CN105284882A - Oyster shell and invisible chlorine dioxide antibacterial material and preparation method and using method thereof - Google Patents
Oyster shell and invisible chlorine dioxide antibacterial material and preparation method and using method thereof Download PDFInfo
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Abstract
The invention discloses an oyster shell and invisible chlorine dioxide antibacterial material and a preparation method and a using method thereof. The oyster shell and invisible chlorine dioxide antibacterial material disclosed by the invention is a mixture of oyster shell powder, sodium chlorite powder and sodium bisulfate powder of which particle sizes are smaller than 50mum, wherein the weight ratio of the oyster shell powder to the sodium chlorite powder to the sodium bisulfate powder is 1:(0.05 to 0.1):(0.1 to 0.2); the oyster shell powder is of a loose porous structure and is high-activity powder prepared by using oyster shells as a raw material and carrying out calcination and grinding. According to the preparation method of the oyster shell and invisible chlorine dioxide antibacterial material, clinkers are prepared by a three-step type heating-up calcination method so as to obtain the oyster shell powder with the loose porous structure and high chemical activity; the using method of the oyster shell and invisible chlorine dioxide antibacterial material, which is used for removing pesticide residues of agricultural products, is simple, safe and efficient and does not generate no secondary pollution. Relative to the prior art, the oyster shell and invisible chlorine dioxide antibacterial material has the characteristics of low cost, energy saving and environmental protection, use safety, high efficiency, green and environmental protection and the like, is suitable for detergent washing processing of various fruits and vegetables, can effectively remove pesticide ingredient residues attached to the surfaces of the fruits and vegetables, and has a broad-spectrum bactericidal effect.
Description
Technical field
The present invention relates to a kind of anti-biotic material and preparation method thereof and using method thereof, particularly relate to the using method of a kind of oyster shell-stealthy chlorine dioxide anti-biotic material and preparation method thereof and Practice for Pesticide Residue in Agricultural Products of dispelling thereof, belong to oyster shell technical field of modification.
Background technology
China's seashells product kind is a lot, and 2014 annual productions reach 1,400 ten thousand tons.Wherein, oyster output is maximum, and annual production reaches 4,100,000 tons.The shell of oyster heavily accounts for more than 75% of oyster gross weight.That is, China every year by produce more than about 3,000,000 tons oyster shell.
Oyster shell solid waste, if be discarded in natural environment, not only can have a negative impact to the attractive in appearance of environment, and take a large amount of usable lands, simultaneously also because it gives out dense fish-stench, and affects the life of urban air-quality and people.
2007, Kanazawa, Japan Security at sea portion assert that oyster shell is waste items, has thus issued the ban forbidding arbitrarily toppling over, and forbade arbitrarily being dropped into by oyster shell marine, to avoid its pollution of marine environment.
In recent years, people have carried out a large amount of benefiting our pursuits and studying for the recycling aspect of harmless treatment and resource thereof how to carry out oyster shell, and achieve a series of technological progress, for the harmless treatment of oyster shell and the recycling of resource thereof hew out the application approach of multiple practicality.Such as:
Chinese patent application CN103087851B discloses a kind of vegetables, the degerming cleaning agent of melon and fruit and preparation method thereof, it is by being respectively the shell mixing of oyster shell 2-4 part, variegated clam shell 3-5 part and scallop shell 2-4 part by parts by weight, 7-9 hour is burned through 800-1600 DEG C, after adding the water reaction accounting for material gross weight 18-22%, through 280-320 DEG C of oven dry; Again the material after drying is burned 5-7 hour at 950-1050 DEG C; Then, complete material will be burned after powder produced by high microcomputer, mix with the chitin accounting for material gross weight 4-6% with the active carbon accounting for material gross weight 7-9%, obtained vegetables, the degerming cleaning agent of melon and fruit.
But technique scheme on the one hand, exists that calcining heat is high, energy resource consumption large, conch meal activity after calcining is on the low side, porosity is also not high enough; On the other hand, it needs interpolation account for the active carbon of material gross weight 7-9% and account for the chitin of material gross weight 4-6%, this is the further rising causing its production cost, and it soaks, vegetables, melon and fruit after leaching drift also needs to use after a large amount of clear water rinses well, could meet safe edible requirement.
Summary of the invention
An object of the present invention is, provides a kind of short texture porous, activity enough high, the oyster shell powder that production cost is low, and based on it oyster shell-stealthy chlorine dioxide anti-biotic material of the residue of pesticide for dispel crop products and fruit of raw material.
The present invention for achieving the above object technical issues that need to address is, how effectively to reduce production cost, utilizes this oyster shell powder, prepares and is suitable for fruit, the cleaning of greengrocery primary agricultural products, to dispel the technical problem of its residue of pesticide composition.
The technical scheme that the present invention is adopted for achieving the above object is, a kind of oyster shell-stealthy chlorine dioxide anti-biotic material, it is characterized in that, for the mixture of the oyster shell powder of particle diameter below 50 μm and sodium chlorite, niter cake powder, in described mixture, the weight ratio of oyster shell powder, sodium chlorite and niter cake powder is 1 ︰ 0.05-0.1 ︰ 0.1-0.2;
Described oyster shell powder has loose and porous structure, is with cheap solid waste biological material oyster shell for raw material, through calcining, grinding, and obtained active powder.
The technique effect that technique scheme is directly brought is, the production cost of oyster shell-stealthy chlorine dioxide anti-biotic material is low, without poisonous and harmful chemical composition, be suitable for the washing of all kinds of fruit, vegetables primary agricultural products, to dispel attachment residue of pesticide composition in its surface, and the Escherichia coli can effectively killed on its surface, its use safety, efficient, the waste liquid/waste water after use is nontoxic pollution-free.
That is, the oyster shell-stealthy chlorine dioxide anti-biotic material of technique scheme is the washing product of primary agricultural products of safety, efficient, environmental protection.
In technique scheme, in the oyster shell powder of loose and porous structure, be aided with stealthy chlorine dioxide raw material sodium chlorite, niter cake, powerful oxidant can be produced in the application: chlorine dioxide.
For understanding this technical characterstic better, be now described in detail as follows:
10NaClO
2+8NaHSO
4＝8ClO
2↑+5Na
2SO
4+4H
2O
Chlorine dioxide environmentally friendly material recognized in the world.
The ostreae testa pulverata of loose and porous structure and stealthy chlorine dioxide raw material sodium chlorite, niter cake are arranged in pairs or groups and will be produced following special-effect:
(1) usual, sodium chlorite and niter cake are can not the taboo collocation property material of mixed storage separately; Loose structure ostreae testa pulverata and its both arrange in pairs or groups, make both protect respectively, serve inertia protective effect, can long-term storage and not reacting.
(2) stealth technique overcomes the defect that Chlorine Dioxide Gas inconvenience is deposited, transported, uses, and it only has just can discharge chlorine dioxide, both safety in use, practical again.
(3) chlorine dioxide is green, high-effective disinfecting, the bactericide of highest level recognized in the world, has the advantages such as efficient, wide spectrum, consumption are few, quick, the duration is long, nontoxic.It to Pseudomonas aeruginosa, Escherichia coli, tubercle bacillus, typhoid bacillus, bacillus, phage, hcrpesviruses, hepatitis B, encephalomyelitis virus, SARS virus, etc. killing rate all up to 100%.It coordinates with loose and porous structure ostreae testa pulverata not only has strong disinfecting cleaning to act on, and loose structure ostreae testa pulverata can adsorb chlorine dioxide, and increase chlorine dioxide slow-release, effect is more lasting; Reduce its volatility simultaneously, prevent local environment chlorine dioxide concentration from exceeding standard and (be greater than 3mg/m
3) operator is damaged.
(4) chlorine dioxide can eliminate formaldehyde, benzene, ammonia, hydrogen sulphide noxious material.Such as, efficiently oxidation of formaldehyde can be become carbonic acid gas and water innocuous substance.Especially common are machine phosphorus or carbamate chemicals for agriculture oxidation, thus its structure be destroyed, becoming Small molecular, its toxicity of degrading.Chlorine dioxide coordinates with the ostreae testa pulverata of loose and porous structure, and the slow release of the ostreae testa pulverata absorption chlorine dioxide of loose and porous structure, makes the toxicity reduction effect of chlorine dioxide more lasting, better effects if.That is, make sodium chlorite and niter cake to arrange in pairs or groups to use, and produce obvious synergistic effect.
Two of object of the present invention is, provides the preparation method of a kind of above-mentioned oyster shell-stealthy chlorine dioxide anti-biotic material.
The present invention is how to improve calcine technology for realizing these object technical issues that need to address, reduces energy consumption, and obtains the technical problem of short texture porous, active sufficiently high oyster shell powder.
The present invention is for solving the problems of the technologies described above, and the technical scheme of employing is, the preparation method of a kind of above-mentioned oyster shell-stealthy chlorine dioxide anti-biotic material, is characterized in that, comprise the following steps:
The first step, first by bank up spontaneous fermentation purification oyster shell first with clean water totally, again through drying or drying in the shade under gravity-flow ventilation condition, after be crushed to the particle that particle diameter is 0.5-3.5mm, make raw material;
Above-mentioned raw material are entered high temperature furnace by second step, adopt three grades of staged intensification calcination methods to obtain grog; Concrete calcining step is as follows:
After being first warming up to 300-350 DEG C with the heating rate of 2 DEG C/min, insulation 10min;
Then, after continuing to be warming up to 650 DEG C with the heating rate of 5 DEG C/min, insulation 15-20min, then, aeration-cooling to 600 DEG C;
After being warming up to 810-830 DEG C with the heating rate of 10 DEG C/min again, insulation 20-40min; Then, aeration-cooling to 750 DEG C, and be incubated 20min, obtain grog;
3rd step, grog takes out after naturally cooling to room temperature; Cooled grog being entered grinding machine grinding becomes particle diameter to be the powder of less than 50 μm;
The above-mentioned powder obtained through grinding is mixed with the weight ratio 1 ︰ 0.05-0.1 ︰ 0.1-0.2 of sodium chlorite powder, niter cake powder, to obtain final product.
The technique effect that technique scheme is directly brought is that calcining heat is low, and one is, its production process is more energy-conservation; What is more important, (oyster shell) grog of calcining gained has excellent chemism, and loose porous in its structure, specific surface area is larger, bulk density is less, thus has very excellent surface adsorption property.
Three of object of the present invention is, provides the using method that a kind of above-mentioned oyster shell-stealthy chlorine dioxide anti-biotic material dispels Practice for Pesticide Residue in Agricultural Products.
The present invention for the technical scheme realizing this object and adopt is, a kind of above-mentioned oyster shell-stealthy chlorine dioxide anti-biotic material is dispelled the using method of Practice for Pesticide Residue in Agricultural Products, it is characterized in that, described agricultural product are fruit, greengrocery primary agricultural products, and described using method comprises the following steps:
The first step, is dissolved in water by oyster shell-stealthy chlorine dioxide anti-biotic material by the mass ratio of 1:500-1000, stirs evenly, be mixed with water for cleaning solution;
Fruit, greengrocery primary agricultural products are immersed in above-mentioned water for cleaning solution by second step, soak 10-15min;
Fruit, greengrocery primary agricultural products are pulled out, and are rinsed well with a small amount of clear water by the 3rd step, to remove the remaining oyster shell-stealthy chlorine dioxide anti-biotic material being attached to its surface, can the food materials of safe edible.
The technique effect that technique scheme is directly brought is, using method is simple, non-secondary pollution produce are raw;
Further, its use cost is low: one is, water for cleaning solution directly dilutes preparation by the mass ratio of oyster shell powder anti-biotic material and water 1:500-1000; Two are, because oyster shell powder anti-biotic material is without any poisonous and harmful chemical composition, itself just fully can meet the basic demand of safe edible, thus, after this oyster shell powder anti-biotic material soaks, dispel the fruits and vegetables of residue of pesticide and killing bacteria, do not needed to re-use too much clear water and rinse.That is, in use procedure, water saving, safety more.
In sum, the present invention with natural oyster shell solid waste for raw material, three step ladder-elevating temperatures are adopted to add thermal bake-out, in conjunction with the calcine technology of ventilation method, obtain having the ostreae testa pulverata of short texture porous, special structure form that chemism is high, be aided with the stealthy chlorine dioxide powder of food-grade again, just can be directly used in the removal of all kinds of vegetables or all kinds of fruit surface residue of pesticide, and the functional material of sterilizing and harmful bacteria.
The present invention, relative to prior art, has following beneficial effect:
1, cheap natural oyster shell is utilized to be raw material, obtain not only or even better washing effect identical with vegetables prepared by the compound of prior art artificial synthetic organic materials or inorganic oxidizer and surfactant, melon and fruit liquid detergent, residue of pesticide and harmful bacteria can also be removed, without Secondary Organic thing, antibiotic residue, natural, non-polluted edible safety is better;
Decontamination degerming functions material prepared by 2, single oyster shell material, than using the better effects if removing residue of pesticide and harmful bacteria with scallop shell, variegated clam shell or mixed shell material;
3, three step ladders add thermal bake-out ventilation method oyster can not only be made to have porous material structure, and absorption property is good, and does not need inert gas shielding, and sintering temperature is lower, and cost is lower, belongs to green energy conservation technical process.
4, in the oyster powder of loose and porous structure, be aided with stealthy chlorine dioxide raw material sodium chlorite, niter cake, the powerful oxidant chlorine dioxide produced in its use procedure is utilized to carry out broad-spectrum sterilization, and utilize the absorption of oyster to chlorine dioxide of loose and porous structure dexterously, to increase chlorine dioxide slow-release, make its effect more lasting; Reduce its volatility simultaneously, prevent local environment chlorine dioxide concentration from exceeding standard and (be greater than 3mg/m
3) operator is damaged.That is, make the toxicity reduction effect of chlorine dioxide more lasting, better effects if.
Accompanying drawing explanation
The oyster shell of Fig. 1 obtained by embodiment 1-stealthy chlorine dioxide anti-biotic material is to colibacillary Bactericidal test result.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
Oyster shell-stealthy chlorine dioxide anti-biotic material is prepared as follows:
The first step, first by bank up spontaneous fermentation purification oyster shell first with clean water totally, again through drying or drying in the shade under gravity-flow ventilation condition, after be crushed to the particle that particle diameter is 0.5-2.5mm, make raw material;
Above-mentioned raw material are entered high temperature furnace by second step, adopt three grades of staged intensification calcination methods to obtain grog; Concrete calcining step is as follows:
After being first warming up to 300 DEG C with the heating rate of 2 DEG C/min, insulation 10min;
Then, after continuing to be warming up to 650 DEG C with the heating rate of 5 DEG C/min, insulation 15min; Then, aeration-cooling to 600 DEG C;
After being warming up to 810 DEG C with the heating rate of 10 DEG C/min again, insulation 40min; Then, aeration-cooling to 750 DEG C, and be incubated 20min, obtain grog;
3rd step, grog takes out after naturally cooling to room temperature; Cooled grog being entered grinding machine grinding becomes particle diameter to be less than 50 μm, obtains oyster shell powder;
Above-mentioned oyster shell powder is mixed by weight 1 ︰ 0.05 ︰ 0.1 with sodium chlorite powder, niter cake powder, to obtain final product.
Embodiment 2
Oyster shell-stealthy chlorine dioxide anti-biotic material is prepared as follows:
The first step, first by bank up spontaneous fermentation purification oyster shell first with clean water totally, again through drying or drying in the shade under gravity-flow ventilation condition, after be crushed to the particle that particle diameter is 2.5-3.5mm, make raw material;
Above-mentioned raw material are entered high temperature furnace by second step, adopt three grades of staged intensification calcination methods to obtain grog; Concrete calcining step is as follows:
After being first warming up to 350 DEG C with the heating rate of 2 DEG C/min, insulation 10min;
Then, after continuing to be warming up to 650 DEG C with the heating rate of 5 DEG C/min, insulation 20min; Then, aeration-cooling to 600 DEG C;
After being warming up to 830 DEG C with the heating rate of 10 DEG C/min again, insulation 20min; Then, aeration-cooling to 750 DEG C, and be incubated 20min, obtain grog;
3rd step, grog takes out after naturally cooling to room temperature; Cooled grog being entered grinding machine grinding becomes particle diameter to be 20-30 μm, obtains oyster shell powder;
Above-mentioned oyster shell powder is mixed by weight 1 ︰ 0.1 ︰ 0.2 with sodium chlorite powder, niter cake powder, to obtain final product.
Embodiment 3
Oyster shell-stealthy chlorine dioxide anti-biotic material is prepared as follows:
The first step, first by bank up spontaneous fermentation purification oyster shell first with clean water totally, again through drying or drying in the shade under gravity-flow ventilation condition, after be crushed to the particle that particle diameter is 0.5-3.5mm, make raw material;
Above-mentioned raw material are entered high temperature furnace by second step, adopt three grades of staged intensification calcination methods to obtain grog; Concrete calcining step is as follows:
After being first warming up to 330 DEG C with the heating rate of 2 DEG C/min, insulation 10min;
Then, after continuing to be warming up to 650 DEG C with the heating rate of 5 DEG C/min, insulation 20min; Then, aeration-cooling to 600 DEG C;
After being warming up to 820 DEG C with the heating rate of 10 DEG C/min again, insulation 30min; Then, aeration-cooling to 750 DEG C, and be incubated 20min, obtain grog;
3rd step, grog takes out after naturally cooling to room temperature; Cooled grog being entered grinding machine grinding becomes particle diameter to be less than 50 μm, obtains oyster shell powder;
Above-mentioned oyster shell powder is mixed by weight 1 ︰ 0.08 ︰ 0.15 with sodium chlorite powder, niter cake powder, to obtain final product.
Choose embodiment 1 representatively property embodiment, test experience is carried out to the oyster shell-stealthy chlorine dioxide antibacterial material product obtained by it.Experimental technique and the testing result of detection are as follows:
(1) water put into by fruits and vegetables containing agricultural chemicals flolimat emulsion 100mgL/L soaks to pull out and dries 3 seconds.
(2) product is put into water in the ratio of 5g/kg water to stir evenly, put into by fruit and vegetable food thereafter, allow water just cover fruits and vegetables, stir 2 times in 10min, pulling control out dry, take clear water as contrast experiment;
(3) method of testing and instrument: adopt LS-SC-32 rapid detector for pesticide residue (instrument trait: adopt enzyme inhibition rate method, meet standard GB/T/T5009.199-2003, persticide residue in energy fast detecting fruits and vegetables sample, Monitoring lower-cut 0.2ppm), test sample residual oxidization Rogor concentration by colour developing colorimetric method.
Computing formula: test absorbance A under 412nm wavelength, persticide residue inhibiting rate represents, is calculated as follows:
S％＝[(△A0-△At)/△A0]×100
In formula: S%---inhibiting rate;
The changing value of △ A0---contrast solution reaction 3min absorbance;
The changing value of △ At---sample solution reaction 3min absorbance.
Persticide residue is with inhibiting rate criterion (standard GB/T/T5009.199-2003):
| The inhibiting rate of fruits and vegetables sample | Fruit-vegetable quality | Evaluation and recommendations |
| 0% < inhibiting rate < 15% | Pollution-free vegetable | Can relievedly export |
| 15% < inhibiting rate < 30% | Green vegetables | Can safe edible |
| 30% < inhibiting rate < 50% | Pollution-free vegetable | Can safe edible |
| 50% < inhibiting rate < 100% | There are pesticide pollution vegetables | Can not safe edible |
Testing result is as following table 1:
Table 1
| Fruits and vegetables kind | Product design (g/kg water) | Inhibiting rate (%) | Escherichia coli detect strain number | Conclusion |
| Clear water contrast experiment | Cucumber | 0 | 79 | 56 | Exceed standard |
| The present invention | Cucumber | 5 | 9 | 0 | Qualified |
| The present invention | Cauliflower | 5 | 13 | 0 | Qualified |
| The present invention | Rape | 5 | 14 | 0 | Qualified |
| The present invention | Apple | 5 | 7 | 0 | Qualified |
| The present invention | Strawberry | 5 | 12 | 0 | Qualified |
Oyster shell-stealthy chlorine dioxide the antibacterial material product chosen obtained by embodiment 2 carries out test experience.The experimental technique detected is identical with the test experience method of embodiment 1, and testing result is as following table 2:
Table 2
| Fruits and vegetables kind | Product design (g/kg water) | Inhibiting rate (%) | Escherichia coli detect strain number | Conclusion | |
| Contrast blank assay | Cucumber | 0 | 83 | 67 | Exceed standard |
| The present invention | Cucumber | 5 | 6 | 0 | Qualified |
| The present invention | Cauliflower | 5 | 12 | 0 | Qualified |
| The present invention | Rape | 5 | 9 | 0 | Qualified |
| The present invention | Apple | 5 | 5 | 0 | Qualified |
| The present invention | Strawberry | 5 | 10 | 0 | Qualified |
The ostreae testa pulverata chosen obtained by embodiment 1 dispels the residual anti-biotic material of agriculture to colibacillary Bactericidal test, and result as shown in Figure 1, can be found out, Bactericidal test result produces for there being obvious inhibition zone 1,2,3,4; , there is not inhibition zone in the blank sample for not applying product represented by middle numeral 0.
Through vernier caliper measurement, antibacterial circle diameter is all at more than 28mm, and the oyster shell obtained by explanation-stealthy chlorine dioxide anti-biotic material is very strong to colibacillary antibacterial effect.
Claims (3)
1. oyster shell-stealthy chlorine dioxide anti-biotic material, it is characterized in that, for the mixture of the oyster shell powder of particle diameter below 50 μm and sodium chlorite powder, niter cake powder, in described mixture, the weight ratio of oyster shell powder, sodium chlorite powder and niter cake powder is 1 ︰ 0.05-0.1 ︰ 0.1-0.2;
Described oyster shell powder has loose and porous structure, is take oyster shell as raw material, through calcining, grinding, and obtained active powder.
2. a preparation method for oyster shell as claimed in claim 1-stealthy chlorine dioxide anti-biotic material, is characterized in that, comprise the following steps:
The first step, first by bank up spontaneous fermentation purification oyster shell first with clean water totally, again through drying or drying in the shade under gravity-flow ventilation condition, after be crushed to the particle that particle diameter is 0.5-3.5mm, make raw material;
Above-mentioned raw material are entered high temperature furnace by second step, adopt three grades of staged intensification calcination methods to obtain grog; Concrete calcining step is as follows:
After being first warming up to 300-350 DEG C with the heating rate of 2 DEG C/min, insulation 10min;
Then, after continuing to be warming up to 650 DEG C with the heating rate of 5 DEG C/min, insulation 15-20min, then, aeration-cooling to 600 DEG C;
After being warming up to 810-830 DEG C with the heating rate of 10 DEG C/min again, insulation 20-40min; Then, aeration-cooling to 750 DEG C, and be incubated 20min, obtain grog;
3rd step, grog takes out after naturally cooling to room temperature; Cooled grog being entered grinding machine grinding becomes particle diameter to be the powder of less than 50 μm;
The above-mentioned powder obtained through grinding is mixed by weight 1 ︰ 0.05-0.1 ︰ 0.1-0.2 with sodium chlorite powder, niter cake powder, to obtain final product.
3. oyster shell as claimed in claim 1-stealthy chlorine dioxide anti-biotic material is dispelled the using method of Practice for Pesticide Residue in Agricultural Products, and it is characterized in that, described agricultural product are fruit, greengrocery primary agricultural products, and described using method comprises the following steps:
The first step, is dissolved in water by oyster shell-stealthy chlorine dioxide anti-biotic material by the mass ratio of 1:500-1000, stirs evenly, be mixed with water for cleaning solution;
Fruit, greengrocery primary agricultural products are immersed in above-mentioned water for cleaning solution by second step, soak 10-15min;
Fruit, greengrocery primary agricultural products are pulled out, and are rinsed well with a small amount of clear water by the 3rd step, to remove the remaining oyster shell-stealthy chlorine dioxide anti-biotic material being attached to its surface, can the food materials of safe edible.
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| CN201510583056.9A CN105284882B (en) | 2015-09-15 | 2015-09-15 | A kind of oyster shell stealth chlorine dioxide anti-biotic material and preparation method thereof and application method |
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| CN105284882B CN105284882B (en) | 2018-03-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097287A (en) * | 2019-12-19 | 2020-05-05 | 绍兴市上虞区理工高等研究院 | Chlorine dioxide air purifying agent and preparation method thereof |
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|---|---|---|---|---|
| CN1122189A (en) * | 1995-06-29 | 1996-05-15 | 叶中良 | Bactericidal disinfectant |
| CN1587029A (en) * | 2004-09-17 | 2005-03-02 | 大连万洁日化有限公司 | Process for preparing mono package sterilizing granule capable of generating chlorine dioxide |
| CN102718247A (en) * | 2012-06-06 | 2012-10-10 | 李静 | Calcium powder and preparation method thereof |
| CN104073377A (en) * | 2014-06-12 | 2014-10-01 | 浙江海洋学院 | Method for preparing pure natural fruit and vegetable cleaning agent |
-
2015
- 2015-09-15 CN CN201510583056.9A patent/CN105284882B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122189A (en) * | 1995-06-29 | 1996-05-15 | 叶中良 | Bactericidal disinfectant |
| CN1587029A (en) * | 2004-09-17 | 2005-03-02 | 大连万洁日化有限公司 | Process for preparing mono package sterilizing granule capable of generating chlorine dioxide |
| CN102718247A (en) * | 2012-06-06 | 2012-10-10 | 李静 | Calcium powder and preparation method thereof |
| CN104073377A (en) * | 2014-06-12 | 2014-10-01 | 浙江海洋学院 | Method for preparing pure natural fruit and vegetable cleaning agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097287A (en) * | 2019-12-19 | 2020-05-05 | 绍兴市上虞区理工高等研究院 | Chlorine dioxide air purifying agent and preparation method thereof |
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| CN105284882B (en) | 2018-03-13 |
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