CN117401649B - Pure activation-free stable chlorine dioxide solution - Google Patents
Pure activation-free stable chlorine dioxide solution Download PDFInfo
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- CN117401649B CN117401649B CN202311724524.0A CN202311724524A CN117401649B CN 117401649 B CN117401649 B CN 117401649B CN 202311724524 A CN202311724524 A CN 202311724524A CN 117401649 B CN117401649 B CN 117401649B
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 257
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 129
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 129
- 229940061605 tetrasodium glutamate diacetate Drugs 0.000 claims abstract description 57
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 claims abstract description 57
- 239000000679 carrageenan Substances 0.000 claims abstract description 20
- 229940113118 carrageenan Drugs 0.000 claims abstract description 20
- 235000010418 carrageenan Nutrition 0.000 claims abstract description 20
- 229920001525 carrageenan Polymers 0.000 claims abstract description 20
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims abstract description 20
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000002562 thickening agent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 95
- 239000007788 liquid Substances 0.000 claims description 28
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 13
- 235000010265 sodium sulphite Nutrition 0.000 claims description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 13
- 239000012498 ultrapure water Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000001580 bacterial effect Effects 0.000 abstract description 12
- 210000000170 cell membrane Anatomy 0.000 abstract description 8
- 230000003213 activating effect Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 5
- 230000000536 complexating effect Effects 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000013522 chelant Substances 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- DLTWOYCDRWJVIM-JEDNCBNOSA-M sodium;(2s)-2-[bis(carboxymethyl)amino]-5-hydroxy-5-oxopentanoate Chemical compound [Na+].OC(=O)CC[C@@H](C([O-])=O)N(CC(O)=O)CC(O)=O DLTWOYCDRWJVIM-JEDNCBNOSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 92
- 239000007789 gas Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 25
- 230000001954 sterilising effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 241000588724 Escherichia coli Species 0.000 description 9
- 238000004659 sterilization and disinfection Methods 0.000 description 9
- 241000191967 Staphylococcus aureus Species 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 239000012880 LB liquid culture medium Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 ferro-manganese ions Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229960004599 sodium borate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 229940073490 sodium glutamate Drugs 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/025—Preparation from chlorites or chlorates from chlorates without any other reaction reducing agent than chloride ions
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
Abstract
The invention belongs to the field of preparation of chlorine dioxide solution, and particularly relates to a pure activation-free stable chlorine dioxide solution. The prepared pure chlorine dioxide gas is absorbed by the monosodium glutamate diacetate solution in a flowing state, so that stable chelate can be formed, the absorption rate of the chlorine dioxide gas at low temperature is obviously improved, and the absorption rate can reach 3.4 g/L; the tetrasodium glutamate diacetate is environment-friendly, and can react with calcium and magnesium ions on bacterial cell membranes in a complexing way to quickly release chlorine dioxide molecules, an activating agent is not required to be added, the fluidity and the permeability of the bacterial cell membranes are enhanced, and the fluidity and the permeability of the bacterial cell membranes are synergistic, so that the bacteriostasis speed and the bacteriostasis capacity of the prepared solution are improved; the natural thickener carrageenan can increase the adhesive capacity of the solution on the surface of an object, and when the solution acts under the illumination condition, chlorine generated by volatilization of the low-concentration solution cannot be scattered into the air, so that the solution is more green and safer.
Description
Technical Field
The invention belongs to the field of preparation of chlorine dioxide solution, and particularly relates to a pure activation-free stable chlorine dioxide solution.
Background
Chlorine dioxide is a strong oxidant, has various functions of disinfection, sterilization, corrosion prevention, deodorization and the like, has low oxidation-reduction potential, can effectively react with organic substances, sulfides, ferro-manganese ions and the like, has high sensitivity, and has a preparation method which is simpler and more convenient than that of a common disinfectant, thus being very widely applied. Chlorine dioxide gas is dissolved in water and does not react with water molecules chemically, but the diffusion speed and the permeability in water are extremely high, but the chlorine dioxide water solution is unstable and easy to decompose at normal temperature, a stabilizer is generally added into the chlorine dioxide solution, the decomposition speed of chlorine dioxide can be delayed after the stabilizer is added, and the chlorine dioxide gas can be kept in the solution for a long time, but when the chlorine dioxide gas is used, acid is added into the steady-state chlorine dioxide solution for activation, and the chlorine dioxide gas can be released after the activation.
The existing technology for preparing the chlorine dioxide solution mainly has the following problems: firstly, a chemical method is used for preparing chlorine dioxide gas, equipment is simple, operation and maintenance are convenient, but the cost of required raw materials is high, impurity gas is generated during preparation, and the solubility of the chlorine dioxide gas at normal temperature and normal pressure is low, so that the waste of raw materials is caused; the common stabilizing agents of the second and stable chlorine dioxide solution are sodium carbonate, sodium percarbonate, sodium borate and sodium perborate, and an acidic activating agent is added to release chlorine dioxide gas molecules during use, so that the operation is more complicated, and the sterilizing effect of the chlorine dioxide solution is mostly influenced by the concentration and the activating time of the activating agent, so that the sterilizing effect is unstable; thirdly, the chlorine dioxide solution with the concentration of 20-200 mg/L is harmless to human bodies, but the low-concentration chlorine dioxide solution has long sterilization time, generally about 10-30 min, and is difficult to adhere to the surface of an object, and the low-concentration chlorine dioxide solution is gradually lost and volatilized during the period, and can be decomposed to generate oxygen and chlorine which is harmful to human bodies.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides a pure activation-free stable chlorine dioxide solution, and in order to solve the problems that the absorption rate of chlorine dioxide gas prepared by a chemical method is low, an acidic activator is required to be added into the stable chlorine dioxide solution when the stable chlorine dioxide solution is used, and the liquid chlorine dioxide solution is difficult to adhere to the surface of an object, the invention proposes that the stable liquid absorbing the chlorine dioxide gas is placed in a spiral stirring kettle and stirred to enable the liquid to be in a flowing state, so that the absorption rate of the chlorine dioxide gas is improved; meanwhile, the degradable tetra sodium glutamate diacetate solution is used for absorbing chlorine dioxide gas, so that pure and stable activation-free chlorine dioxide solution is obtained; in addition, the natural thickener carrageenan is added, so that the adhesion capability of the pure activation-free stable chlorine dioxide solution on the surface of an object is improved, and the environment-friendly and safe chlorine dioxide solution is realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a pure activation-free stable chlorine dioxide solution, which comprises the following components in parts by weight:
2-6 parts of sodium chlorate, 1-3 parts of sodium sulfite, 1-3 parts of concentrated sulfuric acid, 15-20 parts of green degradable complex solution and 4-6 parts of natural thickener.
Preferably, the green degradable complexing solution is tetrasodium glutamate diacetate solution.
Preferably, the preparation method of the tetra sodium glutamate diacetate solution specifically comprises the following steps:
s1, pouring tetra sodium glutamate diacetate powder and sterile ultrapure water into a stirring tank to obtain tetra sodium glutamate diacetate mixture;
s2, stirring the tetra-sodium glutamate diacetate mixture prepared in the step S1 in a stirring tank to obtain tetra-sodium glutamate diacetate solution.
Further, in S1, the tetra sodium glutamate diacetate powder is 40 to 60 parts by weight and the sterile ultra pure water is 100 to 240 parts by weight.
Further, in S2, the stirring speed of the stirring tank is 100-120 r/min, the stirring temperature is 23-26 ℃, and the stirring time is 10-16 min.
Preferably, the natural thickener is carrageenan.
The invention also provides a preparation method of the pure activation-free stable chlorine dioxide solution, which specifically comprises the following steps:
step one: weighing sodium chlorate and sodium sulfite according to parts by weight, putting into a stainless steel reaction kettle, heating and stirring, slowly adding concentrated sulfuric acid, and reacting to obtain pure chlorine dioxide gas;
step two: weighing the green degradable complex liquid and the thickening agent according to parts by weight, pouring the green degradable complex liquid and the thickening agent into a spiral stirring kettle, and stirring to obtain a fluid dynamic green degradable complex liquid;
step three: and (3) introducing the pure chlorine dioxide gas prepared in the step (I) into a spiral stirring kettle through an air duct, stirring and absorbing the pure chlorine dioxide gas into the flowing green degradable complex liquid prepared in the step (II) to obtain the pure activation-free stable chlorine dioxide solution.
Preferably, in the first step, the adding rate of the concentrated sulfuric acid is 1-3 drops/min; the reaction temperature of the stainless steel reaction kettle is 200-230 ℃, the reaction time is 2-5 min, the reaction pressure is 101.3 kPa, and the stirring speed is 1000-1300 r/min.
Preferably, in the second step, the stirring speed of the spiral stirring kettle is 120-150 r/min, the stirring temperature is 23-25 ℃, and the stirring time is 8-12 min.
Preferably, in the third step, the stirring absorption speed of the spiral stirring kettle is 125-140 r/min, the stirring absorption time is 10-20 min, the absorption temperature is 0-5 ℃, and the absorption pressure is 101 kPa.
The beneficial effects obtained by the invention are as follows:
according to the invention, pure chlorine dioxide gas is prepared by heating reaction of sodium chlorate, sodium sulfite and concentrated sulfuric acid, no impurity gas is generated, and the stable liquid for absorbing the chlorine dioxide gas is placed in a spiral stirring kettle and stirred to enable the liquid to be in a flowing state, so that the absorption rate of the chlorine dioxide gas at low temperature is improved, the operation is convenient, the utilization rate of raw materials is improved at normal temperature and normal pressure, and the cost is saved; meanwhile, the tetra sodium glutamate diacetate is mainly prepared from plant-based raw material L-sodium glutamate, is environment-friendly and easy to biodegrade, can be applied in a very wide pH range, and can be used for absorbing chlorine dioxide gas by using tetra sodium glutamate diacetate solution, so that the obtained stable chlorine dioxide solution is more environment-friendly, and the complexing capacity of the tetra sodium glutamate diacetate and calcium and magnesium ions on bacterial cell membranes is very high, so that the chlorine dioxide molecules are quickly released, no activating agent is needed to be added, and the fluidity and permeability of the bacterial cell membranes are enhanced by the tetra sodium glutamate diacetate, the chlorine dioxide molecules are promoted to enter cells, the synergistic effect of the tetra sodium glutamate diacetate and the chlorine dioxide molecules is accelerated, the release and the action speed of the chlorine dioxide are accelerated, and the antibacterial capacity of the prepared pure activation-free stable chlorine dioxide solution is improved; in addition, the natural thickener carrageenan with scientific proportion is added into the tetra sodium glutamate diacetate solution, so that chlorine dioxide molecules can be more stably existing in the stabilizer solution, the adhesion capability of the pure activation-free stable chlorine dioxide solution on the surface of an object can be improved, the chlorine dioxide solution with low concentration cannot be volatilized and lost easily, and chlorine generated by volatilization cannot be diffused into the air under the action of illumination conditions, so that the environment-friendly and safe chlorine dioxide solution is more green and safer.
Drawings
FIG. 1 is a molecular formula diagram of tetrasodium glutamate diacetate;
FIG. 2 is a molecular formula diagram of carrageenan;
FIG. 3 is a standard graph of chlorine dioxide standard;
FIG. 4 is a graph showing the measurement of chlorine dioxide content by ultraviolet spectrophotometry in examples 1-3 and comparative examples 1-3;
FIG. 5 is a graph showing the results of killing E.coli in examples 1-3 and comparative examples 1-3;
FIG. 6 is a graph showing the sterilizing effect of E.coli.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present invention. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the scope of the present application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials and test strains used in the examples described below, unless otherwise specified, were commercially available.
Example 1: the embodiment provides an activation-free stable chlorine dioxide solution, which comprises the following components in parts by weight:
2 parts of sodium chlorate, 1 part of sodium sulfite, 1 part of concentrated sulfuric acid, 15 parts of tetra sodium glutamate diacetate solution and 4 parts of carrageenan.
The preparation method of the tetrasodium glutamate diacetate solution specifically comprises the following steps:
s1, adding 40 parts by weight of tetrasodium glutamate diacetate powder and 100 parts by weight of sterile ultrapure water into a stirring tank to obtain a tetrasodium glutamate diacetate mixture;
s2, stirring the tetra-sodium glutamate diacetate mixture prepared in the step S1 in a stirring tank at the stirring speed of 100 r/min and the stirring temperature of 23 ℃ for 10 min to obtain the tetra-sodium glutamate diacetate solution.
The embodiment also provides a preparation method of the pure activation-free stable chlorine dioxide solution, which specifically comprises the following steps:
step one: weighing sodium chlorate and sodium sulfite according to parts by weight, putting into a stainless steel reaction kettle, heating and stirring, slowly adding concentrated sulfuric acid at a rate of 1 drop/min, reacting at 200 ℃ for 2 min under 101.3 kPa stirring speed of 1000 r/min to obtain pure chlorine dioxide gas;
step two: weighing tetra sodium glutamate diacetate solution and carrageenan according to parts by weight, pouring the tetra sodium glutamate diacetate solution and carrageenan into a spiral stirring kettle, and stirring at the stirring speed of 120 r/min, at the stirring temperature of 23 ℃ for 8 min to obtain a fluid dynamic green degradable complex liquid;
step three: and (3) introducing the pure chlorine dioxide gas prepared in the first step into a spiral stirring kettle through an air duct, stirring and absorbing the pure chlorine dioxide gas into the flowing state green degradable complex liquid prepared in the second step, wherein the stirring and absorbing speed is 125 r/min, the stirring and absorbing time is 10 min, the absorbing temperature is 0 ℃, and the absorbing pressure is 101 kPa, so that the pure activation-free stable chlorine dioxide solution is obtained.
Example 2: the embodiment provides an activation-free stable chlorine dioxide solution, which comprises the following components in parts by weight:
4 parts of sodium chlorate, 2 parts of sodium sulfite, 2 parts of concentrated sulfuric acid, 18 parts of tetrasodium glutamate diacetate solution and 5 parts of carrageenan.
The preparation method of the tetrasodium glutamate diacetate solution specifically comprises the following steps:
s1, adding 50 parts by weight of tetrasodium glutamate diacetate powder and 150 parts by weight of sterile ultrapure water into a stirring tank to obtain a tetrasodium glutamate diacetate mixture;
s2, stirring the tetra-sodium glutamate diacetate mixture prepared in the step S1 in a stirring tank at the stirring speed of 110 r/min and the stirring temperature of 25 ℃ for 13 min to obtain the tetra-sodium glutamate diacetate solution.
The embodiment also provides a preparation method of the pure activation-free stable chlorine dioxide solution, which specifically comprises the following steps:
step one: weighing sodium chlorate, sodium sulfite and concentrated sulfuric acid according to parts by weight, putting into a stainless steel reaction kettle, heating and stirring, slowly adding concentrated sulfuric acid at a rate of 2 drops/min for reaction, wherein the reaction temperature is 220 ℃, the reaction time is 4 min, the reaction pressure is 101.3 kPa, and the stirring speed is 1200 r/min, so that pure chlorine dioxide gas is prepared;
step two: weighing tetra sodium glutamate diacetate solution and carrageenan according to parts by weight, pouring the tetra sodium glutamate diacetate solution and carrageenan into a spiral stirring kettle, and stirring at the stirring speed of 140 r/min and the stirring temperature of 24 ℃ for 10 min to obtain a fluid dynamic green degradable complex liquid;
step three: and (3) introducing the pure chlorine dioxide gas prepared in the first step into a spiral stirring kettle through an air duct, stirring and absorbing the pure chlorine dioxide gas into the flowing state green degradable complex liquid prepared in the second step, wherein the stirring and absorbing speed is 130 r/min, the stirring and absorbing time is 15 min, the absorbing temperature is 3 ℃, and the absorbing pressure is 101 kPa, so that the pure activation-free stable chlorine dioxide solution is obtained.
Example 3: the embodiment provides an activation-free stable chlorine dioxide solution, which comprises the following components in parts by weight:
6 parts of sodium chlorate, 3 parts of sodium sulfite, 3 parts of concentrated sulfuric acid, 20 parts of tetra sodium glutamate diacetate solution and 6 parts of carrageenan.
The preparation method of the tetrasodium glutamate diacetate solution specifically comprises the following steps:
s1, adding 60 parts by weight of tetrasodium glutamate diacetate powder and 240 parts by weight of sterile ultrapure water into a stirring tank to obtain a tetrasodium glutamate diacetate mixture;
s2, stirring the tetra-sodium glutamate diacetate mixture prepared in the step S1 in a stirring tank at the stirring speed of 120 r/min and the stirring temperature of 26 ℃ for 16 min to obtain the tetra-sodium glutamate diacetate solution.
The embodiment also provides a preparation method of the pure activation-free stable chlorine dioxide solution, which specifically comprises the following steps:
step one: weighing sodium chlorate, sodium sulfite and concentrated sulfuric acid according to parts by weight, putting into a stainless steel reaction kettle, heating and stirring, slowly adding concentrated sulfuric acid at a rate of 3 drops/min for reaction, wherein the reaction temperature is 230 ℃, the reaction time is 5 min, the reaction pressure is 101.3 kPa, and the stirring speed is 1300 r/min, so that pure chlorine dioxide gas is prepared;
step two: weighing tetra sodium glutamate diacetate solution and carrageenan according to parts by weight, pouring the tetra sodium glutamate diacetate solution and carrageenan into a spiral stirring kettle, and stirring at the stirring speed of 150 r/min and the stirring temperature of 25 ℃ for 12 min to obtain a fluid dynamic green degradable complex liquid;
step three: and (3) introducing the pure chlorine dioxide gas prepared in the first step into a spiral stirring kettle through an air duct, stirring and absorbing the pure chlorine dioxide gas into the flowing state green degradable complex liquid prepared in the second step, wherein the stirring and absorbing speed is 140 r/min, the stirring and absorbing time is 20 min, the absorbing temperature is 5 ℃, and the absorbing pressure is 101 kPa, so that the pure activation-free stable chlorine dioxide solution is obtained.
Comparative example 1: this comparative example provides a pure chlorine dioxide solution that differs from example 1 only in that the pure chlorine dioxide solution is prepared without tetrasodium glutamate diacetate.
Comparative example 2: this comparative example provides a pure chlorine dioxide solution differing from example 1 only in that the pure chlorine dioxide solution prepared is free of carrageenan.
Comparative example 3: the comparative example provides a method for preparing pure chlorine dioxide solution, which comprises the following steps:
step one: weighing sodium chlorate, sodium sulfite and concentrated sulfuric acid according to parts by weight, putting into a stainless steel reaction kettle, heating and stirring for reaction, wherein the reaction temperature is 230 ℃, the reaction time is 5 min, the reaction pressure is 101.3 kPa, and the stirring speed is 130 r/min, so that pure chlorine dioxide gas is prepared;
step two: weighing tetra sodium glutamate diacetate solution and carrageenan according to parts by weight, pouring the tetra sodium glutamate diacetate solution and the carrageenan into a spiral stirring kettle, stirring at the stirring speed of 150 r/min and the stirring temperature of 25 ℃ for 12 min, and stopping stirring to obtain stationary green degradable complex liquid;
step three: and (3) introducing the pure chlorine dioxide gas prepared in the first step into a spiral stirring kettle through an air duct, and absorbing the pure chlorine dioxide gas into the static green degradable complex liquid prepared in the second step, wherein the absorption time is 20 min, the absorption temperature is 25 ℃, and the absorption pressure is 101 kPa, so that the pure chlorine dioxide solution is obtained.
Experimental example 1: ultraviolet spectrophotometry chlorine dioxide content determination test
The pure activation-free stable chlorine dioxide solution prepared in example 1, example 2 and example 3 and the pure chlorine dioxide solution prepared in comparative example 1, comparative example 2 and comparative example 3 are tested, and the method specifically comprises the following experimental steps:
(1) Connecting a computer with an ultraviolet spectrophotometer, flushing the cuvette after equipment is stable, adding sterile ultrapure water for blank correction, leaving one cuvette with the ultrapure water as blank contrast in the instrument, taking out and cleaning the rest cuvettes, and selecting a spectrum detection mode;
(2) Diluting 250 mg/L standard chlorine dioxide solution with sterile ultrapure water to obtain 10 mg/L, 25 mg/L, 50 mg/L, 75 mg/L, 100 mg/L, 125 mg/L and 150 mg/L standard substances 1-7, respectively taking 1 mL of the above concentration standard chlorine dioxide solution in a 10 mL brown volumetric flask to constant volume, placing in a cuvette, measuring under 359 nm condition in an ultraviolet spectrophotometer, counting the corresponding absorbance of each concentration, and drawing standard curve graph with the statistical detection data, wherein the results are shown in table 1 and figure 3;
(3) The pure activation-free stable chlorine dioxide solutions prepared in the examples 1, 2 and 3, respectively, of which 1 mL is diluted by 100 times with sterile ultrapure water, the pure chlorine dioxide solutions prepared in the comparative examples 1, 2 and 3 are subjected to chlorine dioxide content measurement at the wavelength of 359 nm of an ultraviolet spectrophotometer, the sterile ultrapure water is used as a blank control, and the average value is taken three times repeatedly to calculate the content before chlorine dioxide dilution.
TABLE 1 Standard solution detection results Table
Analysis of results: as shown in FIG. 4, the pure activation-free stable chlorine dioxide solution prepared in example 1, example 2 and example 3 is used as a blank, the chlorine dioxide content in the pure chlorine dioxide solution prepared in comparative example 1, comparative example 2 and comparative example 3 is measured, the chlorine dioxide content in experimental examples 1-3 is higher than the product with the commercial concentration of 2900 mg/L, the chlorine dioxide content in the pure activation-free stable chlorine dioxide solution prepared in experimental examples 1-3 is 3415 mg/L, 3486 mg/L and 3400 mg/L which are 1.1-3.1 times of that in comparative examples 1-3, tetra sodium glutamate diacetate is not added in comparative example 1, the chlorine dioxide concentration is as low as 1120 mg/L, the pure activation-free stable chlorine dioxide solution is prepared by heating sodium chlorate, sodium sulfite and concentrated sulfuric acid to react, a stabilizing solution absorbing the chlorine dioxide gas is placed in a spiral stirring kettle and stirred to enable the liquid to be in a flowing state, the absorption rate of the chlorine dioxide gas at low temperature is improved, the operation is convenient, the chlorine dioxide gas is absorbed by using a tetra-sodium glutamate diacetate solution, the molecular formula of the tetra-sodium glutamate diacetate is shown as figure 1, a chelate can be formed with chlorine dioxide molecules, a natural thickener carrageenan with scientific proportion is added into the tetra-sodium glutamate diacetate solution, the molecular formula of the carrageenan is shown as figure 2, so that the chlorine dioxide molecules are more stably existing in the stabilizing agent solution, and the stability and the chlorine dioxide concentration of the pure activation-free stable chlorine dioxide solution are effectively improved.
Experimental example 2: sterilization effect measurement test
The pure activation-free stable chlorine dioxide solution prepared in example 1, example 2 and example 3 and the pure chlorine dioxide solution prepared in comparative example 1, comparative example 2 and comparative example 3 are tested, and the method specifically comprises the following experimental steps:
(1) Taking out escherichia coli and staphylococcus aureus from a refrigerator at the temperature of-80 ℃ to serve as a test strain;
(2) In a sterile ultra-clean workbench, respectively taking 10 mL escherichia coli and staphylococcus aureus bacterial liquid into 10 mL test tubes filled with sterile LB liquid culture medium, and respectively taking 21 tubes;
(3) Placing the test tube containing the bacterial liquid in the step (2) in a constant-temperature shaking table with the temperature of 37 ℃ and the rotating speed of 120 r/min, and culturing for 24 h;
(4) Taking pure activation-free stable chlorine dioxide solutions prepared in the example 1, the example 2 and the example 3, wherein the pure activation-free stable chlorine dioxide solutions are obtained by diluting 80 mL by a multiple of 1000, respectively directly adding the pure chlorine dioxide solutions prepared in the comparative example 1, the comparative example 2 and the comparative example 3 into test tubes for culturing escherichia coli and staphylococcus aureus bacterial liquid, repeating for 3 times, and adding 80 mL sterile ultrapure water into the test tubes of the comparative group;
(5) Placing the test tube in the step (4) in a constant-temperature shaking table with the temperature of 37 ℃ and the rotating speed of 120 r/min, and carrying out shake culture;
(6) Taking 20mL of the liquid in the test tube in the step (5) in 10 min, 30 min and 60 min of culture in a sterile ultra-clean workbench, and uniformly coating in an LB solid culture dish until friction force is felt;
(7) The LB solid culture dish was sealed, the dish was inverted and incubated in a thermostatic incubator at 37 ℃ for 24 h, the number of plate colonies was observed, the sterilization rate was calculated, the result of killing escherichia coli was shown in fig. 5, the result of killing staphylococcus aureus was shown in table 2, and the sterilization rate (%) = number of control group colonies-number of experimental group colonies/number of control group colonies x 100%.
TABLE 2 results table of killing Staphylococcus aureus
Analysis of results: as shown in FIG. 5 and Table 2, the pure activation-free stable chlorine dioxide solution prepared in the examples 1-3 is convenient to use without activation when being used, the sterilization rate of the pure activation-free stable chlorine dioxide solution prepared in the examples 1-3 reaches 100% when being mixed with escherichia coli and staphylococcus aureus bacterial liquid for 10 min, and the cell wall of the escherichia coli shown in FIG. 6 is destroyed to cause cell disruption and the content flows out to die thoroughly when being observed under an electron microscope. The sterilization rates of the comparative example 1 are 18.4 percent and 16.7 percent for escherichia coli and staphylococcus aureus respectively at 10 minutes, and the sterilization rates are slowly improved at 30 minutes and 60 minutes, so that the capability of complexing the tetra-sodium glutamate diacetate with calcium and magnesium ions on bacterial cell membranes is very high, chlorine dioxide molecules are quickly released, an activating agent is not required to be added, the fluidity and the permeability of the bacterial cell membranes are enhanced due to the tetra-sodium glutamate diacetate, the chlorine dioxide molecules are promoted to enter cells, the synergistic effect of the tetra-sodium glutamate diacetate and the bacterial cell membranes is promoted, the release and the action speed of chlorine dioxide are accelerated, and the antibacterial capability of the prepared pure activation-free stable chlorine dioxide solution is remarkably improved.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (4)
1. The preparation method of the pure activation-free stable chlorine dioxide solution is characterized by comprising the following steps of:
step one: weighing sodium chlorate and sodium sulfite, putting into a stainless steel reaction kettle, heating and stirring, slowly adding concentrated sulfuric acid, and reacting to obtain pure chlorine dioxide gas;
step two: weighing the green degradable complex liquid and the natural thickener, pouring the green degradable complex liquid and the natural thickener into a spiral stirring kettle, and stirring to obtain a fluid dynamic green degradable complex liquid;
step three: the pure chlorine dioxide gas prepared in the first step enters a spiral stirring kettle through an air duct, and is stirred and absorbed into the flowing green degradable complex liquid prepared in the second step to obtain pure activation-free stable chlorine dioxide solution;
in the first step, the components are added according to the weight parts: 2-6 parts of sodium chlorate, 1-3 parts of sodium sulfite and 1-3 parts of concentrated sulfuric acid;
in the second step, the components are added according to the weight parts: 15-20 parts of green degradable complex liquid and 4-6 parts of natural thickener; the green degradable complex liquid is a tetrasodium glutamate diacetate solution; the natural thickener is carrageenan;
the preparation method of the tetra-sodium glutamate diacetate solution specifically comprises the following steps:
s1, pouring tetra sodium glutamate diacetate powder and sterile ultrapure water into a stirring tank to obtain tetra sodium glutamate diacetate mixture;
s2, stirring the tetra-sodium glutamate diacetate mixture prepared in the step S1 in a stirring tank to obtain tetra-sodium glutamate diacetate solution;
in the step S1, the weight parts of the tetra sodium glutamate diacetate powder are 40-60 parts, and the weight parts of the sterile ultrapure water are 100-240 parts;
in the step S2, the stirring speed of the stirring tank is 100-120 r/min, the stirring temperature is 23-26 ℃, and the stirring time is 10-16 min.
2. The method for preparing pure activation-free stable chlorine dioxide solution according to claim 1, wherein in step one, the concentrated sulfuric acid is added at a rate of 1-3 drops/min; the reaction temperature of the stainless steel reaction kettle is 200-230 ℃, the reaction time is 2-5 min, the reaction pressure is 101.3 kPa, and the stirring speed is 1000-1300 r/min.
3. The method for preparing pure activation-free stable chlorine dioxide solution according to claim 2, wherein in the second step, the stirring speed of the spiral stirring kettle is 120-150 r/min, the stirring temperature is 23-25 ℃, and the stirring time is 8-12 min.
4. The method for preparing pure activation-free stable chlorine dioxide solution according to claim 3, wherein in the third step, the stirring absorption speed of the spiral stirring kettle is 125-140 r/min, the stirring absorption time is 10-20 min, the absorption temperature is 0-5 ℃ and the absorption pressure is 101 kPa.
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