CN100377991C - Compositions, devices and methods for stabilizing and increasing the efficacy of halogen dioxide solutions - Google Patents
Compositions, devices and methods for stabilizing and increasing the efficacy of halogen dioxide solutions Download PDFInfo
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- CN100377991C CN100377991C CNB2004800129712A CN200480012971A CN100377991C CN 100377991 C CN100377991 C CN 100377991C CN B2004800129712 A CNB2004800129712 A CN B2004800129712A CN 200480012971 A CN200480012971 A CN 200480012971A CN 100377991 C CN100377991 C CN 100377991C
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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
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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
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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Abstract
Compositions and methods for increasing the stability and/or efficacy of chlorine dioxide, and particularly chlorine dioxide generated via electrolysis of chlorite. The present invention further relates to electrolysis devices for producing chlorine dioxide, comprising the stabilizing and efficacy-increasing compositions of the present invention, as well as methods of using both the chlorine dioxide-stabilizing and efficacy-increasing compositions and devices disclosed herein.
Description
Invention field
The present invention relates to increase the halogen dioxide solutions especially composition and the method for dioxide peroxide stability and effect, wherein halogen dioxide solutions produces by electrolysis halogen dioxide solutions (especially dioxide peroxide) salt.The invention further relates to the electrolyzer that produces halogen dioxide solutions (comprising the effect composition that stabilizes and increases of the present invention), and the stabilize and increase using method of effect composition and device of halogen dioxide solutions disclosed herein.
Background of invention
Dioxide peroxide, ClO
2, be to be used for industry and family expenses to handle with application and be used for one of the most effective SYNTHETIC OPTICAL WHITNER of the commodity and the consumer's goods.The strong oxidizing potential of this molecule makes it be suitable for various application, comprising sterilization, sterilization and bleaching.Concentration known be low to moderate 1,000,000/(ppm) or lower aqueous solution of chlorine dioxide can kill the various microorganism that comprises bacterium, virus, mould, fungi and spore etc.Height can provide stronger sterilization, whitening capacity and make multiple compound oxidation to the dioxide peroxide of the greater concn of hundreds of ppm in multiple application, these application comprise: the processing of the sterilization of papermaking and paper pulp industry, wastewater treatment, Treatment of Industrial Water (for example water coolant), fruit and vegetable, sulfiting, textile industry and the medical waste of petroleum industry.
Compare with chlorine with normally used bleaching material such as hypochlorite, dioxide peroxide has more advantage.Dioxide peroxide can and decompose it with the phenolic compound reaction, thereby removes taste and smell that the middle phenols that anhydrates produces.Dioxide peroxide can also be used for processing drinking water and waste water, to eliminate prussiate, sulfide, aldehyde and mercaptan.With regard to available chlorine, ClO
2Oxidation capacity be 2.5 times of chlorine.Equally, with to it is believed that chlorine/hypochlorite will diminish greater than 7 o'clock biocidal efficacies in the pH value different, the biocidal efficacies that it is believed that dioxide peroxide is still can remain valid in 7 to 10 o'clock in the pH value.In addition, dioxide peroxide can be in suitable concentration range (promptly about 100ppm to 200ppm) make latent whip sporozoite worm inactivation in the water, and chlorine/hypochlorite can not make the latent whip sporozoite worm inactivation in the water owing to conceal the resistibility of whip sporozoite worm to them.Hypochlorite and chlorine all are that the chlorine molecule comes and bleached goal response by inserting in the structure of being bleached target.Although this reactive mode can be effective, this can cause producing one or more chlorizates or by product, and this all is not wish to occur from safety and environmental still from economic angle (removing dealkylation from reaction media).In addition, bleach with hypochlorite and chlorine the SYNTHETIC OPTICAL WHITNER material self is damaged, just need to replenish again chlorine bleach in the therefore follow-up bleaching process.Another shortcoming is that some wants can develop immunity to drugs along with the time with the microorganism that these two kinds normally used bleaching things kill, particularly under the lower situation of the concentration ratio of chlorine or hypochlorite.
Be generally used for the chlorine dioxide content maximum about 1% in the aqueous solution.Because its weak stability and severe corrosive, thereby it is become be difficult to the trouble material that the high concentration solution transports and operates.This just need prepare dioxide peroxide immediately by the final user, adopts precursor compound usually, for example Textone (NaClO
2) or sodium chlorate (NaClO
3).The typical method that utilizes kusa-tohru to prepare dioxide peroxide is an acid catalyzed reaction:
NaClO
3+2HCl→NaCl+1/2Cl
2+ClO
2+H
2O
The easier dioxide peroxide that is converted into of Textone.The typical method that utilizes sodium chlorite salt to make dioxide peroxide is to adopt acid catalyzed reaction:
5NaClO
2+4HCl→4ClO
2+5NaCl+2H
2O
Except that the novel instant generating apparatus that need further be identified for halogen dioxide solutions (especially dioxide peroxide), the demand of going back no less important is to determine to be suitable for to stabilize and increase the composition of the effect of halogen dioxide solutions (especially dioxide peroxide) solution after generating.In some cases, use above-mentioned composition to reduce the needs of instant generation dioxide peroxide by making " life-span " maximization of pregenerated active ClO 2 solution.In other cases, the effect composition of determining to stabilize and increase can generate the stability and the maximizing performance that make them after (no matter being by electrolysis or other method) immediately at halogen dioxide solutions solution.Under any circumstance, halogen dioxide solutions of the present invention stabilize and increase the effect compositions-treated and solved with current dioxide peroxide use relevant, especially with the relevant predicament of halogen dioxide solutions solution weak stability.
Summary of the invention
The present invention relates to stabilize and increase or generation or composition, the apparatus and method of halogen dioxide solutions (especially dioxide peroxide) the solution effect of generation in advance immediately.Hydroxide ion is removed liquid to the effect composition that stabilizes and increases of the present invention and/or interfacial tension (IFT) weakens in the halogen dioxide solutions solution that agent is incorporated into or generate in advance or generate immediately.In halogen dioxide solutions (especially dioxide peroxide) solution, mix hydroxide ion and remove liquid, on adjusting gained solution-pH, play a key role, thereby compare, can stablize gained solution for more time with the situation of not using hydroxide ion to remove system.In addition, it is believed that interfacial tension (IFT) is weakened agent to be removed system with hydroxide ion or mix alone in the halogen dioxide solutions solution, can make performance, microbial resistance or the like the maximization of gained mixture.
Therefore, as described in a first aspect of the present invention, disclose and be used to increase the especially composition of dioxide peroxide stability and/or effect of halogen dioxide solutions.On the one hand, the composition that is used for stablizing or generating or generate immediately in advance ClO 2 solution that uses hydroxide ion to remove system is disclosed.On the other hand, disclose and mixed the composition that is used to increase ClO 2 solution effect, microbial resistance or the like that interfacial tension (IFT) weakens agent.In another aspect of this invention, disclose and mix hydroxide ion and remove halogen dioxide solutions (especially dioxide peroxide) solution that system and interfacial tension (IFT) weaken agent.In others of the present invention, of the present invention stable and/or increase the effect composition and also further comprise one or more ancillary components, be used to gained halogen dioxide solutions solution that some attractive in appearance and/or performance beneficial effect is provided.
In another aspect of this invention, disclose and be used for instant generating stable and the effective electrolyzer of halogen dioxide solutions (especially dioxide peroxide).In one aspect of the invention, described device mixes hydroxide ion and removes system, with the stable halogen dioxide solutions that is wherein generated.In another aspect of this invention, electrolyzer disclosed herein mixes interfacial tension (IFT) and weakens agent, so that the effect maximization of halogen dioxide solutions after generation.In another aspect of this invention, electrolyzer disclosed herein mixes that hydroxide ion is removed liquid and interfacial tension (IFT) weakens agent.The accurate configuration of device and/or the character of composition will be decided by the needs of formulator and/or the purposes of ability and this device of plan use.
In another aspect of this invention, disclose and be used for stable and/or increase or generate in advance or the method for instant halogen dioxide solutions (especially dioxide peroxide) the solution effect that generates.In one aspect of the invention, provide to be used for stablizing halogen dioxide solutions, especially the method for dioxide peroxide.In another aspect of this invention, provide the increase halogen dioxide solutions, especially the method for dioxide peroxide effect.In others, provide the method for using present composition sterilization and/or clean surface.Described method is usually directed to composition one or more aforementioned halogen dioxide solutions is stable and/or that increase its effect and is applied to and needs to increase in the halogen dioxide solutions solution of stability and/or effect.In another aspect of this invention, method disclosed herein relates to the use electrolyzer, uses the present composition to stablize and/or increase the effect of the instant halogen dioxide solutions that generates.Other method disclosed herein relates to the device and the composition of use, to be administered on the matrix that needs sterilization and/or cleaning.The definite step of (with hereinafter further discussing) disclosed herein every kind of method will depend on need mix it stable in halogen dioxide solutions solution and/or increase the concrete needs of effect composition, formulator and/or the application of ability and needs use the inventive method.
Provide dioxide peroxide to generate and recirculation system more on the one hand of the present invention, comprising: a) material aqueous solution source comprises the salt of dioxide peroxide; B) diaphragmless cell comprises anode and negative electrode, and has the chamber, pond of tape entry and outlet; C) parts, these parts make material aqueous solution flow to chamber, described pond, and flow through near described anodic passage, flow out described outlet then; D) current source, this current source make flow through the aqueous solution between described anode and described negative electrode of electric current, so that the described titanium dioxide villaumite of at least a portion in the described passage is converted into dioxide peroxide, thereby form the moisture effluent that comprises dioxide peroxide; E) parts, the moisture effluent of this parts delivery makes it contact with the target compound that consumes dioxide peroxide, thereby makes the described consumption target compound of a part of dioxide peroxide oxidation in the moisture effluent, and restores to the titanium dioxide villaumite; F) the consumption effluent that parts, these parts will comprise described recovery titanium dioxide villaumite is back to described source; And g) parts, this parts delivery hydroxide ion is removed system, to stablize described ClO 2 solution; Or this parts delivery IFT weakens system, with stability and/or the effect that increases described ClO 2 solution.
In others of the present invention, the various product forms and/or the physical form of solution described herein and/or system also disclosed.In one aspect of the invention, the cleaning piece that comprises solution described herein and/or system is disclosed.In another aspect of this invention, provide solution as herein described and/or system with gas form.In another aspect of this invention, provide solution as herein described and/or system with solid form.In another aspect of this invention, provide solution as herein described and/or system with the gel preparation form.
Detailed Description Of The Invention
" stablizing " used herein is intended to refer to use hydroxide ion removing system to regulate the hydroxide ion concentration of described solution in halogen dioxide solutions (preferred dioxide peroxide) solution, so that the stability of gained solution is greater than the stability of the halogen dioxide solutions solution that does not use above-mentioned system.In this regard, term " stability of increase " is intended to refer to the concentration of the halogen dioxide solutions solution of hydroxyl-containing ion removing system at 25 ℃ of halogen dioxide solutions that record after preparing three hours down, than the corresponding halogen dioxide solutions that does not comprise stabilising system 25 ℃ down the concentration height of the halogen dioxide solutions that record after three hours of preparation at least about 5%, preferably at least about 10%.
" increase effect " used herein is intended to refer to that hydroxide ion scavenging agent and/or IFT are weakened agent to be mixed in halogen dioxide solutions (especially dioxide peroxide) solution, to send one or more antimicrobial properties and/or beneficial effect attractive in appearance to described solution.Described beneficial effect includes, but not limited to increase antimicrobial kill ratio and/or logarithm kill ratio in the antimicrobial solutions, improves the odor eliminating effect, selective bleaching or color change, and their combination.In this regard, term " antimicrobial properties of increase " is intended to refer to that hydroxyl-containing ion scavenging agent and/or IFT weaken the halogen dioxide solutions solution of agent on microbe population reduces, than not comprising corresponding halogen dioxide solutions solution that hydroxide ion scavenging agent or IFT weaken agent greatly at least about 5%, preferably at least about 10%.
" hydroxide ion removing system " used herein is intended to any reagent that finger can be used in halogen dioxide solutions (or dioxide peroxide) solution and increase described stability of solution after above-mentioned application, especially when the stability with this solution that does not mix the hydroxide ion scavenging agent compares.In fact, compare (equally 25 ℃ and its preparation measurement after three hours) with the concentration of the corresponding halogen dioxide solutions that does not comprise stabilising system, hydroxide ion scavenging agent of the present invention and/or system are suitable in preparation under 25 ℃ the concentration of halogen dioxide solutions being increased at least about 5%, preferably at least about 10%.
Phrase used herein " IFT weakens agent " and/or " IFT system " are intended to refer to that one or more are suitable for mixing in halogen dioxide solutions (especially dioxide peroxide) solution reagent with the effect that increases described solution, microbial resistance etc.Be applicable to that the reagent that the present invention increases in the composition of efficacy of halogen dioxide solutions will discuss hereinafter in more detail.
Term used herein " pregenerated " or " pre-generate " are intended to refer to before it desires to be used to be preferably greater than about 2 hours greater than about 3 hours, more preferably greater than about 1 hour, generate halogen dioxide solutions, more particularly are dioxide peroxide.Above-mentioned generation can be carried out in the place different with the place of needs use dioxide peroxide, but also can carry out in the place identical with desiring the place to use.
Term used herein " immediately " is intended to refer to before desiring to be used, to be more preferably less than and to generate halogen dioxide solutions (or dioxide peroxide) in about 1 hour preferably less than about 2 hours less than about 3 hours.In one aspect of the invention, " immediately " is intended to refer to generate halogen dioxide solutions in less than about 1 second.By using as electrolyzer hereinafter disclosed and that describe, can realize typically that " immediately " of dioxide peroxide generates.
Term used herein " cleaning and/or sterilization " is intended to refer to for removing and/or the harmful contaminants of passivation is used (optional remove then) method for compositions to surface or environment.
Remove an embodiment of system at the hydroxide ion that is used for the stabilized chlorine chlorine solution of the present invention, this system comprises: by the described gross weight that comprises the chlorine dioxide precursor solution of hydroxide ion scavenging agent, about 0.001% to about 10% hydroxide ion is removed one or more haloid precursors of system and about 0.000001% to about 50%.
In another embodiment of the above-mentioned system of the present invention, comprise: by the described gross weight that comprises the ClO 2 solution of hydroxide ion scavenging agent, about 0.001% to about 10% hydroxide ion is removed the dioxide peroxide of system and about 0.000001% to about 1%.
Be used for composition stable and/or the increase efficacy of halogen dioxide solutions
Hydroxide ion is removed system
In a first aspect of the present invention, the composition that is used for stablizing and/or increasing halogen dioxide solutions (especially dioxide peroxide) effect is disclosed.In one aspect of the invention, above-mentioned composition comprises hydroxide ion removing system.Hydroxide ion removing system of the present invention comprises the hydroxide ion reagent, and it is suitable for regulating the pH value of its ClO 2 solution that adds.Regulate the pH value of ClO 2 solution by adding the hydroxide ion reagent, this solution has long stability.Not bound by theory, it is believed that this long stability is attributable to the reduction of hydroxide ion concentration in the solution, to weaken the interaction of itself and dissolved chlorine dioxide.This stable for a long time possibility that also relates to acid-reaction under low pH value.Reduce hydroxide ion concentration with stabilizing chlorine dioxide, can be used for the solution of quiescent solution and experience high-shear, as under the situation of spraying of halogen dioxide solutions solution turbulent flow or atomizing.
Usually, remove the gross weight of the ClO 2 solution of system by described hydroxyl-containing ion, with about 0.001% to about 10%, preferred 0.01% to about 7.5%, more preferably 0.05% to about 5%, and most preferably 0.1% to about 2.5% content is applied to hydroxide ion removing system of the present invention in the ClO 2 solution.Those of ordinary skill in the art is easy to recognize, the exact amount of the hydroxide ion scavenging agent that the stabilized chlorine chlorine solution is required will depend on many factors, include but not limited to the generation method of the halogen dioxide solutions solution of the character of hydroxide ion scavenging agent, the concentration that need send the halogen dioxide solutions solution that increases stability and consideration.Be applicable to that hydroxide ion scavenging agent of the present invention is selected from: salt of organic acid, organic acid salt, mineral acid, mineral acid or the like.It should be noted that hydroxide ion scavenging agent of the present invention is suitable for stablizing any halogen dioxide solutions solution.
Interfacial tension (IFT) weakens system
In another aspect of the present invention, disclose and be used for interfacial tension (IFT) stable and/or that increase halogen dioxide solutions solution effect and weaken system.Not bound by theory, it is believed that adding one or more IFT in halogen dioxide solutions (especially dioxide peroxide) solution weakens agent, can provide the whole structure that increases described solution effect by reducing the interfacial tension of gained system.Not bound by theory, it is believed that IFT of the present invention weaken agent be suitable for reducing by two things mutually between at the interface tension force, thereby reduce required merit and/or the energy level in expansion interface.It is believed that IFT of the present invention weakens the agent utilization and reduces ability that energy promotes interface expansion and help the infiltration of halogen dioxide solutions (especially dioxide peroxide) and interface and expose and increase.In addition, IFT of the present invention weakens agent and shows to have the synergy consistent with halogen dioxide solutions, thereby helps making microorganism structure and protein denaturation.It is believed that also use can form the tensio-active agent of individual layer tensio-active agent at the atmosphere contact surface, to regulate and distribute the halogen dioxide solutions in the ambient air.This may be to comprising the situation particularly important that IFT of the present invention weakens the halogen dioxide solutions solution of agent via chamber, atomizer or miscellaneous equipment use under the decontamination situation.
Weaken agent according to used spraying plant and IFT, the spray particle diameter that can regulate and optimize the halogen dioxide solutions aqueous solution is to be used for special applications.Sometimes, very little particle diameter can make the barrier effect that surface-area increases to is enough to overcome tensio-active agent, thereby helps lend some impetus to halogen dioxide solutions (especially dioxide peroxide) in the distribution of gas/air in mutually.In the case, take place that dioxide peroxide exposes the transition that exposes to the gas phase dioxide peroxide from water, this can be of value to this theme composition is delivered to and uses the inaccessible zone of aqueous dispersion.Do not wishing also to need to use small particle size under matrix and the situation that the aqueous solution contacts.Equally, a large amount of foams can be used as additional physical barriers on the surface, to prevent that halogen dioxide solutions is from the solution loss of air towards periphery.
Certainly, the present invention IFT of increasing effect definite composition of weakening system will depend on that needs use the purposes of gained ClO 2 solution and the needs and/or the ability of formulator.Yet, weaken the gross weight of the halogen dioxide solutions solution of system by the described IFT of containing, preferably with about 0.00001% to about 10%, preferred about 0.0001% to about 5%, more preferably from about 0.0005% to about 2%, and most preferably 0.001% to about 1% content weakens system with IFT of the present invention and/or weakens agent and mix in the halogen dioxide solutions solution.Certainly, in an especially preferred embodiment of the present invention, with above-mentioned listed amount IFT disclosed herein is weakened agent and mix in the ClO 2 solution that needs increase stability and/or effect.
Can use the IFT of multiple various kinds to weaken agent and stablize and/or increase the effect of halogen dioxide solutions solution as described in the present invention.Though comprised a little mentioned reagent herein, it will be appreciated that other reagent can be the beneficial effect that halogen dioxide solutions solution that they add provides similar increase halogen dioxide solutions solution effect.In fact, for the purpose of the present invention, exist some classes to can be used as the reagent that IFT weakens agent.These kinds include, but are not limited to, and: IFT weakens that polymkeric substance, IFT weaken solvent, IFT weakens tensio-active agent, and their combination.Of the present invention one especially preferred aspect, IFT is weakened tensio-active agent is used for halogen dioxide solutions solution, weaken the above-mentioned beneficial effect that agent provides to send by IFT of the present invention disclosed herein.The IFT that is used to increase halogen dioxide solutions solution effect disclosed herein and/or performance weaken tensio-active agent can be non-ionic, anionic, amphoteric, amphipathic, zwitterionic, cationic, semi-polarity is non-ionic, and their mixture.The non-limiting example of above-mentioned tensio-active agent is disclosed in United States Patent (USP) 5,707, in 950 and 5,576,282, these documents is incorporated herein by reference.The exemplary list of negatively charged ion, nonionic, both sexes and amphoteric ionic surfactant and these kinds of surfactants is provided in to authorize in the United States Patent (USP) 3,664,961 of Norris on May 23rd, 1972, and is incorporated herein by reference.
Can be used for the non-limiting example that IFT of the present invention weakens tensio-active agent and comprise that conventional EO is about C of 1 to 22
8-C
18Alkylethoxylate and/or alcohol ethoxylate (AE) comprise so-called narrow peak alkylethoxylate and C
6-C
12Alkyl phenolic alkoxy thing (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), alkyl dialkyl group amine oxide, alkyloyl glucamide, C
11-C
18(straight chain) alkylbenzene sulfonate (LAS) and primary alkyl, secondary alkyl and random alkyl-sulphate (AS and/or SAS), C
10-C
18Alkyl alkoxy sulfate (AES), C
10-C
18Alkyl polyglycoside and their corresponding sulfation poly glucosides (APG), C
12-C
18α-sulfonated fatty acid ester, C
12-C
18Alkyl and alkyl phenolic alkoxy thing (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C
12-C
18Trimethyl-glycine and sultaine (" sultaine "), C
10-C
18Amine oxide, alpha-olefin sulphonate (AOS), alcohol ethoxy vitriol, paraffin sodium sulfonate, amine propyl group amine, alkyl N-methylglucosamine, nitrilotriacetic acid(NTA) (NTA), an alkali metal salt of natural acid etc.The useful tensio-active agent of other routine is listed in the standard textbook.
In another aspect of this invention, IFT being weakened polymkeric substance and/or IFT weakens in halogen dioxide solutions (especially dioxide peroxide) solution that solvent mixes the stability that need send increase and/or effect.Be applicable to that IFT in the context of the invention weakens polymkeric substance and includes but not limited to: polyalkylene block copolymers.In fact, in the context of the invention, be suitable for the IFT that weakens agent as IFT and weaken solvent and include but not limited to: glycol ether, as the propylene glycol positive propyl ether.Certainly, the selection that the suitable IFT that is used for the context of the invention weakens agent will depend on a number of factors, and wherein some comprise: (1) halogen dioxide solutions and IFT weaken chemical compatibility enough between the agent; (2) need send the character of the halogen dioxide solutions solution that increases stability and/or effect; (3) need use to contain the purposes that gained IFT weakens the halogen dioxide solutions solution of agent; (4) needs of present composition formulator and/or ability.
Hydroxide ion is removed system and IFT
In another aspect of this invention, halogen dioxide compositions disclosed herein comprises that hydroxide ion is removed system and IFT weakens system.Above-mentioned composition is suitable for stablizing for a long time halogen dioxide solutions (especially dioxide peroxide), and sends some attractive in appearance and/or performance beneficial effect to described solution.In fact, be surprisingly found out that and be, to demonstrate synergy by in halogen dioxide solutions solution, using hydroxide ion to remove system simultaneously and IFT weakens system by disclosure of invention proof.Not bound by theory, it is believed that hydroxide ion scavenging agent and IFT weaken the dual use of agent such as tensio-active agent, promote surface-area to cover maximization by reducing interfacial tension, keep higher intrinsic halogen dioxide substrate concentration by suppressing degraded simultaneously, make the maximized whole structure of sending to required interface of halogen dioxide solutions amount thereby provide.In fact, when being used in combination hydroxide ion of the present invention and removing system and I FT and weaken system, remove the gross weight of the ClO 2 solution of system and surfactant system by described hydroxyl-containing ion, its content is about 0.00001% to about 15%, preferred about 0.0001% to about 10%, more preferably from about 0.0005% to about 5%, and most preferably from about 0.001% to about 2.5%.
Ancillary component
In another aspect of this invention, the halogen dioxide solutions effect composition that stabilizes and increases that is used for disclosed herein also will comprise one or more ancillary components, to provide attractive in appearance to resulting composition and/or the performance beneficial effect.In one aspect of the invention, comprise hydroxide ion remove the composition of system will comprise one or more ancillary components (such as hereinafter further argumentation).In another aspect of this invention, comprise the composition that IFT weakens system and will comprise one or more ancillary components.In another aspect of this invention, ancillary component disclosed herein is mixed comprise that hydroxide ion is removed system and IFT weakens in the halogen dioxide solutions solution of system.
Though be not that the object of the invention is necessary, the cleaning auxiliary substance of the some routines that hereinafter illustrate is applicable in the present composition, and can mix aptly in the preferred embodiment of the invention, for example, to promote or to improve clean-up performance, handle substrate to be cleaned, or improve the aesthetic property of the present composition usually with spices, tinting material, dyestuff etc.The definite character of these annexing ingredients and the amount of adding thereof, the physical form that will depend on composition with and use the character of the clean operation that is intended to use it.
The ancillary component that is suitable for mixing in halogen dioxide solutions of the present invention (especially dioxide peroxide) effect that the stabilizes and increases composition comprises; but be not limited to: as United States Patent (USP) 5; 705; 464; 5; 710; 115; 5; 698; 504; 5; 69 5; 679; 5; 686,014 and 5,646; bleach system described in 101; enzyme and enzyme stabilizers; washing assistant; dispersion agent; stain remover; sequestrant; suds suppressor; tenderizer; dye transfer inhibitor; not phosphatic washing assistant; the color spot agent; the silverware protective material; rust-preventive agent and/or corrosion inhibitor; dyestuff; weighting agent; sterilant; the basicity source; hydrotropic agent; antioxidant; spices; solubilizing agent; carrier; processing aid; pigment and pH regulator agent, these patents all are incorporated herein by reference.
The device that comprises the effect composition that stabilizes and increases
In another aspect of this invention, the device that comprises the stable of aforementioned aspect and/or increase the effect composition is disclosed.Described device is limited to usually and is suitable for generating those of halogen dioxide solutions by halogen dioxide solutions salt precursor instant (definition as mentioned).Yet the effect composition that stabilizes and increases of the present invention can be further used for stable and/or increase the pre-effect that generates halogen dioxide solutions.The complete description that is fit to unite the electrolyzer of use with the effect composition that stabilizes and increases of the present invention is included in U.S. Patent Application Serial 09/947, in 846, it submits to United States Patent and Trademark Office September 20 calendar year 2001, and announces on January 9th, 2003.This application for patent is introduced the present invention for your guidance in full.
In one aspect of the invention, be suitable for and the electric current of stablizing and/or increase the common instant generating apparatus application of using of effect system by material aqueous solution between anode and the negative electrode disclosed herein, change the halogen dioxide solutions salt precursor that is dissolved in the solution into halogen dioxide solutions.When water solution flow through the electrolyzer chamber, and when having electric current to pass through between anode and the negative electrode, some chemical reactions take place in other salt and ion of the water that comprises in the solution and one or more.The further feature of these chemical reactions and the generating apparatus that can use in this respect as described herein is described in the common unsettled U.S. Patent Application Serial 09/947,846, and it submits to United States Patent and Trademark Office September 20 calendar year 2001.In view of the above, this paper applicant introduces the theme of this patent application, and especially it relates to the disclosure of the definite feature of instant generating apparatus that is used for the context of the invention.
Comprise the multicellular electrolyzer
In another aspect of this invention, U.S. Patent application 09/947, instant generating apparatus described in 846 (and being incorporated herein by reference) also can comprise additional chamber, and it helps mixing more than one solution, to form the effect composition that stabilizes and increases of the present invention.In fact, when the pH value of using chlorite and total mixture to have less than about 7 and preferably less than about 5 the time, isolate theme composition to delay to mix when the needs use gained halogen dioxide solutions solution, be particularly useful.In one aspect of the invention, by isolating chlorite solution and low pH value surfactant soln, can reach this purpose.In another aspect of this invention, comprise the chlorite solution of tensio-active agent and the low pH value solution that another kind has other composition, can reach this purpose by isolation.
Under the situation that this " immediately " generates, electrolysis as described in the present invention can take place in many ways.Yet under any circumstance, electrolysis should occur in following current place of chlorite based sols or gained mixture.In one aspect of the invention, by mixing two kinds of liquid streams, electrolysis chlorite (rock salt) liquid stream can be realized this purpose subsequently.In another aspect of this invention, also can comprise chloritic total mixture in described mixing back electrolysis, realize instant electrolysis by mixing two kinds of liquid streams.
Implementer of the present invention will know, has some above-mentioned essential blended mechanisms that are suitable for realizing.In one aspect of the invention, can use and a kind ofly be suitable for producing the general service pump that enough suction extracts two kinds of liquid streams and realize essential mixing.In another aspect of this invention, also can use pump to extract a kind of liquid stream, and mix with the Venturi meter extraction and with another kind of liquid stream in its discharging back.In another aspect of this invention, also available two pumps suck blended part-streams behind using pump.In another aspect of this invention, can before or after pump or Venturi meter, carry out electrolysis.Yet more practical usually is to be pumped the back use at all liquid streams and to be suitable for carrying out electrolytic device, with any harmful effect that prevents from by the gas that produces in electrolytic process pump performance to be caused.
In another aspect of this invention, the stabilize and increase device of effect composition of preparation is not limited to form halogen dioxide solutions (dioxide peroxide) by electrolysis.Specifically, can make up and/or set the aforementioned aspect that relates to more than a kind of solution mixture, generate halogen dioxide solutions by chemical reaction so that mix the back.The non-limiting example of above-mentioned setting comprises that the solution and the rock salt solution that make low pH value mix, and by the rock salt acidifying, help the generation of halogen dioxide solutions.In these cases, preferably less than about 2 pH value, with quick formation halogen dioxide solutions.Another embodiment relate under low pH value with the liquid hypochlorite solutions with comprise excessive chloritic solution and mix, to form dioxide peroxide.In these cases, preferably less than about 4 pH value.Form under the situation of halogen dioxide solutions by chemical process in the mixing of two kinds of (or multiple) liquid stream, can include but not limited to by multiple mechanism, a kind ofly produce the general service pump that suction extracts two kinds of liquid stream, the pump that extracts a kind of liquid stream and use the pump (as indicated above) of back blended part-streams as the Venturi meter that mixes inlet with another kind of liquid stream and two suctions at pump, realize mixing in this liquid stream discharging back.
In another aspect of this invention, when additional chloride salt is used to promote that the chlorine electrolysis is dioxide peroxide, Cl
-Be electrolyzed to produce hypochlorite (OCl
-) side reaction also can control by the hydroxide ion scavenging agent that uses special acid buffer agent form.In one aspect, for example needing therein increases under the situation of antimicrobial efficacy, may need some OCl
-Exist simultaneously with dioxide peroxide.In these cases, by using the hydroxide ion scavenging agent and the final pH value being controlled at about 2 to about 7, can help OCl
-Ion is to the conversion of HOCl.For antimicrobial efficacy, the type that HOCl normally preferably uses.When the pH value be higher than about 7 the time, OCl
-Be main species, and when the pH value be lower than about 2 the time, Cl
2Be main species.Do not need therein under the situation of hypochlorite species existence, but obtain solution produces excessive chlorite, this chlorite does not react because of electrolysis.This excessive chlorite can react with electrolytic HOCl subsequently, forms extra dioxide peroxide.The preferred pH value of this type of reaction is less than about 4.
Virtual barrier film
In another aspect of this invention, electrolyzer also can further comprise parallel-plate electrode as described in the present invention, that this electrode is designed to form is virtual (as accurate, puppet) barrier film.Dummy film of the present invention is not nonvolatil tangible barrier film, but the barrier film of flow-like, and it is that flow characteristics during by the electrolysis of fluid solution experience is formed.Specifically, control the fluid within the electrolyzer parallel plate disclosed herein, so that the Reynolds number relevant with this fluid is less than about 2000.Not bound by theory, it is about 2000 that Reynolds number is kept below, and guaranteed the liquid flow state in the electrolyzer, and it is set to the plane form that is parallel to plate.It is believed that this shape helps the transmission by lateral ion in the solution of adding electromotive force generation, minimize and/or eliminate a large amount of fluids simultaneously and mix, to prevent the approaching and/or reaction of undesirable electrolytic reaction by product perpendicular to electrolytic zinc-coated steel sheet.In electrolyzer context disclosed herein, the description of the virtual diaphragm application of the present invention is provided in " embodiment " part of the disclosure of invention.
Use method stable and/or increase effect composition and electrolyzer
The method of the halogen dioxide solutions that stabilizes and increases (especially dioxide peroxide) effect is also disclosed in another aspect of this invention.The method of stable halogen dioxide solutions solution is disclosed in one aspect.Described method comprises removes step in the halogen dioxide solutions that solution mixes needs to increase stability (preferred dioxide peroxide) solution with the hydroxide ion of first aspect as described herein.In another aspect of this invention, the method that increases halogen dioxide solutions solution effect is disclosed.Described method generally includes and the IFT of first aspect is as described herein weakened agent and/or weaken step in the halogen dioxide solutions that system is mixed needs to increase effect and/or performance (preferred dioxide peroxide) solution.The method of the halogen dioxide solutions solution effect that stabilizes and increases is also disclosed in another aspect of this invention.Described method generally includes to be removed solution and IFT with hydroxide ion and weakens system and/or weaken step in the halogen dioxide solutions that agent joins needs to increase stability and/or effect (preferred dioxide peroxide) solution.
In another aspect of this invention, the method for stablizing and/or increase halogen dioxide solutions (especially dioxide peroxide) the solution effect that produces by electrolysis is disclosed.Described method comprises of the present invention stable and/or increase the effect composition and join in the device (as indicated above) that is suitable for electrolysis rock salt, and promotes described stable and/or increase effect composition and gained halogen dioxide solutions mixture blended step.
The halogen dioxide solutions solution that comprises halogen dioxide solutions solution, hydroxyl-containing ion removing system
And/or contain product and/or the physical form that IFT weakens the halogen dioxide solutions solution of system
The various product forms of solution described herein and/or system also are provided in another aspect of this invention.In fact, in one aspect of the invention, solution described herein and/or system are formulated into gel.This aspect as described in the present invention adds any suitable thickening material by removing the halogen dioxide solutions solution of system to halogen dioxide solutions solution, hydroxyl-containing ion and/or containing in the halogen dioxide solutions solution that IFT weakens system, can prepare gel.Not bound by theory, it is believed that solution of the present invention and/or system are mixed in the above-mentioned gel, can help gel need are sent the target surface of this theme solution and/or system and/or the adhesion of matrix.In addition, not bound by theory, it is believed that system of the present invention is mixed with gel, will cause degraded to reduce by mass transfer and/or the loss of restriction halogen dioxide solutions in atmosphere.The technician of this theme field that the present invention belongs to will be easy to recognize multiple thickening material and the method that is applicable to preparation gel of the present invention.
In another aspect of this invention, also solution as herein described and/or system can be mixed in the cleaning piece product.In this aspect of the invention, by being encapsulated in the reactive species capsule in the cleaning piece or on the cleaning piece, producing halogen dioxide solutions.Then,, this cleaning piece is " activated ", thereby produces halogen dioxide solutions by shearing the cleaning piece that this cleaning piece and/or electrolysis comprise one or more halogen dioxide solutions salt precursors.In another aspect of this invention, via halogen dioxide solutions salt precursor take place among the electrolytic electrolytic zinc-coated steel sheet and/or between path, electrolysis comprises the cleaning piece of one or more halogen dioxide solutions salt precursors.In another aspect of this invention, also can handle the cleaning piece that comprises more than one solution disclosed herein and/or system in a chamber, in this chamber, the halogen dioxide solutions salt precursor that is included in the described cleaning piece is produced halogen dioxide solutions by electrolysis.In another aspect of this invention, also can be before being intended to use, with halogen dioxide solutions solution spraying cleaning piece disclosed herein.In another aspect of this invention, also can be before being intended to use, comprise the cleaning piece that hydroxide ion removing system and/or IFT weaken system with the halogen dioxide solutions solution spraying.
In others of the present invention, system disclosed herein and/or solution are mixed with aerosol and/or gas phase, be suitable for fumigating and need send surface stable and/or effectively halogen dioxide solutions and/or regional.In one aspect of the invention, halogen dioxide solutions solution can be present in aerosol and/or the gas phase.In another aspect of this invention, comprising hydroxide ion removes the halogen dioxide solutions solution of system and/or comprises the halogen dioxide solutions solution that IFT weakens system and also can be present in aerosol and/or the gas phase.In another aspect of this invention, halogen dioxide solutions solution disclosed herein, comprise hydroxide ion and remove the halogen dioxide solutions solution of system and/or comprise the halogen dioxide solutions solution that IFT weakens system and also can be present in the solid phase, to send to target surface.
Preparation property embodiment
Embodiment 1: comprise the ClO 2 solution that hydroxide ion is removed system.
Following is the embodiment of ClO 2 solution, and it comprises the hydroxide ion scavenging agent of citric acid form.This solution comprises the dioxide peroxide of about 120ppm.
| Composition | Weight percent (%) |
| Sodium-chlor | 0.057 |
| Textone | 0.024 |
| Dioxide peroxide | 0.012 |
| Sodium hydroxide | 0.009 |
| Yellow soda ash | 0.001 |
| Citric acid | 0.093 |
| Water | 99.804 |
Embodiment 2: the ClO 2 solution that comprises surfactant system
Following is the embodiment of ClO 2 solution, and it comprises anion surfactant Sodium Lauryl Sulphate BP/USP (SLS).This solution comprises the dioxide peroxide of about 120ppm.
| Composition | Weight percent (%) |
| Sodium-chlor | 0.057 |
| Textone | 0.024 |
| Dioxide peroxide | 0.012 |
| Sodium hydroxide | 0.009 |
| Yellow soda ash | 0.001 |
| Sodium Lauryl Sulphate BP/USP | 0.012 |
| Water | 99.885 |
Embodiment 3: the ClO 2 solution that comprises surfactant system
Following is the embodiment of ClO 2 solution, and it comprises nonionogenic tenside APG or alkyl polyglucoside (trade(brand)name Glucopon).This solution comprises the dioxide peroxide of about 120ppm.
| Composition | Weight percent (%) |
| Sodium-chlor | 0.057 |
| Textone | 0.024 |
| Dioxide peroxide | 0.012 |
| Sodium hydroxide | 0.009 |
| Yellow soda ash | 0.001 |
| Glucopon 425 | 0.012 |
| Water | 99.885 |
Embodiment 4: comprise the ClO 2 solution that hydroxide ion is removed system and surfactant system
Following is the embodiment of ClO 2 solution, and it comprises hydroxide ion scavenging agent citric acid and anion surfactant SLS.Add hydroxyl ion source and citric acid and interact, and mixture pH value is adjusted to about 4.This solution comprises the dioxide peroxide of about 100ppm.
| Composition | Weight percent (%) |
| Citric acid (anhydrous) | 0.078 |
| Sodium hydroxide | 0.007 |
| Sodium Lauryl Sulphate BP/USP | 0.010 |
| Yellow soda ash | 0.006 |
| Magnesium basic carbonate | 0.002 |
| PPG 2000 | 0.004 |
| Defoamer 2-4293 | 0.001 |
| Oil of grapefruit | 0.0001 |
| Sodium-chlor | 0.048 |
| Textone | 0.020 |
| Dioxide peroxide | 0.010 |
| Water | 99.8139 |
Embodiment 5: the device that comprises hydroxide ion removing and surfactant system
Use is described in common unsettled U.S. Patent Application Serial Number 09/947, the electrolyzer of the universal design among 846 (announce and be incorporated herein by reference September 20 calendar year 2001) Fig. 1, the aqueous solution that will comprise Textone changes the effluent liquid that comprises dioxide peroxide into.This electrolyzer has a pair of aspectant electrode, and path clearance is about 0.19mm.Anode is made by the ES300-titanium, is coated with ruthenium oxide and iridium oxide.Negative electrode is made by 201 stainless steels.Plane electrode is of a size of long 75.2mm, wide 25.4mm.
The preparation of material aqueous solution be by with 10 liters of deionized waters and 62.6gms technical grade Textone raw material (80% actives, Aldrich Chemical Company, Inc, Milwaukee, WI 53233; Catalog number (Cat.No.) 24415-5) mixes until dissolving with splash bar, form the Textone salts solution of 5000ppm.This material aqueous solution is stored in 15 liters of Glass Containerss that are placed in the lucifuge case, and is cooled to 5 degrees centigrade.Peristaltic pump measures the supplies material aqueous solution with the flow velocity of 300 ml/min and passes through electrolyzer from Glass Containers.Apply 5.72 amperes direct current with direct supply to electrode, so that 4.5 volts the voltage of striding electrolyzer to be provided.Effluent solution is extracted from electrolyzer and is analyzed.Effluent comprises the dioxide peroxide of 109ppm and the unreacted Textone of 4891ppm, and chloritic transformation efficiency is 2.9%.
Preparation the following example proves and uses the single solution comprise hydroxide ion scavenging agent and surfactant system can come through the spray equipment that is equipped with electrolyzer to produce dioxide peroxide in the Textone from solution.Provide based on phosphatic type with based on the type of carbonate.
| Composition | Weight percent (%) | Weight percent (%) |
| Citric acid (anhydrous) | 0.2 | 0.23 |
| NaOH (50% solution) | 0.24 | 0.17 |
| Sodium Lauryl Sulphate BP/USP | 0.05 | 0.05 |
| Na 2HPO 4 | 0.03 | |
| NaH 2PO 4·H 2O | 0.03 |
| NaHCO 3 | - | 0.10 |
| NaClO 2 | 0.5 | 0.50 |
| Water | 98.95 | 98.95 |
The pH value that solution has before electrolysis is for about 6 to 7, and after electrolysis is carried out the pH value remained between 6 to 9.The chlorine dioxide content that expectation gives off from electrolyzer and pump is 85ppm.This solution also can pass through pond/pump recirculation, with further increase chlorine dioxide concentration.Then, the effluent that will give off from pond/pump discharges by atomizing spray nozzle, comprises particulate dioxide peroxide mist with generation.This mist can be used for covering surfaces handling, or is confined to the closed region, to have " fumigating " effect.
For embodiment subsequently, relate to the composition of these components:
I
| Composition | Weight percent (%) |
| Deionized water | 99.9 |
| Textone raw material (technical grade) | 0.05 |
| Sodium-chlor | 0.05 |
II
| Composition | Weight percent (%) |
| Deionized water | 97 |
| NaHCO3 | 1.77 |
| Sodium Lauryl Sulphate BP/USP | 1.23 |
III
| Composition | Weight percent (%) |
| Deionized water | 99.59 |
| Citric acid (anhydrous) | 0.41 |
IV
| Composition | Weight percent (%) |
| Deionized water | 99.42 |
| Acid-negatively charged ion powdered mixture (V) | 0.58 |
V
| Composition | Weight percent (%) |
| Citric acid (anhydrous) | 77.61 |
| Sodium Lauryl Sulphate BP/USP | 10.31 |
| Na2CO3 | 5.28 |
| MgCO3 | 2.00 |
| PPG 2000 | 3.7 |
| Defoamer 2-4293 | 1.00 |
| Oil of grapefruit | 0.10 |
The following example uses above-mentioned composition.
Embodiment A and E: when composition I is pumped through when using 6.6 volts electrolytic zinc-coated steel sheet by electrolysis.Then, generate final mixture, it comprises 83% electrolytic composition I and 17% deionized water.
Embodiment B and F: when composition I is pumped through when using 6.6 volts electrolytic zinc-coated steel sheet by electrolysis.Then, generate final mixture, it comprises 83% electrolytic composition I and 17% composition I I.
Embodiment C and G: when composition I is pumped through when using 6.6 volts electrolytic zinc-coated steel sheet by electrolysis.Then, generate final mixture, it comprises 83% electrolytic composition I and 17% composition I II.
Embodiment D and H: when composition I is pumped through when using 6.6 volts electrolytic zinc-coated steel sheet by electrolysis.Then, generate final mixture, it comprises 83% electrolytic composition I and 17% composition I V.
Use the foregoing description composition A-H, carry out the test of microorganism effect.It is low more to restore logarithmic value, and performance is good more.
Gram-positive microorganism in the surface spray test
Organism: streptococcus aureus
Target ClO
2Strength of solution: 50ppm
5 minute treatment time
| A | B | C | D | |
| ClO only 2 (pH～10.5) | ClO 2+ alkali/tensio-active agent (pH～9) | ClO 2+ citric acid (pH～3.5) | ClO 2+ acid/tensio-active agent (pH～4) |
| Restore logarithmic value | 6.02 | 2.52 | 1.57 | 0.62 |
Gram-negative bacteria in the surface spray test
Organism: Pseudomonas aeruginosa
Target ClO
2Strength of solution: 50ppm
5 minute treatment time
| E | F | G | H | |
| ClO only 2 (pH～10.5) | ClO 2+ alkali/tensio-active agent (pH～9) | ClO 2+ citric acid (pH～3.5) | ClO 2+ acid/tensio-active agent (pH～4) | |
| Restore logarithmic value | 6.32 | 4.79 | 3.16 | 0* |
* (promptly below detectability) all killed in representative
Ensuing embodiment uses the combination of following component.
VI
| Composition | Weight percent (%) |
| Deionized water | 99.75 |
| Textone raw material (technical grade) | 0.25 |
VII
| Composition | Weight percent (%) |
| Deionized water | 99.00 |
| Acid-negatively charged ion powdered mixture (V) | 1.00 |
VIII
| Composition | Weight percent (%) |
| Deionized water | 99.29 |
| Citric acid (anhydrous) | 0.71 |
The following example uses above-mentioned composition.
Embodiment J: when composition VI is pumped through when using 6 volts electrolytic zinc-coated steel sheet by electrolysis.Then, generate final mixture, it comprises 50% electrolytic composition VI and 50% deionized water.
Embodiment K: when composition VI is pumped through when using 6 volts electrolytic zinc-coated steel sheet by electrolysis.Then, generate final mixture, it comprises 50% electrolytic composition VI and 50% composition VIII.
Embodiment L: when composition VI is pumped through when using 6 volts electrolytic zinc-coated steel sheet by electrolysis.Then, generate final mixture, it comprises 50% electrolytic composition VI and 50% composition VII.
Use the foregoing description composition J-L, carry out the test of microorganism effect.It is low more to restore logarithmic value, and performance is good more.
Gram-positive microorganism spore in the suspension test
Organism: bacillus cereus spore
ClO
2Strength of solution :～85ppm
5 minute treatment time
| J | K | L | |
| ClO only 2 (pH～10.5) | ClO 2+ citric acid (pH～3.5) | ClO 2+ acid/tensio-active agent (pH～3.5) | |
| Restore logarithmic value | 0.67 | 0.56 | ＜0.30* |
* (promptly below detectability) all killed in representative
Embodiment 6: by stablizing and effective chlorine dioxide mixture that the spray bottle with two compartments produces
Solution M and N are arranged in independent compartment, and use by small-sized impeller pump and mix, and extract the solution of equivalent from each compartment, and at suction tube and further in pump, mix.Product emits from pump by fog nozzle.Owing to mix two kinds of component M+N, make the mixture of discharging form dioxide peroxide, and this mixture have the distinctive yellow appearance of ClO 2 solution, it keeps stable and contains tensio-active agent, shows as effective antimicrobial product.
M
| Composition | Weight percent (%) |
| Deionized water | 99.12 |
| Citric acid | 0.78 |
| Sodium Lauryl Sulphate BP/USP | 0.10 |
N
| Composition | Weight percent (%) |
| Deionized water | 99.45 |
| NaClO 2Raw material | 0.08 |
| NaOCl raw material (containing the 5.25%NaOCl active substance in the raw material) | 0.47 |
Embodiment 7: measure the Reynolds number (Re) that forms in the virtual membranous parallel-plate electrode:
For complete groove, hydraulic radius equals cross-sectional area divided by wetted perimeter R
h=A/P.For non-round tube, hydraulic diameter equals four times of hydraulic radius.
D
h＝4R
h
For the parallel board slot of wide w and distance s, hydraulic radius equals w*s/ (2* (w+s)).Hydraulic diameter equals 4R
hOr D
h=2w*s/ (w+s).For w wherein＞＞groove of s, D
hBecome and be about 2s.
Re=D
hVp/u (～2sVp/u, when w＞＞during s)
Total volumetric flow rate Q 144cm^3/ minute
The wide W 2.5Cm in pond
Pond interval S 0.02Cm
Liquid stream cross section A 0.05cm^2
N 1 is counted in the pond
Liquid flow density P 1gm/cm^3
Liquid mobilization force viscosity U 1 CP
48 cm/ seconds of pond flow velocity V
Characteristic diameter Dh 0.039683 Cm
Long L 7.2 Cm in pond
Reynolds number Re 190.4762
Retention time RT 0.0025 minute
Pond volume Vol 0.36 cm^3
The relevant portion of all documents of quoting in the present invention describes in detail is incorporated herein by reference; It is to its approval as prior art of the present invention that the quoting of any document not can be regarded as.
Although illustrated and described the present invention with specific embodiments, it will be apparent to those skilled in the art that many other variations and modifications may be made in the case of without departing from the spirit and scope of protection of the present invention.Therefore, in additional claims, comprise all such changes and modifications in the scope of the invention consciously.
Claims (33)
1. a hydroxide ion that is used for the stabilized chlorine chlorine solution is removed system, and described system comprises:
(a) remove system by the hydroxide ion of the gross weight about 0.001% to about 10% of the described chlorine dioxide precursor solution that comprises the hydroxide ion scavenging agent; With
(b) by one or more haloid precursors of the gross weight about 0.000001% to about 50% of the described chlorine dioxide precursor solution that comprises the hydroxide ion scavenging agent;
The reagent that wherein is used for described hydroxide ion removing system is selected from: the salt of organic acid, organic acid salt, mineral acid, mineral acid, and their mixture;
In addition wherein when measuring two kinds of solution under 25 ℃ after dioxide peroxide produces three hours, compare with the concentration of the corresponding ClO 2 solution that does not comprise described hydroxide ion removing system, described hydroxide ion removing system is suitable for making the concentration of ClO 2 solution to increase at least about 5%.
2. hydroxide ion as claimed in claim 1 is removed system, and wherein dioxide peroxide is pregenerated.
3. hydroxide ion as claimed in claim 1 is removed system, and wherein dioxide peroxide is instant the generation.
4. a hydroxide ion that is used for the stabilized chlorine chlorine solution is removed system, and described system comprises:
(a) by the described gross weight that comprises the ClO 2 solution of hydroxide ion scavenging agent, about 0.001% to about 10% hydroxide ion is removed system; With
(b) by the described gross weight that comprises the ClO 2 solution of hydroxide ion scavenging agent, about 0.000001% to about 1% dioxide peroxide;
Wherein said hydroxide ion scavenging agent is selected from: the salt of organic acid, organic acid salt, mineral acid, mineral acid, and their mixture;
In addition wherein when measuring two kinds of solution under 25 ℃ after dioxide peroxide produces three hours, compare with the concentration of the corresponding ClO 2 solution that does not comprise described hydroxide ion removing system, described hydroxide ion removing system is suitable for making the concentration of ClO 2 solution to increase at least about 5%.
5. hydroxide ion as claimed in claim 4 is removed system, and wherein said hydroxide ion removing system is used for the stabilized chlorine chlorine solution.
6. an interfacial tension (IFT) that is used to increase ClO 2 solution stability and/or effect weakens system, and described system comprises:
(a) weaken the gross weight of the chlorine dioxide precursor solution of system by the described IFT of comprising, about 0.00001% to about 10% IFT weakens system;
(b) weaken the gross weight of the chlorine dioxide precursor solution of system by the described I of comprising FT, one or more haloid precursors of about 0.000001% to about 50%;
Wherein being used for the reagent that described IFT weakens system is selected from, and: IFT weakens that polymkeric substance, IFT weaken solvent, IFT weakens tensio-active agent, and their mixture;
Wherein compare with not comprising the corresponding ClO 2 solution that described IFT weakens system in addition, described IFT weakens system and is suitable for making and comprises described IFT and weaken the microbe population decrease sent in the ClO 2 solution of system greatly at least about 5%.
7. an interfacial tension (IFT) that is used to increase ClO 2 solution stability and/or effect weakens system, and described system comprises:
(c) weaken the gross weight of the ClO 2 solution of system by the described IFT of comprising, about 0.00001% to about 10% IFT weakens system;
(d) weaken the gross weight of the ClO 2 solution of system by the described IFT of comprising, about 0.000001% to about 1% dioxide peroxide;
Wherein being used for the reagent that described IFT weakens system is selected from, and: IFT weakens that polymkeric substance, IFT weaken solvent, IFT weakens tensio-active agent, and their mixture;
Wherein compare with not comprising the corresponding ClO 2 solution that described IFT weakens system in addition, described IFT weakens system and is suitable for making the microbe population decrease that comprises in the ClO 2 solution that described IFT weakens system greatly at least about 5%.
8. IFT as claimed in claim 7 weakens system, and wherein said IFT weakens the effect that system can be used for increasing ClO 2 solution.
9. dioxide peroxide effect system that stabilizes and increases, described system comprises that hydroxide ion as claimed in claim 1 is removed system and IFT as claimed in claim 6 weakens system;
The wherein said dioxide peroxide effect system that stabilizes and increases is characterised in that dioxide peroxide produced after three hours, and 25 ℃ of following chlorine dioxide concentration do not stabilize and increase the concentration of corresponding dioxide peroxide of effect system greatly at least about 5% than not comprising described dioxide peroxide;
Wherein compare with not comprising the stabilize and increase corresponding ClO 2 solution of effect system of described dioxide peroxide in addition, the described dioxide peroxide effect system that stabilizes and increases is suitable for making the microbe population reduction greatly at least about 5%.
10. dioxide peroxide effect system that stabilizes and increases, described system comprise that hydroxide ion as claimed in claim 4 is removed system and IFT as claimed in claim 7 weakens system;
The wherein said dioxide peroxide effect system that stabilizes and increases is characterised in that, dioxide peroxide produced after three hours, 25 ℃ down the chlorine dioxide concentration of described systems do not stabilize and increase the concentration of corresponding ClO 2 solution of effect system greatly at least about 5% than not comprising described dioxide peroxide;
Wherein compare with not comprising the stabilize and increase corresponding ClO 2 solution of effect system of described dioxide peroxide in addition, the described dioxide peroxide effect system that stabilizes and increases is suitable for making the microbe population reduction greatly at least about 5%.
11. a dioxide peroxide generation structure, described system comprises:
A) material aqueous solution source, described material aqueous solution source comprises the salt of dioxide peroxide;
B) diaphragmless cell, described electrolyzer comprises anode and negative electrode, and has the chamber, pond of tape entry and outlet;
C) parts, described parts make described material aqueous solution flow to chamber, described pond, and flow through near described anodic passage, flow out described outlet then;
D) current source, described current source make flow through described material aqueous solution in the described passage of electric current, so that a part of described titanium dioxide villaumite is converted into dioxide peroxide, thereby form the moisture effluent that comprises dioxide peroxide; With
E) chamber, described chamber comprise and be selected from following system: the hydroxide ion that is used to stablize described ClO 2 solution is removed system; The IFT that is used to increase described ClO 2 solution stability and/or effect weakens system, and their combination.
12. dioxide peroxide generation structure as claimed in claim 11, wherein said anode and described cathode plane opposite are also coextensive, and the chamber gap is 1.0mm or littler.
13. dioxide peroxide generation structure as claimed in claim 11, wherein said anode and described cathode plane opposite are also coextensive, and the chamber gap is 0.5mm or littler.
14. dioxide peroxide generation structure as claimed in claim 11, wherein said anode and described cathode plane opposite are also coextensive, and the chamber gap is 0.2mm or littler.
15. dioxide peroxide generation structure as claimed in claim 11, wherein said anode are conductive porous anodes.
16. a dioxide peroxide generation structure, described system comprises:
A) material aqueous solution source, described material aqueous solution source comprises the salt of dioxide peroxide;
B) diaphragmless cell, described electrolyzer comprises anode and negative electrode, and has the chamber, pond of tape entry and outlet;
C) parts, described parts make described material aqueous solution flow to chamber, described pond, and flow through near described anodic passage, flow out described outlet then;
D) current source, described current source make flow through material aqueous solution in the described passage of electric current, so that a part of described titanium dioxide villaumite is converted into dioxide peroxide, thereby form the moisture effluent that comprises dioxide peroxide; With
E) chamber, described chamber comprise hydroxide ion removing system and I FT weakens system, with stability and the effect that increases described ClO 2 solution.
17. dioxide peroxide generation structure as claimed in claim 16, wherein said anode and described cathode plane opposite are also coextensive, and the chamber gap is 1.0mm or littler.
18. dioxide peroxide generation structure as claimed in claim 16, wherein said anode and described cathode plane opposite are also coextensive, and the chamber gap is 0.5mm or littler.
19. dioxide peroxide generation structure as claimed in claim 16, wherein said anode and described cathode plane opposite are also coextensive, and the chamber gap is 0.2mm or littler.
20. dioxide peroxide generation structure as claimed in claim 16, wherein said anode are conductive porous anodes.
21. a dioxide peroxide generates and recirculation system, described system comprises:
A) material aqueous solution source, described material aqueous solution source comprises the salt of dioxide peroxide;
B) diaphragmless cell, described electrolyzer comprises anode and negative electrode, and has the chamber, pond of tape entry and outlet;
C) parts, described parts make described material aqueous solution flow to chamber, described pond, and flow through near described anodic passage, flow out described outlet then;
D) current source, described current source make flow through the aqueous solution between described anode and described negative electrode of electric current, so that the described titanium dioxide villaumite of at least a portion in the described passage is converted into dioxide peroxide, thereby form the moisture effluent that comprises dioxide peroxide;
E) parts, the described moisture effluent of described parts delivery makes it contact with the target compound that consumes dioxide peroxide, thereby makes the described consumption target compound of a part of dioxide peroxide oxidation in the described moisture effluent, and restores to the titanium dioxide villaumite;
F) the consumption effluent that parts, described parts will comprise described recovery titanium dioxide villaumite is back to described source; With
G) parts, described parts delivery hydroxide ion is removed system, to stablize described ClO 2 solution.
22. a dioxide peroxide generates and recirculation system, described system comprises:
A) material aqueous solution source, described material aqueous solution source comprises the salt of dioxide peroxide;
B) diaphragmless cell, described electrolyzer comprises anode and negative electrode, and has the chamber, pond of tape entry and outlet;
C) parts, described parts make described material aqueous solution flow to chamber, described pond, and flow through near described anodic passage, flow out described outlet then;
D) current source, described current source make flow through the aqueous solution between described anode and described negative electrode of electric current, so that at least a portion titanium dioxide villaumite in the described passage is converted into dioxide peroxide, thereby form the moisture effluent that comprises dioxide peroxide;
E) parts, the described moisture effluent of described parts delivery makes it contact with consuming the dioxide peroxide target compound, thereby makes the described consumption target compound of a part of dioxide peroxide oxidation in the described moisture effluent, and restores to the titanium dioxide villaumite;
F) the consumption effluent that parts, described parts will comprise described recovery titanium dioxide villaumite is back to described source; With
G) parts, described parts delivery IFT weakens system, with stability and/or the effect that increases described ClO 2 solution.
23. a battery-powered electrolyzer, described device are used for the aqueous solution that instant preparation comprises dioxide peroxide, described device comprises:
A) electrolyzer, described electrolyzer comprises anode and negative electrode, and has the chamber, pond;
B) material aqueous solution that parts, described parts are used for comprising the titanium dioxide villaumite is pumped into chamber, described pond, and flows through near described anodic passage;
C) battery, when described material aqueous solution flowed in chamber, described pond and flows through described passage, described battery was used to make electric current to flow between described anode and described negative electrode, thereby makes a part of described titanium dioxide villaumite be converted into dioxide peroxide; With
D) parts, described parts are used to send hydroxide ion and remove system, to stablize described ClO 2 solution.
24. battery-powered electrolyzer as claimed in claim 23, wherein said device is the solution spray bottle, wherein said pumping parts comprise electric driving pump, described electric driving pump is pumped to solution the described electrolyzer from described bottle, and wherein said electrolyzer comprises anode and face-to-face and coextensive negative electrode, has 1.0mm or littler chamber gap.
25. battery-powered electrolyzer as claimed in claim 23, wherein said device is the solution spray bottle, wherein said pumping parts comprise electric driving pump, described electric driving pump is pumped to solution the described electrolyzer from described bottle, and wherein said electrolyzer comprises anode and face-to-face and coextensive negative electrode, has 0.5mm or littler chamber gap.
26. battery-powered electrolyzer as claimed in claim 23, wherein said device is the solution spray bottle, wherein said pumping parts comprise electric driving pump, described electric driving pump is pumped to solution the described electrolyzer from described bottle, and wherein said electrolyzer comprises anode and face-to-face and coextensive negative electrode, has 0.2mm or littler chamber gap.
27. a battery-powered electrolyzer, described device are used for the aqueous solution that instant preparation comprises dioxide peroxide, described device comprises:
A) electrolyzer, described electrolyzer comprises anode and negative electrode, and has the chamber, pond;
B) material aqueous solution that parts, described parts are used for comprising the titanium dioxide villaumite is pumped into chamber, described pond, and flows through near described anodic passage;
C) battery, when described material aqueous solution flowed in chamber, described pond and flows through described passage, described battery was used to make electric current to flow between described anode and described negative electrode, thereby makes a part of described titanium dioxide villaumite be converted into dioxide peroxide; With
D) parts, described parts delivery I FT weakens system, with stability and/or the effect that increases described ClO 2 solution.
28. battery-powered electrolyzer as claimed in claim 27, wherein said device is the solution spray bottle, wherein said pumping parts comprise electric driving pump, described electric driving pump is pumped to solution the described electrolyzer from described bottle, and wherein said electrolyzer comprises anode and face-to-face and coextensive negative electrode, has 1.0mm or littler chamber gap.
29. battery-powered electrolyzer as claimed in claim 27, wherein said device is the solution spray bottle, wherein said pumping parts comprise electric driving pump, described electric driving pump is pumped to solution the described electrolyzer from described bottle, and wherein said electrolyzer comprises anode and face-to-face and coextensive negative electrode, has 0.5mm or littler chamber gap.
30. battery-powered electrolyzer as claimed in claim 27, wherein said device is the solution spray bottle, wherein said pumping parts comprise electric driving pump, described electric driving pump is pumped to solution the described electrolyzer from described bottle, and wherein said electrolyzer comprises anode and face-to-face and coextensive negative electrode, has 0.2mm or littler chamber gap.
31. comprising to needs, the method for a stabilizing chlorine dioxide, described method increase the step of sending hydroxide ion removing system in the stable ClO 2 solution;
Wherein when after dioxide peroxide produced three hours, measuring 25 ℃ of following two kinds of solution, to remove the concentration of the corresponding ClO 2 solution of system and compare with not comprising described hydroxide ion, described method is suitable for making the concentration of ClO 2 solution to increase at least about 5%; Be suitable for increasing the effect of ClO 2 solution with wherein said method.
32. comprising in the ClO 2 solution of needs increase effect, a method that increases the dioxide peroxide effect, described method send the step that interfacial tension (IFT) weakens system; Wherein said method is suitable for increasing the effect of ClO 2 solution.
33. comprising, a method that increases ClO 2 solution stability and effect, described method in needs increase the ClO 2 solution of stability and effect, send the step that hydroxide ion removing system and interfacial tension (IFT) weaken system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47167003P | 2003-05-19 | 2003-05-19 | |
| US60/471,670 | 2003-05-19 |
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| CN1787963A CN1787963A (en) | 2006-06-14 |
| CN100377991C true CN100377991C (en) | 2008-04-02 |
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| CNB2004800129712A Expired - Fee Related CN100377991C (en) | 2003-05-19 | 2004-05-19 | Compositions, devices and methods for stabilizing and increasing the efficacy of halogen dioxide solutions |
Country Status (9)
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| US (1) | US20040231977A1 (en) |
| EP (1) | EP1626928A1 (en) |
| JP (1) | JP2006526076A (en) |
| KR (1) | KR100803016B1 (en) |
| CN (1) | CN100377991C (en) |
| BR (1) | BRPI0410758A (en) |
| CA (1) | CA2522576A1 (en) |
| MX (1) | MXPA05012437A (en) |
| WO (1) | WO2004103898A1 (en) |
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| ATE459574T1 (en) * | 2004-12-06 | 2010-03-15 | Akzo Nobel Nv | CHEMICAL PROCESS AND PRODUCTION UNIT |
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| US20070196357A1 (en) | 2006-01-20 | 2007-08-23 | Oculus Innovative Sciences, Inc. | Methods of treating or preventing inflammation and hypersensitivity with oxidative reductive potential water solution |
| US8673297B2 (en) | 2006-02-28 | 2014-03-18 | Basf Corporation | Chlorine dioxide based cleaner/sanitizer |
| WO2009093540A1 (en) * | 2008-01-23 | 2009-07-30 | Taiko Pharmaceutical Co., Ltd. | Chlorine dioxide liquid preparation composition |
| JP5469601B2 (en) * | 2008-06-19 | 2014-04-16 | 大幸薬品株式会社 | 1-component electrolytic chlorine production method |
| US10342825B2 (en) | 2009-06-15 | 2019-07-09 | Sonoma Pharmaceuticals, Inc. | Solution containing hypochlorous acid and methods of using same |
| EP2617873B1 (en) * | 2012-01-18 | 2014-06-25 | H-TEC Systems GmbH | Electrolysis device |
| US20140199231A1 (en) * | 2013-01-12 | 2014-07-17 | Darrel George Wolf | System, method and device for generating chlorine dioxide |
| EP2967042B1 (en) * | 2013-03-15 | 2018-01-03 | Solenis Technologies Cayman, L.P. | The use of synergistic blends of antimicrobials for controlling microorganisms in industrial processes |
| CN103334117B (en) * | 2013-06-27 | 2016-02-03 | 陈维军 | A kind of chlorine dioxide generator of efficient electric solution |
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Also Published As
| Publication number | Publication date |
|---|---|
| MXPA05012437A (en) | 2006-01-30 |
| EP1626928A1 (en) | 2006-02-22 |
| BRPI0410758A (en) | 2006-06-27 |
| JP2006526076A (en) | 2006-11-16 |
| KR100803016B1 (en) | 2008-02-14 |
| US20040231977A1 (en) | 2004-11-25 |
| WO2004103898A1 (en) | 2004-12-02 |
| CA2522576A1 (en) | 2004-12-02 |
| KR20060009355A (en) | 2006-01-31 |
| CN1787963A (en) | 2006-06-14 |
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