WO2004103898A1 - Compositions, dispositifs et procedes de stabilisation et d'augmentation de l'efficacite de solutions de dioxyde d'halogene - Google Patents

Compositions, dispositifs et procedes de stabilisation et d'augmentation de l'efficacite de solutions de dioxyde d'halogene Download PDF

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Publication number
WO2004103898A1
WO2004103898A1 PCT/US2004/015730 US2004015730W WO2004103898A1 WO 2004103898 A1 WO2004103898 A1 WO 2004103898A1 US 2004015730 W US2004015730 W US 2004015730W WO 2004103898 A1 WO2004103898 A1 WO 2004103898A1
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Prior art keywords
halogen dioxide
solution
halogen
ift
dioxide
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PCT/US2004/015730
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English (en)
Inventor
Brian Joseph Roselle
Gregory Bruce Huntington
Mario Elmen Tremblay
Charles Allen Pettigrew, Jr.
Freddy Arthur Barnabas
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP2006514897A priority Critical patent/JP2006526076A/ja
Priority to MXPA05012437A priority patent/MXPA05012437A/es
Priority to BRPI0410758-6A priority patent/BRPI0410758A/pt
Priority to CA002522576A priority patent/CA2522576A1/fr
Priority to EP04752705A priority patent/EP1626928A1/fr
Publication of WO2004103898A1 publication Critical patent/WO2004103898A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • 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

Definitions

  • the present invention relates to compositions and methods for increasing the stability and/or efficacy of halogen dioxide, and particularly chlorine dioxide, generated via electrolysis of salts of halogen (and particularly chlorine) dioxide.
  • the present invention further relates to electrolysis devices for producing halogen dioxide, comprising the stabilizing and efficacy- increasing compositions of the present invention, as well as methods of using the halogen dioxide-stabilizing and efficacy-increasing compositions and devices disclosed herein.
  • Chlorine dioxide C10 2
  • Chlorine dioxide is one of the most effective bleaching agents for use in industrial and domestic process and services, and for commercial and consumer products.
  • the strong oxidative potential of the molecule makes it ideal for a wide variety of uses that include disinfecting, sterilizing, and bleaching.
  • Concentrations of chlorine dioxide in an aqueous solution as low as 1 part per million (ppm) or less, are known to kill a wide variety of microorganisms, including bacteria, viruses, molds, fungi, and spores.
  • Higher concentrations of chlorine dioxide, up to several hundred ppms provide even higher disinfection, bleaching and oxidation of numerous compounds for a variety of applications, including the paper and pulp industry, waste water treatment, industrial water treatment (e.g. cooling water), fruit-vegetable disinfection, oil industry treatment of sulfites, textile industry, and medical waste treatment.
  • Chlorine dioxide offers advantages over other commonly used bleaching materials, such as hypochlorite and chlorine. Chlorine dioxide can react with and break down phenolic compounds, and thereby removing phenolic-based tastes and odors from water. Chlorine dioxide is also used in treating drinking water and wastewater to eliminate cyanides, sulf ⁇ des, aldehydes and mercaptans. The oxidation capacity of C10 2 , in terms of available chlorine, is 2.5 times that of chlorine. Also, unlike chlorine/hypochlorite, for which bactericidal efficacy is believed to diminish at a pH greater than 7, the bactericidal efficacy of chlorine dioxide is believed to remain effective at pH levels of 7 to 10. Additionally, chlorine dioxide can inactivate C.
  • parvum oocysts in water at appropriate concentration ranges i.e. about 100 to 200 ppm
  • hypochlorite and chlorine both react with the bleached target by inserting the chlorine molecule into the structure of the target. Though this mode of reaction can be effective, it can result in the formation of one or more chlorinated products, or by-products, which can be undesirable both from a economic sense (to eliminate hydrocarbons from the reaction media) and a safety and environmental standpoint.
  • the step of bleaching by hypochlorite and chlorine results in the destruction of the bleach species itself, such that subsequent bleaching requires a fresh supply of the chlorine bleach.
  • Another disadvantage is that certain microorganisms that are intended to be killed by these two commonly-used bleach materials can develop a resistance over time, specifically at lower concentrations of the chlorine or hypochlorite.
  • Chlorine dioxide is generally used in an aqueous solution at levels up to about 1%. It is a troublesome material to transport and handle at high aqueous concentrations, due to its low stability and high corrosiveness. This has required end users to generate chlorine dioxide on demand, usually employing a precursor such as sodium chlorite (NaC10 2 ) or sodium chlorate (NaC10 3 ).
  • a precursor such as sodium chlorite (NaC10 2 ) or sodium chlorate (NaC10 3 ).
  • a typical process for generating chlorine dioxide from sodium chlorate salt is the acid- catalyzed reaction:
  • Sodium chlorite is easier to convert to chlorine dioxide.
  • a typical process for generating chlorine dioxide from sodium chlorite salt is the acid-catalyzed reaction: 5NaC10 2 + 4HCl - 4C10 2 + 5 NaCl + 2H 2 0
  • compositions that are adapted to stabilize and increase the efficacy of halogen (and particularly) chlorine dioxide solutions upon generation.
  • the use of such compositions would alleviate the need for on-demand chlorine dioxide generation by maximizing the "shelf life" of pre-generated, active chlorine dioxide solutions.
  • the identification of stabilizing and efficacy-increasing compositions would maximize the stability and performance of halogen dioxide solutions following their on-demand generation, whether via electrolysis or otherwise.
  • the halogen dioxide stabilizing and efficacy-increasing compositions of the present invention address and resolve the quandaries associated with the contemporary employment of chlorine dioxide, particularly with respect to the low stability of halogen dioxide solutions.
  • the present invention relates to compositions, devices and methods for stabilizing and increasing the efficacy of halogen (and particularly chlorine) dioxide solutions, whether pre- generated or generated on-demand.
  • the stabilizing and efficacy-increasing compositions of the present invention incorporate a hydroxide ion scavenging solution and/or an Interfacial Tension (IFT) lowering agent into a halogen dioxide solution, whether pre-generated or generated on-demand.
  • IFT Interfacial Tension
  • compositions for increasing the stability and/or efficacy of halogen dioxide, and particularly chlorine dioxide are disclosed and claimed.
  • a composition for stabilizing a chlorine dioxide solution, whether pre-generated or generated on-demand, employing a hydroxide ion scavenging system is disclosed.
  • a composition for increasing the efficacy, antimicrobial and otherwise, of a chlorine dioxide solution, incorporating an Interfacial Tension (IFT) lowering agent is disclosed.
  • halogen dioxide (and particularly chlorine dioxide) solutions incorporating both a hydroxide ion scavenging system and an Interfacial Tension (IFT) lowering agent are disclosed and claimed.
  • the stabilizing and/or efficacy-increasing compositions of the present invention further comprise one or more adjunct ingredients for the provision of certain aesthetic and/or performance benefits to the resultant, halogen dioxide solution.
  • electrolysis devices for the on-demand generation of stable and efficacious halogen dioxide, and particularly chlorine dioxide, are disclosed and claimed.
  • said devices incorporate a hydroxide ion scavenging system for the stabilization of halogen dioxide generated therein.
  • the electrolysis devices disclosed herein incorporate an Interfacial Tension (IFT) lowering agent to maximize the efficacy of the halogen dioxide upon generation.
  • the electrolysis devices disclosed herein incorporate both a hydroxide ion scavenging solution and an Interfacial Tension (IFT) lowering agent.
  • IFT Interfacial Tension
  • halogen dioxide and particularly chlorine dioxide
  • a method for stabilizing halogen dioxide, and particularly chlorine dioxide is provided.
  • a method of increasing the efficacy of halogen dioxide, and particularly chlorine dioxide is provided.
  • methods of sanitizing and/or cleaning surfaces using the present compositions are provided. Said methods generally involve the application of one or more of the aforementioned, halogen dioxide stabilizing and/or efficacy-increasing compositions to a halogen dioxide solution for which increased stability and/or efficacy is desired.
  • the methods disclosed herein relate to the use of an electrolysis device employing the present compositions to stabilize and/or increase the efficacy of halogen dioxide generated on-demand.
  • Other methods disclosed herein relate to the use of the claimed devices and compositions for application onto a substrate for which sanitation and/or cleaning is desired.
  • the precise steps of each method disclosed herein will depend upon the stabilizing and/or efficacy-increasing composition for which incorporation into a halogen dioxide solution is sought, the specific needs and/or abilities of the formulator and the application for which the use of the methods claimed herein is desired.
  • a wipe comprising the solutions and/or systems described herein is disclosed.
  • the solutions and/or systems described herein are provided in a gaseous form.
  • the solutions and/or systems described herein are provided in a solid form.
  • the solutions and/or systems described herein are provided in a gel formulation.
  • stabilizing is intended to refer to the use of a hydroxide ion scavenging system in a halogen dioxide, preferably chlorine dioxide, solution to control the hydroxide ion concentration of said solution such that the stability of the resultant solution is greater than that of a halogen dioxide solution that does not employ such a system.
  • the term “increased stability” is intended to refer to a hydroxide ion scavenging system-comprising halogen dioxide solution having at least about 5%, preferably at least about 10%, higher halogen dioxide concentration at 25 C, three hours following formulation thereof versus the concentration of a corresponding halogen dioxide that does not comprise the stabilizing system, measured at 25 C and three hours following formulation thereof.
  • efficacy-increasing is intended to refer to the incorporation of a hydroxide ion scavenger and/or IFT lowering agents into a halogen dioxide, and particularly chlorine dioxide, solution to convey one or more antimicrobial performance and/or aesthetic benefits to said solution.
  • Said benefits include, but certainly are not limited to, increased antimicrobial kill and/or log reduction in antimicrobial solutions, improved odor elimination, selective bleaching or color modification and combinations thereof.
  • the term "increased antimicrobial performance" is intended to refer to a hydroxide ion scavenger and/or IFT lowering agent-comprising halogen dioxide solution having at least about 5%, preferably at least about 10% greater reduction in the number of microbes than a corresponding halogen dioxide solution that does not comprise the hydroxide ion scavengers or IFT lowering agents.
  • hydroxide ion scavenging system is intended to refer to any agent that can be employed into a halogen (or chlorine) dioxide solution and, upon such employment, increase the stability of said solution, particularly when compared to the stability of such a solution that does not incorporate a hydroxide ion scavenging agent.
  • the hydroxide ion scavenging agents and/or system of the present invention is adapted to increase the concentration of halogen dioxide by at least about 5%, preferably at least about 10%, at 25 C, three hours following formulation in comparison to the concentration of a corresponding halogen dioxide that does not comprise the stabilizing system (also measured at 25 C and three hours following formulation thereof).
  • IFT lowering agents and/or "IFT system” are intended to refer to one or more agents suitable for incorporation into a halogen, and particularly chlorine, dioxide solution to increase the efficacy, antimicrobial and otherwise, of said solution.
  • agents suitable for use in the halogen-dioxide efficacy-increasing compositions of the present invention are discussed in more detail, infra.
  • pre-generated or “pre-generation” are intended to refer to the generation of halogen dioxide, more particularly chlorine dioxide, greater than about 3 hours, preferably greater than about 2 hours, more preferably greater than about 1 hour, prior to its intended deployment. Such generation may occur at a location other than that in which deployment of chlorine dioxide is desired, but may occur at the same location of the intended deployment.
  • on-demand is intended to refer to the generation of halogen (or chlorine) dioxide less than about 3 hours, preferably less than about 2 hours, more preferably less than about 1 hour, prior to the time of intended deployment.
  • on demand is intended to refer to the generation of halogen dioxide in less than about 1 second.
  • On-demand generation of chlorine dioxide may typically be effectuated via the use of an electrolytic device, as disclosed and described infra.
  • cleaning and/or disinfecting are intended to refer to the process of applying (optionally followed by removing) a composition to a surface or environment with the intent of removing and/or inactivating unwanted contaminants.
  • compositions for stabilizing and/or increasing the efficacy of halogen, and particularly chlorine, dioxide are disclosed.
  • such compositions comprise a hydroxide ion scavenging system.
  • the hydroxide ion scavenging system of the present > invention comprises a hydroxyl ion-reacting agent that is adapted to control the pH of the chlorine dioxide solution to which it is added.
  • This prolonged stability may also be related to the potential for acidic reaction at a low pH. Reducing the hydroxyl ion concentration to stabilize the chlorine dioxide is useful in static solutions as well as solutions that undergo high shear, as in the case of turbulent spraying or atomization of halogen dioxide solutions.
  • the hydroxide ion scavenging system of the present invention is employed into a chlorine dioxide solution at a level of from about 0.001 to about 10%, preferably 0.01 to about 7.5%, more preferably 0.05 to about 5%, most preferably 0.1 to about 2.5%, by weight of the total hydroxide ion scavenging system-comprising chlorine dioxide solution.
  • hydroxide ion scavenging agent needed to stabilize a chlorine dioxide solution will depend upon many factors including, but not limited to, the nature of the hydroxide ion scavenging agent, the concentration of the halogen dioxide solution for which the conveyance of increased stability is desired and the generation method of the halogen dioxide solution under consideration.
  • Suitable hydroxide ion scavenging agents for use in the present invention are selected from the group consisting of: organic acids, salts of organic acids, inorganic acids, salts of inorganic acids, and the like. It should be noted that the hydroxide ion scavenging agents of the present invention are adapted to stabilize any halogen dioxide solution.
  • an Interfacial Tension (IFT) lowering system for stabilizing and/or increasing the efficacy of a halogen dioxide solution.
  • IFT Interfacial Tension
  • a halogen dioxide (and particularly chlorine dioxide) solution provides the overall effect of increasing the efficacy of said solution by lowering the Interfacial Tension of the resultant system.
  • the IFT-lowering agents of the present invention are adapted to reduce the tension at the interface between two physical phases — thereby decreasing the level of work and/or energy required to expand the interfaces.
  • the ability of the present IFT-lowering agents to encourage expansion of the interfaces with decreased energy is believed to facilitate penetration and increased interfacial exposure of halogen dioxide (and particularly chlorine dioxide).
  • the IFT-lowering agents of the present invention can exhibit synergy in concert with halogen dioxides - thereby facilitating microbe structure and protein denaturing.
  • surfactants forming a monolayer of surfactant at air interfaces can be used to regulate halogen dioxide partitioning into the surrounding air. This may be of special interest for situations in which halogen dioxide solutions comprising the present IFT-lowering agents are used in the context of decontamination, whether via chamber, spray or other means.
  • the sprayed particle size of the aqueous, halogen dioxide solution can be controlled and optimized for the particular application.
  • very small particle sizes may increase the surface area enough to overcome surfactant barrier effects thus helping to facilitate the partitioning of the halogen (chlorine) dioxide into the gas/air phase.
  • a transition from aqueous chlorine dioxide exposure to gas phase chlorine dioxide exposure occurs, which may be beneficial in delivering the subject compositions to areas that are difficult to reach using aqueous dispersions.
  • Use of small particle sizes may also be desirable for situations in which substrate contact with the aqueous solution is not desired. Copious levels of foam on a surface likewise may serve as an additional physical barrier to halogen dioxide loss from solution to the surrounding atmosphere.
  • the precise composition of the present efficacy-increasing IFT-lowering systems will depend on the purpose for which employment of the resultant chlorine dioxide solution is desired and the needs and/or abilities of the formulator. Nevertheless, the IFT-lowering system and/or agents of the present invention are preferably incorporated into a halogen dioxide solution at a level of from about 0.00001 to about 10%, preferably from about 0.0001 to about 5%, more preferably from about 0.0005 to about 2%, most preferably 0.001 to about 1%, by weight of the total, IFT-lowering system-containing halogen dioxide solution.
  • the IFT-lowering agents disclosed herein are incorporated, in the above-listed amounts, into a chlorine dioxide solution for which increased stability and or efficacy is desired.
  • IFT-lowering agents can be used to stabilize and/or increase the efficacy of a halogen dioxide solution in accordance with the present invention. Although a few such agents have been included herein, it should be appreciated that other agents can provide similar benefits in increasing the efficacy of the halogen dioxide solutions to which they are added. Indeed, there exist several classes of agents that can be used as IFT-lowering agents for purposes of the present invention. These classes include, but certainly are not limited to: IFT- lowering polymers, IFT-lowering solvents, IFT-lowering surfactants and combinations thereof. In a particularly preferred aspect of the present invention, IFT-lowering surfactants are employed into halogen dioxide solutions to convey the aforementioned benefits afforded by the present IFT- lowering agents disclosed herein.
  • IFT-lowering surfactants for use in increasing the efficacy and/or performance of the halogen dioxide solutions disclosed herein can be nonionic, anionic, amphoteric, amphophilic, zwitterionic, cationic, semi-polar nonionic, and mixtures thereof.
  • Nonlimiting examples of such surfactants are disclosed in US Patent Numbers 5,707,950 and 5,576,282, incorporated herein by reference.
  • a typical listing of anionic, nonionic, amphoteric and zwitterionic classes, and species of these surfactants, is provided in US Patent Number 3,664,961 issued to Norris on May 23, 1972, and incorporated herein by reference.
  • IFT-lowering surfactants useful herein include the conventional Cg-Ci g alkyl ethoxylates and/or alcohol ethoxylates (AE), with EO about 1-22, including the so- called narrow peaked alkyl ethoxylates and Cg-Ci2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), alkyl dialkyl amine oxide, alkanoyl glucose amide, C ⁇ 1 - C ⁇ g (linear) alkyl benzene sulfonates (LAS) and primary, secondary and random alkyl sulfates (AS and or SAS), the C ⁇ )-Ci 8 alkyl alkoxy sulfates (AES), the C ⁇ n-C ⁇ g alkyl polyglycosides and their corresponding sulfated polyglycosides (APG), C ⁇ -C ⁇ g alpha-sulfonated fatty acid esters, C ⁇ -C
  • IFT-lowering polymers and/or IFT-lowering solvents are incorporated into halogen dioxide (and particularly chlorine dioxide) solutions for which the conveyance of increased stability and/or efficacy are desired.
  • Suitable IFT-lowering polymers for use in the context of the present invention include, but certainly are not limited to: polyoxyalkylene block copolymers.
  • suitable IFT-lowering solvents for use as IFT- lowering agents, in the context of the present invention include, but certainly are not limited to: glycol ethers such as propylene glycol n-propyl ether.
  • IFT-lowering agent for use in the context of the present invention will depend upon several factors, some of which include: (1) Sufficient chemical compatibility between the halogen dioxide and IFT lowering agent; (2) the nature of the halogen dioxide solution for which the conveyance of increased stability and/or efficacy is desired; (3) the purpose for which deployment of the resultant, IFT-lowering agent-containing halogen dioxide solution is desired; and (4) the needs and/or abilities of the formulator of the present compositions.
  • the halogen dioxide compositions disclosed herein comprise both a hydroxide ion-scavenging system and an IFT-lowering system.
  • Such compositions are adapted to stabilize halogen dioxide, and particularly chlorine dioxide, for a prolonged period and convey certain aesthetic and/or performance benefits to said solution. Indeed, it has been surprisingly discovered, and documented via the present disclosure, that synergy is exhibited via the employment of both a hydroxide ion scavenging and IFT-lowering system in a halogen dioxide solution.
  • an hydroxide ion scavenger and IFT lowering agent like a surfactant serves the integral purpose of maximizing the amount of halogen dioxide delivered to the desired interface by facilitating maximum surface area coverage from lowered interfacial tension while maintaining higher intrinsic halogen dioxide concentrations via inhibited degradation.
  • hydroxide ion scavenging system and IFT-lowering systems of the present invention when employed in combination, are present in an amount of from about 0.00001 to about 15, preferably from about 0.0001 to about 10%, more preferably from about 0.0005 to about 5%, most preferably from about 0.001 to about 2.5%, by weight of the total, hydroxide ion scavenging system and surfactant system-containing chlorine dioxide solution.
  • the halogen dioxide stabilizing and efficacy- increasing compositions disclosed herein will comprise one or more adjunct ingredients for providing aesthetic and/or performance benefits to the resultant composition.
  • the hydroxide ion scavenging containing compositions will comprise one or more adjunct ingredients (as discussed further infra).
  • the IFT-lowering system- containing compositions will comprise one or more adjunct ingredients.
  • the adjunct ingredients disclosed herein are incorporated into a halogen dioxide solution comprising both a hydroxide ion scavenging system and an IFT-lowering system.
  • Adjuncts suitable for incorporation into the halogen (and particularly chlorine) dioxide stabilizing and efficacy-increasing compositions of the present invention include, but certainly are not limited to: bleaching systems, enzymes and enzyme stabilizers, builders, dispersants, soil release agents, chelating agents, suds suppressors, softening agents, dye transfer inhibition agents, non-phosphate builders, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants, perfumes, solubilizing agents, carriers, processing aids, pigments, and pH control agents as described in US Patent Numbers 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101, all of which are incorporated herein by reference.
  • devices comprising the stabilizing and/or efficacy-increasing compositions of the previous aspect are disclosed and claimed. Said devices are generally limited to those that are adapted to generate halogen dioxide from halogen dioxide salt precursors, on-demand (as defined supra). Nevertheless, the stabilizing and efficacy- increasing compositions of the present invention may further be employed to stabilize and/or increase the efficacy of halogen dioxide that is pre-generated.
  • suitable electrolysis devices for use in conjunction with the stabilizing and efficacy-increasing compositions of the present invention is included in US Patent Application Serial Number 09/947,846 filed in the United States Patent and Trademark Office on 20 September 2001, and published on 09 January 2003. This application is incorporated, in its entirety, herein by reference.
  • suitable on-demand generation devices for use with the stabilizing and/or efficacy-increasing systems disclosed herein employ an electrical current passing through an aqueous feed solution between an anode and a cathode to convert a halogen dioxide salt precursor dissolved within the solution into a halogen dioxide.
  • an aqueous solution flows through the chamber of the electrolysis cell, and electrical current is passed between the anode and the cathode, several chemical reactions occur that involve the water, as well as one or more of the other salts or ions contained in the aqueous solution.
  • the on-demand generation device described in US Patent Application Number 09/947,846 may comprise additional chambers that facilitate the mixing of greater than one solution to form the stabilizing and efficacy-increasing compositions of the present invention.
  • separation of the subject compositions to delay mixing until use of the resultant halogen dioxide solution is desired is particularly useful when using chlorite salts and the total mixture comprises a pH that of less than about 7 and preferably less than about 5.
  • this is achieved by separating a chlorite salt solution and a low pH surfactant solution.
  • this is achieved by separating a chlorite salt solution containing the surfactant and a second, low pH solution having other ingredients.
  • electrolysis in accordance with the present invention could occur in a number of ways. Nevertheless, in any instance, electrolysis should occur down stream of the chlorite-based solution or resultant mixture. In one aspect of the present invention, this would be accomplished by mixing two streams, following electrolysis of the chlorite (halite) stream. In yet another aspect of the present invention, on-demand electrolysis could be accomplished by mixing two streams, said mixing being prior to electrolysis of the chlorite-containing total mixture.
  • one common pump which is adapted to create suction sufficient to draw both streams is employed to achieve requisite mixing.
  • a pump is employed to draw one stream and a venturi is employed after discharge thereof to draw and mix in a second stream.
  • two pumps pulling separate streams that are mixed after the pumps are employed.
  • electrolysis can occur before or after a pump or venturi.
  • devices producing the stabilizing and efficacy- increasing compositions are not restricted to formation of halogen (chlorine) dioxide by electrolysis.
  • the aforementioned aspect relating to the mixture of more than one solution can be constructed and/or configured such that the halogen dioxide is produced from chemical reactions upon mixing.
  • Non-limiting examples of such a configuration include mixing a low pH solution with a halite solution to facilitate halogen dioxide production by halite acidification. In such an instance, a pH of less than about 2 is preferred for rapid halogen dioxide formation.
  • Another example relates to the mixing of a liquid hypochlorite solution with a solution containing excess chlorite salt at low pH to form chlorine dioxide.
  • a pH of less than about 4 is preferred.
  • the mixing could be accomplished via a number of mechanisms including, but not limited to, one common pump creating suction to draw both streams, a pump on one stream and a venturi after its discharge which is used as intake to mix in a second stream, and two pumps pulling separate streams that are mixed after the pumps (as hereinbefore described).
  • the side reaction of electrolysis of Cl " to hypochlorite, OCl " may be controlled via use of a hydroxyl ion scavenger in the form of specific acidic buffers.
  • a hydroxyl ion scavenger in the form of specific acidic buffers.
  • HOCl is generally a preferred species to use.
  • OCl " is the predominant species, and at a pH of below about 2, Cl 2 predominates.
  • the solution may be formulated to produce excess chlorite that has not reacted from the electrolysis. This excess chlorite can subsequently react with the HOCl generated from the electrolysis to form additional chlorine dioxide.
  • the preferred pH for this type of a reaction is less than about 4.
  • electrolysis devices in accordance with the present invention further comprise parallel plate electrodes configured such that a virtual (e.g. quasi, pseudo) membrane is formed.
  • the virtual membrane of the present invention is not a permanent physical membrane, but rather, is a fluid-like membrane that is formed by the flow characteristics of the fluid solution undergoing electrolysis.
  • the flow within the parallel plates of the electrolysis devices disclosed herein is controlled such that the Reynolds number associated with the fluid is less than about 2000. Without wishing to be bound by theory, maintaining a Reynolds number below about 2000 establishes a fluid flow regime within the electrolytic cell that is configured in a planar form, parallel to the plates.
  • a method of stabilizing a halogen dioxide solution comprises the steps of incorporating a hydroxide ion-scavenging solution in accordance with the first aspect of the present invention into a halogen, preferably chlorine, dioxide solution for which increased stability is desired.
  • a method for increasing the efficacy of a halogen dioxide solution is disclosed. Said method generally comprises the step of incorporating an IFT-lowering agent and/or system in accordance with the first aspect of the present invention into a halogen, preferably chlorine, dioxide solution for which increased efficacy and/or performance is desired.
  • a method of both stabilizing and increasing the efficacy of a halogen dioxide solution generally comprises the steps of adding both a hydroxide ion-scavenging solution and an IFT-lowering system and or agent to a halogen dioxide, preferably chlorine dioxide, solution for which increased stability and/or efficacy is desired
  • a method of stabilizing and/or increasing the efficacy of halogen (and particularly chlorine) dioxide solutions generated via electrolysis comprises the steps of introducing the stabilizing and/or efficacy- increasing compositions of the present invention into a device adapted to electrolyze halite salt (as hereinbefore described), and facilitating the mixture of said stabilizing and/or efficacy-increasing compositions with the resultant halogen dioxide mixture.
  • the solutions and/or systems described herein are formulated into gel.
  • the gel may be formulated by adding any suitable thickener to a halogen dioxide solution, a hydroxide ion scavenging system-comprising halogen dioxide solution and/or an IFT- lowering system-comprising halogen dioxide solution.
  • incorporation of the present solutions and/or systems into such a gel facilitates adherence of the gel to the target surface and/or substrate for which the conveyance of the subject solution and/or system is desired. Further, and without wishing to be bound by theory, it is believed that formulation of the present systems into a gel will result in lower degradation by limiting mass transfer and/or loss of halogen dioxide to the atmosphere. Those skilled in the art to which the subject invention pertains, will readily appreciate the multitude of thickeners and methods suitable for use in formulation of the present gels.
  • halogen dioxide is generated via encapsulation of reactive species into or onto a wipe.
  • the wipe may then be "activated," thereby generating halogen dioxide, via shearing the wipe and/or by electrolyzing a wipe comprising one or more halogen dioxide salt precursors.
  • the wipe comprising one or more halogen dioxide salt precursors is electrolyzed via passage through and/or between the electrolysis plates between which electrolysis of the halogen dioxide salt precursors occurs.
  • a wipe comprising one more of the solutions and/or systems disclosed herein may be treated in a chamber, in which the halogen dioxide salt precursors included in said wipe are electrolyzed to generate halogen dioxide.
  • the wipe disclosed herein is sprayed with a halogen dioxide solution prior to an intended use.
  • a wipe comprising a hydroxide ion scavenging system and/or an IFT-lowering system is sprayed with a halogen dioxide solution prior to an intended use.
  • the systems and/or solutions disclosed herein are formulated into an aerosol and/or gaseous phase, adapted to fumigate a surface and/or area for which the conveyance of stabilized and/or efficacious halogen dioxide is desired.
  • a halogen dioxide solution is presented in an aerosol and/or gaseous phase.
  • a hydroxide ion scavenging system- comprising halogen dioxide solution and/or an IFT-lowering system-comprising halogen dioxide solution is presented in an aerosol and/or gaseous phase.
  • a hydroxide ion scavenging system- comprising halogen dioxide solution and/or an IFT-lowering system-comprising halogen dioxide solution is presented in an aerosol and/or gaseous phase.
  • the halogen dioxide solution, hydroxide ion scavenging system-comprising halogen dioxide solution and/or an IFT-lowering system-comprising halogen dioxide solution disclosed herein are presented in a solid phase for conveyance to a target surface.
  • Example 1 Chlorine Dioxide Solution Comprising a Hydroxide Ion Scavenging System.
  • the following is an example of a chlorine dioxide solution containing a hydroxide ion scavenger in the form of citric acid. This solution contains about 120 ppm chlorine dioxide.
  • Example 2 Chlorine Dioxide Solution Comprising a Surfactant System
  • Example 3 Chlorine Dioxide Solution Comprising a Surfactant System
  • a chlorine dioxide solution containing the nonionic surfactant APG or AlkylPolyGlucoside (trade name Glucopon). This solution contains about 120 ppm chlorine dioxide.
  • Example 4 Chlorine Dioxide Solution Comprising a Hydroxide Ion Scavenging System and Surfactant System
  • a hydroxyl ion source is added to interact with the citric acid and adjust the mix pH to about 4. This solution contains about 100 ppm chlorine dioxide.
  • Example 5 Device Comprising hydroxide ion scavenging and Surfactant Systems
  • An electrolysis cell of the general design depicted in Figure 1 of copending US Patent Application Serial Number 09/947,846 (published 20 September 2001 and incorporated herein by reference) was used to convert an aqueous solution comprising sodium chlorite into an effluent solution comprising chlorine dioxide.
  • the electrolysis cell had a pair of confronting electrodes having a passage gap of about 0.19 mm.
  • the anode was made of ES300 - titanium, coated with ruthenium oxide and iridium oxide.
  • the cathode was made of 201 stainless steel.
  • the dimensions of the planar electrodes were 75.2 mm long by 25.4 mm wide.
  • the aqueous feed solution was prepared by mixing 10 liters of de-ionized water with 62.6 gms technical grade sodium chlorite stock (80% active, Aldrich Chemical Company, Inc, Milwaukee, WI 53233; Cat. No. 24415-5) with a stirring bar until dissolved, forming a 5000 ppm sodium chlorite salt solution.
  • the aqueous feed solution was retained in a 15 -liter glass container placed within a light-proof box and cooled to 5 degrees Celsius.
  • a peristaltic pump metered the aqueous feed solution from the glass container through the electrolysis cell at a flow rate of 300 ml/minute.
  • a direct current of 5.72 amps was applied across the electrodes by a DC power supply to provide a voltage potential of 4.5 volts across the electrolysis cell.
  • the effluent solution was withdrawn from the electrolysis cell and analyzed.
  • the effluent contained 109 ppm chlorine dioxide and 4891 ppm of un-reacted sodium chlorite, for a chlorite conversion of 2.9%.
  • the following examples were prepared to document use of a single solution containing hydroxide ion scavengers and a surfactant system capable of running through a sprayer device equipped with an electrolysis cell to generate chlorine dioxide from sodium chlorite in the solution.
  • a phosphate based version and carbonate based version are presented.
  • the solutions comprise a pH between about 6 and 7 before the electrolysis, and maintained a pH between 6 and 9 after electrolysis is conducted.
  • the discharge from the electrolysis cell and pump was estimated to have a chlorine dioxide level of 85 ppm. This solution can also be recycled through the cell/pump to further increase the chlorine dioxide concentration.
  • the effluent from the cell/pump was subsequently discharged through a atomizing spray nozzle to create a fine mist of chlorine dioxide containing particles. The mist can be used to cover surfaces for treatment, or confined in a enclosed area to have a "fumigation" effect.
  • composition I was electrolyzed while being pumped through an electrolytic plate using 6.6 volts. A final mixture was then created comprising 83% of electrolyzed composition I and 17% deionized water.
  • composition I was electrolyzed while being pumped through an electrolytic plate using 6.6 volts. A final mixture was then created comprising 83% of electrolyzed composition I and 17% composition II.
  • composition I was electrolyzed while being pumped through an electrolytic plate using 6.6 volts. A final mixture was then created comprising 83% of electrolyzed composition I and 17% composition III.
  • composition I was electrolyzed while being pumped through an electrolytic plate using 6.6 volts. A final mixture was then created comprising 83% of electrolyzed composition I and 17% composition IV.
  • Organism S. aureus
  • Target C10 2 solution concentration 50 ppm
  • Organism P. aeruginosa
  • Target C10 2 solution concentration 50 ppm
  • Example J Composition VI was electrolyzed while being pumped through an electrolytic plate using 6 volts. A final mixture was then created comprising 50% of electrolyzed composition VI and 50% deionized water.
  • Example K Composition VI was electrolyzed while being pumped through an electrolytic plate using 6 volts. A final mixture was then created comprising 50% of electrolyzed composition VI and 50% composition VIII.
  • Example L Composition VI was electrolyzed while being pumped through an electrolytic plate using 6 volts. A final mixture was then created comprising 50% of electrolyzed composition VI and 50% composition VII.
  • Organism Bacillus cereus spores C10 2 solution concentration: ⁇ 85 ppm 5 minute treatment time
  • Example 6 Stable and efficacious chlorine dioxide mixes produced from a spray bottle having two compartments
  • Solutions M and N are in the separate compartments and are mixed together by a small centrifugal pump pulling equal amounts from each compartment and mixing together at the suction, and further in the pump.
  • the product is discharged from the pump through a spray nozzle.
  • the discharge mixture has formed chlorine dioxide as a result of mixing the two components M+N, and the mix has the characteristic yellow appearance of a chlorine dioxide solution which stays stable and with the surfactant represents an effective antibacterial product.
  • the hydraulic diameter is four times the Hydraulic radius.
  • the hydraulic radius For a parallel plate channel of width w, and spacing s, the hydraulic radius would be w*s/(2*(w+s)).
  • D h becomes about 2s.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des compositions et des procédés permettant d'augmenter la stabilité et/ou l'efficacité du dioxyde de chlore, notamment, du dioxyde de chlore engendré par le biais d'une électrolyse du chlorite. Cette invention a aussi pour objet des dispositifs d'électrolyse qui servent à produire du dioxyde de chlore et qui comprennent les compositions de stabilisation et d'augmentation de l'efficacité, ainsi que des procédés d'utilisation des compositions et des dispositifs susmentionnés.
PCT/US2004/015730 2003-05-19 2004-05-19 Compositions, dispositifs et procedes de stabilisation et d'augmentation de l'efficacite de solutions de dioxyde d'halogene WO2004103898A1 (fr)

Priority Applications (5)

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JP2006514897A JP2006526076A (ja) 2003-05-19 2004-05-19 二酸化ハロゲンを安定化させ、且つその有効性を増大させる、組成物、装置、及び方法
MXPA05012437A MXPA05012437A (es) 2003-05-19 2004-05-19 Composiciones, dispositivos y metodos para estabilizar e intensificar la eficacia del dioxido de halogeno.
BRPI0410758-6A BRPI0410758A (pt) 2003-05-19 2004-05-19 composições, dispositivos e métodos para estabilizar o dióxido de halogênio e aumentar sua eficácia
CA002522576A CA2522576A1 (fr) 2003-05-19 2004-05-19 Compositions, dispositifs et procedes de stabilisation et d'augmentation de l'efficacite de solutions de dioxyde d'halogene
EP04752705A EP1626928A1 (fr) 2003-05-19 2004-05-19 Compositions, dispositifs et procedes de stabilisation et d'augmentation de l'efficacite de solutions de dioxyde d'halogene

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US47167003P 2003-05-19 2003-05-19
US60/471,670 2003-05-19

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US (1) US20040231977A1 (fr)
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CN (1) CN100377991C (fr)
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EP4196180A4 (fr) * 2020-08-17 2024-09-25 Lifeclean Int Ab Composition d'aérosol pour éliminer des micro-organismes pathogènes

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JP6033082B2 (ja) 2009-06-15 2016-11-30 オキュラス イノヴェイティヴ サイエンシズ、インコーポレイテッド 次亜塩素酸を含有する溶液及びその使用方法
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UA118554C2 (uk) * 2013-03-15 2019-02-11 Соленіс Технолоджис Кайман, Л.П. Синергетичні суміші антимікробних засобів, корисні для контролю мікроорганізмів у промислових процесах
CN103334117B (zh) * 2013-06-27 2016-02-03 陈维军 一种高效电解法的二氧化氯发生器
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JP2009528351A (ja) * 2006-02-28 2009-08-06 ビーエーエスエフ、カタリスツ、エルエルシー 二酸化塩素ベースのクリーナー／清浄薬
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CA2522576A1 (fr) 2004-12-02
KR20060009355A (ko) 2006-01-31
BRPI0410758A (pt) 2006-06-27
MXPA05012437A (es) 2006-01-30
US20040231977A1 (en) 2004-11-25
CN1787963A (zh) 2006-06-14
JP2006526076A (ja) 2006-11-16
EP1626928A1 (fr) 2006-02-22
CN100377991C (zh) 2008-04-02

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