CN1788567A - Chlorine dioxide composition and preparing method thereof - Google Patents
Chlorine dioxide composition and preparing method thereof Download PDFInfo
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- CN1788567A CN1788567A CN 200410098674 CN200410098674A CN1788567A CN 1788567 A CN1788567 A CN 1788567A CN 200410098674 CN200410098674 CN 200410098674 CN 200410098674 A CN200410098674 A CN 200410098674A CN 1788567 A CN1788567 A CN 1788567A
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Abstract
The present invention provides preparation process of solid chlorine dioxide disinfectant, which may be powder, granule, ingot, tablet, etc. prepared and packed in one component or two component form. It contains hypochloric acid providing compound including chloroisocyanuric acid, bromochloro hydantoin, dibromo hydantoin, hypochlorate, etc. as main component; chlorate, chlorite and stabilizer for reaction with the hypochloric acid providing compound to prepare chlorine dioxide stably; and metal corrosion inhibitor. It has comprehensive functions and uses, and is used as green safe disinfectant for disinfection and deodorizing of medical equipment, food producing apparatus, water treating apparatus, household, etc.
Description
Technical field
The present invention relates to a kind of novel disinfection by chlorine dioxide composition and other preparation method.It relates to the design of instant prescription of effervesce and chemical reaction quantification, and the manufacturing process technology of tablet, granule and other solid product.
Background technology
Adopt the existing long history of simple substance chlorination sterilization, have the characteristics of broad-spectrum high efficacy, but found afterwards that simple substance chlorine and hypochlorous acid can react with the organic matter in the water, form the chlorohydrocarbon compound, the suspicion of bringing out cancer is arranged.Another is nontoxic so simple substance chlorine and hypochlorination's compound be transformed in water, and the compound that bactericidal activity is high again is a new technical problem.Humphrey Davery successfully made chlorine dioxide in 1811, and existing thousands of families water treatment plant and other industry are used chlorine dioxide in the North America at present, mainly be used in except that algae, remove smell, decolouring, sterilization, removing of iron and manganese impurity etc.Use at European chlorine dioxide is more general, because chlorine dioxide can not produce toxic and side effect at disinfecting process, its safety is classified as the A1 level by the World Health Organization, by American-European developed country praise highly be the 4th generation green disinfectant.Yet the liquids and gases of chlorine dioxide are extremely unstable, and concentration only 10% just may be exploded in air, and the stability that solves the chlorine dioxide product also is the emphasis that countries in the world are studied.
Although U.S. Pat 5399288 (1995), US6197215 (2001), US6602442 (2003) adopt chlorite and hypochlorite can make a spot of chlorine dioxide under the effect of acid compound, but product stability is still not good enough, it is permanent to be difficult to preserve, the instant effect of product is also relatively poor in addition, use inconvenient, the corrosivity of product is more serious, influences the scope of application etc.
Summary of the invention
Main purpose of the present invention provides a kind of instant type of two-component packaging that is made of A component and B component, poisonous hypochlorous acid compounds can be changed into the two-component composition and the another kind of monobasic packing list component chlorine dioxide combination of chlorine dioxide, wherein the quality percentage composition of each component is:
(1) two-component composition of chlorine dioxide:
The A component: hypochlorous acid provides agent 20%-60%
Fine silica powder 0.01%-3%
Boric acid 0.5%-8%
Benzoate 0.5%-10%
Carbonate 10%-50%
Cellulose 1%-10%
B component: chlorite 2%-20%
Peracid salt 1%-10%
Disulfate 2%-10%
Zinc sulphate 0.1%-3%
Benzoate 0.5%-10%
Boric acid 0.5%-8%
Cellulosate 1%-10%
Sulphate 25%-45%
Polyphosphate 1%-10%
Fine silica powder 0.01%-3%
(2) one pack system chlorine dioxide combination:
Hypochlorous acid provides agent 20%-60%
Fine silica powder 0.01%-3%
Boric acid 0.5%-8%
Benzoate 0.5%-10%
Peracid salt 20%-60%
Cellulosate 1%-10%
Chlorite 2%-20%
Sodium sulphate 20%-40%
Zinc sulphate 0.1%-3%
The composition of chlorine dioxide as mentioned above, A component hypochlorous acid provides agent, can be chlorinated isocyanuric acid and salt thereof, BCDMH and salt thereof and hypochlorite, can be sodium, potassium or calcium salt, preferably the sodium salt mass percent is 20%-60%, preferably 35%-55%.
The composition of chlorine dioxide as mentioned above, the A component contains fine silica powder, and mass percent is 0.01%-3%, is preferably 0.5%-1%.Mainly play lubricated, moulding and stabilization.
The composition of chlorine dioxide as mentioned above, the A component contains the boric acid quality, and quality hundred percentage 0.5%-8% are preferably 2%-6%
The composition of chlorine dioxide as mentioned above, the A component contains benzoate, and mass percent 0.5%-8% is preferably 3%-7%, can be any salt in the alkali metal family, is preferably sodium salt.
The composition of chlorine dioxide as mentioned above, the A component contains carbonate or acid carbonate, and mass percent 10%-50% is preferably 20%-40%; Can be any salt in the alkali metal family, be preferably sodium salt.
The composition of chlorine dioxide as mentioned above, the A component contains fine little element or its salt, and mass percent 1%-10% is preferably 2%-7%, can be any salt in the alkali metal family, is preferably sodium salt.
The composition of chlorine dioxide as mentioned above, the B component contains chlorite or chlorate, and mass percent 2%-25% is preferably 6%-18%, can be any salt in the alkali metal family, is preferably sodium salt.
The composition of chlorine dioxide as mentioned above, the B component contains zinc sulphate, and mass percent 0.1%-3% is preferably 0.2%-1%.
The composition of chlorine dioxide as mentioned above, the B component contains a kind of per-compound, shared mass percent example 1%-10%, preferably 3%-8%; Can be perborate, percarbonate, solid-state Peracetic acid or percarbamide, preferably secondly perborate be percarbonate.
The composition of chlorine dioxide as mentioned above, the B component contains a kind of disulfate compound, and shared mass percent example 2%-10% is preferably 4%-8%, and disulfate can be any in the alkali metal salt, and preferably secondly sodium salt is sylvite.
The composition of chlorine dioxide as mentioned above, the B component contains a kind of sulphate cpd, proportion 25%-45%, it can be any in the alkali metal salt being preferably 30%-40%. sulphate, preferably secondly sodium salt is sylvite.
The composition of chlorine dioxide as mentioned above, the B component contains the boric acid quality, and mass percent example 0.5%-8% is preferably 2%-6%.
The composition of chlorine dioxide as mentioned above, the B component contains benzoate, and mass percent 0.5%-8% is preferably 3%-7%, can be any salt in the alkali metal family, is preferably sodium salt.
The composition of chlorine dioxide as mentioned above, the B component contains fine little element or its salt, and mass percent is 1%-10%, is preferably 2%-7%, can be any salt in the alkali metal family, is preferably sodium salt.
The composition of chlorine dioxide as mentioned above, the B component contains a kind of polyphosphoric acids salt compound, and shared mass ratio 1%-10% is preferably 4%-8%, polyphosphate. and can be any in the alkali metal salt, preferably secondly sodium salt be sylvite.
The composition of chlorine dioxide as mentioned above, the B component contains a kind of fine silica powder, and proportion 0.01%-3% is preferably 0.5%-1%.
Preparation of compositions technology:
The composition of chlorine dioxide is the mass ratio according to the ratio and the one pack system of component A and B component as mentioned above, pulverize respectively, cross the 80-100 mesh sieve, put into the thermostatic drying chamber temperature control then respectively 90-110 ℃ of drying, the time is controlled at was advisable in 8-12 hour, measure moisture then, according to the accurate weighing of formula ratio, put into 30 minutes married operations of three-dimensional hybrid device, after mensuration content is accurate, can further process according to different purposes.
A, instant type pulvis: can directly pack, seal and be finished product.
B, instant type granule: can adopt suitable solvent, binder by comminutor, make the effervescence granular of various particle diameters, respectively packing.
C, dissolving tablet and lozenge: by selecting different tablet press machines such as rotary 25,33,40 stamping machines for use, select different punch dies again, adopt dry powder direct tabletting,, make the suitable product of hardness and intensity by adjusting the pressure of machine.Sheet is heavy can be 0.5 gram/sheet, 1.0 gram/sheets, 1.50 gram/sheets, 2 gram/sheets, 3 gram/sheets, 20 gram/sheets, 100 gram/sheets, 150 gram/sheets, 300 gram/sheets etc.
The chlorine dioxide combination A part that makes and the shaped article of B part, render in the water simultaneously, the dosage of different instructions for use water does not wait, mutual chemical reaction by 5-30 minute, obtain a kind of aqueous solution of chlorine dioxide of limegreen, effectively chlorine dioxide content can reach 20-60000mg/L.The basic principle of preparation is to adopt the principles of chemistry as figure-1 and figure-2 to realize:
Figure-1 A component main chemical reactions mechanism
Figure-2 A and B component main chemical reactions mechanism
The present invention can make the higher chlorine dioxide of productive rate by a series of like this chemical reaction; By stabilizing agent in the component and chlorine dioxide reaction fully and combine, finally can obtain the chlorine dioxide of stable state again.Main feature of the present invention is that the effervesce dissolving is quick, reacts fast productive rate height, particularly dyad packaging product, and stability is high, safety easy to use, metering easily.Because component has the preferred metal corrosion inhibition through the anticorrosion design, to test under 20 ℃ of conditions, maximum working concentration is when 1000mg/L, and the quality that the immersion metal is measured after 72 hours before and after the metal reduces, thereby determines the metal erosion degree, and the result shows:
Stainless steel does not have corrosion, and carbon steel does not have corrosion substantially, the corrosion of copper moderate, and aluminium base is not had corrosion.
Stability test: 37 ℃ of constant temperature, under the lasting 90 days conditions, measure decline percentage≤8.7% of chlorine dioxide content in the component, meet the requirement of the countries concerned's disinfecting product, the shelf-life of product is 2 years.
Embodiment
Embodiment 1
A kind of novel chlorine dioxide two-component composition, the mass percent of its each component is:
A component: sodium dichloroisocyanate 35%-55%
Fine silica powder 0.5%-1%
Boric acid 2%-6%
Sodium Benzoate 3%-7%
Sodium carbonate 20%-30%
Cellulose 1%-8%
B component: sodium chlorite 2-%-18%
Sodium perborate 2%-9%
Niter cake 2%-8%
Zinc sulphate 0.5%-2%
Sodium Benzoate 2%-8%
Boric acid 2%-6%
Cellulosate 2%-8%
Sodium sulphate 30%-40%
Sodium polyphosphate 1%-10%
Fine silica powder 0.5%-2%
Adopt and pulverize the back drying, cross 100 mesh sieves, direct tablet compressing, adopt 25 or 33 towards rotary tablet machine, select suitable punch die, adjust machine pressure, work continuously, can make 3 gram/sheets, smooth in appearance, pure white, immaculate, no sticking phenomenon have suitable hardness, and molten water test shows: dissolving in 5-8 minute, form lurid clarification aqueous solution of chlorine dioxide, prove and to realize the purpose that designs.
Embodiment 2
A kind of novel chlorine dioxide two-component composition, the mass percent of its each component is:
A component: TCCA (Trichloroisocyanuric acid) 30%-55%
Fine silica powder 0.2%-1%
Boric acid 2%-6%
Sodium Benzoate 1%-8%
Sodium carbonate 20%-50%
Cellulosate 1%-8%
B component: sodium chlorite 2-%-18%
SODIUM PERCARBONATE 2%-9%
Niter cake 2%-8%
Zinc sulphate 0.5%-2%
Sodium Benzoate 2%-8%
Boric acid 2%-8%
Cellulose 2%-8%
Sodium sulphate 30%-40%
Sodium polyphosphate 1%-10%
Fine silica powder 0.5%-2%
Embodiment 3
A kind of novel chlorine dioxide two-component composition, the mass percent of its each component is:
A component: calcium hypochlorite 30%-55%
Fine silica powder 0.2%-1%
Boric acid 2%-6%
Sodium Benzoate 1%-8%
Sodium bicarbonate 20%-40%
Cellulose 1%-8%
B component: sodium chlorate 2-%-18%
SODIUM PERCARBONATE 2%-9%
Niter cake 2%-8%
Zinc sulphate 0.5%-2%
Sodium Benzoate 2%-8%
Boric acid 2%-8%
Cellulosate 2%-8%
Sodium sulphate 30%-40%
Sodium polyphosphate 1%-10%
Fine silica powder 0.5%-2%
Embodiment 4, optimization prescription
A kind of novel chlorine dioxide two-component composition, the mass percent of its each component is
A component: TCCA (Trichloroisocyanuric acid) 35%-55%
Fine silica powder 0.5%-1%
Boric acid 2%-6%
Sodium Benzoate 3%-7%
Sodium bicarbonate 15%-40%
Cellulose 2%-7%
B component: sodium chlorite 6%-18%
Sodium perborate 4%-8%
Niter cake 2%-8%
Zinc sulphate 0.5%-2%
Sodium Benzoate 2%-8%
Boric acid 2%-8%
Sodium cellulosate 2%-7%
Sodium sulphate 30%-40%
Sodium polyphosphate 4%-8%
Fine silica powder 0.5%-1%
Embodiment 5
A kind of novel chlorine dioxide two-component composition, the mass percent of its each component is:
A component: BCDMH 35%-55%
Fine silica powder 0.5%-1%
Boric acid 2%-6%
Sodium Benzoate 2%-8%
Sodium bicarbonate 20%-40%
Sodium cellulosate 1%-8%
B component: sodium chlorite 2-%-18%
SODIUM PERCARBONATE 2%-9%
Niter cake 2%-8%
Zinc sulphate 0.5%-2%
Sodium Benzoate 2%-8%
Boric acid 2%-8%
Cellulose 2%-8%
Sodium sulphate 30%-40%
Sodium polyphosphate 1%-10%
Fine silica powder 0.5%-2%
Embodiment 6
A kind of novel chlorine dioxide monobasic single-component composition, the mass percent of its each component is:
BCDMH 35%-55%
Fine silica powder 0.5%-1%
Boric acid 2%-6%
Sodium Benzoate 2%-8%
SODIUM PERCARBONATE 25%-50%
Sodium cellulosate 1%-8%
Sodium chlorite 2-%-18%
Zinc sulphate 0.2%-2%
Sodium sulphate 20%-40%
Adopt and pulverize the back drying, cross 80 mesh sieves, direct tablet compressing, adopt 33 towards rotary tablet machine, select suitable punch die, adjust machine pressure, work continuously, can make 1.5 gram/sheets, smooth in appearance, pure white, immaculate, no sticking phenomenon have suitable hardness, and molten water test shows: dissolving in 3-8 minute, form lurid clarification aqueous solution of chlorine dioxide, prove and to realize the purpose that designs.
Chlorine dioxide combination bactericidal assay result:
Bacterial classification: withered grass brood cell black mutation bacillus neutralizer: 1% tween+1%Na
2S
2O
3
| Valid density (mg/l) | Action time (min) | Killing rate (△ lg) |
| 125 | 5 10 20 30 | 3 3 4 4 |
| 250 | 5 10 20 30 | 4 4 4 4 |
| 400 | 5 10 20 30 | 4 4 4 4 |
| 800 | 5 10 20 30 | 4 4 4 5 |
| 1000 | 5 10 20 30 | 5 5 5 5 |
Invention is summed up
The chlorine dioxide that the design chemical reaction of chlorine dioxide combination of the present invention by science successfully changes into environment-friendly type with the organochlorine and the inorganic chlorine of toxic side effect; Effervesce A component and B component two-component composition have dissolving and reaction fast in 3-8 minute, form the aqueous solution of clarification.Metal inhibitor system in the component makes in itself and the Metal Contact process to have good compatibility, makes it have wider scope in actual applications.The comprehensive function of design of bi-component shaped article and stabilizing agent makes it have good stable, and accumulating is convenient, safety, and characteristics such as easy metering, in addition, result of the test shows the bactericidal activity of the high-efficiency broad spectrum of product, and the present invention is had broad application prospects.Single-component composition of the present invention is more convenient from using, and make also to realize, but the two-component composition of forming not as A and B is more reliable and more stable.Therefore the present composition can be applied to live water treatment, environment disinfected, hospital, family's vessel, fruit and vegetable sterilization and deodorizing, decolouring etc. safer and more effectively.
Itself contain hypochlorous acid high level broad-spectrum disinfectant exactly from function of use, practical function A components composition in addition, can directly apply to the sterilization of waste water treatment, environment disinfected, hospital surgical equipment etc.Therefore the present invention can have different multiple function and effect according to different purposes, possesses multiple selection function and actual effect.
Claims (7)
1. novel chlorine dioxide combination, it is characterized in that the effervesce quick-dissolving agent of being made up of chlorinated isocyanurates, BCDMH and salt, hypochlorite etc. provides agent component and chlorate, chlorite reaction to obtain the application of method in preparations such as pulvis, granule and tablet of stable chlorine dioxide disinfectant disinfectant as hypochlorous acid; The medicament system that the hypochlorous acid that the present composition contains provides agent, perborate or percarbonate, carbonate, chlorite, chlorate, corrosion inhibiter and acid compound etc. to make by following mass percent, it both can be the two-component packaging bi-component, also can be monobasic packing list components composition:
Two-component composition:
The A component: hypochlorous acid provides agent 20%-60%
Fine silica powder 0.01%-3%
Boric acid 0.5%-8%
Benzoate 0.5%-10%
Carbonate 10%-50%
Cellulose 1%-10%
B component: chlorite 2-%-20%
Peracid salt 1%-10%
Disulfate 2%-10%
Zinc sulphate 0.1%-3%
Benzoate 0.5%-10%
Boric acid 0.5%-8%
Cellulosate 1%-10%
Sulphate 25%-45%
Polyphosphate 1%-10%
Fine silica powder 0.01%-3%
2. according to the described chlorine dioxide two-component composition of claim 1 A component, it is characterized in that, contain a kind of fine silica powder, shared routine 0.01%-3%; Contain a kind of boric acid crystalline compounds, proportion 0.5%-10%; Contain a kind of benzoate crystalline compounds, proportion 0.5%-8%, it can be sodium or sylvite; Contain a kind of carbonate or bicarbonate crystalline compounds, proportion 10%-50%; Contain a kind of cellulose or its salt compound, proportion 1%-10%; Contain a kind of zinc sulphate crystalline compounds, proportion 0.1%-3%.
3. according to the described chlorine dioxide two-component composition of claim 1 B component, it is characterized in that for containing a kind of per-compound, proportion 1%-10% can be perborate, percarbonate, solid-state Peracetic acid or percarbamide; Contain a kind of disulfate compound, proportion 2%-10%; Contain a kind of benzoate crystalline compounds, proportion 0.5%-8%; Contain a kind of boric acid crystalline compounds, proportion 0.5%-8%; Contain a kind of sulphate cpd, proportion 25%-45%; Contain a kind of polyphosphoric acids salt compound, proportion 1%-10%; Contain a kind of fine silica powder, proportion 0.01%-3%.
4. according to the described chlorine dioxide combination of claim 1, it is characterized in that, be according to the ratio of component A and B component, pulverizes respectively, sieves, dries, adopt dry powder package, dry powder direct tabletting or process for granulating, make the production technology of A part and B part two-component packaging product.
5. according to the described chlorine dioxide two-component composition of claim 1, it is characterized in that, it is ratio according to component A and B component, make various two-component packaging shaped articles respectively, put into a certain amount of water during use simultaneously, by the aqueous solution of chlorine dioxide that reaction makes, this shaped article is meant tablet, pulvis, granule or lozenge:
Single-component composition:
Hypochlorous acid provides agent 20%-60%
Fine silica powder 0.01%-3%
Boric acid 0.5%-8%
Benzoate 0.5%-10%
Peracid salt 20%-60%
Cellulosate 1%-10%
Chlorite 2%-20%
Sodium sulphate 20%-40%
Zinc sulphate 0.1%-3%
6. according to the described chlorine dioxide monobasic of claim 1 packing list components composition, it is characterized in that, provide agent, proportion 20%-60% for containing a kind of hypochlorous acid; Contain a kind of fine silica powder, proportion is 0.01%-3%; Contain a kind of boric acid, proportion is 0.5%-8%; Contain a kind of peracid salt compound, proportion 20%-60%; Can be perborate, percarbonate, solid-state Peracetic acid, percarbamide; Contain a kind of cellulose, proportion 1%-10%; Contain a kind of benzoate, proportion 0.5%-10%; Contain a kind of chlorite, proportion 2%-20%; Contain a kind of sodium sulphate, proportion 20%-40%; Contain a kind of zinc sulphate, proportion 0.1%-3%.
7. according to the described chlorine dioxide monobasic of claim 1 packing list components composition, it is characterized in that, ratio according to prescription is pulverized respectively, sieves, is dried, and adopts dry powder package, dry powder direct tabletting or process for granulating, makes the production method of monobasic packing shaped article; During use, put into a certain amount of water, by the stabilizing chlorine dioxide aqueous solution that reaction makes, this shaped article is meant tablet, pulvis, granule or lozenge.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410098674 CN1788567A (en) | 2004-12-16 | 2004-12-16 | Chlorine dioxide composition and preparing method thereof |
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|---|---|---|---|
| CN 200410098674 CN1788567A (en) | 2004-12-16 | 2004-12-16 | Chlorine dioxide composition and preparing method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102283246A (en) * | 2011-05-30 | 2011-12-21 | 石家庄科大绿源科技发展有限公司 | Solid chlorine dioxide effervescent tablet and preparation method thereof |
| CN101496530B (en) * | 2009-02-27 | 2012-07-25 | 深圳清华大学研究院 | Composite disinfecting effervescent tablet and preparation method thereof |
| CN102811946A (en) * | 2010-02-05 | 2012-12-05 | 西帕卡股份有限公司 | System and method for generating chlorine dioxide |
| CN102870805A (en) * | 2012-10-20 | 2013-01-16 | 云南省农业科学院农业环境资源研究所 | Disinfector combination for unapplicable tobacco leaf digested and well-rotted residue |
| CN105233321A (en) * | 2015-11-16 | 2016-01-13 | 广西捷佳润农业科技有限公司 | Automatic disinfection and deodorization method and equipment for workshop environment of waste transfer station |
| CN105409938A (en) * | 2015-11-16 | 2016-03-23 | 韩文贤 | Chlorine-containing disinfection powder |
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| JP2019202918A (en) * | 2018-05-25 | 2019-11-28 | 株式会社環境衛生 | Chlorine dioxide generating powder and chlorine dioxide generator |
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| CN101496530B (en) * | 2009-02-27 | 2012-07-25 | 深圳清华大学研究院 | Composite disinfecting effervescent tablet and preparation method thereof |
| US12077433B2 (en) | 2009-12-17 | 2024-09-03 | Sipka Inc. | Article for generating chlorine dioxide |
| CN102811946A (en) * | 2010-02-05 | 2012-12-05 | 西帕卡股份有限公司 | System and method for generating chlorine dioxide |
| CN102811946B (en) * | 2010-02-05 | 2015-01-07 | 西帕卡股份有限公司 | System and method for generating chlorine dioxide |
| CN102283246B (en) * | 2011-05-30 | 2013-07-31 | 石家庄科大绿源科技发展有限公司 | Solid chlorine dioxide effervescent tablet and preparation method thereof |
| CN102283246A (en) * | 2011-05-30 | 2011-12-21 | 石家庄科大绿源科技发展有限公司 | Solid chlorine dioxide effervescent tablet and preparation method thereof |
| CN102870805A (en) * | 2012-10-20 | 2013-01-16 | 云南省农业科学院农业环境资源研究所 | Disinfector combination for unapplicable tobacco leaf digested and well-rotted residue |
| CN105233321A (en) * | 2015-11-16 | 2016-01-13 | 广西捷佳润农业科技有限公司 | Automatic disinfection and deodorization method and equipment for workshop environment of waste transfer station |
| CN105233321B (en) * | 2015-11-16 | 2018-01-16 | 广西捷佳润科技股份有限公司 | Garbage transfer station workshop condition automatic disinfection deodorizing method |
| CN105409938A (en) * | 2015-11-16 | 2016-03-23 | 韩文贤 | Chlorine-containing disinfection powder |
| CN107188296A (en) * | 2017-07-28 | 2017-09-22 | 辽东学院 | The method that chlorine dioxide mixed oxidization method handles amino phenols waste water from dyestuff |
| CN107188296B (en) * | 2017-07-28 | 2020-08-18 | 辽东学院 | Method for treating aminophenol dye wastewater by chlorine dioxide mixed oxidation method |
| JP2019202918A (en) * | 2018-05-25 | 2019-11-28 | 株式会社環境衛生 | Chlorine dioxide generating powder and chlorine dioxide generator |
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