WO2009011841A1 - Générateur et distributeur d'agent de nettoyage - Google Patents

Générateur et distributeur d'agent de nettoyage Download PDF

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Publication number
WO2009011841A1
WO2009011841A1 PCT/US2008/008623 US2008008623W WO2009011841A1 WO 2009011841 A1 WO2009011841 A1 WO 2009011841A1 US 2008008623 W US2008008623 W US 2008008623W WO 2009011841 A1 WO2009011841 A1 WO 2009011841A1
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WO
WIPO (PCT)
Prior art keywords
cleansing agent
anolyte
compartment
solution
catholyte
Prior art date
Application number
PCT/US2008/008623
Other languages
English (en)
Inventor
Ashok Joshi
Shekar Balagopal
Original Assignee
Ceramatec, Inc.
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 Ceramatec, Inc. filed Critical Ceramatec, Inc.
Priority to EP08794491A priority Critical patent/EP2171783A4/fr
Priority to AU2008276573A priority patent/AU2008276573A1/en
Priority to JP2010516073A priority patent/JP2010533570A/ja
Publication of WO2009011841A1 publication Critical patent/WO2009011841A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/026—Treating water for medical or cosmetic purposes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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
    • 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
    • C02F2201/4612—Controlling or monitoring
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46145—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
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • 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
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • C02F2201/46185—Recycling the cathodic or anodic feed
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/29—Chlorine compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Definitions

  • the present invention relates to a point-of-use electrochemical generator and dispenser of cleansing, sanitizing, and antimicrobial agents.
  • Household appliances e.g. dishwashers, clothes washers, etc.
  • a cleansing agent e.g. disinfectants, bleaching solutions, whiteners, deodorizers, or in other words, a cleansing agent.
  • Common surfaces often require cleansing or sanitizing. It would be an advancement to provide an apparatus for generating and dispensing cleansing, sanitizing, and antimicrobial agents as needed for appliances or surfaces that may require such agents.
  • sodium hypochlorite is prepared by absorbing chlorine gas into cold sodium hydroxide solution to induce the following reaction:
  • the sodium hydroxide and chlorine reagents input into this process may be commercially produced by the chloralkali process.
  • NaOCl may be prepared in an industrial setting by electrolyzing sodium chloride solution without any separation or barrier between the anode and the cathode.
  • the reaction solution is generally maintained at a temperature below about 40 °C in order to prevent the formation of sodium chlorate.
  • commercially-prepared sodium hypochlorite solutions generally contain amounts of sodium chloride as a primary byproduct.
  • Hypochlorous acid also known as chloric(I) acid
  • HClO is used as a bleach, an oxidizer, a deodorant, and a disinfectant.
  • HClO has also been approved for use on human skin as a cleansing and sanitizing agent. It is also reported to promote wound healing. Addition of chlorine to water gives both hypochlorous acid and hydrochloric acid (HCl):
  • NaOCl sodium hypochlorite
  • HOCl hypochlorous acid
  • Other known methods require the storage and transport of sodium hydroxide and of chlorine gas which is a highly toxic substance.
  • the present invention overcomes this problem using electrochemical processes for the production of sodium hypochlorite or hypochlorous acid. More particularly, the present invention provides an electrochemical process for producing sodium hypochlorite or hypochlorous acid using readily available and safe starting materials.
  • the present invention is drawn to an electrochemical apparatus and method to generate and dispense a cleansing, sanitizing, or antimicrobial agent on demand and at the point-of-use (POU).
  • the present invention in particularly adapted for use with household, industrial, and water treatment applications.
  • common table salt (NaCl) salt water, waste streams from certain products, or other feed stocks; a moderate amount of electricity; and the proper apparatus it is possible to generate sodium hypochlorite (NaOCl) or hypochlorous acid (HOCl) on an as needed basis.
  • NaOCl sodium hypochlorite
  • HOCl hypochlorous acid
  • These compounds can serve as cleansing, sanitizing, or antimicrobial agents. They may even function as bleach for removal of stains.
  • Other methods for formation of these compounds need the transport and storage of chlorine gas which is a highly toxic material. Because HOCl is not stable for long-term storage, the ability to generate these compounds at suitable concentrations at the point of use is particularly advantages.
  • a cleansing, sanitizing, or antimicrobial agent is generated and used in various types of apparatuses such as a washing machine, a dishwasher, a scrub brush, a floor brush or mop, a toilet bowl apparatus, skin patch, or any application where a dose of a cleansing agent is desired.
  • Sodium hypochlorite may be effectively generated using an electrolytic process using a sodium ion conductive ceramic membrane, such as a sodium super ionic conductor (hereinafter "NaSICON") membrane.
  • a sodium ion conductive ceramic membrane such as a sodium super ionic conductor (hereinafter "NaSICON") membrane.
  • NaSICON sodium super ionic conductor
  • Hypochlorous acid may be prepared using an electrolytic process using an anionic conductive membrane.
  • chloride ions are extracted from a solution containing chloride ions, such as dilute hydrochloric acid.
  • the extracted chloride ions react with water on the other side of the membrane to form a solution of hypochlorous acid and hydrochloric acid.
  • a cleansing agent generator is an electrochemical cell.
  • the electrochemical cell can be configured in a variety of ways to produce the cleansing agent.
  • cationic membranes are utilized that may be selective to only certain types of cations. The cations move across the membrane when voltage is applied across the electrodes of electrochemical cell.
  • an anionic membrane which can transport anions, such as chloride, is used.
  • the cleansing agent distributor may be configured in numerous forms depending on the point-of-use application for the cleansing agent. Examples of such forms, include but are not limited to, personal and household applications such as a washing machine, a dishwasher, a scrub brush, a floor brush or mop, a toilet bowl apparatus, and a skin patch; industrial applications such as water treatment systems, public sanitizing applications in hospitals, hotels, schools, ocean vessels, and in applications where cleansing, sanitizing, or antimicrobial agent are used.
  • personal and household applications such as a washing machine, a dishwasher, a scrub brush, a floor brush or mop, a toilet bowl apparatus, and a skin patch
  • industrial applications such as water treatment systems, public sanitizing applications in hospitals, hotels, schools, ocean vessels, and in applications where cleansing, sanitizing, or antimicrobial agent are used.
  • Figure 1 is a schematic view of an embodiment of a cleaning agent generator that may be used to produce sodium hypochlorite within the scope of the present invention
  • Figure 2 is a schematic view of an embodiment of a cleaning agent generator that may be used to produce hypochlorous acid within the scope of the present invention
  • Figure 3 is a is a schematic view of a cleansing agent dispersement system within the scope of the present invention.
  • Figure 4 is a is a schematic view of a cleansing agent dispersement system applied to a washing machine
  • Figure 5 is a schematic representation of a system to generate and dispense a cleansing agent at the point-of-use in the form of a topical skin patch, a scrub brush, or a floor brush or mop.
  • Figure 6 is another schematic representation of a system to generate and dispense a cleansing agent at the point-of-use in the form of a topical skin patch, a scrub brush, or a floor brush or mop.
  • substantially impermeable to water when used in the instant application to refer to a membrane, means that a small amount of water may pass through the membrane, but that the amount that passes through is not of a quantity to diminish the usefulness of the present invention.
  • essentially impermeable to water as used herein in reference to a membrane, means that no water passes through the membrane, or that if water passes through the membrane, its passage is so limited so as to be undetectable by conventional means.
  • the words “substantially” and “essentially” are used similarly as intensifiers in other places within this specification.
  • FIG. 1 illustrates a cleansing agent generator 10 that may be used to produce sodium hypochlorite.
  • the cleansing agent generator 10 comprises an electrolytic cell 11 that uses a sodium ion conductive ceramic membrane 12 that divides the electrochemical cell 10 into two compartments: an anolyte compartment 14 and a catholyte compartment 16.
  • An electrochemically active anode 18 is housed in the anolyte compartment 14 where oxidation reactions take place, and an electrochemically active cathode 20 is housed in the catholyte compartment 16 where reduction reactions take place.
  • the sodium ion conductive ceramic membrane 12 selectively transfers sodium ions 22 from the anolyte compartment 14 to the catholyte compartment 16 under the influence of an electrical potential 24 while preventing water transportation from either compartment to the other side.
  • the electrolytic cell 11 is operated by feeding an aqueous sodium chloride solution 26 into the anolyte compartment 14 from a feeder 27.
  • the sodium chloride solution 26 may come from any source, including naturally occurring seawater or brine sources.
  • the sodium chloride solution may be prepared by dissolving salt containing sodium chloride in water.
  • the water need not be pure de-ionized water, but it can be tap water or unpurified water from any source.
  • the concentration of sodium chloride in the aqueous solution should be below its saturation limit in water.
  • the concentration of sodium chloride in the aqueous solution is between about 0.1 % by weight and about 26 % by weight of the solution, and more preferably between about 3 % by weight and 26% by weight of the solution.
  • Water 28 is fed into the catholyte compartment 16 from feeder 29. At least initially, the water 28 preferably includes sodium ions, which may be in the form of an unsaturated sodium hydroxide solution. The concentration of sodium hydroxide is between about 0.1 % by weight and about 50% by weight of the solution. In one embodiment, the
  • the source of sodium ions may be provided by sodium ions 22 transporting across the sodium ion conductive ceramic membrane 12 from the anolyte compartment 14 to the catholyte compartment 16.
  • the anode 18 may be fabricated of various materials, including those discussed in U.S. Patent Application Publication No. 2007/0138020, incorporated by reference. In one embodiment, the anode 18 is fabricated of titanium coated with advanced metal oxides.
  • the cathode 20 may also be fabricated of various materials, including those discussed in U.S. Patent Application Publication No. 2007/0138020. In one embodiment, the cathode 20 is fabricated of nickel/stainless steel. Under the influence of electric potential 24, electrochemical reactions take place at the anode 18 and cathode 20. Oxidation of chloride ions to chlorine gas occurs at the anode 18, and reduction of water to form hydrogen gas 30 and hydroxy 1 ions occurs at the cathode 20.
  • sodium ions 22 are transported from the anolyte compartment 14 across the sodium ion conductive ceramic membrane 12 into the catholyte compartment 16. If non-sodium ions, such as protons, calcium, magnesium, etc, are also present in the anolyte compartment 14, they are prevented from moving to the catholyte compartment 16 by the solid electrolyte 12 due to ionic size differences and electroneutrality constraints when compared with the sodium ions. Due to this reason, the current sodium efficiency is expected to be between from about 95 to about 100% in some embodiments.
  • the transported sodium ions 22 combine with the hydroxyl ions produced by the reduction of water at the cathode 20 to form a sodium hydroxide solution.
  • this sodium hydroxide solution 32 is transported to the anolyte compartment 14 of the cell to control anolyte pH and produce sodium hypochlorite solution.
  • Sodium hypochlorite solution 34 may be removed from the anolyte compartment 14.
  • the solution comprising sodium hypochlorite is removed from the anolyte compartment 14 for on-site or point-of-use.
  • point- of-use refers to use of the produced cleansing agent in a personal, commercial or industrial process located proximate to the cleansing agent generator, so that expensive storage or transportation facilities for the cleansing agent are not required.
  • catholyte compartment 2H 2 O + 2e " ⁇ 2OH " + H 2
  • the pH control of the anolyte solution is especially important when feed to the anolyte solution is an impure sodium chloride solution containing calcium, magnesium, or other precipitable cations.
  • Such sodium chloride solutions include, but are not limited to, seawater, brine, industrial process streams, or salt solutions containing sodium chloride.
  • Such salt solutions may be prepared with pure or impure salt or with pure or impure water.
  • the pH of the solution within the anolyte compartment 14 is preferably maintained at a pH less than 14, usually in preferred pH in the range from 7 to 12. Because calcium and magnesium precipitate at a pH greater than about 8, it is preferred to maintain the pH less than about 8 when operating with impure sodium chloride solutions.
  • the anolyte solution may have higher pH. With pH control, precipitation reactions at the anode, formation of calcium and magnesium hydroxides, may be avoided, thereby producing a clear solution of sodium hypochlorite.
  • the sodium conductive ceramic membrane 12 preferably blocks diffusion of calcium or magnesium ions to the catholyte compartment 16 during electrolysis. Thus, precipitation of calcium and magnesium is avoided in the catholyte compartment. In contrast, precipitation is unpreventable with organic membranes, such as Nafion® membranes, as they are, unlike NaSICON membranes, not able to completely prevent the diffusion of calcium and magnesium ions to the catholyte compartment 16, causing precipitation of calcium and magnesium not only in the catholyte compartment 16 but also in the interstices of membrane, gradually eroding the membrane's effectiveness. This drawback of the organic membranes limits their use in sodium hypochlorite generation to only salt solution feeds containing just sodium chloride.
  • the voltage required by the electrolytic cell 11, at constant current, is dependent on factors such as concentration of anolyte (sodium chloride solution), concentration of catholyte (sodium hydroxide solution), membrane thickness, conductivity of the membrane, and local mass transfer conditions which dictate the electrolytic cell's power consumption for a given production rate of sodium hypochlorite.
  • Figure 2 illustrates a cleansing agent generator 50 that may be used to produce hypochlorous acid (HClO).
  • the cleansing agent generator 50 comprises an electrolytic cell
  • an anion conductive membrane 52 that divides the electrochemical cell 51 into two compartments: an anolyte compartment 54 and a catholyte compartment 56.
  • An electrochemically active anode 58 is housed in the anolyte compartment 54 where oxidation reactions take place, and an electrochemically active cathode 60 is housed in the catholyte compartment 56 where reduction reactions take place.
  • the anion conductive membrane 52 selectively transfers chloride ions 62 from the catholyte compartment 56 to the anolyte compartment 54 under the influence of an electrical potential 64.
  • the electrolytic cell 51 is operated by feeding a dilute hydrochloric acid (HCl) solution 66 into the catholyte compartment 56 from a feeder 67.
  • HCl hydrochloric acid
  • the water need not be pure de-ionized water, but it can be tap water or unpurified water from any source.
  • Water 68 is fed into the anolyte compartment 54 from feeder 69.
  • the source of chloride ions that react at the anode to form chlorine may be provided by chloride ions 62 transporting across the anion conductive membrane 62 from the catholyte compartment 56 to the anolyte compartment 54.
  • the anode 58 and cathode 60 may be fabricated of various materials, including those discussed above and in U.S. Patent Application Publication No. 2007/0138020. Under the influence of electric potential 64, electrochemical reactions take place at the anode 58 and cathode 60. Oxidation of chloride ions to chlorine gas occurs at the anode 58, and reduction of water to form hydrogen gas 70 and hydroxyl ions occurs at the cathode 60.
  • chloride ions 62 are transported from the catholyte compartment 56 across the anion conductive membrane 52 into the anolyte compartment 54.
  • the transported chloride ions 62 react at the anode 58 to form chlorine which reacts with water to form to form a hypochlorous acid solution 72.
  • Hypochlorous acid solution 72 may be dispensed from the anolyte compartment 54 for on-site or point-of-use into a device or apparatus such those described herein.
  • catholyte compartment 2H + + 2e ⁇ ⁇ H 2
  • the pH control of the anolyte solution is important to promote formation of HOCl.
  • the pH of the solution within the anolyte compartment 54 is preferably maintained at a pH less than 11 , usually with a preferred pH in the range from 5 to 11, and more preferably between 6 and 8. With a pH less than 5, HCl formation is favored over HOCl.
  • the anion conductive membrane 52 as employed herein is defined to include membranes which have selective permeability, i.e., permselectivity, by allowing passage of chloride anions (Cl " ), but not cations.
  • Anion conductive membranes may be strongly, mildly or weakly basic, and may be comprised of quaternary or tertiary ammonium groups, for example.
  • Anion conductive membranes should be stable in the electrolytic environment and have a low resistance to the anion being transported.
  • Anion conductive membranes may include commercially available anion exchange membranes.
  • Representative anion exchange membranes include polystyrene-polydivinyl- benzene polymeric base materials, such as Tokuyama Neosepta AMH or Asahi Glass Selemion AMV, and perfluorinated radiation grafted materials, such as Pall Raipore. Solvay Morgane products may also be used.
  • the cleansing agent generators described herein can be operated in a continuous or batch mode.
  • the cleansing agent generator may be operated in a continuous mode.
  • the electrolytic cell is initially filled with anolyte and catholyte solutions and then, during operation, additional solutions are fed into the cell and products, by-products, and/or diluted solutions are removed from the cell without ceasing operation of the cell.
  • the reactant solutions may be fed into the anolyte and catholyte compartments continuously or they may be fed intermittently, meaning that the flow of a given solution is initiated or stopped according to the need for the solution and/or to maintain desired concentrations of solutions in the cell, without emptying one or both compartments.
  • the removal of solutions from the anolyte compartment and the catholyte compartment may also be continuous or intermittent.
  • Control of the addition and/or removal of solutions from the cleansing agent generator may be done by any suitable means.
  • Such means include manual operation, such as by one or more human operators, and automated operation, such as by using sensors, electronic valves, laboratory robots, etc. operating under computer or analog control.
  • automated operation a valve or stopcock may be opened or closed according to a signal
  • FIG 3 shows a non-limiting schematic drawing of a cleansing agent dispersement system 100.
  • a cleansing agent generator 110 of the type mentioned above in connection with Figures 1 and 2 may be used.
  • the cleansing agent generator 110 may be an electrochemical cell of the type known in the art. It could be configured with an anode in an anolyte compartment and a cathode in a catholyte compartment. The amount and content of material in each compartment along with the type of selective membrane is determined based upon the desired cleansing agent to be output.
  • the electrochemical cell As power is supplied to the system, the electrochemical cell generates the cleansing agent which is then dispensed by the dispensing unit 112.
  • the dispensing unit 112 may include various types of conduits, and may be used in conjunction with a variety of valves or pumps to control the release of the cleansing agent according to known fluid handling systems.
  • a controller 114 may include a timing circuit module 116, a feed stock detector module 118, a power source module 120, and/or a pH detector module 122. These modules could include software, hardware, firm ware, instruction codes, and the like.
  • the controller 114 may determine whether enough cleansing agent has been produced, whether certain parameters of the cleansing agent have been met, such as pH, temperature, content, concentration, and the like.
  • the controller 114 working with or without the apparatus that will utilize the cleansing agent, may determine when to disperse the cleansing agent.
  • the controller may also control the power source and vary the current applied to the electrochemical cell to thereby control the rate and amount of cleansing agent generated.
  • one or more feeders may resupply one or more of the catholyte compartment or anolyte compartment of the electrochemical cell.
  • the controller may detect levels within each compartment of the electrochemical cell in order to replenish it and also the levels of the feeder reservoirs.
  • the system 100 may have an audio or visual output (not shown) that conveys to a user the status of the system. The status may include whether the cleansing agent has been generated, whether and when it has be dispersed, pH, concentration,
  • the controller may notify a user of the need to replenish the salt solution into the cell.
  • Figure 4 illustrates a non-limiting example where the controller 114 may control when cleansing agents are dispersed into a washing machine 126. While Figure 4 is illustrated and discussed in relation to a washing machine, it will be appreciated that other appliances may be used in place of the washing machine.
  • the controller 114 may detect whether the cleansing agent generator 110 comprising an electrochemical cell (EC) contains the proper contents to make the desired cleansing agent. If the EC does not contain the proper contents, the controller automatically fills each compartment with the desired material. In one embodiment, it could be a salt or HCl solution 128.
  • EC electrochemical cell
  • the feedstock could be a powder or solid and the system utilizes water from the washing machine to make the right solution either in the EC, or before it is deposited in the EC.
  • the controller taking an electric or other signal from the washing machine 126, applies power to the electrochemical cell so that it generates the cleansing agent.
  • the cleansing agent is dispersed into the washing machine 126.
  • the controller 114 may wait until a particular rinse or fill cycle in order apply the proper cleaning effect without damaging or discoloring the clothes. Unused cleansing agent, source material, or by products may then be removed from the EC. Gaseous byproducts such as hydrogen may be vented from the EC. The reservoir feeder may then refill the EC.
  • the controller 114 may be coupled to the various components of the system, including the washing machine 126, cleansing agent generator 1 10, valves and sensors, including dispensing unit 112, feeders, and such as feedstock source 128.
  • One suggested application of the apparatus illustrated in Figure 4 is to generate NaOCl as a part of an apparatus to provide bleaching agent to a washing machine.
  • an electronic control system would generate a solution of NaOCl ( ⁇ 5 weight %) and introduce that solution into the wash water at an appropriate time in the wash cycle.
  • the percentage of NaOCl could be varied dependent upon the temperature, fabric, and agitation selections. The gradual introduction of the sodium hypochlorite would prevent any damage to fabrics.
  • a second non -limiting application would be to generate NaOCl as part of an apparatus to provide disinfectant to a dishwasher.
  • an electronic control In this embodiment an electronic control
  • a third non-limiting application would be to generate NaOCl on board a ship to generate disinfectant on an as needed basis.
  • salt water could serve as the input if the ship were located in the ocean. This has the potential to reduce the spread of infectious bacteria as has occurred on cruise ships in the past.
  • the generator could also be incorporated with numerous portions of the ship's apparatus (e.g. washing machine, dishwasher, reverse osmosis system, etc).
  • Figure 5 is a schematic representation of a system to generate and dispense a cleansing agent at the point-of-use in the form of a topical skin patch, a scrub brush, or a floor brush or mop.
  • the cleansing agent generator 210 shown in Figure 5 has similar components to the apparatus illustrated in Figure 1 and may be used to produce sodium hypochlorite.
  • the cleansing agent generator 210 comprises an electrolytic cell that uses a sodium ion conductive ceramic membrane 212 that divides the electrochemical cell into two compartments: an anolyte compartment 214 and a catholyte compartment 216.
  • An electrochemically active anode 218 is housed in the anolyte compartment 214 where oxidation reactions take place, and an electrochemically active cathode 220 is housed in the catholyte compartment 216 where reduction reactions take place.
  • the sodium ion conductive ceramic membrane 212 selectively transfers sodium ions from the anolyte compartment 214 to the catholyte compartment 216 under the influence of an electrical potential 224 while preventing water transportation from either compartment to the other side. It may be advantages to include one or more conventional buffering agents, such as NaHCO 3 , within the anolyte compartment 214 to control the operating pH.
  • the cleansing agent generator 210 comprises a porous membrane 226 which allows cleansing agent to pass from the anolyte compartment 214 to the exterior of the device.
  • the porous membrane may define an active cleansing surface.
  • the cleansing agent generator may be configured for use in scrub brush, or a floor brush by adding a handle.
  • the generator may be constructed with thin flexible membranes and provided with suitable skin adhesive material for use as a topical skin patch.
  • the cleansing agent generator 210 may be configured for one-time batch use or it may be configured to permit replenishment of the anolyte and catholyte compartments for continuing use or repeated use.
  • Figure 6 is a schematic representation of a system to generate and dispense a cleansing agent at the point-of-use in the form of a topical skin patch, a scrub brush, or a floor brush or mop similar to the embodiment illustrated in Figure 5.
  • the cleansing agent generator 210 shown in Figure 6 has similar components to the apparatus illustrated in Figure 2 and may be used to produce hypochlorous acid. HCl may also be produced concurrently with the hypochlorous acid as a mixed oxidant stream.
  • the cleansing agent generator 250 comprises an electrolytic cell that uses an anion conductive membrane 252 that divides the electrochemical cell into two compartments: an anolyte compartment 254 and a catholyte compartment 256.
  • An electrochemically active anode 258 is housed in the anolyte compartment 254 where oxidation reactions take place, and an electrochemically active cathode 260 is housed in the catholyte compartment 256 where reduction reactions take place.
  • the anion conductive membrane 252 selectively transfers chloride ions from the anolyte compartment 254 to the catholyte compartment 256 under the influence of an electrical potential 264. It may be advantages to include one or more conventional buffering agents within the anolyte compartment 254 to control the operating pH and promote the formation of HOCl.
  • the cleansing agent generator 250 comprises a porous membrane 266 which allows hypochlorous acid cleansing agent to pass from the anolyte compartment 254 to the exterior of the device.
  • the porous membrane may define an active cleansing surface.
  • the cleansing agent generator may be configured for use in scrub brush, or a floor brush by adding a handle.
  • the generator may be constructed with thin flexible membranes and provided with suitable skin adhesive material for use as a topical skin patch.
  • the cleansing agent generator 250 may be configured for one-time batch use or it may be configured to permit replenishment of the anolyte and catholyte compartments for continuing use or repeated use.
  • Example 1 The following non-limiting example is provided below which discusses the construction and use of a specific embodiment within the scope of the present invention. This embodiment is exemplary in nature and should not be construed to limit the scope of the invention in any way. [0074] Example 1 :
  • An apparatus to provide bleach (NaOCl) to a washing machine is prepared.
  • the washing machine value is approximately 10 gallons.
  • the amount of bleach to be added to a typical wash cycle is 50 ml of 5 wt. % NaOCl, which corresponds to 2.5 g of 100% bleach.
  • the concentration of the bleach in the washing machine is about 007 wt. % bleach in 10 gallons of water. If the washing machine fills in five minutes, the cleansing agent generator must operate to produce NaOCl at a rate which results in 0.007 wt. % bleach through the cycle. To operate at this rate, the cleansing agent generator should comprise an electrolytic cell of the type described herein having a volume of about 100 cm 3 and active electrode area of about 100 cm 2 . The anolyte NaCl concentration in water is > 18 wt. %, and the catholyte NaOH concentration is water is > 9.5 wt. %. Operating at 20 amps at 12 volts, the cell produces 50 cm 3 of 5 wt. % NaOCl in five minutes, sufficient to meet the requirements of the washing machine.
  • the present invention provides a point-of-use electrochemical generator and dispenser of cleansing, sanitizing, and antimicrobial agents such as sodium hypochlorite and hypochlorous acid.
  • the system to generate and dispense the cleansing agent at the point-of-use includes an electrolytic cell, such as those described herein, which produce sodium hypochlorite or hypochlorous acid as needed and a controller to efficiently control the operation of system.
  • the cleansing agent may be generated on demand and used in household, industrial, and water treatment applications.
  • the cleansing agent may be used in various types of apparatuses such as a washing machine, a dishwasher, a scrub brush, a floor brush or mop, a toilet bowl apparatus, topical skin patch, fruit or vegetable washing apparatus, or any application where a dose of a cleansing agent is desired.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un appareil électrochimique (10) et des procédés pour la production délocalisée d'agents de nettoyage, d'aseptisation et antimicrobiens, tels que de l'hypochlorite de sodium (NaOCl) (34) ou de l'acide hypochlorique (HOCl). Les procédés peuvent être utilisés pour produire du NaOCl à partir d'eau de mer, de solutions salines à base de NaCl ou non adoucies de faible pureté (26). Du HOCl peut être produit à partir de solutions de HCl et d'eau. Du NaOCl (34) est produit en utilisant une membrane céramique conductrice d'ion sodium (12), telle des membranes à base de matériaux de type NASICON, dans une cellule électrolytique (11). Du HOCl est produit en utilisant une membrane conductrice d'anion dans une cellule électrolytique. L'agent de nettoyage, d'aseptisation et antimicrobien peut être généré sur demande et utilisé pour des applications ménagères, industrielles et de traitement des eaux.
PCT/US2008/008623 2007-07-13 2008-07-14 Générateur et distributeur d'agent de nettoyage WO2009011841A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP08794491A EP2171783A4 (fr) 2007-07-13 2008-07-14 Générateur et distributeur d'agent de nettoyage
AU2008276573A AU2008276573A1 (en) 2007-07-13 2008-07-14 Cleansing agent generator and dispenser
JP2010516073A JP2010533570A (ja) 2007-07-13 2008-07-14 洗浄剤発生・分配装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US94980207P 2007-07-13 2007-07-13
US60/949,802 2007-07-13

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WO2009011841A1 true WO2009011841A1 (fr) 2009-01-22

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JP (1) JP2010533570A (fr)
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WO (1) WO2009011841A1 (fr)

Cited By (20)

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EP2168604A1 (fr) * 2008-09-26 2010-03-31 Bissell Homecare, Inc. Dispositif de nettoyage de surface avec générateur de javel
US7891046B2 (en) 2006-02-10 2011-02-22 Tennant Company Apparatus for generating sparged, electrochemically activated liquid
US8007654B2 (en) 2006-02-10 2011-08-30 Tennant Company Electrochemically activated anolyte and catholyte liquid
US8012339B2 (en) 2006-02-10 2011-09-06 Tennant Company Hand-held spray bottle having an electrolyzer and method therefor
US8012340B2 (en) 2006-02-10 2011-09-06 Tennant Company Method for generating electrochemically activated cleaning liquid
US8016996B2 (en) 2006-02-10 2011-09-13 Tennant Company Method of producing a sparged cleaning liquid onboard a mobile surface cleaner
US8025786B2 (en) 2006-02-10 2011-09-27 Tennant Company Method of generating sparged, electrochemically activated liquid
US8025787B2 (en) 2006-02-10 2011-09-27 Tennant Company Method and apparatus for generating, applying and neutralizing an electrochemically activated liquid
US8046867B2 (en) 2006-02-10 2011-11-01 Tennant Company Mobile surface cleaner having a sparging device
WO2012041357A1 (fr) * 2010-10-01 2012-04-05 Actides Berlin Gmbh Procédé de production d'un agent désinfectant à base d'acide hypochloreux ou d'hypochlorite par activation électrochimique d'une solution de chlorure
US8236147B2 (en) 2008-06-19 2012-08-07 Tennant Company Tubular electrolysis cell and corresponding method
US8319654B2 (en) 2008-06-19 2012-11-27 Tennant Company Apparatus having electrolysis cell and indicator light illuminating through liquid
US8337690B2 (en) 2007-10-04 2012-12-25 Tennant Company Method and apparatus for neutralizing electrochemically activated liquids
US8485140B2 (en) 2008-06-05 2013-07-16 Global Patent Investment Group, LLC Fuel combustion method and system
EP2625317A2 (fr) * 2010-10-08 2013-08-14 Ceramatec, Inc Systèmes et procédés électrochimiques pour le fonctionnement d'une cellule électrochimique dans un anolyte acide
WO2014004975A1 (fr) * 2012-06-29 2014-01-03 Tennant Company Générateur et procédé de formation d'acide hypochloreux
WO2015119414A1 (fr) * 2014-02-04 2015-08-13 국립대학법인 울산과학기술대학교 산학협력단 Accumulateur produisant de l'eau douce
US9540259B2 (en) 2011-08-25 2017-01-10 Electrolytic Ozone, Inc. Apparatus for producing and delivering ozonated water
WO2018109169A1 (fr) 2016-12-15 2018-06-21 Adept Water Technologies A/S Dispositif de production de liquide aqueux contenant du chlore libre disponible (cld)
CN110352523A (zh) * 2017-03-06 2019-10-18 懿华水处理技术有限责任公司 用于自清洁电氯化装置的半电池电化学配置

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US20040267190A1 (en) * 2003-06-02 2004-12-30 Dov Tamarkin Kit, device and method for controlled delivery of oxidizing agent into the skin
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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8025786B2 (en) 2006-02-10 2011-09-27 Tennant Company Method of generating sparged, electrochemically activated liquid
US7891046B2 (en) 2006-02-10 2011-02-22 Tennant Company Apparatus for generating sparged, electrochemically activated liquid
US8007654B2 (en) 2006-02-10 2011-08-30 Tennant Company Electrochemically activated anolyte and catholyte liquid
US8012339B2 (en) 2006-02-10 2011-09-06 Tennant Company Hand-held spray bottle having an electrolyzer and method therefor
US8012340B2 (en) 2006-02-10 2011-09-06 Tennant Company Method for generating electrochemically activated cleaning liquid
US8016996B2 (en) 2006-02-10 2011-09-13 Tennant Company Method of producing a sparged cleaning liquid onboard a mobile surface cleaner
US8025787B2 (en) 2006-02-10 2011-09-27 Tennant Company Method and apparatus for generating, applying and neutralizing an electrochemically activated liquid
US8046867B2 (en) 2006-02-10 2011-11-01 Tennant Company Mobile surface cleaner having a sparging device
US8719999B2 (en) 2006-02-10 2014-05-13 Tennant Company Method and apparatus for cleaning surfaces with high pressure electrolyzed fluid
US8156608B2 (en) 2006-02-10 2012-04-17 Tennant Company Cleaning apparatus having a functional generator for producing electrochemically activated cleaning liquid
US8603320B2 (en) 2006-02-10 2013-12-10 Tennant Company Mobile surface cleaner and method for generating and applying an electrochemically activated sanitizing liquid having O3 molecules
US8337690B2 (en) 2007-10-04 2012-12-25 Tennant Company Method and apparatus for neutralizing electrochemically activated liquids
US8485140B2 (en) 2008-06-05 2013-07-16 Global Patent Investment Group, LLC Fuel combustion method and system
US8319654B2 (en) 2008-06-19 2012-11-27 Tennant Company Apparatus having electrolysis cell and indicator light illuminating through liquid
US8236147B2 (en) 2008-06-19 2012-08-07 Tennant Company Tubular electrolysis cell and corresponding method
EP2168604A1 (fr) * 2008-09-26 2010-03-31 Bissell Homecare, Inc. Dispositif de nettoyage de surface avec générateur de javel
US8662782B2 (en) 2008-09-26 2014-03-04 Bissell Homecare, Inc. Surface cleaning device with a bleach generator
WO2012041357A1 (fr) * 2010-10-01 2012-04-05 Actides Berlin Gmbh Procédé de production d'un agent désinfectant à base d'acide hypochloreux ou d'hypochlorite par activation électrochimique d'une solution de chlorure
EP2625317A2 (fr) * 2010-10-08 2013-08-14 Ceramatec, Inc Systèmes et procédés électrochimiques pour le fonctionnement d'une cellule électrochimique dans un anolyte acide
EP2625317A4 (fr) * 2010-10-08 2014-05-14 Ceramatec Inc Systèmes et procédés électrochimiques pour le fonctionnement d'une cellule électrochimique dans un anolyte acide
US9540259B2 (en) 2011-08-25 2017-01-10 Electrolytic Ozone, Inc. Apparatus for producing and delivering ozonated water
WO2014004975A1 (fr) * 2012-06-29 2014-01-03 Tennant Company Générateur et procédé de formation d'acide hypochloreux
WO2015119414A1 (fr) * 2014-02-04 2015-08-13 국립대학법인 울산과학기술대학교 산학협력단 Accumulateur produisant de l'eau douce
WO2018109169A1 (fr) 2016-12-15 2018-06-21 Adept Water Technologies A/S Dispositif de production de liquide aqueux contenant du chlore libre disponible (cld)
CN110352523A (zh) * 2017-03-06 2019-10-18 懿华水处理技术有限责任公司 用于自清洁电氯化装置的半电池电化学配置
CN110352523B (zh) * 2017-03-06 2023-09-08 懿华水处理技术有限责任公司 用于自清洁电氯化装置的半电池电化学配置

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EP2171783A4 (fr) 2011-10-26
JP2010533570A (ja) 2010-10-28
EP2171783A1 (fr) 2010-04-07
AU2008276573A1 (en) 2009-01-22

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