CN1984846A - Water treatment - Google Patents
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- CN1984846A CN1984846A CN 200580023316 CN200580023316A CN1984846A CN 1984846 A CN1984846 A CN 1984846A CN 200580023316 CN200580023316 CN 200580023316 CN 200580023316 A CN200580023316 A CN 200580023316A CN 1984846 A CN1984846 A CN 1984846A
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Abstract
A composition and a process for using the composition to treat water for clarifying, sanitizing, or disinfecting water wherein the composition comprises an active oxygen compound and one or more precursors for generating chlorine dioxide (ClO<SUB>2</SUB>), and the process comprises contacting water with a solid composition comprising an active oxygen compound and precursors for generating ClO<SUB>2</SUB> and is characterized in that, upon the contacting, at least 10 grams of the composition can be dissolved in about 3.8 liters of water at 25 DEG C in less than about 60 minutes, thereby generating a solution containing at least about 40 ppm ClO<SUB>2</SUB>, is disclosed.
Description
Invention field
The present invention relates to a kind of water treatment method, this method adopts a kind of composition that comprises reactive oxygen compounds and can produce the precursor of dioxide peroxide.
Background of invention
The sterilization of water can be undertaken by chlorination.Yet, when making the surface water chlorination, produce haloform, for example it was reported to belong to carcinogenic chloroform.The municipal water supply system that surpasses the highest haloform level of 100ppb of USEPA (EPA) regulation must switch to change sterilisation system.
Dioxide peroxide (ClO
2) can be used as biocide and/or discoloring agent is used for handling swimming pool, recuperates with mineral spring, and other amusement and decorate waters such as water body, but it can be deleterious when slipping up when using.People must use very carefully, could keep any human or animal not to be exposed to safe limit.Substitute as a kind of, can adopt metal chlorite, under controlled condition, use to produce ClO
2Acidifying.
For example, patent application WO 03/055797 discloses a kind of by making the reaction generation and oxygen blended ClO in the presence of redox initiator (for example peroxydisulfate or oxalic acid) in acidic aqueous solution of a kind of chlorite and peroxy-monosulfate
2Method.Can add a kind of chloride salt, better sodium-chlor and/or hydrosulfate, in the hope of promoting reaction at low temperatures.This application also discloses a kind of test kit that is used to carry out this reaction, and wherein a kind of composition contains a kind of chlorite, and second kind of independent composition contains a kind of and this redox initiator blended peroxy-monosulfate.In one embodiment, these two kinds of dry compositions can be the form of two kinds of independent tablets.All embodiment show that above two kinds of compositions import separately in the pyritous water.This generation ClO
2Do not provide a kind of single easily molten composition with the method for the mixture of oxygen.
Therefore, need a kind of single supporting formulation, this formulation when soluble in water, in one period short period of time, just to produce a kind ofly to be applicable to deodorizing purpose and sterilisation purpose, contain active oxygen and safe concentration ClO
2The aqueous solution.People wish to have a kind of specialization and expensive ClO
2The replacement scheme of generation equipment, promptly provide a kind of predetermined, easily dosage, this dosage be easy use and safety operation and storage, can be with the lasting security operant level with ClO
2Be transported in the solution and do not stay any insoluble substance.In addition, people also wish the ClO that no longer needs
2Take place and store a large amount of Textones and acid.The invention provides a kind of like this single dose composition, be used to make Textone to change into ClO expeditiously
2
Brief summary of the invention
The invention provides a kind of water treatment method, comprise: water is contacted with a kind of solids composition, wherein said composition comprises a kind of reactive oxygen compounds and one or more are used to take place the precursor of dioxide peroxide, b) make described composition＜be dissolved in about 25 ℃ described water in about 60 minutes, and c) produce a kind of solution that contains at least about the 40ppm dioxide peroxide.Better, described composition is tablet form, and described water body comprises Chi Shui, recuperate usefulness mineral water or amusement and decoration water body, and described amusement comprises spring, reflection tank water or decorates Chi Shui with the decoration water body.
The present invention also comprises a kind of composition, said composition comprises a kind of reactive oxygen compounds and one or more are used to take place the precursor of dioxide peroxide, wherein said composition＜be dissolved in about 25 ℃ water in about 60 minutes, produce a kind of solution that contains at least about the 40ppm dioxide peroxide.
The present invention also comprises a kind of composition, and said composition comprises by weight
A) about 20wt%～about 90wt% sulfur-bearing alcohol acid;
B) about 3wt%～about 25wt% solubility chlorite;
C) about 3wt%～about 12wt% alkali metal halide or alkaline earth metal halide or its mixture;
D) about 0.001wt%～about 37wt% filler;
E) about 0.001wt%～about 5wt% carbohydrate; With
F) randomly, a kind of alkaline carbonate, alkaline earth metal carbonate, alkali metal hydrocarbonate, alkali metal bicarbonates or its mixture; A kind of binding agent; A kind of lubricant; A kind of stamping surface release agent; A kind of sweetener; A kind of acid except that this alcohol acid; The perhaps wherein combination of two or more;
Prerequisite is that the positively charged ion of described alkali metal halide, described alkaline earth metal halide, described alkaline carbonate, described alkaline earth metal carbonate, described alkali metal hydrocarbonate or described alkali metal bicarbonates does not generate the vitriol of solubleness in the water＜1%.
The present invention further comprises a kind of water become health or disinfectant method of making, comprise this water is contacted with the composition that one or more are used to produce the precursor of dioxide peroxide with a kind of reactive oxygen compounds that comprises, b) make described composition＜be dissolved in about 25 ℃ described water in about 60 minutes, and c) produce a kind of solution that contains at least about the 40ppm dioxide peroxide.
Detailed description of the Invention
Trade mark is represented with capitalization in this article." tablet " used herein this term means the close solid material entity of, Mu Cause common compression moulding, molding or extrusion molding, that various physical form such as plate brick, dish, piece or unit are arranged.Tablet is characterised in that enough hardness resists breaking of operating period.
" ppm " used herein this term means microgram/gram (μ g/g).
" microorganism " used herein this term means any acellular or unicellular (comprising colony) biology.Microorganism comprises all prokaryotic organism.Microorganism comprises bacterium (comprising blue or green bacterium and flesh bacterium), lichens, fungi, mould, Protozoa, virus particle, viroid, virus and some algae.
" microbe " used herein is the synonym of microorganism.
" biocide " used herein this term means a kind of energy destroy microorganisms or the medicament that makes it lose ability and suppress microorganism growth.
" sunitizing " used herein (sanitizer) this term means a kind of medicament that antimicrobial acivity can be provided.EPA (US EPA) standard-required killed 10 in 30 seconds
5Bacterium.
" sterilizing agent " used herein (disinfectant) this term means a kind of medicament that antimicrobial acivity can be provided.The EPA standard-required killed 10 in 10 minutes
3The specific pathogen bacterium.These bacteriums are S.aureus, P.aeruginosa and S.choleraesuis.
The present invention relates to a kind of composition for water treatment and water treatment method.Said composition comprises a kind of reactive oxygen compounds and one or more can produce the compound of dioxide peroxide.This method comprises to be made water contact, make described composition dissolves with said composition and produce 40ppm dioxide peroxide at least in solution.Make at least 10g or 50g or even the 100g said composition less than or etc. be dissolved at least about 3.8 premium on currency in about 60 minutes, and this water is in about 15～about 50 ℃, better about 20～about 45 ℃, better about 25 ℃, produces a kind of solution that contains reactive oxygen compounds and dioxide peroxide.Better said composition is to be less than or equal in about 50 minutes, better to be less than or equal in about 30 minutes even better to be less than or equal to dissolved in about 25 minutes.The concentration of the dioxide peroxide that is produced is more than or equal to about 40ppm.Better produce at least about the 50ppm dioxide peroxide, better at least about 75ppm, better at least about 100ppm.Use best the composition and the compressing tablet condition, can reach 20 minutes or shorter dissolution time and to produce concentration in solution be the dioxide peroxide of 50ppm at least.
Although any water body can be handled, this method better be used for treating pond water, recuperate with mineral water, and other amusement and decorate water body, comprise for example fountain, reflection tank and ornamental pond.
The composition that uses in the inventive method can be any physical form for example powder agent, gelifying agent, tablet or the wherein combination of two or more, and is Any shape.For example, a kind of easy solvellae is used to produce a kind of dioxide peroxide and the active oxygen aqueous solution easily, to be used as the general objects sterilant and the reodorant of water.Said composition comprises the precursor that a kind of reactive oxygen compounds and one or more (at least a) can produce dioxide peroxide, wherein said composition is dissolved in about 25 ℃ water in less than about 60 minutes, produces a kind of solution that contains at least about the 40ppm dioxide peroxide.The advantage of composition of the present invention is that all components or composition all are water miscible, thereby does not have insoluble sludge to stay on the disinfectant surface.
The reactive oxygen compounds that is suitable for is active oxygen source can be provided and those of health effect source can be provided.Be preferably sulfur-bearing alcohol acid for example peroxosulphuric and salt thereof.Example comprises permonosulphuric acid and peroxy-disulfuric acid and salt thereof.Be applicable to that the precursor that produces dioxide peroxide comprises a kind of solvability chlorite, a kind of an alkali metal salt or alkaline earth salt and a kind of acid.
Better, said composition comprises following ingredients in weight percent (wt%), and prerequisite is that these percentage totals are up to 100%:
A) about 20%～about 90% sulfur-bearing alcohol acid,
B) about 3%～about 25% solubility chlorite and
C) about 3%～about 12% alkali metal halide or alkaline earth metal halide, prerequisite are that the positively charged ion of this alkali metal halide or alkaline earth metal halide is not created in 25 ℃ of water＜vitriol of 1% solubleness,
D) about 0.001%～about 5% carbohydrate, for example water soluble starch or treated starch and
E) about 0.001%～about 37% filler, for example basic metal (or alkaline-earth metal) vitriol.
Randomly, said composition also comprises:
F) about 0.001～about 10wt% of said composition or better 0.1wt%～about 5wt% alkaline carbonate, alkaline earth metal carbonate, alkali metal hydrocarbonate or alkali metal bicarbonates, prerequisite is the vitriol that the positively charged ion of this metal carbonate or supercarbonate is not created on solubleness＜1% in 25 ℃ of water
F) about 0.001～about 15% water-soluble tablets binding agent, for example sugar alcohol, Star Dri 5 or corn-syrup solids;
G) about 0.001～about 5% lubricant, for example tablet lubricants, better water-soluble tablets lubricant;
H) about 0.001～about 5% stamping surface antisticking agent, better water-soluble flush pressure surface antisticking agent;
I) about 0.001～about 5% sweetener; Or
J) about 0.001～about 20% a kind of acid except that this alcohol acid.
A kind of main component of said composition comprises a kind of sulfur-bearing alcohol acid (a), and the latter had both supplied with this active oxygen and also generated dioxide peroxide with the reaction of solvability chlorite.This sulfur-bearing alcohol acid comprises a kind of basic metal one persulphate and/or two persulphates, or a Potassium Persulphate, sal enixum and vitriolate of tartar triple salt, and this is approx by 2KHSO
5KHSO
4K
2SO
4The representative of this chemical formula and can be under the OXONE trade(brand)name available from E.I.duPont de Nemours andCompany (Wilmington, DE).Its amount in said composition is about 20wt%～about 90wt% or about 20wt%～about 80wt% or about 20wt%～about 75wt% or about 23wt%.
Said composition also comprises a kind of solvability chlorite (b), and the latter can produce dioxide peroxide with this alcohol acid reaction in water.The chloritic example of such solvability comprises an alkali metal salt or alkaline earth salt.Better, this solvability chlorite is a chlorite.Its amount in said composition is about 3wt%～about 25wt% or better about 3wt%～about 20wt%.
Said composition further comprises a kind of alkali metal halide or alkaline earth metal halide (c), and prerequisite is the vitriol that its positively charged ion is not created on solubleness＜1% in 25 ℃ of water.This halide salts better is selected from magnesium chloride, sodium-chlor, zinc chloride, zinc bromide, reaches the wherein combination of two or more.Better, this solvability magnesium halide is a magnesium chloride.This halide salts can play a kind of effect that can quicken the catalyzer of dioxide peroxide generation.When using some halide salts for example during magnesium chloride, they also can provide a kind of because therefore the local heating effect that its solution heat causes also promotes the generation of this tablet dissolved and dioxide peroxide.The amount of this halide salts in this tablet is about 3wt%～about 12wt% or better about 5wt%～about 10wt% or better about 8wt%.
Said composition further comprises about 0.001wt%～about 5wt% or better about 1wt%～about 3wt% or better about 1wt%～about 2wt% carbohydrate (d) for example water soluble starch or treated starch.Can use any this kind of starch that gets, comprise from the starch of corn, wheat, soybean, rice, potato or cellulose-derived.This starch can provide the inlet point of water thereby help the dissolving of this tablet in water.
Said composition can further comprise a kind of filler (e).There are various fillers to be suitable for using, for example, basic metal (or alkaline-earth metal) vitriol in about 0.001wt%～about 37wt% scope.Vitriolate of tartar and sodium sulfate are the examples of this type of filler.
Said composition also randomly further comprises a kind of alkaline carbonate or supercarbonate or alkaline earth metal carbonate or supercarbonate (g), prerequisite be its positively charged ion do not generate a kind of in 25 ℃ of water the vitriol of solubleness＜1%.Example comprises sodium bicarbonate, yellow soda ash, saleratus, salt of wormwood, Magnesium hydrogen carbonate, magnesiumcarbonate, reaches the wherein combination of two or more.Better it is a sodium bicarbonate.Its amount can be about 0.001wt%～about 10wt% or better about 0.01wt%～about 10wt% or better about 0.1wt%～about 10wt% of said composition.Though do not think bound by theory, except that its effect aspect regulator solution pH, believe that carbonate or supercarbonate react and the effervescent effect that produces carbonic acid gas and cause thus in the aqueous acid medium, thereby further promote the said composition dissolving.
Said composition randomly comprises for example water-soluble tablets binding agent (g) of 0.001～about 15wt% binding agent, to improve the solubleness of this tablet in water and to serve as the compressing tablet binding agent to improve the hardness of this tablet.Can use any this type of binding agent that gets.Such as the such binding agent of sugar alcohol, Star Dri 5 or corn-syrup solids is preferably.Better, this binding agent is a kind of sugar alcohol.Better, this sugar alcohol is a Sorbitol Powder.The amount of this tablet binding agent can be about 1wt%～about 10wt% or better about 4wt%～about 5wt%.
Said composition also randomly comprises about 0.001～about 5wt% such as a kind of tablet lubricants (h), comprises polyoxyethylene glycol, Sodium Benzoate, stearate for example Magnesium Stearate, sucrose stearate etc., mineral oil and silicone lubricant.Lubricant and compression moulding auxiliary agent can be guaranteed the good demoulding of solid such as tablet in the tablet mould, and are well-known in the industry.For example, can usage quantity be the water-soluble polyethylene glycol of about 1wt%～about 2wt%.Better, its molecular weight be about 3000～about 10000, better about 3000～about 9000, better about 7000～about 9000, polyoxyethylene glycol 180 (PEG 180, can available from Dow Chemicals, available) for example.This lubricant also can act on sidewall during the compressing tablet process, thereby helps avoid the maintenance problem of sheeting equipment and guarantee the appropriate tablet demoulding and tablet integrity.
Said composition also randomly contains have an appointment 0.001～about 5wt% or better 1～about 2wt% stamping surface antisticking agent (i).Be preferably for example Sodium Benzoate of water-soluble flush pressure surface antisticking agent.This is such as by providing T﹠B stamping surface lubricant to help the compressing tablet process.This helps avoid the maintenance problem of sheeting equipment and helps to guarantee the appropriate tablet demoulding and tablet integrity.
Said composition also randomly contains 0.001～about 5wt% or 0.001～about 0.5wt% sweetener (j).Any sweetener that gets, especially stable sweetener all can use in the presence of oxygenant.
Said composition also randomly contains the 0.001～about 20wt% that has an appointment, and to help acid (k) for one kind be a kind of acid except that this alcohol acid, so that be ClO where necessary
2The best take place and pH value of solution adjusted to about 2.5～about 5.0.This helps acid can be hexanodioic acid, oxysuccinic acid, thionamic acid, citric acid, tartrate, sodium pyrosulfate or the wherein combination of two or more.
That said composition can easily be dissolved in is about 15～water of about 50 ℃ temperature in.For example, swimming-pool water may be in various differing tempss.The time possibility that a kind of particular composition is dissolved in the water required is because of different such as such factor: the physical form of said composition, size, number and shape, its surface and inner hardness, its surface roughness or glazing degree, its moisture content, the dissolving water temp, the water yield, stirring extent, homogeneity of the granularity of each composition and this adulterant etc. in this adulterant.
Those skilled in the art known any method is for example mixed, kneading, fusion, granulation, compressing tablet or extrude, and all can be used to the production said composition.Compressing tablet is disclosed in herein as a kind of embodiment.The manufacturing processed of said composition is for example carried out about 1 minute to about some hrs under normal temperature and the normal pressure in any suitable means.For example, compressing tablet can be used for producing and can easily be dissolved in the water but the tablet of the disruptive hardness that is enough to reduce packing and operating period is arranged, and the detailed description of such method is omitted for simplicity's sake in this article.For example, each composition can be weighed, sieve, make a kind of adulterant with the size that reduces agglomerate (if having), physical combination with such as using a Hobart mixing machine to mix.Perfume compound when existing typically can with one or more other composition premixs, to reduce the loss and to be easy to fusion.This adulterant feed can be advanced a tabletting machine for example Stokes DD2 Rotarytabletpress (can be available from DT Converting Technologies, 400 Kidd ' s Hill Road, Hyannis, Massachusetts) in.This tabletting machine can be adjusted to such an extent that can carry the tablet of desired size and hardness.
The present invention further comprises a kind ofly makes clarification of water, the health that becomes or disinfectant method, this method comprise make this water and a kind of as mentioned above, comprise a kind of reactive oxygen compounds and one or more can produce ClO
2Precursor composition contact, make described composition dissolves and produce a kind of solution of 40ppm dioxide peroxide at least that contains.This method has reduced or eliminated the turbidity of this water or opaqueness to reach transparency.This method also makes this water become health and sterilization, and wherein said composition plays the effect of biocide.Water temperature, dissolution time and resulting chlorine dioxide concentration such as above be that water treatment method of the present invention is disclosed.
Following examples are illustrative, but are not interpreted as the inappropriate restriction to the scope of the invention.
Analyze
Chlorine dioxide concentration and active oxygen can be measured as follows.Earlier with a kind of tablet dissolved in 3.785 liters of deionized waters.Use Hach DR/890 series colorimeter and Hach Method8345 (can be available from The Hach Company, P.O.Box 389, Loyeland Colordo80539) measures chlorine dioxide concentration.In order to determine that the ppm active oxygen-breviary that causes owing to dioxide peroxide is " ppmAO (ClO
2) ", above result be multiply by 0.593.
Owing to ppm active oxygen-breviary that OXONE causes is as follows for " ppmAO (OXONE) "-mensuration.At first, measure the total active oxygen content of above-mentioned solution.With a kind of tablet dissolved in 3.785 liters of deionized waters.In the 50g of this solution sample, add 10ml 20% sulfuric acid and 10ml 25% potassiumiodide.Then, (can be as DuPont technical bulletin for OXONE available from E.I.du Pont de Nemours and Company, Barley Mill Plaza 23,4417Lancaster Pike, Wilmington, DE19805) and internet " http://www.dupont.com/oxone/techinfo/ " disclosed like that, with this solution of Sulfothiorine titration.Then, with the ppmAO (ClO of this numerical value by the above mensuration of deduction
2) revised, determine ppmAO (OXONE).
Embodiment 1
The production sample tablet.Every 100g tablet comprises OXONE (72.6g), magnesium chloride (8g), Sorbitol Powder (4g), Textone (5g), sodium bicarbonate (5g), starch (2.6g), polyoxyethylene glycol PEG-180 (1.5g), Sodium Benzoate (0.9g) and perfume compound (0.4g).Each component is with a large-scale on-ground weigher weighing.Pre-grinding Textone that granularity has been diminished and perfume compound mix with Sorbitol Powder so that shift, with 10kg mixture altogether with " for kitchen use " Hobart mixing machine fusion that blade arranged 10 minutes.Feed a StokesDD2 rotary tablet machine with the powder of fusion.This tablet " hardness " is 5, shows the minimum hardness that reaches commerciality packing purpose.The size of this tablet is that every approximate weight is 2.6g.
When by being dissolved in when testing in 26 ℃ of water, this tablet dissolved time was less than 5 minutes.Test the stability of this tablet, it has 27ppm ClO at first
2With 766ppm OXONE (37ppmAO (OXONE) and 16ppmAO (ClO
2)).After 5 weeks at room temperature, this tablet has 27.3ppmClO
2With 860ppm OXONE (41ppmAO (OXONE) and 16ppmAO (ClO
2)), show that said composition is very stable.Made hardness and be three kinds of sample tablets of 5,6.5 and 11.The solubility test of tablet (every 5g) shows that the tablet of hardness 5 dissolved (3.785 premium on currency) in about 5 minutes, produce about 27ppm ClO
2, and the tablet of hardness 11 also dissolved in about 5 minutes and produce about 11.5ppm ClO
2
Under 1250 pounds～20000 pounds different pressures, also made every 5g and formed identical a series of tablets.All tablets are all at about 9 minutes (tablet of making under 1250 pounds of pressure)～be dissolved in 3.785 about 25～27 ℃ premium on currency in (tablet of making under 200000 pounds of pressure) in about 20 minutes, the chemical property that shows these tablets be very constant and no matter compressing tablet pressure how, and only show dissolution time is produced perceptible influence, especially true at the low side of this pressure yardstick.
Embodiment 2～6 and Comparative examples A～D
Produce a series of tablets (every 2.6g) in embodiment 1, different is to use the various chemical of equivalent to replace magnesium chlorides.As shown in table 1, have only the ClO of halide salts generation＞10ppm
2, and magnesium chloride obviously is better than other halogenide of being tested.Zinc chloride and zinc bromide composition also are gratifying.
Table 1
| Embodiment number | MgCl 2Or surrogate | Water temperature ℃ | Dissolution time (min.) | pH | ClO 2Ppm (test 1 1) | ClO 2Ppm (test 2 1) | ClO 2AO ppm | OXONE ppm |
| 2 | MgCl 2 | 25 | 8 | 4.5 | 11.8 | 12.9 | 7 | 47 |
| A | CaCl 2 | 25 | 60 2 | 3.4 | 2.1 | 3.4 | 1 | - |
| B | CaCl 2(2 tests) | 26 - | 60 60+ | NM 3 | 13.8 16.6 | 13.9 - | 8 10 | - - |
| C | CaBr 2 | 24 27 | 20 460+ | 3.7 3.5 | 11.3 4.3 | 11.6 - | 7 3 | 44 42 |
| 3 | ZnCl 2(2 tests) | 25 26 | 24 20 | 3.6 3.8 | 17.6 14 | 18.3 19 | 10 8 | 47 48 |
| 4 5 | ZnBr 2(2 tests) | 27 27 | 25 30 | 4.1 4.2 | 21.1 19.2 | 21.7 - | 13 11 | 39 37 |
| D | Na 3PO 4(2 tests) | 27 25 | 15 14 | 6.1 5.9 | 7.3 7.5 | - - | 4 4 | 50 48 |
| 5 | FeCl 3 | 25 | 12 | 3 | 42.9 6 | - | 25 | 32 |
| 6 | NaCl | 26 | 10 | 5.3 | 11.8 | 12.8 | 7 | 50 |
1Carry out ClO
2The time of test is depended on tablet dissolved speed thereby changes thereupon.
2If this tablet not exclusively dissolved, then stop this experiment when finishing in 60 minutes.
3NM, undetermined.
4The 1st test has stirring.
52 tests all have stirring.
6Ferric chloride test is owing to obviously be subjected to ClO
2The yellow color of test interferential and interrupting.Calcium Bromide also provides orange, and this may be subjected to the result and disturb.
Embodiment 7～9
Use the composition production test tablet of embodiment 1, different is to replace OXONE with Potassium Persulphate or sodium.With a Carver tabletting machine, this mixture of 5g is made 3 kinds of roughly the same tablets of size.These tablets are placed 1 gallon of (3.785 liters) water, make its dissolving.As shown in table 2, Sodium Persulfate and Potassium Persulphate can both produce ClO in solution
2
Table 2
| Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| OXONE | Potassium Persulphate | Sodium Persulfate | |
| Water temperature | 26C | 27C | 24C |
| pH | 4.4 | 6.8 | 6.8 |
| Tablet weight | 5 | 5.02 | 4.96 |
| Dissolution time | 5 minutes | 60 minutes | 30 minutes |
| ppm ClO2 | 27ppm | 11ppm | 16ppm |
| ppm OXONE | 766ppm | NA | NA |
| ppmAO OXONE | 37ppm | NA | NA |
| ppm AO ClO2 | 16ppm | 6.5ppm | 9.5ppm |
The NA=No data can be used
Embodiment 10 and Comparative examples A
All tablets are produced all in embodiment 1.Make a collection of 50g material, each embodiment takes out 10g and be pressed into tablet on a Carver tabletting machine.The results are shown in the following table 3.
Table 3
| Component (g) | Comparative examples A | 10-1 | 10-2 | 10-3 | 10-4 | 10-5 |
| Oxone | 2 | 2.4 | 2.35 | 2.5 | 2.3 | 2.3 |
| Magnesium chloride | 0.8 | 0.75 | 0.8 | 0.8 | 0.8 | |
| Textone | 1.5 | 1.5 | 1.5 | 1.5 | 2 | 2.5 |
| Sorbitol Powder | 0.5 | |||||
| Starch-food grade | 0.1 | 0.26 | 0.18 | 0.18 | ||
| PEG 180 | 0.1 | 0.15 | 0.15 | 0.15 | ||
| Sodium Benzoate | 0.05 | 0.06 | 0.06 | 0.15 | ||
| Sodium sulfate | 6.5 | 5.3 | 5.15 | 4.73 | 4.51 | 3.42 |
| ClO 2Reading | 42.3 | 9.9 | 7.9 | 8.1 | 8.6 | 10.1 |
| Dilution | 1∶10 | 1∶10 | 1∶10 | 1∶10 | 1∶10 | |
| The ClO that adjusts 2，ppm | 99 | 79 | 81 | 86 | 101 | |
| Temperature () | 80 | 80 | 80 | 80 | 80 | 80.0 |
| Time (minute) | ＞60 | ＞50 | 18 | 14 | 20 | 20 |
Table 3 shows, without tablet water fast in the desirable time of magnesium chloride making.
Embodiment 11
The tablet that as the above, prepares the prescription that embodiment 1 is arranged.By 2 pieces of tablet dissolved are prepared the Xingqi microorganism drug effect test of going forward side by side of a kind of solution in 2 gallons of (about 3.5 liters) deionized waters.
The inoculum preparation: test organisms comprises aurococcus (Staphylococcusaureus ATCC 6538), Pseudomonas aeruginosa (Pseudomonas aeruginosa ATCC15442) and cholera Salmonellas (Salmonella Chole-raesuis ATCC 10708).Use improved AOAC experimental program 965.13, wherein every kind of culture shifted in 3 days once a day on TRYPTICASE Soy Agar (TSA).The suspension of every kind of bacterium is all by adding the aseptic Butter-field buffer reagent of 5ml (BB) to the TSA plate and using suspend this bacterium colony of an aseptic L shaped loop-carrier to make.This suspension is moved on in the aseptic Nephalo flask.Other 5ml BB is added on this plate, this plate is reverberated, and resulting suspension is added in the same Nephalo flask.Get a Klett reading, this suspension further with BB dilution to provide one about 24～29 Klett reading (～89%T; This is equivalent to～1.0E+08CFU/ml).To lay in inoculum and further dilute 1: 100, so that density as shown in table 4 to be provided.
Pilot system: 0.1ml is tested the inoculum aliquots containig add in the 9.9ml substances, this test tube is mixed, and start timing register.After 10 minute exposure time, on TSA, carry out serial dilution plate counting.Use D/E (Dey/Engley) neutralising fluid substratum (can be available from Becton Diekinson, Billerica MA) carries out neutralization in the first serial dilution pipe.The inoculum controlled trial is also added among the 9.9ml BB and is carried out by 0.1ml being tested inoculum, and cultivates on the TSA plate after 10 minute exposure time.All plates are all cultivated 18～24h at 35 ℃, carry out enumeration and bulk density.In order to verify neutralization, a bacterium colony from 24h TSA plate is added in the 9.9ml BB pipe, and will be inoculated into from 1 μ l loopful in this pipe in every Dey/Engley pipe and show improvement not.The 0.1ml aliquot sample is placed on the TSA plate, cultivates 48h at 35 ℃, carries out enumeration.Place the 0.1ml aliquot sample on the TSA plate to cause about 200 bacterium colonies/plate.Each test organisms is all carried out this step.
(Textone of stabilization can be available from IDI, and North Kingston RI), prepares a kind of ClO in the MILLIPORE of filter sterilised water with dense HCl acidifying Anthium Dioxide in use
2Contrast solution.The ClO of prepared solution
2Concentration is to use a kind of 0～50ppmHach kit measurement.Carry out replication 3 times: (1) 23.2mg/l, (2) 23.0mg/l and (3) 23.5mg/l, average ClO
2Concentration is 23.2ppm.The results are shown in the table 4.
Table 4
| Plate counting @ dilution | Deposit inoculum density | |
| S.aureus | 102/108@-5 | 1.1E+08CFU/ml |
| P.aeruginosa | 39/44@-5 | 4.2E+07CFU/ml |
| S.choleraesuis | 144/154@-5 | 1.5E+08CFU/ml |
Density of the bacterium of being challenged and bacterium effectiveness results concerning every kind of bacterium, are shown in respectively among following table 5A～5C.In table 4,5A, 5B and 5C, E+ or-two these symbols of numeral mean a kind of index, 10 the power that two numeral points out that the number with the E front multiplies each other.For example, 1.1E+08 is 1.1 * 10
8
Table 5A
| Exposure duration | Describe | The plate counting | Extension rate | CFU/mL * | Δt | ||
| Rep A | RepB | Mean value | |||||
| NA 30sec 30sec 30sec 30sec 30sec | Do not cultivate the contrast inoculum: S.aureus embodiment 11=1,008ppm Oxone+55.5ppm Chlorite 1,008ppm Oxone contrast 55.5ppm Chlorite contrast 23.2ppm ClO2 contrast | 0 90 0 145 109 0 | 0 181 0 159 136 0 | 0 136 0 152 123 0 | 1 0.001 1 0.001 0.001 1 | 0.00E+00 1.36E+06 1.00E+01 1.52E+06 1.23E+06 1.00E+01 | NA NA 5.1 0.0 0.0 5.1 |
| 10min 10min 10min 10min 10min | Inoculum: S.aureus embodiment 11=1,008ppm Oxone+55.5ppm Chlorite 1,008ppm Oxone contrast 55.5ppm Chlorite contrast 23.2ppm ClO2 contrast | 157 0 60 113 0 | 164 0 63 126 0 | 161 0 62 120 0 | 0.001 1 0.001 0.001 1 | 1.61E+06 1.00E+01 6.15E+05 1.20E+06 1.00E+01 | NA 5.2 0.4 0.1 5.2 |
| 10min | Inoculum: S.aureus-pH4.5 buffer reagent | 135 | 162 | 149 | 0.001 | 1.49E+06 | NA |
*Low detection level is 1.0E+01CFU/mL (a CFU=colony-forming unit)
Δ t is test density and the difference logarithmic value that contrasts density
NA=is inapplicable
Table 5B
| Exposure duration | Describe | The plate counting | Extension rate | CFU/ml * | Δt | ||
| RepA | RepB | Mean value | |||||
| NA 30sec | Do not cultivate contrast inoculum: P.aeruginosa | 0 95 | 0 108 | 0 102 | 1 0.001 | 0.00E+00 1.02E+06 | NA NA |
| 30sec 30sec 30sec 30sec | Embodiment 11=1,008ppmm Oxone+55.5ppm Chlorite 1,008ppm Oxone contrast 55.5ppm Chlorite contrast 23.2ppmClO2 contrast | 0 71 104 0 | 0 119 129 0 | 0 95 117 0 | 1 0.001 0.001 1 | 1.00E+01 9.50E+05 1.17E+06 1.00E+01 | 5.0 0.0 -0.1 5.0 |
| 10min 10min 10min 10min 10min | Inoculum: P.aeruginosa embodiment 11=1,008ppm Oxone+55.5ppm Chlorite 1,008ppm Oxone contrast 55.5ppm Chlorite contrast 23.2ppmClO2 contrast | 127 0 0 105 0 | 128 0 0 136 0 | 128 0 0 121 0 | 0.001 1 1 0.001 1 | 1.28E+06 1.00E+01 1.00E+01 1.21E+06 1.00E+01 | NA 5.1 5.1 0.0 5.1 |
| 10min | Inoculum: P.aeruginosa-pH4.5 buffer reagent | 114 | 118 | 116 | 0.001 | 1.16E+06 | NA |
*Low detection level is 1.0E+01CFU/mL (a CFU=colony-forming unit)
Δ t is test density and the difference logarithmic value that contrasts density
NA=is inapplicable
Table 5C
| Exposure duration | Describe | The plate counting | Extension rate | CFU/ml * | Δt | ||
| RepA | RepB | Mean value | |||||
| NA 30sec | Do not cultivate contrast inoculum: S.choleraesuis | 0 137 | 0 144 | 0 140.5 | 1 0.001 | 0.00E+00 1.41E+06 | NA NA |
| 30sec 30sec 30sec 30sec | Embodiment 11=1,008ppm Oxone+55.5ppm Chlorite 1,008ppm Oxone contrast 55.5ppm Chlorite contrast 23.2ppm ClO2 contrast | 0 209 306 0 | 0 218 312 0 | 0 213.5 309 0 | 1 0.001 0.001 1 | 1.00E+01 2.14E+06 3.09E+06 1.00E+01 | 5.1 -0.2 -0.3 5.1 |
| 10min 10min 10min 10min 10min | Inoculum: S.choleraesuis embodiment 11=1,008ppm Oxone+55.5ppm Chlorite 1,008ppm Oxone contrast 55.5ppm Chlorite contrast 23.2ppm ClO2 contrast | 200 0 29 115 0 | 241 0 30 138 0 | 220.5 0 29.5 126.5 0 | 0.001 1 0.1 0.001 1 | 2.21E+06 1.00E+01 2.95E+03 1.27E+06 1.00E+01 | NA 5.3 2.9 0.2 5.3 |
| 10min | Inoculum: S.choleraesuis-pH4.5 buffer reagent | 199 | 209 | 204 | 0.001 | 2.04E+06 | NA |
*Low detection level is 1.0E+01CFU/mL (a CFU=colony-forming unit)
Δ t is test density and the difference log that contrasts density
10Value
NA=is inapplicable
Be dissolved in 2 gallons of tablets of the present invention in (about 7.6 liters) water and kill all bacteriums very effectively, bacterium reduces 10 in 30 seconds
5Doubly.For aurococcus (S.aureus), this activity level is probably owing to ClO in the solution
2Generation (23.2ppm) is because ClO
2Control group also confirms 30 seconds interior identical levels of killing (seeing Table 5A) of kind.Similarly, for Pseudomonas aeruginosa (P.aeruginosa), 10
5Doubly kill the ClO that exposes owing to 30 seconds probably
2Take place, although also confirmed that OXONE is independent 1 when exposing in 10 minutes, the drug effect of 008ppm (seeing Table 5B).ClO during 30 seconds
2Contrast has confirmed to kill fully and (has promptly reduced 10
5Doubly).On the other hand, OXONE has also confirmed to kill fully and (has reduced 10 10 minutes the time
5.1Doubly).For cholera Salmonellas (S.choleraesuis), the ClO that this activity level also exposes owing to 30 seconds kinds probably
2Take place, this exposure has confirmed to kill fully and (has promptly reduced 10
5.1Doubly).Confirmed when exposing in 10 minutes that OXONE is independent 1, certain drug effect of 008ppm (promptly kills 10
2.9Doubly) (seeing Table 5C).
Embodiment 12
This test has been done some improvement to the AOAC sterilizing agent Fungicidally active experimental program Method955.17 that publishes.Allow Aspergillus fumigatus (Aspergillus fumigatus ATCC 1098) Malt Extract Agar (can be available from Becton Dickinson, Billerica MA) grows on the plate, and results spore.Spore is stored in-20 ℃ the filter sterilised Millipore water.Below describe the spore preparation that is used for this experiment in detail.With deicing of refrigerator storing solution and the dilution of Aspergillus fumigatus (A.fumigatus), obtain a kind of inoculum suspension that is used for this experiment.It is about 5 * 10 that this inoculum preparation is estimated
6Conidium/ml.Use the MILLIPORE water of filter sterilised, in the 4L bottle of water vapor sterilization, prepare following testing liquid:
Water contrast: (only filter sterilised water), pH6.28.
The OXONE contrast: 3.78g OXONE is using 0.98g NaHCO
3And 5.25g10%H
2SO
4Be buffered in 1 gallon of (about 3.8 liters) sterilized water of pH4.43.
The Chlorite contrast: the 0.26g Textone is being buffered to pH4.55 (1.8g10%H
2SO
4) 1 gallon of sterilized water in.
The buffer reagent contrast: sodium bicarbonate, pH adjusts to 4.4.
Dioxide peroxide: (Textone of stabilization can be available from IDI, and North Kingston RI), uses the HCl acidifying for Anthium Dioxide.
The CLOROX contrast: 4.17 (v/v) %CLOROX SYNTHETIC OPTICAL WHITNER in the MILLIPORE water (can be available from Clorox Company, Oakland, CA), by 4.17ml Clorox SYNTHETIC OPTICAL WHITNER and water are mixed into the preparation of 100ml cumulative volume.
(embodiment 12: with 2 pieces of embodiment 1 tablet dissolved in 1 gallon of (about 3.8 liters) deionized water for the tablet testing liquid.The tablet total weight amount is 5.13g.The pH of resultant solution is 5.2.
Reaction tubes: every kind of testing liquid 5ml is distributed in the 25 * 150mm test culture tube, adds a cover and according to table 6 mark.Interpolation 9ml D/E (Dey/Engley) neutralising fluid substratum in each of 28 test tubes (can be available from Becton Dickinson, Billerica MA) and with these test tubes adds a cover.Butterfield buffer reagent blank in and dilution of sample arrange, Malt Extract Agar plate is by the spore counting numbering of dilution, neutral sample.With a graduated transfer pipet with 0.5ml spore inoculating thing (about 10
6Conidium/ml) add in the first pipe testing liquid, sway gently.After each testing liquid exposed respectively 5 minutes and 15 minutes, sway gently, from every kind of reaction mixture (spore testing liquid), take out the 1ml sample and place 9ml D/E (Dey/Engley) neutralising fluid substratum with an Eppendorf transfer pipet.This inoculum further is diluted to about 10
4Conidium/ml.Among refabrication 2 side reaction pipes (water and OXONE-chlorite) and 4 Dey/Engley and pipe, to assess this sheet agent solution in this reaction tubes 10
4The drug effect of the final inoculum density of conidium/ml.Sample only reacted 15 minutes.Prepare in each and dilution of sample liquid.The 100 μ l aliquot sample of all samples in D/E (Dey/Engley) neutralising fluid substratum are placed on the Malt Extract Agar plate and 25 ℃ of cultivations and occur until bacterium colony for each 2 parts.After cultivation about 4 days, after bacterium colony occurs, plate is counted.Some kinds of diluents of this inoculum spore suspension are also placed on the Malt Extract Agar plate, with the accurate counting of the spore alive that obtains being used as inoculum.These samples are 25 ℃ of cultivations, and after the cultivation about 4 days, after bacterium colony occurs, count.
(A.fumigatus) is inoculated in contrast solution and the testing liquid with Aspergillus fumigatus, and reaching final densities is about 5.6～6.25 * 10
5Conidium/ml, and contrast with water contrast and buffer reagent and to be confirmed.This inoculum solution also places on the plate, counting, and this counting be multiply by the volume (0.5ml) that adds in contrast solution and the testing liquid to estimate density; 2.57 * 10
5Conidium/ml is corresponding well with water contrast and buffer reagent contrast.Get the buffer reagent contrasting data after 15 minutes.After handling 5 minutes, get the CLOROX contrasting data.
The result shows, tablet of the present invention, ClO
2(about 23 ppm) and 4.17%CLOROX solution can kill 10 in 5 minutes
5Aspergillus fumigatus spores; ClO
2With CLOROX is to contrast.In addition, the contrast of OXONE contrast and chlorite all can not make this biological load minimizing handling in 15 minutes.
Drug effect is subjected to this biological load density and organic dirt influence.Prepare the lower inoculum of a kind of density, about 6.7 * 10
3Conidium/ml, and with tablet testing liquid (2 pieces of tablet/gallons) challenge 15 minutes.This test is in higher inoculum density (10
5Carry out under the situation of conidium/ml) not influenced by this processing.The tablet testing liquid that embodiment 12 handles is also killed this (density) lower inoculum.
The solution of tablet of the present invention can be killed all Aspergillus fumigatus (A.fumigatus) spore (5～6 * 10 fully in 5 minutes
5Conidium/ml).Contrast shows that the OXONE solution and the sodium chlorite solution that are equivalent to measured amount in this sheet agent solution can not reduce the fungal organism load effectively.With the identical prepared at concentrations ClO 2 solution in contrast that produces with tablet; 23ppm ClO
2Solution also can be killed Aspergillus fumigatus (A.fumigatus) inoculum fully in 5 minutes.
The sheet agent solution of embodiment 12 has produced the ClO that is enough to kill fully this inoculum
2The independent component of this tablet, promptly OXONE and sodium chlorite solution are independent, this biological load are reduced, though the result of their reactions in solution is mycocidal strongly to Aspergillus fumigatus (A.fumigatus).The results are shown in Table 6.
Table 6 survival biological load counting (sprout spore, conidium/ml)
| 1×10 5Inoculum in conidium/ml reaction mixture, 2 revision test mean values | |||||||
| Time | Water pH6.28 | Buffer reagent pH4.4 | 2 pieces of tablets of embodiment 12-, 3.8L | Oxone | Chlorite | Dioxide peroxide | CLOROX |
| 5mm | 5.60E+05 | Not test (N.T.) | 0.00E+00 | 3.45E+05 | 4.25E+05 | 0.00E+00 | 0.00E+00 |
| stdevp | 1.00E+04 | Not test (N.T.) | 0.00E+00 | 7.25E+04 | 1.43E+05 | 0.00E+00 | 0.00E+00 |
| 15min | 6.25E+05 | 6.00E+05 | 0.00E+00 | 5.70E+05 | 6.25E+05 | 0.00E+00 | Not test (N.T.) |
| stdevp | 6.50E+04 | 1.13E+05 | 0.00E+00 | 7.50E+04 | 5.25E+04 | 0.00E+00 | Not test (N.T.) |
| 1×10 3Inoculum in conidium/ml reaction mixture, 2 revision test mean values | ||
| Time | Water pH6.28 | Embodiment 12-2 piece tablet/3.8L |
| 15min | 6.70E+03 | 0.00E+00 |
| stdevp | 6.25E+02 | 0.00E+00 |
| Inoculum checking conidium/ml, 1 revision test | ||
| Time | 1×10 5Inoculum | 1×10 3Inoculum |
| 5min | 2.57E+05 | 3.77E+03 |
Claims (13)
1. water treatment method, comprise: water is contacted with a kind of solids composition, wherein said composition comprises a kind of reactive oxygen compounds and one or more are used to take place the precursor of dioxide peroxide, b) make described composition＜be dissolved in about 25 ℃ described water in about 60 minutes, and c) produce a kind of solution that contains at least about the 40ppm dioxide peroxide.
2. the process of claim 1 wherein that described composition comprises by weight
A) about 20wt%～about 90wt% sulfur-bearing alcohol acid;
B) about 3wt%～about 25wt% solubility chlorite;
C) about 3wt%～about 12wt% alkali metal halide or alkaline earth metal halide or its mixture;
D) about 0.001wt%～about 37wt% filler;
E) about 0.001wt%～about 5wt% carbohydrate; With
F) randomly, a kind of alkaline carbonate, alkaline earth metal carbonate, alkali metal hydrocarbonate, alkali metal bicarbonates or its mixture; A kind of binding agent; A kind of lubricant; A kind of stamping surface release agent; A kind of sweetener; A kind of acid except that this alcohol acid; The perhaps wherein combination of two or more;
Prerequisite is that the positively charged ion of described alkali metal halide, described alkaline earth metal halide, described alkaline carbonate, described alkaline earth metal carbonate, described alkali metal hydrocarbonate or described alkali metal bicarbonates does not generate the vitriol of solubleness in the water＜1%.
3. the method for claim 2, wherein said sulfur-bearing alcohol acid comprises a Potassium Persulphate, two Potassium Persulphates or its mixture, better comprises 2KHSO
5KHSO
4K
2SO
4Three geavy salt of this chemical formula.
4. the method for claim 2, wherein said solubility chlorite is a Textone.
5. the method for claim 2, wherein said an alkali metal salt or alkaline earth metal halide salt are magnesium chloride, zinc chloride, zinc bromide, sodium-chlor or its mixture; It better is magnesium chloride.
6. the method for claim 2, wherein said an alkali metal salt or alkaline earth metal carbonate or supercarbonate are sodium bicarbonates.
7. the method for claim 2, wherein said composition further comprises about 0.001～about 10wt% alkaline carbonate, alkaline earth metal carbonate, alkali metal hydrocarbonate, alkali metal bicarbonates or its mixture; About 0.001～about 15wt% binding agent; About 0.001～about 5wt% lubricant; About 0.001～about 5wt% stamping surface antisticking agent; About 0.001～about 5wt% sweetener; About 0.001～about 20wt% acid except that this alcohol acid; Or the wherein combination of two or more.
8. the method for claim 7, wherein said sugar alcohol is a Sorbitol Powder, and described lubricant about polyoxyethylene glycol of 3000～about 10000 that is molecular weight.
9. claim 1 or 7 method, wherein this water is Chi Shui, recuperates with mineral water, fountain water, reflection tank water or decorate pool water.
One kind make clarification of water, the health that becomes or disinfectant method, comprise this water is contacted with a kind of composition, said composition comprises a kind of reactive oxygen compounds can produce the precursor of dioxide peroxide when described the contact with one or more, and described composition＜be dissolved in about 25 ℃ described water in about 60 minutes, thereby produce a kind of solution that contains at least about the 40ppm dioxide peroxide.
11. the method for claim 10, wherein said composition comprises by weight
A) about 20wt%～about 90wt% sulfur-bearing alcohol acid;
B) about 3wt%～about 25wt% solubility chlorite;
C) about 3wt%～about 12wt% alkali metal halide or alkaline earth metal halide or its mixture;
D) about 0.001wt%～about 37wt% filler;
E) about 0.001wt%～about 5wt% carbohydrate; With
F) randomly, a kind of alkaline carbonate, alkaline earth metal carbonate, alkali metal hydrocarbonate, alkali metal bicarbonates or its mixture; A kind of binding agent; A kind of lubricant; A kind of stamping surface release agent; A kind of sweetener; A kind of acid except that this alcohol acid; The perhaps wherein combination of two or more;
Prerequisite is that the positively charged ion of described alkali metal halide, described alkaline earth metal halide, described alkaline carbonate, described alkaline earth metal carbonate, described alkali metal hydrocarbonate or described alkali metal bicarbonates does not generate the vitriol of solubleness in the water＜1%.
12. composition, comprise a kind of reactive oxygen compounds and can produce the precursor of dioxide peroxide when described the contact with one or more, wherein said composition＜be dissolved in about 25 ℃ described water in about 60 minutes, thereby produce a kind of solution that contains at least about the 40ppm dioxide peroxide.
13. the composition of claim 12, said composition comprises by weight
A) about 20wt%～about 90wt% sulfur-bearing alcohol acid;
B) about 3wt%～about 25wt% solubility chlorite;
C) about 3wt%～about 12wt% alkali metal halide or alkaline earth metal halide or its mixture;
D) about 0.001wt%～about 37wt% filler;
E) about 0.001wt%～about 5wt% carbohydrate; With
F) randomly, a kind of alkaline carbonate, alkaline earth metal carbonate, alkali metal hydrocarbonate, alkali metal bicarbonates or its mixture; A kind of binding agent; A kind of lubricant; A kind of stamping surface release agent; A kind of sweetener; A kind of acid except that this alcohol acid; The perhaps wherein combination of two or more;
Prerequisite is that the positively charged ion of described alkali metal halide, described alkaline earth metal halide, described alkaline carbonate, described alkaline earth metal carbonate, described alkali metal hydrocarbonate or described alkali metal bicarbonates does not generate the vitriol of solubleness in the water＜1%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58972604P | 2004-07-21 | 2004-07-21 | |
| US60/589,726 | 2004-07-21 | ||
| US11/116,485 | 2005-04-28 |
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ID=38166696
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785480A (en) * | 2010-03-15 | 2010-07-28 | 成都润兴消毒药业有限公司 | Water purifying and sterilizing disinfectant |
| CN104995133A (en) * | 2013-03-29 | 2015-10-21 | 大曹株式会社 | Tablet for preparing solution of chlorine dioxide |
| CN105217802A (en) * | 2015-10-29 | 2016-01-06 | 余姜 | A kind of water quality cleansing agent |
| CN108002509A (en) * | 2017-12-07 | 2018-05-08 | 清远海贝生物技术有限公司 | A kind of aquaculture substrate improvement tablet and preparation method thereof |
| CN111573930A (en) * | 2020-05-20 | 2020-08-25 | 山东大学 | Visible light photocatalysis-ClO2Method for efficiently removing organic pollutants in wastewater by oxidation combined process |
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2005
- 2005-07-20 CN CN 200580023316 patent/CN1984846A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785480A (en) * | 2010-03-15 | 2010-07-28 | 成都润兴消毒药业有限公司 | Water purifying and sterilizing disinfectant |
| CN104995133A (en) * | 2013-03-29 | 2015-10-21 | 大曹株式会社 | Tablet for preparing solution of chlorine dioxide |
| CN105217802A (en) * | 2015-10-29 | 2016-01-06 | 余姜 | A kind of water quality cleansing agent |
| CN108002509A (en) * | 2017-12-07 | 2018-05-08 | 清远海贝生物技术有限公司 | A kind of aquaculture substrate improvement tablet and preparation method thereof |
| CN111573930A (en) * | 2020-05-20 | 2020-08-25 | 山东大学 | Visible light photocatalysis-ClO2Method for efficiently removing organic pollutants in wastewater by oxidation combined process |
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