CN101356925A - Chlorine dioxide disinfection tablet capable of continuously generating high oxidation reduction potential - Google Patents
Chlorine dioxide disinfection tablet capable of continuously generating high oxidation reduction potential Download PDFInfo
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- CN101356925A CN101356925A CNA2008101190703A CN200810119070A CN101356925A CN 101356925 A CN101356925 A CN 101356925A CN A2008101190703 A CNA2008101190703 A CN A2008101190703A CN 200810119070 A CN200810119070 A CN 200810119070A CN 101356925 A CN101356925 A CN 101356925A
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Abstract
A chlorine dioxide disinfectant tablet can continuously produce high oxidation-reduction potential, and consists of the following components by proportions: 2-4 parts of chlorine oxide, 1-3 parts of solid acid, 1-3 parts of acid salt, 0.2-1 part of a stabilizer and 0-1 part of other adjuvants. When one chlorine dioxide disinfectant tablet is dissolved into 100ml of water, the PH value of the solution is 4.5-5, the oxidation-reduction potential is 900-1,100mv, and the effective concentration of the chlorine dioxide is 2,000-3,000mg/L. When the disinfectant of the chlorine dioxide disinfectant tablet is put into water, the solid acid and the acid salt activate the chlorine oxide to produce the chlorine dioxide and the high oxidation-reduction potential for double disinfection, which greatly improves the antiseptic function. Very good disinfection effect can be achieved when the concentration of the chlorine dioxide is 32.5-130ppm. The oxidation-reduction potential of the ordinary chlorine dioxide disinfectants is less than 850mV, therefore, the disinfection effect which is the same as the chlorine dioxide disinfectant can be achieved when the effective concentration is 65-140ppm. The solid acid and the acid salt activate together, therefore, the activation rate of the chlorine dioxide is increased by about 10%. The chlorine oxide is added with water soluble polymer material for passivation treatment to cause the product to become a monophyletic solid tablet, thus having convenient use.
Description
Technical field
The present invention relates to a kind of solid chlorine dioxide disinfectant, more specifically to the technical field under a kind of disinfection by chlorine dioxide sheet of sustainable generation high redox potential.
Background technology
Stability chlorine dioxide be a kind of efficient, the safety of research and development both at home and abroad in recent years, fast, the novel oxidative disinfectant of effect wide spectrum.Because its no carcinogenic, mutagenesis and teratogenesis is widely used in sterilization, sterilization, bleaching, anti-corrosive fresh-keeping, water treatment etc. at present.
Can be divided into by preparation method's solid preparation of chlorine dioxide: absorbent-type, response type and spacetabs type;
1. absorbent-type: utilize solid absorbent absorption ClO 2 solution, cooperate some adhesives, deliquescent agent, sustained release agent again, be pressed into chlorine dioxide solid.The main feature of this series products is preparation ClO 2 solution, absorption then earlier.The preparation ClO 2 solution requires to use special apparatus, and chlorine dioxide loss simultaneously is many, pollutes big.
2. response type: the solid chemicals that will prepare chlorine dioxide directly mixes, and adds adjuvant, is packaged into solid preparation of chlorine dioxide, throws into during use in the water, and solid chemicals (mainly being sodium chlorite and acidulant such as citric acid) reacts, the generation chlorine dioxide.The main feature of this series products be solid chemicals under the storing condition, react because of the high temperature or the moisture absorption, make product failure.
3. spacetabs type: chlorine dioxide is adsorbed onto on the solid absorbent, mixes with the solid acid sustained release agent again, make it reaction, thereby discharge chlorine dioxide slowly, constantly, be mainly used in air cleaning, deodorizing, fresh-keeping etc.
The sterilization notion of high redox potential comes from Japanese research to electrolyzed oxidizing water (EOW) in 1987, and its bactericidal action principle is the death that high redox potential can quicken bacterium.Bacteria live is (aerobic bacteria can only tolerate the oxidizing potential of 300-400mV, and anaerobic bacteria is below 100mV) in the ORP of appropriateness scope.High redox potential can have been accelerated breaking of microorganism adventitia, or the permeability of change microorganism adventitia, help sterilization component and in microbial cell, permeate, shortened disinfecting time (Qiu Cuihuan. strong peroxide deionized water sterilization mechanism pre-test [J]. Chinese medicine physics magazine, 1999; 16 (3): 175).
The present invention is based on the preparation principle of response type solid chlorine dioxide, developed a kind of solid chlorine dioxide disinfectant of sustainable generation high redox potential.
Summary of the invention
The object of the present invention is to provide a kind of solid chlorine dioxide disinfectant of sustainable generation high redox potential, its redox potential is between 900-1100mV, and pH is between 4.5-5.
For achieving the above object, the present invention takes following design:
A kind of disinfection by chlorine dioxide sheet of sustainable generation high redox potential, this sterilization sheet comprises following composition and parts by weight proportioning: oxides of chlorine 2-4 part, solid acid 1-3 part, ackd salt 1-3 part, other assistant agents 0-1 part;
This sterilization sheet also comprises stabilizing agent 0.1-1 part.
This sterilization sheet is a solid dosage forms, and a slice (1 gram/sheet) is rendered in the 100mL water, can dissolve in 5-10 minute to finish, and the pH value of solution value after the dissolving is 4.5-5, redox potential 900-1100mv, chlorine dioxide valid density 2000-3000mg/L.
Oxides of chlorine comprises: one or more in sodium chlorite, sodium chlorate, DCCA, TCCA (Trichloroisocyanuric acid), calcium hypochlorite, the clorox.
Solid acid comprises one or more in citric acid, citric acid derivant, oxalic acid, oxalic acid derivative, malonic acid, malonate derivative, succinic acid, butanedioic acid derivative, glutaric acid and the glutaric acid derivatives.
Ackd salt comprises: one or more in ferric trichloride, alchlor, the niter cake.
Stabilizing agent comprises: one or more of polyacrylamide, polyacrylic resin, polyethylene glycol, crospolyvinylpyrrolidone, dodecyl sodium sulfate, sodium carboxymethylcellulose, sodium carboxymethyl starch, sodium phosphate trimer.
Other assistant agents comprise: one or more in SODIUM PERCARBONATE, sodium carbonate, kaolin, starch, calcium chloride, the magnesium chloride.
The film-making process that the present invention uses is as follows: raw material is put 40 ℃ of dry 24h, pulverize respectively, 50 orders sieve, dewater, by the parts by weight proportioning raw materials weighing of disinfection by chlorine dioxide sheet of the present invention, mix, 20Kg pressure presses down the disinfection by chlorine dioxide sheet of heavy 1g in blocks.
High redox potential refers to that promptly solid sterilizing sheet dissolving rear oxidation reduction potential is between 900-1100mV among the present invention.
Advantage of the present invention is:
1, acidulant is adjusted, and has increased a kind of ackd salt, can make the sustainable generation high redox potential of ClO 2 solution.
The redox potential of common solid chlorine dioxide solution has only 700-800mV, the solid chlorine dioxide wiring solution-forming of our development, and redox potential reaches 900-1100mV; High redox potential can shorten sterilizing time, thereby reduces the consumption of disinfectant, reduces environmental pollution.
2, the present invention increases a kind of ackd salt, and ackd salt promotes the activation of chlorine dioxide, improves activation rate, and can reduce the consumption of solid acid, reduces cost.
3, solid chlorine dioxide wiring solution-forming of the present invention, pH be in this scope of 4.5-5, and commercially available response type solid chlorine dioxide is made into ClO 2 solution with the invention same concentrations at present, and pH is below 4.5, and acidity is greater than this disinfectant (referring to table 1).The corrosivity of solution is stronger under the acid condition, and disinfectant of the present invention has reduced corrosivity because of having improved pH in the sterilization use.
4, the present invention increases a kind of macromolecular material used as stabilizers in solid chemicals, has reduced contacting of chlorous acid and solid acid, thereby has improved the stability of product.
5, response type disinfection agent of chlorine dioxide of the present invention is the monobasic packing, and other response type chlorine dioxide are two-component packaging, and the monobasic packing is used more convenient.
Embodiment
The umber of each component in following examples is weight portion.
Embodiment 1:
6 parts of sodium chlorites, 3 parts of citric acids, 1 part of niter cake, 1 part of alchlor, 1 part of ferric trichloride mixes above-mentioned raw materials, is pressed into 2 gram/sheets, gets a slice and is dissolved in the 100ml water, the redox potential 1130mV of the aqueous solution, pH4.7, chlorine dioxide content 3100mg/L.
Embodiment 2:
2 parts of sodium chlorites, 2 parts of calcium hypochlorites, 3 parts of lemon acids, 3 parts of ackd salts, 0.8 part of stabilizing agent, above-mentioned raw materials is mixed, be pressed into 2 gram/sheets, get a slice and be dissolved in the 100mL water, the redox potential 1100mV of the aqueous solution, pH4.5, chlorine dioxide content 3300mg/L.
Embodiment 3:
Increase ackd salt and the contrast that does not add ackd salt
Sodium chlorite 1 gram, lemon acid 1 gram are made into the 100mL aqueous solution, and the concentration of chlorine dioxide is about 2700mg/L;
Sodium chlorite 1 gram, lemon acid 0.5 gram, ackd salt 0.5 gram is made into the 100mL aqueous solution, and the concentration of chlorine dioxide is about 3000mg/L.
Promptly add ackd salt 0.5 gram, the lemon acid consumption can reduce half, and activation rate improves 10%.
Embodiment 4:
Add stabilizing agent and the contrast that does not add stabilizing agent
2 parts of sodium chlorites, 1 part of lemon acid, the ratio that ackd salt is 1 part after mixing, is divided into two parts.0.2 part of stabilizing agent of a interpolation, another part do not add stabilizing agent, and (54 ℃) are deposited a week under identical condition, and chlorine dioxide valid density descends 11.2% and 16.7% respectively, illustrates to add the decline that stabilizing agent can reduce active ingredient.
Embodiment 5:
This disinfectant and of the comparison of commercially available other disinfection agent of chlorine dioxide in physicochemical property
2 parts of sodium chlorites, 1 part of lemon acid, 1 part of ackd salt, 0.2 part of stabilizing agent mixes above-mentioned raw materials, is pressed into 2 gram/sheets, gets a slice and is dissolved in the 100mL water, the redox potential 1040mV of the aqueous solution, pH4.8, chlorine dioxide content 3000mg/L;
To this disinfectant and magnificent 206 disinfectants (Shanghai Wenhua Sterilization Medicinal Science and Tech. Co., Ltd.'s product of literary composition, 20070208), very reveal disinfection by chlorine dioxide powder (Jiyuan Sci. ﹠ Tech. Co., Ltd., Shanghai's product, lot number 20070202), (herd culture goods and materials Co., Ltd product clearly by the safe fishing in Tangshan City for hundred poison, lot number 20071019), green pioneer (the green pioneer's environmental protection in Beijing science and technology limited Company production, lot number 20070304) compare, the prescription of other response type disinfection agent of chlorine dioxide is as follows:
The strange chlorine dioxide prescription that reveals: A agent citric acid 12.3 gram/every bags; B agent sodium chlorite 5.7 gram/every bags.
Hundred poison are clear: A agent citric acid 100 grams/every bag; B agent sodium chlorite 100 grams/every bottle.
Green pioneer: A agent citric acid 5 grams/every bag; B agent sodium chlorite 5 grams/every bottle.
The prescription of other reaction chlorine dioxide, citric acid: sodium chlorite ≈ 1: 1 or 2: 1.And used (ackd salt+citric acid) of the present invention: sodium chlorite ≈ 1: 1 has reduced the consumption of lemon acid.The result shows the high 150-200mV of this disinfectant solution redox potential, and pH also is higher than other commercially available chlorine dioxide, more approaching neutrality.
This disinfectant of table 1 compares with commercially available other disinfectant physicochemical properties
| The disinfectant title | Compound method | ORP value (mV) | Valid density (mg/L) | The pH value |
| Magnificent 206 disinfectants of literary composition | A, each a slice of B agent are dissolved in the 100mL water | 780 | 1400 | 3.9 |
| Hundred poison are clear | A agent, each 1 gram of B agent are dissolved in the 100mL water | 744 | 1900 | 2.1 |
| The strange disinfection by chlorine dioxide powder that reveals | A agent 1.23 grams, B agent 0.57 gram are dissolved in the 100mL water in proportion | 730 | 2850 | 2.6 |
| Green pioneer | A agent, each 1 gram of B agent are dissolved in the 100mL water | 755 | 2365 | 3.3 |
| This disinfectant | Getting 2g is dissolved in the 100mL water | 1040 | 3000 | 4.8 |
Embodiment 6:
This disinfectant compares with chlorine dioxide wiring solution-forming rear oxidation reduction potential continuation such as civilian China 206, green pioneer, clear, the strange dew of hundred poison
This disinfectant of table 2 compares (unit: mV) with commercially available other disinfectant redox potential continuation
| The disinfectant kind | Place 0h | Place 24h | Place 48h | Place 72h | Place 720h |
| This disinfectant | 1113 | 1113 | 1100 | 1098 | 1050 |
| Literary composition China 206 | 780 | 732 | 713 | 700 | 570 |
| Green pioneer | 755 | 719 | 698 | 627 | 535 |
| Hundred poison are clear | 744 | 699 | 685 | 625 | 533 |
| Strange revealing | 730 | 697 | 687 | 613 | 540 |
Embodiment 7:
The comparison of this disinfectant and commercially available other disinfection agent of chlorine dioxide bacteriocidal concentrations
1. Minimum Bactericidal method
1.1 the bacterium liquid for preparing is carried out count plate, and with the dilution of 0.03M phosphate buffer, the bacteria containing amount that makes test organisms liquid is 5 * 10 then
5-5 * 10
6Cfu/mL.
1.2 10 in medium size test tube is listed on the rack for test tube, finish writing label, indicate the disinfectant dilution factor.
1.3 every pipe adds sterile distilled water 2.5mL, puts in 20 ℃ of water-baths.
Use liquid 2.5mL 1.4 add disinfectant in the 1st pipe, behind the mixing, get 2.5mL to the 2 pipes by the 1st pipe, draw 2.5mL to the 3 pipes from the 2nd pipe again behind the mixing, to the 9th pipe, get 2.5mL after the mixing again and discard by that analogy, the 10th pipe does not add the sterilization soup in contrast.
Add bacterium liquid 2.5mL in each pipe 1.5 add the speed of a pipe with per half a minute, make bacteria containing amount reach 10
6Cfu/mL, mixing.
1.6 adding bacterium in the time of 30 minutes, every pipe is got in the 4.5mL liquid nutrient medium that 0.5mL adds the sodium thiosulfate contain 0.5% mass percent, mixing.
1.7 with the culture tube of inoculated bacteria, put 37 ℃ and cultivated 24 hours, promptly represent to have bacterial growth if muddiness takes place.Can on solid culture medium, differentiate in case of necessity and cultivate or smear for microscopic examination, to judge whether the being purpose bacteria growing.The meat soup nondiscolouring should continue to cultivate 7 days, and still not long bacterium is judged to be asepsis growth.
1.8 positive control should be done viable bacteria simultaneously and cultivate counting, with confirmed test bacterium number.The test triplicate.
Negative control is answered asepsis growth, and the thimerosal least concentration of testing equal asepsis growth with each time is a minimum bactericidal valid density.
2. Minimum Bactericidal result
This disinfectant, magnificent 206 disinfectants of literary composition, hundred poison clearly, very reveal 10 minutes minimal bactericidal concentration experimental results to Escherichia coli and staphylococcus aureus of disinfection by chlorine dioxide powder effect and show, the required minimal bactericidal concentration of this disinfectant is lower than commercially available disinfection agent of chlorine dioxide: hundred poison clearly, very reveal disinfection by chlorine dioxide powder, green pioneer (see Table 3, table 4), illustrate that the sterilizing ability of this disinfectant is stronger.
As can be seen from Table 5, this disinfectant is 65mg/L to the minimal bactericidal concentration of spores of bacillus subtilin, and the clear concentration of hundred poison are 97.5mg/L, illustrate this disinfectant to spores of bacillus subtilin to kill ability stronger.
Table 3 adds 10 minutes five kinds of disinfectants of bacterium to colibacillary minimum bactericidal assay
| Concentration (mg/L) | 130 | 65 | 32.50 | 16.25 | 8.13 | 4.07 | Positive control | Negative control |
| This disinfectant | - | - | - | + | + | + | + | - |
| Magnificent 206 disinfectants of literary composition | - | - | - | + | + | + | + | - |
| Hundred poison are clear | - | - | + | + | + | + | + | - |
| The strange disinfection by chlorine dioxide powder that reveals | - | - | + | + | + | + | + | - |
| Green pioneer | - | - | + | + | + | + | + | - |
Annotate :-expression asepsis growth ,+expression has bacteria growing, and institute adds bacterial concentration and is: 3.17 * 10
6Cfu/mL
Table 4 adds the minimum bactericidal assay of 10 minutes five kinds of disinfectants of bacterium to staphylococcus aureus
| Concentration (mg/L) | 180 | 90 | 45 | 22.5 | 11.25 | 5.63 | Positive control | Negative control |
| This disinfectant | - | - | - | + | + | + | + | - |
| Magnificent 206 disinfectants of literary composition | - | - | - | + | + | + | + | - |
| Hundred poison are clear | - | - | + | + | + | + | + | - |
| The strange disinfection by chlorine dioxide powder that reveals | - | - | + | + | + | + | + | - |
| Green pioneer | - | - | + | + | + | + | + | - |
Annotate :-expression asepsis growth ,+expression has bacteria growing, and institute adds bacterial concentration and is: 5.99 * 10
6Cfu/mL
Table 5 adds the minimum bactericidal assay of 10 minutes three kinds of disinfectants of bacterium to spores of bacillus subtilin
| This decontaminant concentration (mg/L) | 260 | 130 | 65 | 32.5 | 16.25 | 8.18 | Positive control | Negative control |
| Experimental result | - | - | - | + | + | + | + | - |
| The clear concentration (mg/L) of hundred poison | 195 | 97.5 | 48.8 | 24.4 | 12.2 | 6.1 | Positive control | Negative control |
| Experimental result | - | - | + | + | + | + | + | - |
Annotate :-expression asepsis growth ,+expression has bacteria growing, and institute adds bacterial concentration and is: 5.99 * 10
6Cfu/mL
Embodiment 8:
Quantitative disinfecting test
When testing several disinfectants to Escherichia coli and staphylococcus aureus minimum sterilization bacteria concentration, this disinfectant is better than other disinfection agent of chlorine dioxide, substantially there is not obviously difference with magnificent 206 disinfectants of literary composition, still with bacillus subtilis black variety gemma for killing object, carried out this disinfectant with the literary composition magnificent 206 disinfectant quantitative disinfecting test observation on effect.During test, two kinds of disinfectants are diluted to same concentrations (160mg/L), and the 1.0mL bacteria suspension is added in the test tube, add in the 4.0mL thimerosal, mixing also starts stopwatch and picks up counting in the beginning mixing, and effect was to 10 minutes, inhale 0.5mL to the test tube that the 4.5mL neutralizer is housed, mixing.In and behind the 10min, inhaling 1.0mL is that medium count by dull and stereotyped tilt-pour process with the nutrient agar, the result shows that the bactericidal effect of this disinfectant is better than civilian magnificent 206 disinfectants (table 6):
This disinfectant of table 6 and the killing effect of magnificent 206 disinfectants of literary composition to bacillus subtilis black variety gemma
Positive controls bacterium several 5.0 * 10
7Cfu/mL
Claims (7)
1, a kind of disinfection by chlorine dioxide sheet is characterized in that:
This sterilization sheet comprises following composition and parts by weight proportioning: oxides of chlorine 2-4 part, solid acid 1-3 part, ackd salt 1-3 part, other assistant agents 0-1 part.
2, disinfection by chlorine dioxide sheet according to claim 1 is characterized in that, this sterilization sheet also comprises stabilizing agent 0.1-1 part.
3, disinfection by chlorine dioxide sheet according to claim 1, it is characterized in that: described oxides of chlorine comprises: one or more in sodium chlorite, sodium chlorate, DCCA, TCCA (Trichloroisocyanuric acid), calcium hypochlorite, the clorox.
4, disinfection by chlorine dioxide sheet according to claim 1 is characterized in that: described solid acid comprises one or more in citric acid, citric acid derivant, oxalic acid, oxalic acid derivative, malonic acid, malonate derivative, succinic acid, butanedioic acid derivative, glutaric acid and the glutaric acid derivatives.
5, disinfection by chlorine dioxide sheet according to claim 1, it is characterized in that: described ackd salt comprises: one or more in ferric trichloride, alchlor, the niter cake.
6, disinfection by chlorine dioxide sheet according to claim 1 is characterized in that: described other assistant agents comprise: one or more in SODIUM PERCARBONATE, sodium carbonate, kaolin, starch, calcium chloride, the magnesium chloride.
7, disinfection by chlorine dioxide sheet according to claim 2, it is characterized in that: described stabilizing agent comprises: one or more of polyacrylamide, polyacrylic resin, polyethylene glycol, crospolyvinylpyrrolidone, dodecyl sodium sulfate, sodium carboxymethylcellulose, sodium carboxymethyl starch, sodium phosphate trimer.
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