US20130341200A1 - Series cell electrochemical production of modified anolyte solution - Google Patents
Series cell electrochemical production of modified anolyte solution Download PDFInfo
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- US20130341200A1 US20130341200A1 US13/568,491 US201213568491A US2013341200A1 US 20130341200 A1 US20130341200 A1 US 20130341200A1 US 201213568491 A US201213568491 A US 201213568491A US 2013341200 A1 US2013341200 A1 US 2013341200A1
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- anolyte
- catholyte
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
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- 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
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
- C02F2001/46185—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only anodic or acidic water, e.g. for oxidizing or sterilizing
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- 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
Definitions
- the present invention generally relates to production of anolyte solutions with electrochemical cells.
- Electrochemical cells typically include an anode, a cathode, and a membrane therebetween.
- anolyte solution is produced in an anolyte space between the anode and the membrane.
- Catholyte solution may also be produced in a catholyte space between the membrane and the cathode.
- a liquid such as a brine solution, is coupled into the anolyte space to produce anolyte solution when the anode and cathode are powered.
- Pure water is advantageously coupled into the catholyte space, although brine solution could also be coupled into that space instead.
- pure water may be coupled into the anolyte space and brine solution coupled into the catholyte space.
- the anolyte solution, and often the catholyte solution, produced by such membrane-based electrochemical cells have been considered to provide cleaning capabilities such as for laundry, clean-in-place, and surface cleaning purposes.
- the anolyte solution produced thereby is usually a low pH acid, which can be corrosive, may have an excess of free chlorine which might gas off, and may not be sufficiently stable in storage.
- the present invention provides a system and method for producing a modified anolyte solution possessing desirable cleaning capabilities, but without the drawbacks of the anolyte solutions produced by typical electrochemical cells.
- a membrane-less electrochemical cell is provided with the anolyte solution from a membrane-based electrochemical cell coupled into the membrane-less electrochemical cell to further process the anolyte solution from the membrane-based electrochemical cell to produce a modified anolyte solution.
- a membrane-less electrochemical cell is characterized in that it has an anode, a cathode, and a fluid space therebetween uninterrupted by a membrane so as to produce modified anolyte solution from at least the anolyte solution in the fluid space when the anode and cathode thereof are powered.
- the modified anolyte solution obtained is still acidic and provides desirable cleaning characteristics. But, unlike the anolyte solution produced by the membrane-based cell, the modified anolyte solution has a higher pH and so is less corrosive, reduces the off-gassing, and is more stable for storage. If desired, some brine solution may also be coupled into the fluid space of the second electrochemical cell such that the modified anolyte solution is produced from the anolyte solution and the brine solution in the fluid space when the anode and cathode thereof are powered.
- the membrane-based cell may be fluidically coupled as appropriate to sources of liquid, such as pure water and/or brine solution.
- the fluid space of the membrane-less electrochemical cell is coupled to the anolyte space of the membrane-based cell and, if desired, may also be coupled to a source of brine solution, which may be the same source as used to supply brine solution to the membrane-based cell or different sources so as to obtain different brine solutions (or different concentrations of otherwise similar brine solutions).
- the modified anolyte solution may be coupled to an anolyte tank for use and/or storage.
- the catholyte solution produced by the membrane-based cell may be coupled to a catholyte tank for use and/or storage, or may be disposed of as appropriate. In any event, because the anolyte solution from the first cell is coupled into and further processed by the second cell, the two cells may be seen as being in series, at least fluidically.
- FIG. 1 is a diagrammatic depiction of a system of a fluidically series membrane-based electrochemical cell and a membrane-less electrochemical cell for producing modified anolyte solution in accordance with the principles of the present invention
- FIG. 2 is a diagrammatic depiction of a system for producing modified anolyte solution including the system of series parallel electrochemical cells of FIG. 1 ;
- FIG. 3 is an exploded, schematic view of an alternative embodiment of a membrane-based electrochemical cell for use in place of the membrane-based electrochemical cell of the systems of FIGS. 1 and 2 ;
- FIG. 4 is an exploded, schematic view of an alternative embodiment of a membrane-less electrochemical cell for use in place of the membrane-less electrochemical cell of the systems the systems of FIGS. 1 and 2 .
- System 10 includes a first electrochemical cell 14 and a second electrochemical cell 16 fluidically coupled in series as will be described herein.
- the first electrochemical cell 14 may be a conventional membrane-based electrochemical cell and includes a pair of foraminous electrodes 20 , 22 , the electrode 20 being an anode and the electrode 22 being a cathode.
- An ion exchange membrane 24 is situated between the anode 20 and the cathode 22 such that the first electrochemical cell 14 may be seen as being a membrane-based electrochemical cell.
- An anolyte space 30 is provided between the anode 20 and the membrane 24
- a catholyte space 32 is provided between the cathode 22 and the membrane 24 .
- a first liquid 34 may be introduced into the anolyte space 30 via a first input 35 coupled to the anolyte space 30 .
- the first input 35 may be connected directly into the anolyte space 30 and/or indirectly through the anode 20 , such as through apertures 20 ′ therein ( FIG. 3 ).
- a second liquid 36 may be introduced into the catholyte space 32 via a second input 37 coupled to the catholyte space 32 .
- the second input 37 may be connected directly into the catholyte space 32 and/or indirectly through the cathode 22 , such as through apertures 22 ′ therein ( FIG. 3 ).
- a first anolyte solution 40 is produced in the anolyte space 30 from the first liquid 34 and is accessible at a first output 41 coupled to the anolyte space 30 .
- a catholyte solution 42 is produced in the catholyte space 32 from the second liquid 36 and is accessible at a second output 43 coupled to the catholyte space 32 .
- the first output 41 may be connected directly into the anolyte space 30 and/or indirectly through the anode 20 , such as through apertures 20 ′ therein.
- the second output 43 may be connected directly into the catholyte space 32 and/or indirectly through the cathode 22 , such as through apertures 22 ′ therein.
- inputs 35 and 37 are to one side of electrochemical cell 14 with outputs 41 and 43 being disposed to an opposite side thereof.
- the first liquid 34 is advantageously a brine solution.
- the second liquid 36 may be either a brine solution or pure water.
- the second liquid 36 is advantageously a brine solution, and the first liquid 34 may be either a brine solution or pure water.
- the second electrochemical cell 16 may be a conventional non-membrane-based electrochemical cell and includes a pair of solid, i.e., non-foraminous, electrodes 50 , 52 , the solid electrode 50 being an anode and the solid electrode 52 being a cathode.
- a fluid space 54 between the solid electrodes 50 , 52 is uninterrupted by a membrane, such that the second electrochemical cell 16 may be seen as being a membrane-less electrochemical cell.
- the anolyte solution 40 from the anolyte space 30 of the first electrochemical cell 14 is introduced into the fluid space 54 via a third input 61 coupled to the fluid space 54 and in fluid communication with the first outlet 41 .
- electrodes 50 , 52 are powered such as by a power supply 38 ( FIG.
- the modified anolyte solution 12 is produced in the fluid space 54 from at least the anolyte solution 40 (further brine solution may be added via the input 61 or another input, not shown, coupled to the fluid space 54 ).
- the modified anolyte solution 12 is accessible at a third output 63 coupled to the fluid space 54 .
- the third input 61 may be connected directly into the fluid space 54 .
- the third output 63 may be connected directly into the fluid space 54 .
- anode 50 and cathode 52 are advantageously solid, if either or both of them are foraminous, then the third input 61 or the third output 63 may be connected indirectly into the fluid space 54 through the anode 50 or cathode 52 via apertures (not shown) therein.
- input 61 is to one side of electrochemical cell 16 with output 63 being disposed to an opposite side thereof.
- the cells 14 and 16 are fluidically in series.
- the anolyte space 30 is coupled to the fluid space 54 to produce the modified anolyte solution 12 .
- the first output 41 and the third input 61 are coupled together so that the first anolyte solution 40 is introduced into the fluid space 54 .
- Inputs 35 and 37 may be coupled together such that the first and second liquids 34 and 36 introduced into the anolyte space 30 and the catholyte space 32 may be the same and from a common source. Or the inputs 35 and 37 may be independent such that first and second liquids 34 and 36 introduced into the anolyte space 30 and the catholyte space 32 may be from different sources and so can be different liquids.
- a typical brine solution used for either or both of the first and second liquids 34 and 36 is a saline solution wherein the electrolyte is NaCl at a concentration of 0.5 to 2.5 g/l.
- the electrolyte could be KCl.
- a system 70 for producing modified anolyte solution 12 includes the fluidically series first and second electrochemical cells 14 , 16 of system 10 with membrane 24 being a cation exchange membrane, as well as a liquid input assembly 72 for producing the first and second liquids 34 , 36 and a product output assembly 74 for handling the catholyte solution 42 and the modified anolyte solution 12 .
- the liquid input assembly 72 includes a tap water conduit 78 connectable with a supply of water 80 , such as a municipal water source.
- a tap water control valve 82 is coupled with the tap water conduit 78 and regulates the flow of tap water through the tap water conduit 78 .
- the tap water control valve 82 can be actuated manually or electronically.
- the tap water conduit 78 is also coupled with a water filter 84 , which may be any appropriate water filter the selection of which may depend on the qualities of the supply of water used.
- the water filter 84 may include diatomaceous earth or carbon media, filter elements of various porosity sizes, such as 25-microns, 10-microns, and 5-microns, combinations of the same, or other appropriate filtering devices.
- a filtered water conduit 86 receives water that has been processed by the water filter 84 and is coupled with a water softener 88 or a reverse osmosis unit.
- the selection of the water softener 88 may also depend on the qualities of the supply of water used.
- the water softener 88 can be a standard ion exchange water softener.
- a water purification device (not shown) can also advantageously be included in the liquid input assembly 72 .
- Water that has passed through the water filter 84 and the water softener 88 is referred to herein as pure water and coupled through a pure water conduit 90 to be available as the second liquid 36 for the first electrochemical cell 14 via a second conduit 92 coupled to the input 37 and via a third conduit 94 to a brine tank 100 as will be described.
- the pure water could also be diverted and stored in a tank (not shown) for later use.
- the liquid input assembly 72 further includes the brine tank 100 and a brine pump 102 .
- Pure water is coupled with the brine tank 100 via the conduits 90 , 94 to create a brine solution precursor.
- the brine solution precursor formed in the brine tank 100 is pumped at controlled levels by the brine pump 102 through a brine solution precursor conduit 104 and into a fourth conduit 105 which couples pure water from conduit 90 as to mix with the brine solution precursor to form a brine solution to be available as the first liquid 34 for the first electrochemical cell 14 via a fifth conduit 106 coupled to the inlet 35 (and as a further input to the fluid space 54 of the second electrochemical cell 16 along with the first anolyte solution 40 if desired).
- the brine pump 102 is advantageously controlled so that the brine solution achieves a target electrical conductivity.
- a controller 108 receives a signal from a conductivity sensor 109 which measures the electroconductivity of the brine solution in the fifth conduit 106 . That signal is used by controller 108 to control the rate or speed of brine pump 102 whereby to adjust the amount of brine precursor solution to mix with the pure water. In one embodiment, the controller 108 generates a control signal to the pump 102 in the range of 4-20 mA.
- Input conduit control valves 110 a and 110 b are provided in the conduits 92 and 106 , respectively for controlling the flow of the respective liquids into the respective spaces of the electrochemical cell 14 .
- the input conduit control valves 110 a , 110 b can be actuated manually or electronically.
- Controller 108 also causes the power supply 38 to power the anodes and cathodes 20 , 22 and 50 , 52 of the cells 14 , 16 to produce the first anolyte solution 40 , the catholyte solution 42 , and the modified anolyte solution 12 .
- the product output assembly 74 includes a catholyte conduit 112 and a catholyte tank 114 .
- the catholyte conduit 112 is coupled with the second output 43 and the catholyte tank 114 to fluidically couple the catholyte space 32 and the tank 114 which receives the catholyte solution 42 .
- the product output assembly 74 also includes a modified anolyte conduit 120 and an anolyte tank 122 .
- the modified anolyte conduit 120 is coupled with the output 63 and the anolyte tank 122 to fluidically couple the modified anolyte solution 12 to be received in the anolyte tank 122 .
- the pH of the modified solution 12 is monitored with a pH sensor 124 coupled to the modified anolyte conduit 120 . Signals from the pH sensor 124 are coupled to the controller 108 which generates control signals to the power supply 38 to cause the power supply 38 to power the anode 50 and cathode 52 at a constant current, which may be adjusted or set as desired.
- the modified anolyte solution 12 is advantageously a pH of 4-5.
- the controller 108 causes the constant current output from the power supply 38 to adjust to a level sufficient to result in a pH for the modified anolyte solution 12 which will cause the solution 12 to have a pH of approximately 4-5.
- the pH of the catholyte solution 42 may also be monitored with a pH sensor 124 ′ coupled to the catholyte conduit 112 . Signals from the pH sensor 124 ′ are coupled to the controller 108 which generates control signals to the power supply 38 to cause the power supply 38 to power the anode 20 and cathode 22 at a constant current.
- the catholyte solution 42 may be at a pH of 11.5-12.
- the controller 108 causes the constant current output from the power supply 38 to adjust to a level sufficient to result in a pH for the catholyte solution 42 which will cause the solution 42 to have a pH of approximately 11.5-12.
- power supply 38 may be used to power electrodes 50 , 52 of the second electrochemical cell 16 and a separate power supply (not shown) may be used to power the electrodes 20 , 22 of the first electrochemical cell 14 .
- That separate power supply may also get control signals from controller 108 , but the signals may be preset or user adjustable, rather than in response to any characteristic of the liquids involved in the system 70 , unless the signals from pH sensor 124 ′ are utilized for control instead of simply for monitoring purposes.
- catholyte solution 40 is shown as being received in a catholyte tank 114 , it could alternatively be disposed of directly rather than via such a tank.
- the modified anolyte solution 12 and the catholyte solution 40 are available for immediate use from the tanks 122 , 114 respectively, or for later use with the tanks 122 , 114 serving as storage vessels for the respective solutions.
- the liquids 34 and 36 are coupled with the first electrochemical cell 14 and anode 20 and cathode 22 powered to create the first anolyte solution 40 .
- That solution 40 is coupled with the second electrochemical cell 16 , and its anode 50 and cathode 52 powered to produce the modified anolyte solution 12 from the first anolyte solution 12 (alone or with added brine solution, not shown).
- catholyte solution 42 is produced from cell 14 .
- the modified anolyte solution 12 can be coupled with, or directed to, the anolyte tank 122
- the catholyte solution 42 can be coupled with, or directed to, the catholyte tank 114 .
- the modified anolyte solution, and the catholyte solution if desired, may be used for cleaning purposes such as for laundry, surface cleaning, or within piping such as for clean-in-place applications.
- the first anolyte solution 40 produced in the first electrochemical cell 14 will have a pH in the range of about 1-3, and the catholyte solution 42 produced in the first electrochemical cell 14 will have a pH in the range of about 11.5-12.
- the further processing of the first anolyte solution 40 in the second electrochemical cell 16 will result in a modified anolyte solution 12 with a pH in the range of about 4-5.
- the modified anolyte solution 12 has a higher pH than the first anolyte solution 40 alone.
- a pH of about 4-5 increases the solubility of active chlorine in the modified anolyte solution 12 and decreases the corrosion potential associated with lower pH values.
- the modified anolyte solution 12 has a less extreme pH value than the first anolyte solution 40 and while it provides the desired cleaning properties, it overcomes the drawbacks that would have been expected from the first anolyte solution 40 .
- the first electrochemical cell 14 includes only one pair of electrodes 20 , 22 and one membrane 24 .
- multiple pairs of electrodes 20 , 22 each with a respective membrane 24 therebetween could be employed.
- FIG. 3 an alternative embodiment of a conventional membrane-based first electrochemical cell 14 ′ is shown in an exploded, schematic view with like parts between cells 14 and 14 ′ bearing the same reference numbers.
- FIG. 3 shows that the first electrochemical cell 14 ′ can include a plurality of anolyte spaces 30 and catholyte spaces 32 .
- the plurality of anodes 20 and cathodes 22 are arranged so as to provide adjacent anolyte spaces 30 and catholyte spaces 32 . Adjacent respective anolyte spaces 30 and catholyte spaces 32 are separated by a spacer 130 .
- the anodes 20 and cathodes 22 in adjacent anolyte and catholyte spaces 30 , 32 are arranged in an opposite manner so that the same types of electrodes (either anodes or cathodes) border the spacers 130 between the spaces 30 , 32 .
- a set of components in the first electrochemical cell 14 may be arranged in the following order: anode-membrane-cathode-spacer-cathode-membrane-anode-spacer. This pattern is repeated for the number of anolyte and catholyte spaces 30 , 32 in the cell.
- a gasket 132 separates adjacent components in the first electrochemical cell 14 .
- a gasket 132 is positioned between each anode 20 and membrane 24 , between each cathode 22 and membrane 24 , and between each cathode 22 or anode 20 and each spacer 130 .
- spacers 130 and associated end plates 133 are included at each end to close off the last of the plurality of anodes 20 and anolyte spaces 30 , and the last of the plurality of cathodes 22 and catholyte spaces 32 .
- the anodes 20 , cathodes 22 , and membranes 24 in the first electrochemical cell 14 ′ are generally planar, and can have any suitable composition.
- the gaskets 132 , spacers 130 , and end plates 133 are also planar such that when compressed together from end to end, they can be secured such as by bolts (not shown) drawing the end plates 133 together with the components therebetween brought together into a fluid tight (except for the inlets and outlets) assembly.
- the anodes 20 are foraminous (thus having apertures 20 ′ therethrough) and are made of pure titanium coated with RuO 2 and IrO 2
- the cathodes 22 are foraminous (thus having apertures 22 ′ therethrough) and are made of uncoated pure titanium, although in other embodiments they could be solid.
- the RuO 2 and IrO 2 of the anode coating are preferably present in equal amounts, but the ratio may also vary from about 60/40 to about 40/60.
- the membranes 24 in the first electrochemical cell 14 ′ are advantageously cation exchange membranes but could be anion exchange membranes.
- each input 35 is associated with a respective spacer 130 adjacent an anolyte space 30 (or between adjacent anolyte spaces 30 ) so as to fluidically couple the first liquid 34 into the respective anolyte spaces 30 through the apertures 20 ′ in the anodes 20 .
- the inputs 35 are also fluidically coupled to the conduit 106 so the same liquid (brine solution) can be coupled to each anolyte space 30 .
- each input 37 is associated with a respective spacer 130 adjacent a catholyte space 32 (or between adjacent catholyte spaces 32 ) so as to fluidically couple the second liquid 36 into the respective catholyte spaces 32 through the apertures 22 ′ in the cathodes 22 .
- each output 41 is associated with a respective spacer 130 adjacent an anolyte space 30 (or between adjacent anolyte spaces 30 ) so as to fluidically couple the first anolyte solution 40 out of the respective anolyte spaces 30 through the apertures 20 ′ in the anodes 20 .
- the outputs 41 of the anolyte spaces 30 are fluidically coupled to the fluid space 54 of the cell 16 .
- each output 43 is associated with a respective spacer 130 adjacent a catholyte space 32 (or between adjacent catholyte spaces 32 ) so as to fluidically couple the catholyte solution 42 out of the respective catholyte spaces 32 through the apertures 22 ′ in the cathodes 22 .
- the outputs 43 of the catholyte spaces 32 are fluidically coupled to the catholyte conduit 112 to combine the catholyte solution 42 for receipt by the catholyte tank 114 .
- each anolyte space 30 and each catholyte space 32 extends lengthwise between an area generally adjacent a respective input 35 , 37 to an area generally adjacent a respective output 41 , 43 .
- FIG. 4 an alternative embodiment of a conventional non-membrane-based second electrochemical cell 16 ′ is shown in an exploded, schematic view with like parts between cells 16 and 16 ′ bearing the same reference numbers.
- second electrochemical cell 16 ′ a spacer 134 is included between the anode 50 and the cathode 52 , and gaskets 136 are positioned between the anode 50 and the spacer 134 , the cathode 52 and the spacer 134 , and between the anode 50 and cathode 52 and respective end plates 137 .
- the third inlet 61 and third output 63 are associated with opposite ends of the spacer 134 to couple the first anolyte solution 40 (as well as brine solution if also included) into, and the modified anolyte solution 12 out of, the fluid space 54 defined within spacer 134 between anode 50 and cathode 52 .
- the anode 50 and cathode 52 of the second electrochemical cell 16 ′ may advantageously be solid metal plates of pure titanium (the anode may also be coated with RuO 2 and IrO 2 like the anodes 20 of the first electrochemical cells 14 , 14 ′).
- the components of cell 16 ′ are advantageously planar and may be compressed and secured together into a fluid tight (except for the inlet 61 and outlet 63 ) assembly.
- first and second electrochemical cells 14 ′, 16 ′ each function in a similar manner as the first and second electrochemical cells 14 , 16 described above.
- the membrane-based cells 14 , 14 ′ include a single membrane between the anode(s) and the cathode(s) thereof, the principles described herein are equally applicable to other configurations.
- a second membrane could be included between the first membrane and the cathode, with the catholyte space being defined between the second membrane and the cathode.
- the catholyte space is still necessarily between the first membrane and the cathode as well.
- the space between the two membranes could contain a brine solution with other liquids in the anolyte and catholyte spaces, such as pure water and/or other brine solutions.
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Abstract
A membrane-based electrochemical cell produces a first anolyte solution and a membrane-less electrochemical cell processes the first anolyte solution to produce a modified anolyte solution.
Description
- This application claims priority to U.S. Provisional Patent Application Nos. 61,662,912 filed Jun. 21, 2012 and 61/662,917 filed Jun. 22, 2012, the disclosures of both of which are incorporated herein by reference in their entireties.
- The present invention generally relates to production of anolyte solutions with electrochemical cells.
- Electrochemical cells typically include an anode, a cathode, and a membrane therebetween. When the anode and cathode are powered, anolyte solution is produced in an anolyte space between the anode and the membrane. Catholyte solution may also be produced in a catholyte space between the membrane and the cathode. In such typical electrochemical cells a liquid, such as a brine solution, is coupled into the anolyte space to produce anolyte solution when the anode and cathode are powered. Pure water is advantageously coupled into the catholyte space, although brine solution could also be coupled into that space instead. Alternatively, pure water may be coupled into the anolyte space and brine solution coupled into the catholyte space.
- The anolyte solution, and often the catholyte solution, produced by such membrane-based electrochemical cells have been considered to provide cleaning capabilities such as for laundry, clean-in-place, and surface cleaning purposes. But the anolyte solution produced thereby is usually a low pH acid, which can be corrosive, may have an excess of free chlorine which might gas off, and may not be sufficiently stable in storage.
- The present invention provides a system and method for producing a modified anolyte solution possessing desirable cleaning capabilities, but without the drawbacks of the anolyte solutions produced by typical electrochemical cells. To that end, and in accordance with one feature of the present invention, a membrane-less electrochemical cell is provided with the anolyte solution from a membrane-based electrochemical cell coupled into the membrane-less electrochemical cell to further process the anolyte solution from the membrane-based electrochemical cell to produce a modified anolyte solution. In particular, a membrane-less electrochemical cell is characterized in that it has an anode, a cathode, and a fluid space therebetween uninterrupted by a membrane so as to produce modified anolyte solution from at least the anolyte solution in the fluid space when the anode and cathode thereof are powered.
- The modified anolyte solution obtained is still acidic and provides desirable cleaning characteristics. But, unlike the anolyte solution produced by the membrane-based cell, the modified anolyte solution has a higher pH and so is less corrosive, reduces the off-gassing, and is more stable for storage. If desired, some brine solution may also be coupled into the fluid space of the second electrochemical cell such that the modified anolyte solution is produced from the anolyte solution and the brine solution in the fluid space when the anode and cathode thereof are powered.
- The membrane-based cell may be fluidically coupled as appropriate to sources of liquid, such as pure water and/or brine solution. The fluid space of the membrane-less electrochemical cell is coupled to the anolyte space of the membrane-based cell and, if desired, may also be coupled to a source of brine solution, which may be the same source as used to supply brine solution to the membrane-based cell or different sources so as to obtain different brine solutions (or different concentrations of otherwise similar brine solutions). The modified anolyte solution may be coupled to an anolyte tank for use and/or storage. Also, the catholyte solution produced by the membrane-based cell may be coupled to a catholyte tank for use and/or storage, or may be disposed of as appropriate. In any event, because the anolyte solution from the first cell is coupled into and further processed by the second cell, the two cells may be seen as being in series, at least fluidically.
- By virtue of the foregoing, there is thus provided a system and method for producing a modified anolyte solution possessing desirable cleaning capabilities, but without the drawbacks of the anolyte solutions produced by typical electrochemical cells. These and other advantages of the present invention shall be made apparent from the accompanying drawings and the description thereof.
- The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the general description of the invention given above and the detailed description of the embodiments given below, serve to explain the principles of the present invention.
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FIG. 1 is a diagrammatic depiction of a system of a fluidically series membrane-based electrochemical cell and a membrane-less electrochemical cell for producing modified anolyte solution in accordance with the principles of the present invention; -
FIG. 2 is a diagrammatic depiction of a system for producing modified anolyte solution including the system of series parallel electrochemical cells ofFIG. 1 ; -
FIG. 3 is an exploded, schematic view of an alternative embodiment of a membrane-based electrochemical cell for use in place of the membrane-based electrochemical cell of the systems ofFIGS. 1 and 2 ; and -
FIG. 4 is an exploded, schematic view of an alternative embodiment of a membrane-less electrochemical cell for use in place of the membrane-less electrochemical cell of the systems the systems ofFIGS. 1 and 2 . - With reference to
FIG. 1 , there is shown asystem 10 for producing modified anolyte solution as at 12 in accordance with the principles of the present invention.System 10 includes a firstelectrochemical cell 14 and a secondelectrochemical cell 16 fluidically coupled in series as will be described herein. The firstelectrochemical cell 14 may be a conventional membrane-based electrochemical cell and includes a pair offoraminous electrodes electrode 20 being an anode and theelectrode 22 being a cathode. Anion exchange membrane 24 is situated between theanode 20 and thecathode 22 such that the firstelectrochemical cell 14 may be seen as being a membrane-based electrochemical cell. Ananolyte space 30 is provided between theanode 20 and themembrane 24, and acatholyte space 32 is provided between thecathode 22 and themembrane 24. - A
first liquid 34 may be introduced into theanolyte space 30 via afirst input 35 coupled to theanolyte space 30. Thefirst input 35 may be connected directly into theanolyte space 30 and/or indirectly through theanode 20, such as throughapertures 20′ therein (FIG. 3 ). Asecond liquid 36 may be introduced into thecatholyte space 32 via asecond input 37 coupled to thecatholyte space 32. Thesecond input 37 may be connected directly into thecatholyte space 32 and/or indirectly through thecathode 22, such as throughapertures 22′ therein (FIG. 3 ). When theelectrodes FIG. 2 ), afirst anolyte solution 40 is produced in theanolyte space 30 from thefirst liquid 34 and is accessible at afirst output 41 coupled to theanolyte space 30. Also, acatholyte solution 42 is produced in thecatholyte space 32 from thesecond liquid 36 and is accessible at asecond output 43 coupled to thecatholyte space 32. Thefirst output 41 may be connected directly into theanolyte space 30 and/or indirectly through theanode 20, such as throughapertures 20′ therein. Similarly, thesecond output 43 may be connected directly into thecatholyte space 32 and/or indirectly through thecathode 22, such as throughapertures 22′ therein. As can be seen,inputs electrochemical cell 14 withoutputs - Where the
membrane 24 is a cation exchange membrane, thefirst liquid 34 is advantageously a brine solution. Thesecond liquid 36 may be either a brine solution or pure water. Where the membrane is an anion exchange membrane, thesecond liquid 36 is advantageously a brine solution, and thefirst liquid 34 may be either a brine solution or pure water. - The second
electrochemical cell 16 may be a conventional non-membrane-based electrochemical cell and includes a pair of solid, i.e., non-foraminous,electrodes solid electrode 50 being an anode and thesolid electrode 52 being a cathode. Afluid space 54 between thesolid electrodes electrochemical cell 16 may be seen as being a membrane-less electrochemical cell. Theanolyte solution 40 from theanolyte space 30 of the firstelectrochemical cell 14 is introduced into thefluid space 54 via athird input 61 coupled to thefluid space 54 and in fluid communication with thefirst outlet 41. Whenelectrodes FIG. 2 ), the modifiedanolyte solution 12 is produced in thefluid space 54 from at least the anolyte solution 40 (further brine solution may be added via theinput 61 or another input, not shown, coupled to the fluid space 54). The modifiedanolyte solution 12 is accessible at athird output 63 coupled to thefluid space 54. Thethird input 61 may be connected directly into thefluid space 54. Similarly, thethird output 63 may be connected directly into thefluid space 54. It will be appreciated that whileanode 50 andcathode 52 are advantageously solid, if either or both of them are foraminous, then thethird input 61 or thethird output 63 may be connected indirectly into thefluid space 54 through theanode 50 orcathode 52 via apertures (not shown) therein. As can be seen,input 61 is to one side ofelectrochemical cell 16 withoutput 63 being disposed to an opposite side thereof. - In accordance with the principles of the present invention, the
cells anolyte space 30 is coupled to thefluid space 54 to produce the modifiedanolyte solution 12. In that regard, thefirst output 41 and thethird input 61 are coupled together so that thefirst anolyte solution 40 is introduced into thefluid space 54. -
Inputs second liquids anolyte space 30 and thecatholyte space 32 may be the same and from a common source. Or theinputs second liquids anolyte space 30 and thecatholyte space 32 may be from different sources and so can be different liquids. - A typical brine solution used for either or both of the first and
second liquids - Referring next to
FIG. 2 , asystem 70 for producing modifiedanolyte solution 12 includes the fluidically series first and secondelectrochemical cells system 10 withmembrane 24 being a cation exchange membrane, as well as aliquid input assembly 72 for producing the first andsecond liquids product output assembly 74 for handling thecatholyte solution 42 and the modifiedanolyte solution 12. - The
liquid input assembly 72 includes atap water conduit 78 connectable with a supply ofwater 80, such as a municipal water source. A tapwater control valve 82 is coupled with thetap water conduit 78 and regulates the flow of tap water through thetap water conduit 78. The tapwater control valve 82 can be actuated manually or electronically. Thetap water conduit 78 is also coupled with awater filter 84, which may be any appropriate water filter the selection of which may depend on the qualities of the supply of water used. For example, thewater filter 84 may include diatomaceous earth or carbon media, filter elements of various porosity sizes, such as 25-microns, 10-microns, and 5-microns, combinations of the same, or other appropriate filtering devices. A filteredwater conduit 86 receives water that has been processed by thewater filter 84 and is coupled with awater softener 88 or a reverse osmosis unit. The selection of thewater softener 88 may also depend on the qualities of the supply of water used. For example, thewater softener 88 can be a standard ion exchange water softener. A water purification device (not shown) can also advantageously be included in theliquid input assembly 72. - Water that has passed through the
water filter 84 and thewater softener 88 is referred to herein as pure water and coupled through apure water conduit 90 to be available as thesecond liquid 36 for the firstelectrochemical cell 14 via a second conduit 92 coupled to theinput 37 and via athird conduit 94 to abrine tank 100 as will be described. Advantageously, the pure water could also be diverted and stored in a tank (not shown) for later use. - The
liquid input assembly 72 further includes thebrine tank 100 and abrine pump 102. Pure water is coupled with thebrine tank 100 via theconduits brine tank 100 is pumped at controlled levels by thebrine pump 102 through a brinesolution precursor conduit 104 and into afourth conduit 105 which couples pure water fromconduit 90 as to mix with the brine solution precursor to form a brine solution to be available as thefirst liquid 34 for the firstelectrochemical cell 14 via afifth conduit 106 coupled to the inlet 35 (and as a further input to thefluid space 54 of the secondelectrochemical cell 16 along with thefirst anolyte solution 40 if desired). Thebrine pump 102 is advantageously controlled so that the brine solution achieves a target electrical conductivity. - To that end, a
controller 108 receives a signal from aconductivity sensor 109 which measures the electroconductivity of the brine solution in thefifth conduit 106. That signal is used bycontroller 108 to control the rate or speed ofbrine pump 102 whereby to adjust the amount of brine precursor solution to mix with the pure water. In one embodiment, thecontroller 108 generates a control signal to thepump 102 in the range of 4-20 mA. - Input
conduit control valves conduits 92 and 106, respectively for controlling the flow of the respective liquids into the respective spaces of theelectrochemical cell 14. The inputconduit control valves -
Controller 108 also causes thepower supply 38 to power the anodes andcathodes cells first anolyte solution 40, thecatholyte solution 42, and the modifiedanolyte solution 12. - The
product output assembly 74 includes acatholyte conduit 112 and acatholyte tank 114. Thecatholyte conduit 112 is coupled with thesecond output 43 and thecatholyte tank 114 to fluidically couple thecatholyte space 32 and thetank 114 which receives thecatholyte solution 42. Theproduct output assembly 74 also includes a modifiedanolyte conduit 120 and ananolyte tank 122. The modifiedanolyte conduit 120 is coupled with theoutput 63 and theanolyte tank 122 to fluidically couple the modifiedanolyte solution 12 to be received in theanolyte tank 122. - The pH of the modified
solution 12 is monitored with apH sensor 124 coupled to the modifiedanolyte conduit 120. Signals from thepH sensor 124 are coupled to thecontroller 108 which generates control signals to thepower supply 38 to cause thepower supply 38 to power theanode 50 andcathode 52 at a constant current, which may be adjusted or set as desired. The modifiedanolyte solution 12 is advantageously a pH of 4-5. Hence, thecontroller 108 causes the constant current output from thepower supply 38 to adjust to a level sufficient to result in a pH for the modifiedanolyte solution 12 which will cause thesolution 12 to have a pH of approximately 4-5. - The pH of the
catholyte solution 42 may also be monitored with apH sensor 124′ coupled to thecatholyte conduit 112. Signals from thepH sensor 124′ are coupled to thecontroller 108 which generates control signals to thepower supply 38 to cause thepower supply 38 to power theanode 20 andcathode 22 at a constant current. Thecatholyte solution 42 may be at a pH of 11.5-12. Hence, thecontroller 108 causes the constant current output from thepower supply 38 to adjust to a level sufficient to result in a pH for thecatholyte solution 42 which will cause thesolution 42 to have a pH of approximately 11.5-12. While only onepower supply 38 is shown for bothelectrochemical cells controller 108. For example,power supply 38 may be used topower electrodes electrochemical cell 16 and a separate power supply (not shown) may be used to power theelectrodes electrochemical cell 14. That separate power supply may also get control signals fromcontroller 108, but the signals may be preset or user adjustable, rather than in response to any characteristic of the liquids involved in thesystem 70, unless the signals frompH sensor 124′ are utilized for control instead of simply for monitoring purposes. - Further, while the
catholyte solution 40 is shown as being received in acatholyte tank 114, it could alternatively be disposed of directly rather than via such a tank. In any event, the modifiedanolyte solution 12 and thecatholyte solution 40 are available for immediate use from thetanks tanks - In use, the
liquids electrochemical cell 14 andanode 20 andcathode 22 powered to create thefirst anolyte solution 40. Thatsolution 40 is coupled with the secondelectrochemical cell 16, and itsanode 50 andcathode 52 powered to produce the modifiedanolyte solution 12 from the first anolyte solution 12 (alone or with added brine solution, not shown). Also,catholyte solution 42 is produced fromcell 14. The modifiedanolyte solution 12 can be coupled with, or directed to, theanolyte tank 122, and thecatholyte solution 42 can be coupled with, or directed to, thecatholyte tank 114. The modified anolyte solution, and the catholyte solution if desired, may be used for cleaning purposes such as for laundry, surface cleaning, or within piping such as for clean-in-place applications. - In particular, the
first anolyte solution 40 produced in the firstelectrochemical cell 14 will have a pH in the range of about 1-3, and thecatholyte solution 42 produced in the firstelectrochemical cell 14 will have a pH in the range of about 11.5-12. The further processing of thefirst anolyte solution 40 in the secondelectrochemical cell 16 will result in a modifiedanolyte solution 12 with a pH in the range of about 4-5. Thus, the modifiedanolyte solution 12 has a higher pH than thefirst anolyte solution 40 alone. Without being limited to any particular theory or mechanism, it is believed that a pH of about 4-5 increases the solubility of active chlorine in the modifiedanolyte solution 12 and decreases the corrosion potential associated with lower pH values. Thereby, the modifiedanolyte solution 12 has a less extreme pH value than thefirst anolyte solution 40 and while it provides the desired cleaning properties, it overcomes the drawbacks that would have been expected from thefirst anolyte solution 40. - In the
systems electrochemical cell 14 includes only one pair ofelectrodes membrane 24. Alternatively, multiple pairs ofelectrodes respective membrane 24 therebetween could be employed. To that end, and with reference toFIG. 3 , an alternative embodiment of a conventional membrane-based firstelectrochemical cell 14′ is shown in an exploded, schematic view with like parts betweencells -
FIG. 3 shows that the firstelectrochemical cell 14′ can include a plurality ofanolyte spaces 30 andcatholyte spaces 32. As shown, the plurality ofanodes 20 andcathodes 22 are arranged so as to provideadjacent anolyte spaces 30 andcatholyte spaces 32. Adjacentrespective anolyte spaces 30 andcatholyte spaces 32 are separated by aspacer 130. Theanodes 20 andcathodes 22 in adjacent anolyte andcatholyte spaces spacers 130 between thespaces electrochemical cell 14 may be arranged in the following order: anode-membrane-cathode-spacer-cathode-membrane-anode-spacer. This pattern is repeated for the number of anolyte andcatholyte spaces - A
gasket 132 separates adjacent components in the firstelectrochemical cell 14. Thus, agasket 132 is positioned between eachanode 20 andmembrane 24, between eachcathode 22 andmembrane 24, and between eachcathode 22 oranode 20 and eachspacer 130. In addition,spacers 130 and associatedend plates 133 are included at each end to close off the last of the plurality ofanodes 20 andanolyte spaces 30, and the last of the plurality ofcathodes 22 andcatholyte spaces 32. - The
anodes 20,cathodes 22, andmembranes 24 in the firstelectrochemical cell 14′ are generally planar, and can have any suitable composition. Thegaskets 132,spacers 130, andend plates 133 are also planar such that when compressed together from end to end, they can be secured such as by bolts (not shown) drawing theend plates 133 together with the components therebetween brought together into a fluid tight (except for the inlets and outlets) assembly. Advantageously, theanodes 20 are foraminous (thus havingapertures 20′ therethrough) and are made of pure titanium coated with RuO2 and IrO2, and thecathodes 22 are foraminous (thus havingapertures 22′ therethrough) and are made of uncoated pure titanium, although in other embodiments they could be solid. Also advantageously, the RuO2 and IrO2 of the anode coating are preferably present in equal amounts, but the ratio may also vary from about 60/40 to about 40/60. Themembranes 24 in the firstelectrochemical cell 14′ are advantageously cation exchange membranes but could be anion exchange membranes. - As shown, each
input 35 is associated with arespective spacer 130 adjacent an anolyte space 30 (or between adjacent anolyte spaces 30) so as to fluidically couple the first liquid 34 into therespective anolyte spaces 30 through theapertures 20′ in theanodes 20. Theinputs 35 are also fluidically coupled to theconduit 106 so the same liquid (brine solution) can be coupled to eachanolyte space 30. Likewise, eachinput 37 is associated with arespective spacer 130 adjacent a catholyte space 32 (or between adjacent catholyte spaces 32) so as to fluidically couple the second liquid 36 into therespective catholyte spaces 32 through theapertures 22′ in thecathodes 22. - The
inputs 37 are also fluidically coupled to the conduit 92 so that the same liquid (pure water) can be coupled to eachcatholyte space 32. In a similar manner, eachoutput 41 is associated with arespective spacer 130 adjacent an anolyte space 30 (or between adjacent anolyte spaces 30) so as to fluidically couple thefirst anolyte solution 40 out of therespective anolyte spaces 30 through theapertures 20′ in theanodes 20. Theoutputs 41 of theanolyte spaces 30 are fluidically coupled to thefluid space 54 of thecell 16. Similarly, eachoutput 43 is associated with arespective spacer 130 adjacent a catholyte space 32 (or between adjacent catholyte spaces 32) so as to fluidically couple thecatholyte solution 42 out of therespective catholyte spaces 32 through theapertures 22′ in thecathodes 22. Theoutputs 43 of thecatholyte spaces 32 are fluidically coupled to thecatholyte conduit 112 to combine thecatholyte solution 42 for receipt by thecatholyte tank 114. - Given the generally planar construction of the
anodes 20,cathodes 22, andmembranes 24, the anolyte andcatholyte spaces inputs outputs anolyte space 30 and eachcatholyte space 32 extends lengthwise between an area generally adjacent arespective input respective output - Referring next to
FIG. 4 , an alternative embodiment of a conventional non-membrane-based secondelectrochemical cell 16′ is shown in an exploded, schematic view with like parts betweencells electrochemical cell 16′ aspacer 134 is included between theanode 50 and thecathode 52, andgaskets 136 are positioned between theanode 50 and thespacer 134, thecathode 52 and thespacer 134, and between theanode 50 andcathode 52 andrespective end plates 137. Thethird inlet 61 andthird output 63 are associated with opposite ends of thespacer 134 to couple the first anolyte solution 40 (as well as brine solution if also included) into, and the modifiedanolyte solution 12 out of, thefluid space 54 defined withinspacer 134 betweenanode 50 andcathode 52. Further, theanode 50 andcathode 52 of the secondelectrochemical cell 16′ may advantageously be solid metal plates of pure titanium (the anode may also be coated with RuO2 and IrO2 like theanodes 20 of the firstelectrochemical cells cell 14′, the components ofcell 16′ are advantageously planar and may be compressed and secured together into a fluid tight (except for theinlet 61 and outlet 63) assembly. - In use, the first and second
electrochemical cells 14′, 16′ each function in a similar manner as the first and secondelectrochemical cells - By virtue of the foregoing, there is provided a system and method for producing a modified anolyte solution possessing desirable cleaning capabilities, but without the drawbacks of the anolyte solutions produced by typical electrochemical cells.
- While the present invention has been illustrated by a description of particular embodiments thereof and specific examples, and while the embodiments have been described in some detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. Additional advantages and modifications will readily appear to those skilled in the art. For example, the membrane-based
cells
Claims (25)
1. A system for producing modified anolyte solution comprising:
a first electrochemical cell having a first anode, a first cathode, and an ion exchange membrane therebetween, and having an anolyte space between the membrane and the first anode and a catholyte space between the membrane and the first cathode, whereby a first anolyte solution is produced from a liquid in the anolyte space with the first anode and first cathode being powered; and
a second electrochemical cell having a second anode and a second cathode and having a fluid space between the second anode and the second cathode uninterrupted by a membrane, the anolyte space of the first electrochemical cell being coupled to the fluid space of the second electrochemical cell, whereby a modified anolyte solution is produced from at least the first anolyte solution in the fluid space with the second anode and second cathode being powered.
2. The system of claim 1 , the first electrochemical cell including an output coupled to the anolyte space whereby to output the first anolyte solution, the second electrochemical cell including an input coupled to the first electrochemical cell whereby to couple the first anolyte solution into the fluid space.
3. The system of claim 1 further comprising an anolyte tank in fluid communication with the fluid space of the second electrochemical cell whereby to receive the modified anolyte solution.
4. The system of claim 1 , whereby a catholyte solution is produced from liquid in the catholyte space with the first anode and first cathode being powered, the system further comprising a catholyte tank in fluid communication with the catholyte space for receiving the catholyte solution.
5. The system of claim 4 further comprising an output coupled to the catholyte space, the output being fluidically coupled to the catholyte tank.
6. The system of claim 1 , the membrane being a cation exchange membrane.
7. The system of claim 1 , the membrane being an anion exchange membrane.
8. The system of claim 1 , the first anode and first cathode being foraminous, and the second anode and second cathode being solid.
9. The system of claim 1 , the first electrochemical cell comprising a plurality of first anodes, a plurality of first cathodes, and a plurality of respective ion exchange membranes therebetween to define a plurality of anolyte spaces between the respective membranes and first anodes and a plurality of catholyte spaces between the respective membranes and first cathodes, whereby a first anolyte solution is produced from a liquid in the anolyte spaces with the first anodes and first cathodes being powered.
10. The system of claim 9 , the plurality of anolyte spaces and plurality of catholyte spaces being arranged to provide adjacent anolyte spaces and adjacent catholyte spaces.
11. The system of claim 10 further comprising spacers between the anolyte spaces of adjacent anolyte spaces and between the catholyte spaces of adjacent catholyte spaces.
12. The system of claim 11 , the spacers between the anolyte spaces of adjacent anolyte spaces having inputs and outputs in fluid communication with the anolyte spaces.
13. The system of claim 12 , the anodes including apertures therein whereby to couple liquid into the anolyte spaces and first anolyte solution out of the anolyte spaces.
14. The system of claim 12 , the spacers between the catholyte spaces of adjacent catholyte spaces having inputs and outputs in fluid communication with the catholyte spaces.
15. The system of claim 14 , the cathodes including apertures therein whereby to couple liquid into and out of the catholyte spaces.
16. The system of claim 1 , the first cathode and first anode being generally planar.
17. The system of claim 1 , the second cathode and second anode being generally planar.
18. The system of claim 1 , the membrane being generally planar.
19. A method of producing modified anolyte solution comprising:
producing a first anolyte solution in an anolyte space between a first anode and an ion exchange membrane of a first electrochemical cell having the first anode, a first cathode, and the membrane therebetween;
coupling the first anolyte solution to a fluid space between a second anode and a second cathode of a second electrochemical cell having the second anode and the second cathode uninterrupted by a membrane therebetween; and
producing a modified anolyte solution from at least the first anolyte solution in the fluid space.
20. The method of claim 19 , producing the first anolyte solution including coupling a brine solution to the anolyte space and powering the first anode and cathode.
21. The method of claim 20 , producing the modified anolyte solution including powering the second anode and cathode.
22. The method of claim 21 further comprising coupling liquid to a catholyte space between the membrane and the cathode of the first electrochemical cell.
23. The method of claim 21 further comprising producing a catholyte solution in the catholyte space.
24. The method of claim 19 wherein the first anode and the first cathode are foraminous, and the second anode and the second cathode are solid.
25. The method of claim 19 further comprising coupling the modified anolyte to an anolyte tank.
Priority Applications (2)
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US13/568,491 US20130341200A1 (en) | 2012-06-21 | 2012-08-07 | Series cell electrochemical production of modified anolyte solution |
PCT/US2012/056034 WO2013191716A1 (en) | 2012-06-21 | 2012-09-19 | Series cell electrochemical production of modified anolyte solution |
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US201261662912P | 2012-06-21 | 2012-06-21 | |
US201261662917P | 2012-06-22 | 2012-06-22 | |
US13/568,491 US20130341200A1 (en) | 2012-06-21 | 2012-08-07 | Series cell electrochemical production of modified anolyte solution |
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US13/568,491 Abandoned US20130341200A1 (en) | 2012-06-21 | 2012-08-07 | Series cell electrochemical production of modified anolyte solution |
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Cited By (4)
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US10900132B2 (en) | 2017-01-26 | 2021-01-26 | Diversey, Inc. | Neutralization in electro-chemical activation systems |
US20220042964A1 (en) * | 2019-04-29 | 2022-02-10 | Shenzhen Angel Drinking Water Industrial Group Corporation | Water hardness detection probe, sensor, detection method and water softener |
US11326261B2 (en) | 2016-05-17 | 2022-05-10 | Diversey, Inc. | Alkaline and chlorine solutions produced using electro-chemical activation |
WO2023106079A1 (en) * | 2021-12-06 | 2023-06-15 | 株式会社ナイスシーズ | Slightly acidic electrolyzed water activation treatment device, slightly acidic electrolyzed water production system, method for producing slightly acidic electrolyzed water, and method for activating slightly acidic electrolyzed water |
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US20090211918A1 (en) * | 2007-03-20 | 2009-08-27 | Industrie De Nora S.P.A. | Electrochemical cell and method for operating the same |
US20090314657A1 (en) * | 2008-06-19 | 2009-12-24 | Tennant Company | Electrolysis cell having conductive polymer electrodes and method of electrolysis |
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NL8502355A (en) * | 1985-08-27 | 1987-03-16 | Magneto Chemie Bv | METHOD AND APPARATUS FOR PREPARING A DISINFECTANT FOR WATER, SUCH AS DRINKING OR SWIMMING WATER |
US6805787B2 (en) * | 2001-09-07 | 2004-10-19 | Severn Trent Services-Water Purification Solutions, Inc. | Method and system for generating hypochlorite |
JP4955015B2 (en) * | 2005-12-20 | 2012-06-20 | セラマテック・インク | Electrolytic process of sodium hypochlorite production using Na ion conductive ceramic membrane |
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2012
- 2012-08-07 US US13/568,491 patent/US20130341200A1/en not_active Abandoned
- 2012-09-19 WO PCT/US2012/056034 patent/WO2013191716A1/en active Application Filing
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US20090211918A1 (en) * | 2007-03-20 | 2009-08-27 | Industrie De Nora S.P.A. | Electrochemical cell and method for operating the same |
US20090314657A1 (en) * | 2008-06-19 | 2009-12-24 | Tennant Company | Electrolysis cell having conductive polymer electrodes and method of electrolysis |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11326261B2 (en) | 2016-05-17 | 2022-05-10 | Diversey, Inc. | Alkaline and chlorine solutions produced using electro-chemical activation |
US10900132B2 (en) | 2017-01-26 | 2021-01-26 | Diversey, Inc. | Neutralization in electro-chemical activation systems |
US20220042964A1 (en) * | 2019-04-29 | 2022-02-10 | Shenzhen Angel Drinking Water Industrial Group Corporation | Water hardness detection probe, sensor, detection method and water softener |
US11927584B2 (en) * | 2019-04-29 | 2024-03-12 | Shenzhen Angel Drinking Water Industrial Group Corporation | Water hardness detection probe, sensor, detection method and water softener |
WO2023106079A1 (en) * | 2021-12-06 | 2023-06-15 | 株式会社ナイスシーズ | Slightly acidic electrolyzed water activation treatment device, slightly acidic electrolyzed water production system, method for producing slightly acidic electrolyzed water, and method for activating slightly acidic electrolyzed water |
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