WO1998058880A1 - Method and apparatus for the electrochemical treatment of water and aqueous salt solutions - Google Patents

Method and apparatus for the electrochemical treatment of water and aqueous salt solutions Download PDF

Info

Publication number
WO1998058880A1
WO1998058880A1 PCT/GB1998/001864 GB9801864W WO9858880A1 WO 1998058880 A1 WO1998058880 A1 WO 1998058880A1 GB 9801864 W GB9801864 W GB 9801864W WO 9858880 A1 WO9858880 A1 WO 9858880A1
Authority
WO
WIPO (PCT)
Prior art keywords
inner electrode
electrode
auxiliary
chamber
apertures
Prior art date
Application number
PCT/GB1998/001864
Other languages
French (fr)
Inventor
Alexey Yurievich Popov
Dmitriy Alekseyevich Popov
Original Assignee
Sterilox Technologies International Limited
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 Sterilox Technologies International Limited filed Critical Sterilox Technologies International Limited
Priority to AU82239/98A priority Critical patent/AU8223998A/en
Publication of WO1998058880A1 publication Critical patent/WO1998058880A1/en

Links

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
    • 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • 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
    • C02F2201/002—Construction details of the apparatus
    • C02F2201/003—Coaxial constructions, e.g. a cartridge located coaxially within another
    • 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
    • C02F2201/4611—Fluid flow
    • 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
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/02—Fluid flow conditions
    • C02F2301/024—Turbulent
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/02—Fluid flow conditions
    • C02F2301/026—Spiral, helicoidal, radial

Definitions

  • the present invention relates to the electrochemical treatment of water and aqueous solutions of salt with the aim of altering the oxidising and reducing .properties of the water or the aqueous solutions of salt.
  • electrochemical treatment may take the form of anodic treatment for obtaining disinfectant solutions, cathodic water- softening treatment, or other treatments.
  • GB 2 253 860 It is known from GB 2 253 860, the disclosure of which is incorporated into the present application by reference, to treat water by passing this through an electrolytic cell having anode and cathode flow chambers separated by a semi-permeable membrane, one of the chambers being a working chamber through which water to be treated passes in an upward direction, and the other being an auxiliary chamber, which is in closed communication with a gas-separating chamber located at a higher level than the electrolytic cell.
  • the electrolytic cell comprises a tubular outer electrode and a rod-shaped inner electrode, the two electrodes being concentric and separated by the semi- permeable membrane so as to define the working and auxiliary chambers.
  • the working and auxiliary chambers are hermetically isolated from each other by way of elastic separator collars and each have entry apertures in the lower part and exit apertures in the higher part.
  • Water having a higher mineral content than the water to be treated passes upwardly through the auxiliary chamber to the gas-separating chamber and recirculates to the auxiliary chamber by convection and by the shearing forces applied to the water through the rise of bubbles of gas which are generated on the electrode in the auxiliary chamber.
  • the auxiliary solution circulates around a closed contour.
  • the water pressure in the working chamber is higher than that in the auxiliary chamber, and gaseous electrolysis products are vented from the gas-separating chamber by way of a gas-relief valve.
  • auxiliary solution may be removed by way of the gas-relief valve or from the gas-separating chamber.
  • This method allows the pH value of the water being treated to be reduced from 7 to around 2 when the anode chamber is used as the working chamber. If instead the cathode chamber is used as the working chamber, the pH value of the water to be treated can be increased to around 12.
  • This known method of electrolytic treatment is applied only to water having a relatively low concentration of dissolved salts and minerals (less than lOgdm "3 ) , and the electricity supplied for the electrolytic treatment of water in the working chamber is only around 200 to 3000CdmA Because the water to be treated has such a low concentration of dissolved salts and minerals, there is consequently a low concentration of useful electrolysis products (such as the chlorate (I) ion CIO " which is produced when a sodium chloride solution is used in the auxiliary chamber and which acts as a disinfecting agent) .
  • useful electrolysis products such as the chlorate (I) ion CIO " which is produced when a sodium chloride solution is used in the auxiliary chamber and which acts as a disinfecting agent
  • One way of estimating the effectiveness of a sterilising solution produced by the electrolytic treatment of a salt solution is to measure the concentration of "free chlorine", by which is understood the concentration of hypochlorous acid in water and the concentration of the chlorate ion (formed by the dissociation of hypochlorous acid) .
  • the concentration of free chlorine in water which has been treated in the anode chamber of the electrolytic cell of GB 2253860 does not usually exceed 0.2 to 0.6gdm "3 , although the solubility of gaseous chlorine in water is much higher (7.3gdm -3 at 20°C) . It is therefore apparent that water which has been under electrolytic treatment in accordance with the known method has a concentration of free chlorine not more than 3 to 10% of the possible maximum. This low concentration is a result of the fact that only a small proportion of the chloride ions which are drawn across the permeable membrane from the cathode flow chamber to the anode flow chamber .actually reach the anode to be combined so as to form gaseous chlorine. Most of the chloride ions in the anode chamber are carried out of the electrolytic cell with the output of the anode flow chamber before reaching the anode itself.
  • an apparatus for the electrolytic treatment of aqueous salt solutions comprising an electrolytic cell having a first, outer, generally tubular electrode and a second, inner, generally tubular electrode, the first and second electrodes being disposed substantially coaxially and separated from each other by a generally tubular semi-permeable membrane also disposed substantially coaxially with the electrodes so as to form an outer, working chamber defined as the volume bounded by the inner surface of the outer electrode and the outer surface of the semi-permeable membrane and an inner, auxiliary chamber defined as the volume bounded by the inner surface of the semi-permeable membrane and the outer surface of the inner electrode, the electrodes having upper and lower ends when the electrolytic cell is positioned vertically, characterised in that the tubular wall of the inner electrode is provided with exit apertures at its upper end region and entry apertures at its lower end region end region allowing communication between the inner, auxiliary chamber and the interior of the inner electrode.
  • an apparatus for the electrolytic treatment of aqueous salt solutions comprising a generally vertical midstream diaphragm electrolyser containing an outer tubular .electrode inside which an inner electrode is coaxially positioned, a tubular semi-permeable ceramic diaphragm coaxially positioned between the electrodes and dividing the inter-electrodal area into an inner and an outer electrode chamber which are hermetically isolated one from the other by dielectric separators, the outer electrode chamber being a working chamber connected to lines for inputting and outputting the aqueous salt solutions being treated, and the inner electrode chamber being an auxiliary chamber provided with a circulation contour and connected to lines for inputting and outputting an auxiliary solution, characterised in that the inner electrode takes the form of a hollow cylinder which in its lower part is connected through its hollow section with the auxiliary solution input line and in its upper part is connected through its hollow section with the auxiliary solution output line, and in that the inner electrode is provided with input and
  • a method of treating aqueous salt solutions in a generally vertical electrolytic cell comprising a first, outer, generally tubular electrode and a second, inner, generally tubular electrode, the first and second electrodes being disposed substantially coaxially and separated from each other by a generally tubular semi- permeable membrane also disposed substantially coaxially with the electrodes so as to form an outer, working chamber defined as the volume bounded by the inner surface of the outer electrode and the outer surface of the semi-permeable membrane and an inner, auxiliary chamber defined as the volume bounded by the .inner surface of the semi-permeable membrane and the outer surface of the inner electrode, the inner electrode being provided with apertures at its lower and upper ends allowing communication between the inner, auxiliary chamber and the interior of the inner electrode, wherein: i) a working aqueous salt solution is supplied to a lower end of the working chamber by an input line and taken from a higher end of the working chamber by an output line; i
  • the total area of the exit apertures in the inner electrode is advantageously greater than that of the entry apertures . It is also advantageous for the exit apertures to be configured so as to impart a tangential velocity component to the auxiliary gas- liquid mixture as this passes from the upper end of the auxiliary chamber into the hollow section of the inner electrode. This may be done by forming the apertures such that their axes are not disposed radially with respect to the inner electrode, but are angled relative thereto.
  • the semi-permeable diaphragm may be made of a ceramic material, such as zirconium oxide.
  • Embodiments of the present invention are more compact than the prior art apparatus and have fewer and shorter fluid connecting lines, thereby reducing leaks and pressure losses and thereby providing enhanced reliability and efficiency.
  • This is a result of the auxiliary solution circulation contour being located internally, i.e. the external expansion tank of the prior art is replaced by the interior of the hollow inner electrode, with the connecting pipes in the auxiliary solution circulation contour being replaced by the apertures in the wall of the inner electrode.
  • a product solution produced by the method of the third aspect as defined hereinabove .
  • FIGURE 1 shows a vertical cross-section through an embodiment of the present invention.
  • the electrolytic cell of Figure 1 includes an outer tubular electrode 1, a coaxially positioned inner electrode 2 having a hollow section 3, and a semi-permeable ceramic diaphragm 4 coaxially positioned between the electrodes 1 and 2.
  • a working chamber 5 is defined as the space bounded by the inside of the outer electrode 1 and the outside of the ceramic diaphragm 4
  • an auxiliary chamber 6 is defined as the space bounded by the inside of the ceramic diaphragm 4 and the outside of the inner electrode 2.
  • the working and auxiliary chambers 5,6 are hermetically isolated one from the other (notwithstanding the semi-permeable ceramic diaphragm 4) by elastic, dielectric separators
  • Entry apertures 8 are provided in the wall of the outer electrode 1 for supplying aqueous salt solution to the working chamber 5 (the entry apertures 8 being positioned in the lower part of the outer electrode 1) .
  • Exit apertures 9 are provided in the upper part of the outer electrode 1 and are used for letting processed aqueous salt solution out of the working chamber 5.
  • the inner electrode 2 is also provided with entry apertures 10 (in the lower part) and exit apertures 11 (in the upper part) .
  • the former are used for supplying auxiliary solution into the auxiliary chamber 6, and the latter for allowing processed auxiliary solution to be removed from the auxiliary chamber 6.
  • the outer electrode 1 is disposed between lower and upper dielectric blocks 12,13.
  • a connection 14 is positioned in the lower block 12 for supplying aqueous salt solution to the working chamber 5 via the entry aperture 8.
  • a feed pipe (not shown) is joined to the connecting pipe 14 and is used for bringing aqueous salt solution to the electrolyser .
  • a connecting pipe ,15 is positioned in the upper dielectric block 13 for allowing processed aqueous salt solution to exit the working chamber 5 through the exit apertures 9.
  • An outlet pipe (not shown in the diagram) is joined to the connecting pipe 15 and is used for carrying the processed aqueous salt solution out of the electrolyser.
  • the connecting pipes 14 and 15 are hermetically sealed by elastic separators 16.
  • the inner electrode 2 is positioned within dielectric sleeves 17 (lower) and 18 (upper) .
  • Connecting pipes 19 (entry) and 20 (exit) positioned on the ends of the inner electrode 2, are hermetically sealed by elastic separators 21.
  • the connecting pipe 19 is used for supplying the auxiliary solution into the hollow section 3 of the inner electrode 2.
  • a feed pipe for the auxiliary solution (not shown) is joined to the connecting pipe 19 and is used for supplying the auxiliary solution to the electrolyser.
  • An outlet pipe for the auxiliary solution (not shown) is joined to the connecting pipe 20 and is used for letting the processed auxiliary solution and electrolytic gases out of the electrolyser.
  • the apparatus is equipped with elastic separators 22 and 23.
  • the electrolyser is provided with electrical terminals 24 and 25, which are positioned on the outer electrode 1 and the inner electrode 2 respectively, so as to permit connection of a current supply (not shown) .
  • aqueous salt solution to be processed is supplied through the entry connecting pipe 14 and the entry aperture 8 so as substantially to fill working chamber 5.
  • Auxiliary aqueous salt solution is supplied through the entry connecting pipe 19 and into the hollow section 3 of the inner electrode 2.
  • the auxiliary solution passes into and substantially fills the auxiliary chamber 6 by way ,of the entry apertures 10.
  • the supply of auxiliary solution is then cut off or reduced.
  • the pressure of the working solution flowing through the working chamber 5 is set higher than the pressure of the auxiliary solution in the auxiliary chamber 6.
  • a potential difference is applied across the terminals 24 and 25 so as to cause an electric current to flow between the outer and the inner electrodes 1,2 through the working and auxiliary solutions.
  • auxiliary solution is drawn by rising bubbles of electrolytic gases (the gas-lift) generated in the auxiliary chamber 6 during electrolysis into the upper part of the auxiliary chamber 2 and, together with the electrolytic gases, leaves the auxiliary chamber 6 through the exit apertures 11 and enters the hollow section 3 of the inner electrode 2.
  • electrolytic gases the gas-lift
  • auxiliary solution is carried down to the entry apertures 10 and, under the action of the discharge created by the gas-lift described above, is drawn through the entry apertures 10 into the auxiliary chamber 6.
  • circulation of the auxiliary solution around a closed contour formed by the auxiliary chamber 6, the exit apertures 11, the hollow section 3 of the inner electrode 2 and the entry apertures 10 is achieved.
  • the volume of auxiliary solution in the electrolyser is replenished, over time, by way of solution which filters through the semi- permeable ceramic diaphragm 3 down the pressure gradient between the working and auxiliary chambers ,5,6. Any excess of auxiliary solution is taken from the electrolyser through the exit connecting pipe 20 together with the electrolytic gases.
  • the volume of the gas and liquid mixture leaving the auxiliary chamber 6 is greater than the volume of the auxiliary solution entering the auxiliary chamber 6, and the overall area of the exit apertures 11 may be greater than the overall area of the entry apertures 10.
  • the exit apertures 11 may be disposed with a tangential as well as a radial component, i.e. the exit apertures 11 may be angled so as to impart a tangential velocity component to the auxiliary gas-liquid mixture as this passes from the auxiliary chamber 6 into the hollow section 3 of the inner electrode 2.
  • the cyclonic motion thus imparted to the auxiliary gas-liquid mixture in the hollow section 3 of the inner electrode 2 tends to throw the heavier auxiliary liquid against the wall of the inner electrode 2 and concentrates the lighter gas components near the axis for removal from the electrolyser through the exit connecting pipe 20.
  • the electrolytic cell is configured such that the outer electrode is an anode and the inner electrode a cathode.
  • aqueous salt solutions can be electrolytically treated to obtain, for example, a disinfectant solution, with a saturated solution of sodium chloride being used as the auxiliary solution.
  • the working solution has a higher mineral content, i.e. concentration of dissolved salts, than the auxiliary .solution.
  • the apparatus may be arranged in alternative configurations, e.g. with the outer electrode 1 being the cathode and the inner electrode 2 the anode, thereby enabling cathodic water softening or other processes to take place.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

A method and apparatus for the electrolytic treatment of aqueous salt solutions, the apparatus comprising a diaphragm midstream electrolytic cell having coaxial tubular outer and inner electrodes (1, 2) separated by a semi-permeable diaphragm (4) so as to define an outer, working chamber (5) and an inner, auxiliary chamber (6). The inner electrode (2) is provided with apertures (10, 11) at either end allowing communication between the auxiliary chamber (6) and the interior (3) of the inner electrode (2). A working aqueous salt solution is passed upwards through the working chamber (5), while the auxiliary chamber (6) and the interior (3) of the inner electrode (2) is filled with an auxiliary aqueous salt solution. In use, a current is applied between the electrodes (1, 2), and gas bubbles formed in the auxiliary chamber (6) rise upwards and cause the auxiliary solution to circulate around the auxiliary chamber (6) and the interior (3) of the inner electrode (2) by way of the apertures (10, 11).

Description

METHOD AND APPARATUS FOR THE ELECTROCHEMICAL TREATMENT OF WATER AND AQUEOUS SALT SOLUTIONS
The present invention relates to the electrochemical treatment of water and aqueous solutions of salt with the aim of altering the oxidising and reducing .properties of the water or the aqueous solutions of salt. Such electrochemical treatment may take the form of anodic treatment for obtaining disinfectant solutions, cathodic water- softening treatment, or other treatments.
It is known from EP 0 394 232 to provide an electrolytic cell in which a tubular cathode is positioned within a tubular anode. An additional anode, in the form of a rod, is positioned within the tubular cathode . The anodes and the cathode are divided from each other by dielectric spiral elements. The apparatus is relatively compact, since the water is effectively subjected to electrolytic treatment in two electrolysis cells, one located inside the other.
It is known from GB 2 253 860, the disclosure of which is incorporated into the present application by reference, to treat water by passing this through an electrolytic cell having anode and cathode flow chambers separated by a semi-permeable membrane, one of the chambers being a working chamber through which water to be treated passes in an upward direction, and the other being an auxiliary chamber, which is in closed communication with a gas-separating chamber located at a higher level than the electrolytic cell. The electrolytic cell comprises a tubular outer electrode and a rod-shaped inner electrode, the two electrodes being concentric and separated by the semi- permeable membrane so as to define the working and auxiliary chambers. Notwithstanding the semi-permeable membrane, the working and auxiliary chambers are hermetically isolated from each other by way of elastic separator collars and each have entry apertures in the lower part and exit apertures in the higher part. Water having a higher mineral content than the water to be treated passes upwardly through the auxiliary chamber to the gas-separating chamber and recirculates to the auxiliary chamber by convection and by the shearing forces applied to the water through the rise of bubbles of gas which are generated on the electrode in the auxiliary chamber. In this way, the auxiliary solution circulates around a closed contour. The water pressure in the working chamber is higher than that in the auxiliary chamber, and gaseous electrolysis products are vented from the gas-separating chamber by way of a gas-relief valve. Some of the working solution will tend to pass from the working chamber to the auxiliary chamber across the semi-permeable membrane by virtue of the pressure gradient between the working and auxiliary chambers. Surplus auxiliary solution may be removed by way of the gas-relief valve or from the gas-separating chamber.
This method allows the pH value of the water being treated to be reduced from 7 to around 2 when the anode chamber is used as the working chamber. If instead the cathode chamber is used as the working chamber, the pH value of the water to be treated can be increased to around 12. This known method of electrolytic treatment is applied only to water having a relatively low concentration of dissolved salts and minerals (less than lOgdm"3) , and the electricity supplied for the electrolytic treatment of water in the working chamber is only around 200 to 3000CdmA Because the water to be treated has such a low concentration of dissolved salts and minerals, there is consequently a low concentration of useful electrolysis products (such as the chlorate (I) ion CIO" which is produced when a sodium chloride solution is used in the auxiliary chamber and which acts as a disinfecting agent) . In addition, water with a low concentration of salts and minerals tends to have a high ohmic resistance, which means that energy is used inefficiently when performing electrolysis. Furthermore, the small amount of electricity (200 to 30Q0Cdιτr3) applied to the water in the working chamber is insufficient to ensure the full transformation of the ions of dissolved salts (such as chloride ions Cl") into useful electrolysis products (such as chlorate (I) ions CIO") . The incomplete electrolysis of dissolved salts means that a greater than theoretically necessary amount of salt must initially be dissolved in order to provide a required concentration of electrolysis products. This excess of dissolved salt can mean that the output of the electrolytic cell is overly corrosive, and when used as a disinfectant wash, tends to leave a coating of crystalline salt on surfaces which have been washed. Furthermore, the prior art apparatus of GB 2253860 is of relatively cumbersome size and has a large number of connecting pipes and separate elements, which can result in low efficiency and reliability due to the likelihood of solution leakage. It is useful to consider the basic chemical reactions which take place in the anode and cathode chambers of the electrolytic cell. If the working chamber contains the anode, then the following reactions take place: Chloride ions transform into gaseous chlorine at the anode in accordance with the following equation:
2C1" → Cl2 + 2e" Gaseous chlorine dissolves in water and forms hypochlorous acid in accordance with the following equation:
Cl2 + H20 → H+ + Cl' + HC10 Electrolysis of water also takes place in the anode chamber. The equation is as follows:
2H20 → 4H+ + 02 + 4e" As a result of this reaction, gaseous oxygen is .liberated and the water becomes saturated with hydrogen ions. Consequently, the pH of the water falls in the anode chamber. The solubility of chlorine in the water reduces as the pH is lowered, and gaseous chlorine is liberated with oxygen. Electrolysis of water takes place in the cathode chamber. The equation is as follows:
2H20 + 2e_ → 20H" + H2 Consequently gaseous hydrogen is liberated at the cathode, and the concentration of hydroxide ions rises, thereby increasing the water pH in the cathode chamber.
It follows from this analysis that the oxidizing ability of water is determined by the concentration of hypochlorous acid, and the reduction ability by the concentration of hydroxide ions. Water which has been under electrolytic treatment according to the method described in GB 2253860 has a low concentration of hypochlorous acid and hydroxide ions due to the low mineralisation of the initial water.
One way of estimating the effectiveness of a sterilising solution produced by the electrolytic treatment of a salt solution is to measure the concentration of "free chlorine", by which is understood the concentration of hypochlorous acid in water and the concentration of the chlorate ion (formed by the dissociation of hypochlorous acid) .
The concentration of free chlorine in water which has been treated in the anode chamber of the electrolytic cell of GB 2253860 does not usually exceed 0.2 to 0.6gdm"3, although the solubility of gaseous chlorine in water is much higher (7.3gdm-3 at 20°C) . It is therefore apparent that water which has been under electrolytic treatment in accordance with the known method has a concentration of free chlorine not more than 3 to 10% of the possible maximum. This low concentration is a result of the fact that only a small proportion of the chloride ions which are drawn across the permeable membrane from the cathode flow chamber to the anode flow chamber .actually reach the anode to be combined so as to form gaseous chlorine. Most of the chloride ions in the anode chamber are carried out of the electrolytic cell with the output of the anode flow chamber before reaching the anode itself.
According to a first aspect of the present invention, there is provided an apparatus for the electrolytic treatment of aqueous salt solutions, the apparatus comprising an electrolytic cell having a first, outer, generally tubular electrode and a second, inner, generally tubular electrode, the first and second electrodes being disposed substantially coaxially and separated from each other by a generally tubular semi-permeable membrane also disposed substantially coaxially with the electrodes so as to form an outer, working chamber defined as the volume bounded by the inner surface of the outer electrode and the outer surface of the semi-permeable membrane and an inner, auxiliary chamber defined as the volume bounded by the inner surface of the semi-permeable membrane and the outer surface of the inner electrode, the electrodes having upper and lower ends when the electrolytic cell is positioned vertically, characterised in that the tubular wall of the inner electrode is provided with exit apertures at its upper end region and entry apertures at its lower end region end region allowing communication between the inner, auxiliary chamber and the interior of the inner electrode.
According to a second aspect of the present invention, there is provided an apparatus for the electrolytic treatment of aqueous salt solutions, the apparatus comprising a generally vertical midstream diaphragm electrolyser containing an outer tubular .electrode inside which an inner electrode is coaxially positioned, a tubular semi-permeable ceramic diaphragm coaxially positioned between the electrodes and dividing the inter-electrodal area into an inner and an outer electrode chamber which are hermetically isolated one from the other by dielectric separators, the outer electrode chamber being a working chamber connected to lines for inputting and outputting the aqueous salt solutions being treated, and the inner electrode chamber being an auxiliary chamber provided with a circulation contour and connected to lines for inputting and outputting an auxiliary solution, characterised in that the inner electrode takes the form of a hollow cylinder which in its lower part is connected through its hollow section with the auxiliary solution input line and in its upper part is connected through its hollow section with the auxiliary solution output line, and in that the inner electrode is provided with input and output apertures which connect the hollow section of the inner electrode with the auxiliary chamber and which form a circulation contour for the auxiliary solution.
According to a third aspect of the present invention, there is provided a method of treating aqueous salt solutions in a generally vertical electrolytic cell, the cell comprising a first, outer, generally tubular electrode and a second, inner, generally tubular electrode, the first and second electrodes being disposed substantially coaxially and separated from each other by a generally tubular semi- permeable membrane also disposed substantially coaxially with the electrodes so as to form an outer, working chamber defined as the volume bounded by the inner surface of the outer electrode and the outer surface of the semi-permeable membrane and an inner, auxiliary chamber defined as the volume bounded by the .inner surface of the semi-permeable membrane and the outer surface of the inner electrode, the inner electrode being provided with apertures at its lower and upper ends allowing communication between the inner, auxiliary chamber and the interior of the inner electrode, wherein: i) a working aqueous salt solution is supplied to a lower end of the working chamber by an input line and taken from a higher end of the working chamber by an output line; ii) an auxiliary aqueous salt solution is supplied to a lower end of the inner electrode by an input line so as substantially to fill the interior of the inner electrode and the auxiliary chamber by way of the apertures; iii) an electric current is applied between the outer and the inner electrodes; iv) gases formed by electrolysis in the auxiliary chamber are allowed to rise and escape through the apertures provided at an upper end of the inner electrode and are passed out by way of an output line provided at an upper end of the inner electrode; and v) auxiliary solution in the auxiliary chamber is driven by bubbles of said gases and passes upwards through the auxiliary chamber, through the apertures at the upper end of the inner electrode, down through the interior of the inner electrode, and back into the lower end of the auxiliary chamber through the apertures at the lower end of the inner electrode.
Because the combined volume of auxiliary solution and gases which is output per unit time from the auxiliary chamber is generally greater than the volume of auxiliary solution which is input per unit time, the total area of the exit apertures in the inner electrode is advantageously greater than that of the entry apertures . It is also advantageous for the exit apertures to be configured so as to impart a tangential velocity component to the auxiliary gas- liquid mixture as this passes from the upper end of the auxiliary chamber into the hollow section of the inner electrode. This may be done by forming the apertures such that their axes are not disposed radially with respect to the inner electrode, but are angled relative thereto. In this way, a cyclonic flow into the hollow section of the inner electrode is achieved, with the heavier liquid component of the auxiliary gas- liquid mixture being urged towards the wall of the inner electrode by centrifugal force, and the lighter gas component conversely being urged towards the central axis of the inner electrode, thereby assisting the gas-liquid separation process.
The semi-permeable diaphragm may be made of a ceramic material, such as zirconium oxide.
Embodiments of the present invention are more compact than the prior art apparatus and have fewer and shorter fluid connecting lines, thereby reducing leaks and pressure losses and thereby providing enhanced reliability and efficiency. This is a result of the auxiliary solution circulation contour being located internally, i.e. the external expansion tank of the prior art is replaced by the interior of the hollow inner electrode, with the connecting pipes in the auxiliary solution circulation contour being replaced by the apertures in the wall of the inner electrode. According to a fourth aspect of the present invention, there is provided a product solution produced by the method of the third aspect as defined hereinabove .
For a better understanding of the present invention, and to show how it may be carried into effect, reference shall now be made by way of example to the accompanying drawing, in which:
FIGURE 1 shows a vertical cross-section through an embodiment of the present invention.
The electrolytic cell of Figure 1 includes an outer tubular electrode 1, a coaxially positioned inner electrode 2 having a hollow section 3, and a semi-permeable ceramic diaphragm 4 coaxially positioned between the electrodes 1 and 2. A working chamber 5 is defined as the space bounded by the inside of the outer electrode 1 and the outside of the ceramic diaphragm 4, and an auxiliary chamber 6 is defined as the space bounded by the inside of the ceramic diaphragm 4 and the outside of the inner electrode 2. The working and auxiliary chambers 5,6 are hermetically isolated one from the other (notwithstanding the semi-permeable ceramic diaphragm 4) by elastic, dielectric separators
7. Entry apertures 8 are provided in the wall of the outer electrode 1 for supplying aqueous salt solution to the working chamber 5 (the entry apertures 8 being positioned in the lower part of the outer electrode 1) . Exit apertures 9 are provided in the upper part of the outer electrode 1 and are used for letting processed aqueous salt solution out of the working chamber 5.
The inner electrode 2 is also provided with entry apertures 10 (in the lower part) and exit apertures 11 (in the upper part) . The former are used for supplying auxiliary solution into the auxiliary chamber 6, and the latter for allowing processed auxiliary solution to be removed from the auxiliary chamber 6. The outer electrode 1 is disposed between lower and upper dielectric blocks 12,13. A connection 14 is positioned in the lower block 12 for supplying aqueous salt solution to the working chamber 5 via the entry aperture 8. A feed pipe (not shown) is joined to the connecting pipe 14 and is used for bringing aqueous salt solution to the electrolyser . A connecting pipe ,15 is positioned in the upper dielectric block 13 for allowing processed aqueous salt solution to exit the working chamber 5 through the exit apertures 9. An outlet pipe (not shown in the diagram) is joined to the connecting pipe 15 and is used for carrying the processed aqueous salt solution out of the electrolyser. The connecting pipes 14 and 15 are hermetically sealed by elastic separators 16. The inner electrode 2 is positioned within dielectric sleeves 17 (lower) and 18 (upper) . Connecting pipes 19 (entry) and 20 (exit) , positioned on the ends of the inner electrode 2, are hermetically sealed by elastic separators 21. The connecting pipe 19 is used for supplying the auxiliary solution into the hollow section 3 of the inner electrode 2. A feed pipe for the auxiliary solution (not shown) is joined to the connecting pipe 19 and is used for supplying the auxiliary solution to the electrolyser. An outlet pipe for the auxiliary solution (not shown) is joined to the connecting pipe 20 and is used for letting the processed auxiliary solution and electrolytic gases out of the electrolyser. In order to seal the working chamber 5 and the auxiliary chamber 6, the apparatus is equipped with elastic separators 22 and 23. The electrolyser is provided with electrical terminals 24 and 25, which are positioned on the outer electrode 1 and the inner electrode 2 respectively, so as to permit connection of a current supply (not shown) .
When the apparatus is in use, aqueous salt solution to be processed is supplied through the entry connecting pipe 14 and the entry aperture 8 so as substantially to fill working chamber 5. Auxiliary aqueous salt solution is supplied through the entry connecting pipe 19 and into the hollow section 3 of the inner electrode 2. The auxiliary solution passes into and substantially fills the auxiliary chamber 6 by way ,of the entry apertures 10. The supply of auxiliary solution is then cut off or reduced. The pressure of the working solution flowing through the working chamber 5 is set higher than the pressure of the auxiliary solution in the auxiliary chamber 6. A potential difference is applied across the terminals 24 and 25 so as to cause an electric current to flow between the outer and the inner electrodes 1,2 through the working and auxiliary solutions. This brings about electrolytic treatment of the working solution in the working chamber 5, from which the treated solution leaves the electrolyser by way of the exit aperture 9 and the exit connecting pipe 15. The auxiliary solution is drawn by rising bubbles of electrolytic gases (the gas-lift) generated in the auxiliary chamber 6 during electrolysis into the upper part of the auxiliary chamber 2 and, together with the electrolytic gases, leaves the auxiliary chamber 6 through the exit apertures 11 and enters the hollow section 3 of the inner electrode 2. An expansion of the flow occurs in the hollow section 3, whereby the electrolytic gases are separated from the auxiliary solution and leave the electrolyser through the exit connecting pipe 20. The separated auxiliary solution is carried down to the entry apertures 10 and, under the action of the discharge created by the gas-lift described above, is drawn through the entry apertures 10 into the auxiliary chamber 6. In this way, circulation of the auxiliary solution around a closed contour formed by the auxiliary chamber 6, the exit apertures 11, the hollow section 3 of the inner electrode 2 and the entry apertures 10 is achieved. The volume of auxiliary solution in the electrolyser is replenished, over time, by way of solution which filters through the semi- permeable ceramic diaphragm 3 down the pressure gradient between the working and auxiliary chambers ,5,6. Any excess of auxiliary solution is taken from the electrolyser through the exit connecting pipe 20 together with the electrolytic gases. If it becomes necessary to provide additional auxiliary solution or to replace the auxiliary solution, this may be done by way of the entry connecting pipe 19. As a result of the formation of electrolytic gases, the volume of the gas and liquid mixture leaving the auxiliary chamber 6 is greater than the volume of the auxiliary solution entering the auxiliary chamber 6, and the overall area of the exit apertures 11 may be greater than the overall area of the entry apertures 10.
In order to obtain a more effective isolation of the electrolytic gases from the auxiliary solution in the hollow section 3 of the inner electrode 2, the exit apertures 11 may be disposed with a tangential as well as a radial component, i.e. the exit apertures 11 may be angled so as to impart a tangential velocity component to the auxiliary gas-liquid mixture as this passes from the auxiliary chamber 6 into the hollow section 3 of the inner electrode 2. The cyclonic motion thus imparted to the auxiliary gas-liquid mixture in the hollow section 3 of the inner electrode 2 tends to throw the heavier auxiliary liquid against the wall of the inner electrode 2 and concentrates the lighter gas components near the axis for removal from the electrolyser through the exit connecting pipe 20. For most applications, the electrolytic cell is configured such that the outer electrode is an anode and the inner electrode a cathode. In this way, aqueous salt solutions can be electrolytically treated to obtain, for example, a disinfectant solution, with a saturated solution of sodium chloride being used as the auxiliary solution. In some applications, the working solution has a higher mineral content, i.e. concentration of dissolved salts, than the auxiliary .solution.
The apparatus may be arranged in alternative configurations, e.g. with the outer electrode 1 being the cathode and the inner electrode 2 the anode, thereby enabling cathodic water softening or other processes to take place.

Claims

CLAIMS ;
1. An apparatus for the electrolytic treatment of aqueous salt solutions, the apparatus comprising an .electrolytic cell having a first, outer, generally tubular electrode and a second, inner, generally tubular electrode, the first and second electrodes being disposed substantially coaxially and separated from each other by a generally tubular semi-permeable membrane also disposed substantially coaxially with the electrodes so as to form an outer, working chamber defined as the volume bounded by the inner surface of the outer electrode and the outer surface of the semi- permeable membrane and an inner, auxiliary chamber defined as the volume bounded by the inner surface of the semi-permeable membrane and the outer surface of the inner electrode, the electrodes having upper and lower ends when the electrolytic cell is positioned vertically, characterised in that the tubular wall of the inner electrode is provided with exit apertures at its upper end region and entry apertures at its lower end region end region allowing communication between the inner, auxiliary chamber and the interior of the inner electrode.
2. An apparatus for the electrolytic treatment of aqueous salt solutions, the apparatus comprising a generally vertical midstream diaphragm electrolyser containing an outer tubular electrode inside which an inner electrode is coaxially positioned, a tubular semi-permeable ceramic diaphragm coaxially positioned between the electrodes and dividing the inter-electrodal area into an inner and an outer electrode chamber which are hermetically isolated one from the other by dielectric separators, the outer electrode chamber being a working chamber connected to lines for inputting and outputting the aqueous salt solutions being treated, and the inner electrode chamber being an auxiliary chamber provided with a circulation contour and connected to lines for inputting and outputting an auxiliary solution, characterised in that the inner electrode takes the form of a hollow cylinder which in its lower part is connected through its hollow section with the auxiliary solution input line and in its upper part is connected through its hollow section with the auxiliary solution output line, and in that the inner electrode is provided with input and output apertures which connect the hollow section of the inner electrode with the auxiliary chamber and which form a circulation contour for the auxiliary solution.
3. An apparatus as claimed in claim 1 or 2 , wherein the overall area of the exit apertures in the inner electrode is greater than the overall area of the entry apertures .
4. An apparatus as claimed in claim 1, 2 or 3 , wherein the exit apertures in the inner electrode have major axes which are directed with a tangential component relative to radii of the generally tubular inner electrode.
5. An apparatus as claimed in any preceding claim, wherein the outer electrode is an anode and the inner electrode is a cathode.
6. An apparatus as claimed in any of claims 1 to 4, wherein the outer electrode is a cathode and the inner electrode is an anode.
7. A method of treating aqueous salt solutions in a generally vertical electrolytic cell, the cell comprising a first, outer, generally tubular electrode and a second, inner, generally tubular electrode, the first and second electrodes being disposed substantially coaxially and separated from each other by a generally tubular semi-permeable membrane also disposed substantially coaxially with the electrodes so as to form an outer, working chamber defined as the volume bounded by the inner surface of the outer electrode and the outer surface of the semi-permeable membrane and an inner, auxiliary chamber defined as the volume bounded by the inner surface of the semi- permeable membrane and the outer surface of the inner electrode, the inner electrode being provided with apertures at its lower and upper ends allowing communication between the inner, auxiliary chamber and the interior of the inner electrode, wherein: i) a working aqueous salt solution is supplied to a lower end of the working chamber by an input line and taken from a higher end of the working chamber by an output line; ii) an auxiliary aqueous salt solution is supplied to a lower end of the inner electrode by an input line so as substantially to fill the interior of the inner electrode and the auxiliary chamber by way of the apertures; iii) an electric current is applied between the outer and the inner electrodes; iv) gases formed by electrolysis in the auxiliary chamber are allowed to rise and escape through the apertures provided at an upper end of the inner electrode and are passed out by way of an output line provided at an upper end of the inner electrode; and v) auxiliary solution in the auxiliary chamber is driven by bubbles of said gases and passes upwards through the auxiliary chamber, through the apertures at the upper end of the inner electrode, down through the interior of the inner electrode, and back into the lower end of the auxiliary chamber through the apertures at the lower end of the inner electrode.
8. A method according to claim 7, wherein the auxiliary solution and said gases are given a cyclonic motion upon entry into the interior of the inner electrode by means of the apertures at the upper end of the inner electrode being disposed with major axes having a tangential component relative to radii of the inner electrode.
9. A product solution produced by the method of claims 7 or 8.
PCT/GB1998/001864 1997-06-25 1998-06-25 Method and apparatus for the electrochemical treatment of water and aqueous salt solutions WO1998058880A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU82239/98A AU8223998A (en) 1997-06-25 1998-06-25 Method and apparatus for the electrochemical treatment of water and aqueous saltsolutions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU97110693A RU2132821C1 (en) 1997-06-25 1997-06-25 Electrolytic water treatment device
RU97110693 1997-06-25

Publications (1)

Publication Number Publication Date
WO1998058880A1 true WO1998058880A1 (en) 1998-12-30

Family

ID=20194560

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/001864 WO1998058880A1 (en) 1997-06-25 1998-06-25 Method and apparatus for the electrochemical treatment of water and aqueous salt solutions

Country Status (3)

Country Link
AU (1) AU8223998A (en)
RU (1) RU2132821C1 (en)
WO (1) WO1998058880A1 (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6225441B1 (en) 1998-07-10 2001-05-01 The Johns Hopkins University Human fast-1 protein
WO2004009498A1 (en) * 2002-07-23 2004-01-29 Sterilox Technologies Inc. Electrochemical cells
EP1486459A2 (en) * 2003-06-11 2004-12-15 Electricité de France Service National Process and apparatus for producing chlorine dioxide
EP1538128A2 (en) * 2003-12-04 2005-06-08 Aquastel International B.V. End cap for an electrolytic cell
CN1303004C (en) * 2003-01-29 2007-03-07 松村正利 Method of electrolytic treatment of industrial or aquaculture waste water
US7374645B2 (en) 2006-05-25 2008-05-20 Clenox, L.L.C. Electrolysis cell assembly
WO2010064946A1 (en) * 2008-12-03 2010-06-10 Bakhir Vitold M Electrochemical modular cell for processing electrolyte solutions
US8062500B2 (en) 2001-12-05 2011-11-22 Oculus Innovative Sciences, Inc. Method and apparatus for producing negative and positive oxidative reductive potential (ORP) water
US8147444B2 (en) 2006-01-20 2012-04-03 Oculus Innovative Sciences, Inc. Methods of treating or preventing peritonitis with oxidative reductive potential water solution
RU2454489C1 (en) * 2011-01-12 2012-06-27 Марат Гайярович Измайлов Electrochemical cell for treatment of electrolyte solutions
US8323252B2 (en) 2005-03-23 2012-12-04 Oculus Innovative Sciences, Inc. Method of treating skin ulcers using oxidative reductive potential water solution
EP2597070A1 (en) * 2010-07-21 2013-05-29 Vladimir Vikentievich Vinogradov Device for electrochemically processing water or aqueous solutions
EP2631334A1 (en) * 2012-02-24 2013-08-28 Caliopa AG Electrolysis cell, particularly for use in an assembly for creating an electrochemically activated table salt solution, and assembly with a number of such electrolysis cells
ES2401448R1 (en) * 2009-12-10 2013-11-06 Vladimir Vikentievich Vinogradov Device for electrochemical treatment of water or aqueous solutions
US9168318B2 (en) 2003-12-30 2015-10-27 Oculus Innovative Sciences, Inc. Oxidative reductive potential water solution and methods of using the same
US9498548B2 (en) 2005-05-02 2016-11-22 Oculus Innovative Sciences, Inc. Method of using oxidative reductive potential water solution in dental applications
US10342825B2 (en) 2009-06-15 2019-07-09 Sonoma Pharmaceuticals, Inc. Solution containing hypochlorous acid and methods of using same
RU194041U1 (en) * 2019-10-01 2019-11-26 Общество с ограниченной ответственностью Научно-производственный центр "Современные технологии" (ООО НПЦ "Современные технологии") PORTABLE ELECTROLYZER FOR PRODUCING SODIUM HYPOCHLORITE SOLUTION
RU2729184C1 (en) * 2019-12-12 2020-08-05 Сергей Владимирович Силин Electrochemical reactor and apparatus for electrochemical synthesis of a mixture of oxidants
GB2607288A (en) * 2021-05-28 2022-12-07 Ecomotus Ltd Method and means for increasing the efficiency of an internal combustion engine
EE202100019A (en) * 2021-06-30 2023-02-15 Valeri Iltðenko Electrolyser for production of catholyte

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2297981C1 (en) * 2005-10-21 2007-04-27 Владимир Викентиевич Виноградов Device for the electrochemical treatment of the water and the water solutions
RU2367616C2 (en) * 2007-11-30 2009-09-20 Владимир Викентиевич Виноградов Device for electrochemical treatment of water or aqueous solutions
EA013774B1 (en) * 2009-02-04 2010-06-30 Владимир Викентиевич ВИНОГРАДОВ Device for the electrochemical treatment of the water and the water solutions
CN102337579A (en) * 2011-09-30 2012-02-01 东莞市五株电子科技有限公司 Electroplating liquid temperature control system

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2227084A1 (en) * 1972-06-03 1973-12-13 Huels Chemische Werke Ag ELECTROCHEMICAL CELL
US3984303A (en) * 1975-07-02 1976-10-05 Diamond Shamrock Corporation Membrane electrolytic cell with concentric electrodes
US4006067A (en) * 1973-03-05 1977-02-01 Gussack Mark C Oxidation-reduction process
US4784735A (en) * 1986-11-25 1988-11-15 The Dow Chemical Company Concentric tube membrane electrolytic cell with an internal recycle device
US4964970A (en) * 1988-10-05 1990-10-23 Hoh Water Technology Corp. Compact low volume water purification apparatus
EP0693459A2 (en) * 1994-07-19 1996-01-24 Kabushiki Kaisha Alone World Ionized water, and method and apparatus for manufacturing same
DE19517652A1 (en) * 1995-05-17 1996-11-21 Grundfos As Reducing nitrate or nitrite content in water by electrolytic and catalytic treatment

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2227084A1 (en) * 1972-06-03 1973-12-13 Huels Chemische Werke Ag ELECTROCHEMICAL CELL
US4006067A (en) * 1973-03-05 1977-02-01 Gussack Mark C Oxidation-reduction process
US3984303A (en) * 1975-07-02 1976-10-05 Diamond Shamrock Corporation Membrane electrolytic cell with concentric electrodes
US4784735A (en) * 1986-11-25 1988-11-15 The Dow Chemical Company Concentric tube membrane electrolytic cell with an internal recycle device
US4964970A (en) * 1988-10-05 1990-10-23 Hoh Water Technology Corp. Compact low volume water purification apparatus
EP0693459A2 (en) * 1994-07-19 1996-01-24 Kabushiki Kaisha Alone World Ionized water, and method and apparatus for manufacturing same
DE19517652A1 (en) * 1995-05-17 1996-11-21 Grundfos As Reducing nitrate or nitrite content in water by electrolytic and catalytic treatment

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6225441B1 (en) 1998-07-10 2001-05-01 The Johns Hopkins University Human fast-1 protein
US8062500B2 (en) 2001-12-05 2011-11-22 Oculus Innovative Sciences, Inc. Method and apparatus for producing negative and positive oxidative reductive potential (ORP) water
US7422668B2 (en) 2002-07-23 2008-09-09 Puricore International Limited Electrochemical cells
WO2004009498A1 (en) * 2002-07-23 2004-01-29 Sterilox Technologies Inc. Electrochemical cells
GB2391018B (en) * 2002-07-23 2005-08-17 David Edward Cross Electrochemical cells
CN1303004C (en) * 2003-01-29 2007-03-07 松村正利 Method of electrolytic treatment of industrial or aquaculture waste water
EP1486459A2 (en) * 2003-06-11 2004-12-15 Electricité de France Service National Process and apparatus for producing chlorine dioxide
EP1486459A3 (en) * 2003-06-11 2011-12-14 Electricité de France Process and apparatus for producing chlorine dioxide
US7691249B2 (en) 2003-12-04 2010-04-06 Clenox, LLC Method and apparatus for making electrolyzed water
EP1538128A3 (en) * 2003-12-04 2005-11-09 Aquastel International B.V. End cap for an electrolytic cell
GB2409465B (en) * 2003-12-04 2008-07-09 Medipure Ltd End cap for an electrolytic cell
US8002955B2 (en) 2003-12-04 2011-08-23 Clenox, L.L.C. Cylindrical electrolysis cell
GB2409465A (en) * 2003-12-04 2005-06-29 Medipure Ltd End cap for an electrolytic cell
EP1538128A2 (en) * 2003-12-04 2005-06-08 Aquastel International B.V. End cap for an electrolytic cell
US9168318B2 (en) 2003-12-30 2015-10-27 Oculus Innovative Sciences, Inc. Oxidative reductive potential water solution and methods of using the same
US10016455B2 (en) 2003-12-30 2018-07-10 Sonoma Pharmaceuticals, Inc. Method of preventing or treating influenza with oxidative reductive potential water solution
US9642876B2 (en) 2003-12-30 2017-05-09 Sonoma Pharmaceuticals, Inc. Method of preventing or treating sinusitis with oxidative reductive potential water solution
US8840873B2 (en) 2005-03-23 2014-09-23 Oculus Innovative Sciences, Inc. Method of treating second and third degree burns using oxidative reductive potential water solution
US8323252B2 (en) 2005-03-23 2012-12-04 Oculus Innovative Sciences, Inc. Method of treating skin ulcers using oxidative reductive potential water solution
US9498548B2 (en) 2005-05-02 2016-11-22 Oculus Innovative Sciences, Inc. Method of using oxidative reductive potential water solution in dental applications
US8834445B2 (en) 2006-01-20 2014-09-16 Oculus Innovative Sciences, Inc. Methods of treating or preventing peritonitis with oxidative reductive potential water solution
US8147444B2 (en) 2006-01-20 2012-04-03 Oculus Innovative Sciences, Inc. Methods of treating or preventing peritonitis with oxidative reductive potential water solution
US9072726B2 (en) 2006-01-20 2015-07-07 Oculus Innovative Sciences, Inc. Methods of treating or preventing inflammation and hypersensitivity with oxidative reductive potential water solution
US9782434B2 (en) 2006-01-20 2017-10-10 Sonoma Pharmaceuticals, Inc. Methods of treating or preventing inflammation and hypersensitivity with oxidative reductive potential water solution
EP1860209A3 (en) * 2006-05-25 2008-10-22 Aquastel International B.V. Electrolysis cell assembly
US7374645B2 (en) 2006-05-25 2008-05-20 Clenox, L.L.C. Electrolysis cell assembly
WO2010064946A1 (en) * 2008-12-03 2010-06-10 Bakhir Vitold M Electrochemical modular cell for processing electrolyte solutions
GB2479286A (en) * 2008-12-03 2011-10-05 Bakhir Vitold M Electrochemical modular cell for processing electrolyte solutions
US8961750B2 (en) 2008-12-03 2015-02-24 Vitold Mikhailovich Bakhir Electrochemical modular cell for processing electrolyte solutions
DE112008004180T5 (en) 2008-12-03 2012-08-30 Vitold Michailovič Bakhir Electrochemical modular cell for processing electrolyte solutions
GB2479286B (en) * 2008-12-03 2013-09-18 Bakhir Vitold M Electrochemical modular cell for processing electrolyte solutions
US10342825B2 (en) 2009-06-15 2019-07-09 Sonoma Pharmaceuticals, Inc. Solution containing hypochlorous acid and methods of using same
ES2401448R1 (en) * 2009-12-10 2013-11-06 Vladimir Vikentievich Vinogradov Device for electrochemical treatment of water or aqueous solutions
EP2597070A4 (en) * 2010-07-21 2013-08-28 Vladimir Vikentievich Vinogradov Device for electrochemically processing water or aqueous solutions
EP2597070A1 (en) * 2010-07-21 2013-05-29 Vladimir Vikentievich Vinogradov Device for electrochemically processing water or aqueous solutions
RU2454489C1 (en) * 2011-01-12 2012-06-27 Марат Гайярович Измайлов Electrochemical cell for treatment of electrolyte solutions
EP2631334A1 (en) * 2012-02-24 2013-08-28 Caliopa AG Electrolysis cell, particularly for use in an assembly for creating an electrochemically activated table salt solution, and assembly with a number of such electrolysis cells
WO2013124076A1 (en) * 2012-02-24 2013-08-29 Caliopa Ag Electrolysis cell, in particular for use in a plant for producing an electrochemically activated sodium chloride solution, and plant having a number of such electrolysis cells
RU194041U1 (en) * 2019-10-01 2019-11-26 Общество с ограниченной ответственностью Научно-производственный центр "Современные технологии" (ООО НПЦ "Современные технологии") PORTABLE ELECTROLYZER FOR PRODUCING SODIUM HYPOCHLORITE SOLUTION
RU2729184C1 (en) * 2019-12-12 2020-08-05 Сергей Владимирович Силин Electrochemical reactor and apparatus for electrochemical synthesis of a mixture of oxidants
GB2607288A (en) * 2021-05-28 2022-12-07 Ecomotus Ltd Method and means for increasing the efficiency of an internal combustion engine
GB2607288B (en) * 2021-05-28 2024-01-10 Ecomotus Ltd Method and means for increasing the efficiency of an internal combustion engine
EE202100019A (en) * 2021-06-30 2023-02-15 Valeri Iltðenko Electrolyser for production of catholyte
EE05855B1 (en) * 2021-06-30 2023-06-15 ILTšENKO VALERI Electrolyser for production of catholyte
US11807949B2 (en) 2021-06-30 2023-11-07 Valeri Iltsenko Electrolyser for production of catholyte

Also Published As

Publication number Publication date
AU8223998A (en) 1999-01-04
RU2132821C1 (en) 1999-07-10

Similar Documents

Publication Publication Date Title
WO1998058880A1 (en) Method and apparatus for the electrochemical treatment of water and aqueous salt solutions
US4804449A (en) Electrolytic cell
US5427658A (en) Electrolytic cell and method for producing a mixed oxidant gas
CA1197489A (en) Electrolytic swimming pool chlorination
US5871623A (en) Apparatus for electrochemical treatment of water and/or water solutions
US4596648A (en) Continuous electrolytic gas generator
KR0142607B1 (en) Wet treatment device, electrolytic active water producing method, and wet treating method
JPS6323273B2 (en)
CN107849713B (en) The reduction method and electrolysis system of carbon dioxide are utilized for electrochemistry
US20010022273A1 (en) Electrochemical treatment of water and aqueous salt solutions
MXPA03007923A (en) Method and apparatus for producing negative and positive oxidative reductive potential (orp) water.
KR101361651B1 (en) A device using electrolyzer with a bipolar membrane and the method of producing hypochlorite solution and hydrogen gas thereby
EP0838434A2 (en) Electrolytic treatment of aqueous salt solutions
KR100634889B1 (en) An electrolytic apparatus for producing sodium hypochloride
KR20160054471A (en) Chlorine dioxide production device and chlorine dioxide production method
EA013774B1 (en) Device for the electrochemical treatment of the water and the water solutions
US11306402B2 (en) Device for obtaining electrolysis products from an alkali metal chloride solution
JP2020531686A5 (en)
RU2110483C1 (en) Electrochemical water treatment apparatus
CN109642334B (en) Chlorine dioxide generator and chlorine dioxide generating method
RU2157793C1 (en) Method of preparing disinfecting neutral anolite solution neutral anolite
RU2148027C1 (en) Method of preparing disinfecting solution in the form of neutral anodic liquor
CN112030180A (en) Hypochlorous acid generator
RU2349682C2 (en) Electrolytic installation for obtaining sodium hypochlorite
JP3893693B2 (en) Electrolyzed water production equipment

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1999504015

Format of ref document f/p: F

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA