CN1590281A - Chlorite-acid salt chlorine dioxide produstion system, its mono element packaged powder, tablet and its preparation method - Google Patents
Chlorite-acid salt chlorine dioxide produstion system, its mono element packaged powder, tablet and its preparation method Download PDFInfo
- Publication number
- CN1590281A CN1590281A CN 03155570 CN03155570A CN1590281A CN 1590281 A CN1590281 A CN 1590281A CN 03155570 CN03155570 CN 03155570 CN 03155570 A CN03155570 A CN 03155570A CN 1590281 A CN1590281 A CN 1590281A
- Authority
- CN
- China
- Prior art keywords
- chlorine dioxide
- chlorite
- parts
- tablet
- acid salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
A ClO2 generating system in the form solid (powder or tablet) or liquid for the environmental and medical disinfecting, industrial bleaching, water treating, etc is composed of chlorite and acidic salt.
Description
Technical Field
The invention relates to a chlorine dioxide generating system, an integrated packaging stable powder and a tablet thereof and a preparation method thereof. The chlorine dioxide generating system can be used for preparing unitary packaged stable chlorine dioxide powder and tablets with or without a passivator. The chlorine dioxide generating system and the stable powder and tablet prepared by the chlorine dioxide generating system can be used in the industrial fields of environmental protection, sanitation, aquaculture, medical disinfection, bleaching, deodorization, cleaning and the like.
Background
Chlorine dioxide, i.e. ClO2As disinfectants, bleaches, deodorants and cleaners are gaining widespread use in their related fields.For example, there is an increasing use in the fields of meat, fruit and vegetable processing, milk and dairy processing, paper, tanning and textile, recirculating cooling water and wastewater, sewage treatment, oil and gas contamination, aquaculture and environmental protection, hygiene and medical disinfection. In particular, chlorine dioxide forms little chloroform CHCl in drinking water disinfection3And the organic halide does not generate and destroy carcinogens in water, and can kill bacteria, viruses, algae and plankton more effectively than liquid chlorine, so that the organic halide has wider application prospect in the aspect of water treatment. Chlorine dioxide has proven to replace conventional liquid chlorine to specialty ozone O for over 20 years3And the like, or industrial bleaching agents.
The preparation of chlorine dioxide is particularly important because of its extremely wide use. The current methods for producing chlorine dioxide include chemical methods and electrolytic methods. Chemical methods include the chlorate method and the chlorite method. Wherein the chlorite process produces chlorine dioxide, including Cl, from sodium chlorite2Oxidation, acidification, persulfate ion (S)2O8 2-) Oxidation, electrochemical processes and organic or transition metals (e.g. Fe)3+) Oxidation methods, and the like. Wherein the electrochemical method and transition goldThe oxidation method is not so much related to the present invention. The oxidation, acidification and persulfate oxidation principles are asfollows:
1.Cl2an oxidation method:
gaseous Cl2With NaClO2The reaction of (a) is:
aqueous solution with NaClO2Reaction:
side reaction:
2. an acidification method comprises the following steps:
at present, the acidification method is mainly hydrochloric acid or sulfuric acid/NaClO2The method comprises the following steps:
3. and (3) an organic acid acidification method:
in addition, the lactic acid/chlorite ion system is used for preparing chlorine dioxide, so that the method has potential application capability and an unknown mechanism.
4. Persulfate ion oxidation process:
the persulfate oxidation method adopts sodium persulfate/NaClO2Chlorine dioxide is generated in the system:
each of the above-described methods has advantages and disadvantages. Cl2The oxidation process inevitably leaves Cl in the product2With side reactions also involving Cl-And (4) forming. The chlorine reacts with organic matters in water to generate carcinogenic chloride, and in addition, the preparation of chlorine or liquid chlorine is difficult, the cost is high, and the transportation is inconvenient. Acidification methods typically use liquid hydrochloric or sulfuric acid. These processes require special equipment for the production of chlorine dioxide. Another important problem is that it is inconvenient to package, transport and presents a certain risk in the handling operations. A further significant problem is that none of these processes can be made solid, limiting their application. In order to make it solid, persulfate ion oxidation has recently emerged. In this method, sodium chlorite and sodium persulfate can be packaged together, so that the unified packaging of solid is realized, and the generation of chlorine dioxide is relatively easy. But relatively speaking, of the oxidizing agent sodium persulfateThe preparation technology is complex and is not easy to obtain at present, so that the preparation technology cannot be widely applied. China has manufacturers who adopt a chlorine dioxide generation system synthesized by sodium chlorite and organic solid acid to realize unified packaging. However, most of the used organic acids are expensive, the product price is high, the economy is poor, and the popularization and the application are difficult. In addition, when used in large amount for a long time, the organic acid in the water can also cause waterThe source is eutrophicated, causing secondary pollution.
Disclosure of Invention
To address the above-described deficiencies of the prior art, the present inventors have surprisingly discovered a novel chlorine dioxide generating system comprising a chlorite salt and an acid salt (for making a liquid system) or comprising a chlorite salt, an acid salt and a passivating agent (formaking a powder or tablet system). According to the invention, the chlorine dioxide generating system with small pollution, low cost, safe transportation, high efficiency and convenient use is obtained.
According to one aspect of the present invention, a chlorine dioxide generating system is provided comprising a chlorite salt, an acid salt, and optionally a passivating agent.
The term "acid salt" as used herein refers to salts which exhibit acidity when dissolved in water and includes acid salts, strong acid and weak base salts, preferably acid sulfates and acid sulfites.
The term "chlorite" refers to salts composed of chlorite and a metal or an atom or group of atoms having a metallic nature, preferably alkali metal or alkaline earth metal salts of chlorous acid, more preferably sodium chlorite and potassium chlorite.
The term "passivating agent" refers to a substance that renders powders and tablets safer and does not participate in the generation and activation reactions of chlorine dioxide. For example, magnesium sulfate, sodium sulfite, etc. may be selected.
According to another aspect of the present invention there is provided a unitary packaged chlorine dioxide powder or tablet, characterised in that the unitary package contains both chlorite, an acid salt and optionally a phlegmatising agent. In the powder and the tablet without adding the passivator, the ratio of the chlorite to the acid salt is 1: 0.8-5. When the water-soluble paint is used, 10-100 times of water by weight can be added firstly, and then the water-soluble paint is diluted to the required concentration. In the powder and tablet added with the passivator, 1-3 parts of acid salt, 1-3 parts of chlorite and 3-6 parts of passivator are added. When the water-soluble paint is used, the water-soluble paint is firstly added into 10-100 times of water and then diluted to the required concentration. Generally, the activation degree (the proportion of chlorine dioxide contained in chlorite salt that is released as reactive free chlorine dioxide) is as high as 90% or more.
According to a further aspect of the present invention there is provided the use of an acid salt in the preparation of a system for the production of chlorine dioxide.
While not wishing to be bound by theory, the principle of producing chlorine dioxide using an acidic salt system is illustrated by the following equation, taking sodium chlorite as an example:
in the reaction formula (1), a, b, c, d, e and f represent the number of molecules participating in the reaction or forming the substance, and X representsmHnYoIs an acid salt, X is a metal element or an atomic group exhibiting metallic properties and showing 1 valence, divalent or trivalent, and m is the number of metal atoms and can be 1 or 2; h is an ionizable hydrogen atom in the acid salt, n is the number of hydrogen atoms, and can be generally 0, 1 or 2; y is an acid radical and o is the number of acid radicals, and is generally also 1 or 2.
For example, in the form of 1-valent metal acid sulfates, such as sodium bisulfate NaHSO4KHSO, potassium hydrogen sulfate4Ammonium hydrogen sulfate NH4HSO4In the formula, X is Na, K or NH4Showing a valence of 1, m is 1; n is 1; y is SO4O is 1; reaction with sodium chlorite to produce ClO2The equation of (1) is:
in the form of acid sulfates of metals having a valence of 2, e.g. calcium hydrogen sulfate Ca (HSO)4)2And magnesium hydrogen sulfate Mg (HSO)4)2Wherein X is Ca and Mg, showing 2 valence, m is 1; n can be considered to be 0; y can be regarded as HSO4And o is 2. Reaction with sodium chlorite to produce ClO2The equation of (1) is:
in some strong acid weak base salts, e.g. aluminium sulphate Al2(SO4)3In the formula, X is Al and shows trivalent, and m is 2; n is zero; y is sulfate SO4And o is 3. The equation for the reaction with sodium chlorite to produce chlorine dioxide is:
the method for preparing chlorine dioxide by using the solution raw material and chlorite and hydrogen sulfate in a ratio of 1: 0.2-10, preferably 1: 0.5-5, more preferably 1: 0.5-2 is suitable for large-scale application of drinking water treatment, environment-friendly and sanitary sewage purification, industrial wastewater treatment, industrial bleaching, deodorization, cleaning processes and the like of a tap water plant. The raw materials used in the reaction are easy to obtain and low in price. And because the used raw materials can be solid and are dissolved into liquid at the use place, the storage, the packaging and the transportation are very convenient. At the same time, the solid raw materials of thereaction system can be packaged together, do not react when being insoluble in water, and are stable, so that the reaction system can be prepared into acid-free unitary packaged solid powder or tablets, and after being dissolved in water, the acid salt makes the aqueous solution acidic, and chlorite therein is promoted to release active chlorine dioxide. The powder is suitable for large-scale application, such as the applications, disinfection of swimming pools and aquaculture, and the like. The tablet is more suitable for small-scale application such as hospital, restaurant, room, household, cooker, vegetable and fruit disinfection, etc. And the passivant is added, so that the powder and the tablet are safer and more stable.
The raw materials of the system can be packaged together to prepare powder and tablets of solid monobasic chlorite-acid salt chlorine dioxide generating system by the following method:
the first step is that no passivating agent is added: grinding sodium bisulfate, sieving, uniformly stirring and mixing sodium chlorite and sodium bisulfate in a ratio of 1: 0.2-10, preferably 1: 0.5-5, more preferably 1: 0.8-2, and packaging or tabletting. When the water-soluble polymer is used, the water is added into 10-100 times of the weight of water, stirring is carried out while adding, and the water-soluble polymer is diluted to the required concentration after dissolution. The activation rate reaches more than 90 percent.
(II) adding a single passivating agent: grinding 0.3-30 parts of magnesium sulfate, preferably 1-10 parts of magnesium sulfate, more preferably 3-6 parts of magnesium sulfate into fine powder, and sieving the fine powder with a sieve of 80-120 meshes. 0.4-10 parts of sodium bisulfate, preferably 0.6-6 parts of sodium bisulfate, more preferably 1-3 parts of sodium bisulfate and magnesium sulfate are uniformly mixed. And finally, taking 0.2-10 parts, preferably 0.4-6 parts, more preferably 1-3 parts of sodium chlorite and mixed powder of sodium bisulfate and magnesium sulfate, stirring and mixing uniformly, and packaging. When in use, the active chlorine dioxide is added into water with the weight of 10-100 times of that of the active chlorine dioxide and stirred simultaneously, and then the active chlorine dioxide is dissolved to generate the required concentration. The activation rate reaches more than 90 percent.
(III) adding a composite passivator: more than two composite passivators can be added into the raw material composition: grinding 0.3-30 parts of magnesium sulfate, preferably 1-10 parts, more preferably 3-6 parts, 0.3-30 parts of sodium sulfate, preferably 1-10 parts, more preferably 3-6 parts into fine powder (mixture 1), and sieving with a sieve of 80-120 meshes. 0.4-10 parts, preferably 0.6-6 parts, more preferably 1-3 parts of sodium bisulfate are uniformly mixed with the mixture 1 (mixture 2). And finally, 0.2-10 parts, preferably 0.4-6 parts, more preferably 1-3 parts of sodium chlorite is taken to be uniformly stirred with the mixture 2 and packaged. When in use, the active chlorine dioxide is added into water with the weight of 10-100 times of that of the active chlorine dioxide and stirred simultaneously, and then the active chlorine dioxide is dissolved to generate the required concentration. The activation rate reaches more than 90 percent.
(IV) directly preparing tablets: the powder added with the passivating agent is uniformly mixed and can be directly tabletted to obtain the stable tablet. When in use, the tablet is added into water with the weight of 10-100 times of that of the tablet, active chlorine dioxide is generated after the tablet is dissolved, and then the active chlorine dioxide is diluted to the required concentration. The activation rate is more than 90.
(V) adding auxiliary materials for tabletting: in order to improve the tabletting quality, 1-5 hard magnesium can be added into the powder to ensure that the surface of the tablet is more smooth and complete; the dissolution rate of the tablet can be increased by adding 1-5 parts of sodium bicarbonate. The usage is the same as above. The activation rate can reach 90%.
Brief description of the drawings
FIG. 1 is a schematic diagram of the apparatus used in the system for generating chlorine dioxide from an oxysalt and an acid salt.
Fig. 2 is a schematic diagram of a system for generating chlorine dioxide using a solid.
Detailed Description
The following are combined with practical application to the novel chlorine dioxide preparation system of the invention: the preparation method of the chlorite-acid salt chlorine dioxide generating system and the solid powder and tablet of the reaction system is further explained. These examples are intended to illustrate the invention and are not intended to be limiting.
Industrial, water source purification and sewage treatment application
Synthesizing a chlorine dioxide generation system from a raw material solution: referring to the attached figure 1, the using device of the invention mainly comprises a chlorite solution supply pump 1, an acid salt solution supply pump 2, a reaction area 3 and an output pipeline 4. Sodium chlorite 1 part and sulfur were supplied from a raw material feed pump0.5 part of sodium hydrogen sulfate solution or 1 part of each of sodium chlorite and sodium hydrogen sulfate is fed into a reaction zone, and ClO is generated in the reaction zone2And is output and applied through an output pipeline.
(II) synthesizing a chlorine dioxide generation system by using raw material solids: the equipment using this system is simpler. Referring to fig. 2, a solid chlorine dioxide generating system (the preparation method is the same as the preparation of unitary packaged solid chlorine dioxide powder tablets described below) is directly fed into a reaction zone 6 through a feeding hopper 5, and the generated chlorine dioxide is output and applied through an output pipeline 7.
Secondly, preparing a solid unitary packaging chlorite-acid salt chlorine dioxide generating system:
firstly, 50g of sodium bisulfate is ground and sieved, and 50g of sodium chlorite is uniformly mixed with the ground sodium bisulfate and packaged or tabletted. When the water-soluble polymer is used, the water is added into 10-100 times of the weight of water, stirring is carried out while adding, and the water-soluble polymer is diluted to the required concentration after dissolution. The activation rate reaches 98 percent, namely the yield of the active chlorine dioxide is 298mg/g powder.
And (II) grinding 25g of sodium bisulfate, sieving, uniformly mixing 60g of sodium chlorite with the ground sodium bisulfate, and packaging or tabletting. The application method is the same as above. The activation rate is 90 percent, namely the yield of the active chlorine dioxide is 500mg/g powder.
And (III) taking 100g of magnesium sulfate, grinding into fine powder, and sieving with a 100-mesh sieve. 60g of sodium bisulfate is uniformly mixed with magnesium sulfate. And finally, mixing 40g of sodium chlorite with the mixed powder of sodium bisulfate and magnesium sulfate, stirring uniformly, and packaging. When in use, the active chlorine dioxide is added into water with the weight of 10-100 times of that of the active chlorine dioxide and stirred simultaneously, and then the active chlorine dioxide is dissolved to generate the required concentration. The activation rate is 98 percent, namely the yield of the active chlorine dioxide is 117mg/g powder.
And (IV) taking 60g of magnesium sulfate and 60g of sodium sulfate, grinding into fine powder (mixture 1), and sieving by a 100-mesh sieve. 40g of sodium bisulfate is taken and ground, and is sieved by a 100-mesh sieve, and is uniformly mixed with the mixture 1 (mixture 2). Finally, 40g of sodium chlorite is uniformly mixed with the mixture 2. The activation rate is 96 percent, namely the yield of the active chlorine dioxide is 114mg/g powder.
And (V) taking 100g of the powder prepared by the step (III) and adding the passivant, and pressing into tablets with the weight of 1g to obtain the stable tablets. When in use, the tablet is added into water with the weight of 10-100 times of that of the tablet, active chlorine dioxide is generated after the tablet is dissolved, and then the active chlorine dioxide is diluted to the required concentration. The activation rate is 95 percent, namely the yield of the active chlorine dioxide is 113 mg/tablet.
And sixthly, taking 92g of powder prepared by the step four, adding 3g of magnesium stearate and 5g of sodium bicarbonate, uniformly mixing, and pressing into tablets with weight of 1 g. The usage is the same as above. The activation rate is 98 percent, namely the yield of the active chlorine dioxide is 106 mg/tablet.
Having thus described the invention in full, it will be appreciated by those skilled in the art that the invention can be practiced within a wide range of parameters within what is claimed, without departing from the spirit and scope of the invention.
Claims (10)
1. Chlorine dioxide generating system, characterized in that said system comprises chlorite, acid salt.
2. The chlorine dioxide-generating system of claim 1, which is a solid and further comprises a passivating agent.
3. The chlorine dioxide generating system of claim 1, wherein the acid salt is selected from the group consisting of water soluble salts that exhibit acidity, preferably acid sulfates and acid sulfites.
4. A chlorine dioxide generating system as defined in any one of claims 1-3, wherein the system is a solution or a solid.
5. A process for preparing a solid chlorine dioxide generating system comprises grinding and uniformly mixing together a chlorite salt, an acid salt, and optionally a passivating agent.
6. A unitary packaged powder or tablet of a chlorine dioxide generating system, characterized in that said unitary package contains both chlorite and an acid salt.
7. A unitary packaged powder or tablet according to claim 6 wherein the ratio of chlorite to acid sulfate is from 1: 0.2 to 10, preferably from 1: 0.5 to 5, more preferably from 1: 0.8 to 2.
8. A unitary packaged powder or tablet according to claim 6 further comprising a single or multiple deactivants.
9. A unitary packaged powder or tablet according to claim 8 wherein the one or more deactivants is from 0.3 to 30 parts, preferably from 1 to 10 parts, more preferably from 3 to 6 parts; 0.4-10 parts of sodium bisulfate, preferably 0.6-6 parts of sodium bisulfate, and more preferably 1-3 parts of sodium bisulfate; 0.2 to 10 parts of sodium chlorite, preferably 0.4 to 6 parts, and more preferably 1 to 3 parts.
10. Use of an acidic sulphate in the preparation of a chlorine dioxide generating system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031555705A CN1328155C (en) | 2003-08-29 | 2003-08-29 | Chlorite-acid salt chlorine dioxide produstion system, its mono element packaged powder, tablet and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031555705A CN1328155C (en) | 2003-08-29 | 2003-08-29 | Chlorite-acid salt chlorine dioxide produstion system, its mono element packaged powder, tablet and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1590281A true CN1590281A (en) | 2005-03-09 |
| CN1328155C CN1328155C (en) | 2007-07-25 |
Family
ID=34598164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031555705A Expired - Fee Related CN1328155C (en) | 2003-08-29 | 2003-08-29 | Chlorite-acid salt chlorine dioxide produstion system, its mono element packaged powder, tablet and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1328155C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348237B (en) * | 2008-08-22 | 2010-06-02 | 穆超银 | Reducer for preparing chlorine dioxide by chlorate method |
| CN101228868B (en) * | 2008-02-27 | 2010-06-09 | 河北科技大学 | Unitary solid chlorine dioxide effervescent tablet and preparation method thereof |
| CN102283247A (en) * | 2011-07-23 | 2011-12-21 | 中国农业科学院兰州畜牧与兽药研究所 | Veterinary disinfection powder and preparation method thereof |
| CN106305771A (en) * | 2015-06-19 | 2017-01-11 | 山西云大中天环境科技有限公司 | Soil sterilizer and preparation method thereof |
| CN108991007A (en) * | 2018-08-20 | 2018-12-14 | 青岛大学 | A kind of safe slow released ClO 2 disinfectant and preparation method thereof |
| CN109819999A (en) * | 2019-04-04 | 2019-05-31 | 开封恩科生物科技有限公司 | Chlorine dioxide solid releasing agent and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432322B1 (en) * | 2000-02-02 | 2002-08-13 | Engelhard Corporation | Massive bodies for producing highly converted solutions of chlorine dioxde |
-
2003
- 2003-08-29 CN CNB031555705A patent/CN1328155C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228868B (en) * | 2008-02-27 | 2010-06-09 | 河北科技大学 | Unitary solid chlorine dioxide effervescent tablet and preparation method thereof |
| CN101348237B (en) * | 2008-08-22 | 2010-06-02 | 穆超银 | Reducer for preparing chlorine dioxide by chlorate method |
| CN102283247A (en) * | 2011-07-23 | 2011-12-21 | 中国农业科学院兰州畜牧与兽药研究所 | Veterinary disinfection powder and preparation method thereof |
| CN106305771A (en) * | 2015-06-19 | 2017-01-11 | 山西云大中天环境科技有限公司 | Soil sterilizer and preparation method thereof |
| CN108991007A (en) * | 2018-08-20 | 2018-12-14 | 青岛大学 | A kind of safe slow released ClO 2 disinfectant and preparation method thereof |
| CN109819999A (en) * | 2019-04-04 | 2019-05-31 | 开封恩科生物科技有限公司 | Chlorine dioxide solid releasing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1328155C (en) | 2007-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Patil et al. | Treatment of laundry wastewater containing residual surfactants using combined approaches based on ozone, catalyst and cavitation | |
| CN101437754B (en) | Chlorine dioxide based cleaner/sanitizer | |
| RU2276657C2 (en) | Method of synthesizing of the oxidizing agent and its application | |
| US6428696B2 (en) | Process for preparing a chlorine-dioxide-containing disinfectant solution for water treatment | |
| Canle et al. | Photocatalyzed degradation/abatement of endocrine disruptors | |
| Mei et al. | A novel Fenton-like system of Fe2O3 and NaHSO3 for Orange II degradation | |
| Seid-Mohammadi et al. | Photocatalytic degradation of metronidazole (MNZ) antibiotic in aqueous media using copper oxide nanoparticles activated by H2O2/UV process: Biodegradability and kinetic studies | |
| JP5556838B2 (en) | Slime control method in pulp and paper manufacturing process | |
| US7927508B2 (en) | Composition and process for enhanced sanitation and oxidation of aqueous systems | |
| CN101318707A (en) | Method for preparing steady composite potassium ferrate solution | |
| CN1406208A (en) | Massive bodies for producing highly converted solutions of chlorine dioxide | |
| JP2007301459A (en) | Treatment method of waste water containing ammonia nitrogen and cod component at high concentration | |
| CN1590281A (en) | Chlorite-acid salt chlorine dioxide produstion system, its mono element packaged powder, tablet and its preparation method | |
| CN101717146B (en) | Method for treating catalytic ozone oxidation water | |
| US20080031805A1 (en) | Method For The Production Of Chlorine Dioxide | |
| CN110810435A (en) | Oxidation water purification disinfectant for aquaculture and preparation method thereof | |
| CN105417673B (en) | A kind of method that utilization singlet oxygen removes algae | |
| CN1556046A (en) | Synergism type chlorine dioxide bactericide and its manufacturing method and use in aquatic culture | |
| JP3992614B2 (en) | Disinfectant and water-based disinfecting method using the disinfectant | |
| US6878289B2 (en) | Method of reducing chemical oxygen demand in water | |
| CN108585168A (en) | A kind of preparation method and application of novel ferrate and the compound pre- oxygen agent of chlorine dioxide | |
| JP2004267896A (en) | Contamination preventing method for industrial/waste water system | |
| RU2679261C2 (en) | Method for generating chloride dioxide | |
| JP3851932B2 (en) | Chlorine dioxide water production method | |
| CN104402102A (en) | Enhanced pre-treatment coagulant for printing and dyeing wastewater and preparation method of enhanced pre-treatment coagulant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070725 Termination date: 20210829 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |