that the conducting member is protected from the electrolyte.
  • the cell is sealed prior to use, and the cell head space is provided with suitable inlet and outlet passages for water make-up, where necessary, and the withdrawal of the gases evolved from the cathode (where hydrogen is produced) and from the anode.
  • Two discrete gas removal systems may, where necessary, be used to keep the cathode gases separate from the anode gases. Nitrogen and/or air may be used to keep the cathode gases separate from the anode gases. Nitrogen and/or air may
  • the gas handling system in order to entrain the evolved cathode and anode gases and carry them from the cell to the exterior where they may be stored or utilised in the desired application.
  • the anode and cathode structures are connected by the
  • aforementioned electrical leads optionally through a conducting member, to a source of power external to the cell.
  • the cell is operated at electrical potentials in the order of 3-7 volts.
  • the current density at the anode surface may be in the range from about a tenth of
  • Figure 1 is a diagrammatic partly cut away view of an electrolytic cell according to the invention
  • Figure 2 is a view in section along the line A-A in figure 1.
  • Figure 3 is a view in section through the cell of Figure 1 along the line B-B in figure 2, 5
  • Figure 4 is a view in section through the cell of Figure 1 along the line C-C in figure 2
  • Figure 5 is a view in section along the line D-D in figure 3
  • Figure 6 is a view in section along the line E-E in figure
  • Figure 7 is a view in section along the line F-F in figure 3.
  • an electrolytic cell suitable for the generation of ozone shown generally as 1 in.
  • Figure 1 comprises a main cell body 2, having top and bottom portions 4, 6 and spaced columns 8 extending therebetween. Although three such columns 8 are present in the illustrated
  • a pair of end columns 8A and an intermediate column 8B there may be more or less according to the number of anode structures employed.
  • the columns 8, which support the anodes and cathodes in spaced relation with one another, constitute means for bounding, together with active surfaces 16 of the air cathodes 10 and parts only of the outer surfaces of the anodes 18 which are in 5 confronting relation with the active surfaces of the air cathodes, electrolyte chambers 20.
  • the electrolyte chambers 20 extend longitudinally from the top portion 4 to the bottom portion 6 and at each end open into upper and lower cell spaces, 22, 24 respectively (see Figure 3) within the 0 top and bottom portions 4 and 6, the arrangement being such that each cell space is in communication with a pair of electrolyte chambers 20 on opposite sides of an anode 14.
  • the columns have a wedge-like configuration and have inwardly directed surfaces 26, the surfaces of adjacent columns converging from the cathode to the anode at an angle of convergence so as to define a longitudinally extending active anode surface having an area half that of the cathode surface 16 which is bounded by the columns.
  • the required differential in active anode and cathode surface ares thereby achieved provides in use the required current density differential between the active anode and cathode surfaces but allows a mean distance between the active and cathode surfaces of less than 4mm.
  • the columns 8 mask the remainder of the anode surfaces 28 from the surfaces of the cathodes and are formed with grooves or channels which constitute re-circulation channels 30 of curved, e.g. semi-circular profile, adjacent at least a part 28a of the inactive surfaces of the anodes 14.
  • Each channel 30 extends longitudinally from the top portion to the bottom portion 6 and at each end opens into upper and lower cell spaces 22, 24 (see figure 4) within the top and bottom portions 4, 6, the arrangement being such that each cavity 22, 24 is in communication with a pair of channels 30 associated with adjacent columns and a pair of electrolyte chambers 20 as described previously.
  • Fluid tight seals are maintained between the surface of the anodes and the columns of the cell body by longitudinally extending resiliently deformable seals 32 which prevent circumferential flow of electrolyte about the periphery of the anode from the electrolyte chambers 20 to the re-circulation channels 30.
  • the lumen 34 of each anode is provided with copper conductors 36 adjacent the active surfaces of the anodes ...6 through which electrical connection is made between each electrolytically active surface of the anodes 18 and the source of electrical power.
  • the anodes are constructed from glassy carbon which possesses poor electrical conductivity and which therefore serves to reduce the tendency for current to leak to the inactive anode surfaces adjacent the re-circulation channels 30.
  • the lumen 34 also provides the flow path for circulation of a cool.nt in heat transfer relation with both the active and inactive surfaces of the anode structures.
  • FIG. 3 shows the flow of electrolyte from the cell head space 22 downwardly through the recirculati .. channels 30 which extend lengthwise of the anode structure to the lower cell space 24
  • figure 4 shows the flow of electrolyte from the lower cell space 24 upwardly through the electrolyte chambers 20, which also extend lengthwise of the anode structure to the cell head space 22.
  • Product gases are collected through gas outlet 38 provided from the cell head space.
  • Figures 5 to 7 show clearly the provision within the cell of the cell head space 22 ( Figure 5) and lower cell space 24 (figure 7), into and from which electrolyte from both the recirculation cnannels and the electrolyte chambers flows .
  • electrolyte is charged tc the cell and the electrodes 10 and 14 are connected tc a source of electrical power (not shown) .
  • Air is pumped through tat- air chambers 12 by an air pump (not shown) , and a coolant fluid, for example a refrigerant, is caused to flow through the anode lumen 34 from a refrigeration system (not shown) externally of the cell.
  • a coolant fluid for example a refrigerant
  • Gaseous products of electrolysis formed at the electrolytically active anode surface 18 cause the electrolyte to flow upwardly through the electrolyte chambers 20 to the cell head space 22 where the gaseous products are disentrained, the electrolyte thence flowing downwardly through the recirculation channels 30 adjacent the masked and electrolytically inactive anode surfaces at which no gaseous products of electrolysis are formed. Product gases are collected via the gas outlet 38.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Primary Cells (AREA)

Abstract

Cellule électrolytique possédant une première (14) et une deuxième (10) structure d'électrode, dans laquelle la première structure d'électrode possède une zone de surface (28) se trouvant en relation de transfert thermique avec l'électrolyte, une partie (18) seulement de ladite zone de surface étant électrolytiquement active. La première structure d'électrode peut être une structure d'anode appropriée pour produire de l'ozone et la partie restante (28) de la zone de surface de ladite structure d'anode peut être rendue électrolytiquement inactive en masquant ladite partie par rapport à la structure de cathode. La surface masquée de la structure d'anode est maintenue en relation de transfert thermique avec l'électrolyte.
PCT/GB1992/002157 1991-12-03 1992-11-20 Cellule electrochimique WO1993011281A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
FI942600A FI942600L (fi) 1991-12-03 1992-11-20 Sähkökemiallinen kenno
EP92923892A EP0611401A1 (fr) 1991-12-03 1992-11-20 Pile electrochimique
AU29503/92A AU665037B2 (en) 1991-12-03 1992-11-20 Electrochemical cell
JP5509920A JPH07501852A (ja) 1991-12-03 1992-11-20 電解槽
NO942059A NO942059L (no) 1991-12-03 1994-06-02 Elektrokjemisk celle

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919125680A GB9125680D0 (en) 1991-12-03 1991-12-03 Electrochemical cell
GB9125680.0 1991-12-03

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WO1993011281A2 true WO1993011281A2 (fr) 1993-06-10
WO1993011281A3 WO1993011281A3 (fr) 1993-07-08

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PCT/GB1992/002157 WO1993011281A2 (fr) 1991-12-03 1992-11-20 Cellule electrochimique

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EP (1) EP0611401A1 (fr)
JP (1) JPH07501852A (fr)
CN (1) CN1074954A (fr)
AU (1) AU665037B2 (fr)
CA (1) CA2124318A1 (fr)
FI (1) FI942600L (fr)
GB (2) GB9125680D0 (fr)
NO (1) NO942059L (fr)
NZ (1) NZ245265A (fr)
TW (1) TW288215B (fr)
WO (1) WO1993011281A2 (fr)
ZA (1) ZA929103B (fr)

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Publication number Priority date Publication date Assignee Title
DE102012011314A1 (de) * 2012-06-06 2013-12-12 Manfred Völker Elektrochemischer Ozonerzeuger undWasserstoff-Generator
FR3038456B1 (fr) * 2015-06-30 2019-10-18 Jomi Leman Dispositif electrochimique pour le stockage de l’energie electrique.
CN110093621B (zh) * 2019-04-24 2020-08-25 浙江工业大学 一种无氢连续电化学氧化io3-转化生成io4-的方法
CN111058055B (zh) * 2019-12-20 2021-01-15 江苏安凯特科技股份有限公司 一种离子膜电解槽的阴极结构

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* Cited by examiner, † Cited by third party
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US3575839A (en) * 1968-02-15 1971-04-20 Mikhail Alexeevich Melnikov Ei Electrolyzer with solid electrodes
JPS4837668B1 (fr) * 1969-05-14 1973-11-13
JPH01123086A (ja) * 1987-11-05 1989-05-16 Japan Storage Battery Co Ltd 電気化学的オゾン発生装置
DE4008612A1 (de) * 1990-03-17 1991-09-19 Peter Dr Faber Rotazon-geraet

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NZ245265A (en) 1996-02-27
FI942600A0 (fi) 1994-06-02
TW288215B (fr) 1996-10-11
NO942059L (no) 1994-08-01
FI942600L (fi) 1994-06-02
CN1074954A (zh) 1993-08-04
WO1993011281A3 (fr) 1993-07-08
NO942059D0 (no) 1994-06-02
AU665037B2 (en) 1995-12-14
GB9224261D0 (en) 1993-01-06
GB9125680D0 (en) 1992-01-29
AU2950392A (en) 1993-06-28
ZA929103B (en) 1994-03-10
EP0611401A1 (fr) 1994-08-24
JPH07501852A (ja) 1995-02-23
CA2124318A1 (fr) 1993-06-10

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