CN1175350A - Process for producing solid chlorine dioxide - Google Patents
Process for producing solid chlorine dioxide Download PDFInfo
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- CN1175350A CN1175350A CN 96109562 CN96109562A CN1175350A CN 1175350 A CN1175350 A CN 1175350A CN 96109562 CN96109562 CN 96109562 CN 96109562 A CN96109562 A CN 96109562A CN 1175350 A CN1175350 A CN 1175350A
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Abstract
A process for preparing ClO2 solid includes reaction of diluted sulfuric acid solution with methanol and solid sodium chlorate in reaction tower in the presence of NaCl as catalyst to obtain ClO2 gas, cooling in cooler, adsorbing ClO2 by water, regulating pH to 8-9, spraying the ClO2 solution dissolved in water to absorbent, stirring and tabletting, and features convenient preparation and transportation, high purity and high sterilization effect.
Description
The invention relates to a production process of solid chlorine dioxide, which is characterized in that a chlorine dioxide solution is prepared into a solid tablet by a physical method, and the use is very convenient.
Chlorine dioxide has been recognized worldwide as a new type of disinfectant and has shown its wide development prospects. Especially, people find that the common chlorine-containing preparation can generate harmful substances such as trichloromethane and the like which are harmful to human bodies in water, and have great interest in the high-efficiency and harmless action of chlorine dioxide. The united states environmental protection agency and the united states food and drug administration have approved the use of specific chlorine dioxide formulations in food processing industry, drinking water, hospital and pharmaceutical industry for disinfection and mold prevention, dental disinfection and deodorization, food (including vegetables, fruits, aquatic products, etc.) disinfection and preservation, farm disinfection and deodorization, hospital and industrial wastewater treatment, etc.
The application information of chlorine dioxide enters China from the beginning of the 80 s, and a small amount of chlorine dioxide is not used in 80 s. The current production process is an electrolytic method, and the produced chlorine dioxide is liquid. Its disadvantages are: the liquid chlorine dioxide has the characteristics of strong irritation, instability, high concentration, easy explosion and the like, so the production, the packaging and the transportation of the chlorine dioxide are greatly limited; chlorine dioxide produced by electrolysis contains many impurities such as sodium hypochlorite and calcium hypochlorite.
The invention aims to solve the defects in the prior art and provides a production process of solid chlorine dioxide. The process is advanced, and the produced solid chlorine dioxide tablet is pure and free of impurities.
The purpose of the invention is realized as follows:
the production process of solid chlorine dioxide utilizes chemical reaction:
the generated chlorine dioxide is made into solid tablets by a physical method, and the production process comprises the following steps:
① feeding dilute sulfuric acid solution and methanol from the jet orifice and solid sodium chlorate from the feed inlet into the reaction tower;
② accelerating the reaction speed byusing a catalyst which is NaCL;
③ heating the reaction by heating pipes;
④ explosion-proof, wherein an explosion-proof device for eliminating free radicals is additionally arranged on the reaction tower;
⑤ cooling, wherein chlorine dioxide gas is cooled by a cooling tower;
⑥ corrosion prevention, namely, performing production circulation by using a jet pump as power;
⑦, water absorption, namely absorbing the cooled chlorine dioxide by water and adjusting the pH value to 8-9;
⑧ stirring and adsorbing, namely spraying the chlorine dioxide solution dissolved in water onto the absorbent to stir;
⑨ tabletting, namely tabletting the stirred sticky matter (chlorine dioxide adsorbed on the adsorbent) into a finished product.
The process method of the invention can be further improved by the following steps:
in the production process of solid chlorine dioxide, the optimum temperature for the reaction of materials in the reaction tower is controlled60-70 ℃; MgCL may also be used as catalyst in the reaction2、KCL、Na2SO4(ii) a The adsorbent is synthetic calcium silicate, and may be particulate silica, activated carbon, volcanic ash, etc.
The invention is provided with a drawing which is a best embodiment of the invention and can also be used as a drawing of an abstract of the specification.
FIG. 1 is a simple flow chart of the present invention.
Compared with the prior art, the invention has the advantages that the solid chlorine dioxide tablet prepared from ① is not easy to explode, the production and transportation are safe and convenient, the ② product is pure and free of impurities, the ③ product is convenient to use, and the disinfection effect is good.
The process of the present invention is further described below with reference to the accompanying drawings.
The reaction equation for producing chlorine dioxide is:
the technological process of the present invention is as shown in figure 1, dilute sulfuric acid solution and methanol are first sprayed into the reaction tower 6 via the spray port 1, solid sodium chlorate is then added into the reaction tower 6 via the feed port 2, the material is reacted in the reaction tower 6 with the temperature required for the reaction being heated in the heating pipe 8 and the optimal reaction temperature being controlled in 60-70 deg.c. To accelerate the reaction, a catalyst is added through the feed opening 5. The added catalyst is NaCl or MgCL2、KCL、Na2SO4. In order to prevent explosion accidents, according to the principle of explosion, the theory of eliminating free radicals is adopted, and two explosion-proof devices 3 are added. The chlorine dioxide gas generated after the reaction is cooled by a cooling tower 4, the cooled chlorine dioxide enters an absorption tower 9 through a pipeline, and water enters the absorption towerAbsorbing, wherein the water solution absorbing chlorine dioxide enters a water tank 13 through a valve 10 and is subjected to secondary absorption through an absorption tower 12. The water required for absorbing chlorine dioxide is supplied by the ejector pump 11. Because chlorine dioxide has strong oxidizability, the material of the reactor is titanium, and the titanium has good corrosion resistance and impact resistance. During production circulation, the common acid and alkali resistant pump cannot adapt to the production circulation, and the injection pump is adopted, so that the circulation problem and the corrosion problem are solved. Chlorine dioxide is dissolved in water, but the solubility is small and generally can reach 7000PPM, the chlorine dioxide is too high, and because the chlorine dioxide is unstable, danger is easy to occur, and if the chlorine dioxide absorption fluid is changed from water to peroxycarbonate for absorption in production, the stable composite chlorine dioxide solution can be prepared. The concentration can reach 50000-200000 PPM, the stability is very high, and the stable period can reach three years. The peroxycarbonate is a complex of sodium carbonate and hydrogen peroxide, and the molecular formula can be approximately written as 2Na2CO3·3H2And O. The stable chlorine dioxide acidification can release chlorine dioxide, and the chlorine dioxide aqueous solution has all chemical properties of common chlorine dioxide aqueous solutions. The absorbed solution flows through valves 14, 15 and 16 to enter a stirring kettle 19, and an adsorbent of chlorine dioxide solution is filled in the stirring kettle 19. A good alkaline adsorbent should have a good adsorption capacity of at least 50%, preferably more than 75-200% or more, which has a large surface area of 95-150M2The fine particles of the water soluble polymer preferably have a diameter of 1.5-5 μ M, the alkaline absorbent comprises calcium silicate, microsilica, activated carbon, volcanic ash, etc., and the absorbent is usually acidic, and has a pH of 8-9, and the alkaline absorbent for adjusting the pH is sodium carbonate, sodium bicarbonate or sodium hydroxide, and preferably has a pH of 8 or more, or a combination thereofCalcium silicate is most suitable, and the pH value of the calcium silicate is 8-9. Therefore, synthetic calcium silicatewas put into the stirring vessel 19 and stirred by the stirrer 17. Stirring to obtain sticky substance, and tabletting into solid chlorine dioxide by using a tabletting machine 18.
The preparation of the dry powdery solid chlorine dioxide is to mix stable composite chlorine dioxide solution (the concentration is 2000-200000 PPM) with alkaline absorbent synthetic calcium silicate, and the stable chlorine dioxide is adsorbed on the calcium silicate.
If the concentration is 50000PPM steady chlorine dioxide solution and the weight ratio is 3: 2 by spraying a steady mist of chlorine dioxide into the calcium silicate while stirring.
Solid chlorine dioxide can also be made with sodium chlorite solution. Such as: adjusting the pH value of a 6% sodium chlorite solution to 8.3-8.5 by using sodium carbonate, and then adsorbing the sodium chlorite solution by using synthetic calcium silicate according to the weight ratio of 1: 1 (the production method is the same as the above).
The dry powder chlorine dioxide has the same chemical property with the stable chlorine dioxide, and the chlorine dioxide can be released after acidification.
The powdery chlorine dioxide is mixed with proper alkaline starch under the action of pressure to prepare the solid chlorine dioxide with different shapes such as tablets, blocks and the like.
The release rate of chlorine dioxide from solid chlorine dioxide is controlled by the amount of the acidic substance added to the solid chlorine dioxide or the concentration of the acidic substance. It can be directly sprayed on deodorant without acidification. The acidic species on the waste can excite the generation of chlorine dioxide, oxidizing hydrogen sulfide, benzoic acid, mercaptans, ammonia, and other species. For example, solid chlorine dioxide and citric acid can be mixed at a ratio of 5: 1 forfresh-keeping. Weighing 2 g of mixture, placing the mixture in a banana carton to be shipped, sealing the carton, and even carrying out long-distance transportation on the bananas in the carton on the sea due to slow release of chlorine dioxide, so that the bananas are not damaged by bacteria and fungi, the effect of keeping fresh is achieved, and no residue is left on the fruits.
Claims (4)
1. A process for producing solid chlorine dioxide, which is characterized by comprising the following steps: the reaction equation is:
the reaction process comprises the following steps:
① feeding dilute sulphuric acid solution and methanol from a jet orifice (1), and adding solid sodium chlorate from a feed inlet (2) into a reaction tower (6);
② accelerating the reaction speed by using a catalyst which is NaCL;
③ the reaction is heated by a heating pipe (8);
④ explosion-proof, adding an explosion-proof device (3) for eliminating free radicals on the reaction tower (6);
⑤ cooling, namely cooling the chlorine dioxide gas by a cooling tower (4);
⑥ corrosion prevention, namely, performing production circulation by using a jet pump as power;
⑦, water absorption, namely absorbing the cooled chlorine dioxide by water and adjusting the pH value to 8-9;
⑧ stirring and adsorbing, namely spraying the chlorine dioxide solution dissolved in water onto the adsorbent to stir;
⑨ tabletting, namely tabletting the stirred sticky matter (chlorine dioxide adsorbed on the adsorbent) into a finished product.
2. The process for the production of solid chlorine dioxide as claimed in claim 1, characterized in that: the optimal temperature of the reaction is controlled between 60 and 70 ℃.
3. The process for the production of solid chlorine dioxide as claimed in claim 1, characterized in that: MgCL may also be used as the catalyst2、KCL、Na2SO4。
4. The process for the production of solid chlorine dioxide as claimed in claim 1, characterized in that: the adsorbent is synthetic calcium silicate, and may be particulate silica, activated carbon, volcanic ash, etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109562A CN1053427C (en) | 1996-08-30 | 1996-08-30 | Process for producing solid chlorine dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109562A CN1053427C (en) | 1996-08-30 | 1996-08-30 | Process for producing solid chlorine dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175350A true CN1175350A (en) | 1998-03-11 |
| CN1053427C CN1053427C (en) | 2000-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109562A Expired - Fee Related CN1053427C (en) | 1996-08-30 | 1996-08-30 | Process for producing solid chlorine dioxide |
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| Country | Link |
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| CN (1) | CN1053427C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102106375A (en) * | 2009-12-29 | 2011-06-29 | 新疆大学 | Solid chloride dioxide generating agent |
| CN102173386A (en) * | 2011-01-24 | 2011-09-07 | 陆清 | Preparation method of stable-state chlorine dioxide solution of food additive |
| CN102275878A (en) * | 2010-06-11 | 2011-12-14 | 广西博世科环保科技股份有限公司 | Low-acidity energy-saving production process for high-purity chlorine dioxide |
| CN108782552A (en) * | 2018-08-09 | 2018-11-13 | 中昊(大连)化工研究设计院有限公司 | The new process for producing of chlorine dioxide slow-release piece |
| CN111771907A (en) * | 2020-08-03 | 2020-10-16 | 中山大学 | Antivirus nano material for slowly releasing chlorine dioxide and preparation method and application thereof |
| CN113207904A (en) * | 2021-04-30 | 2021-08-06 | 深圳市安保医疗感控科技股份有限公司 | Chlorine dioxide slow-release material, manufacturing method of related fabric and foot product |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4473540A (en) * | 1983-07-07 | 1984-09-25 | Erco Industries Limited | High efficiency chlorine dioxide process |
| CN1075298A (en) * | 1992-02-13 | 1993-08-18 | 青岛海洋大学 | A kind of method of producing chlorine dioxide of high concentration and stable state |
-
1996
- 1996-08-30 CN CN96109562A patent/CN1053427C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102106375A (en) * | 2009-12-29 | 2011-06-29 | 新疆大学 | Solid chloride dioxide generating agent |
| CN102275878A (en) * | 2010-06-11 | 2011-12-14 | 广西博世科环保科技股份有限公司 | Low-acidity energy-saving production process for high-purity chlorine dioxide |
| CN102275878B (en) * | 2010-06-11 | 2013-04-17 | 广西博世科环保科技股份有限公司 | Low-acidity energy-saving production process for high-purity chlorine dioxide |
| CN102173386A (en) * | 2011-01-24 | 2011-09-07 | 陆清 | Preparation method of stable-state chlorine dioxide solution of food additive |
| CN102173386B (en) * | 2011-01-24 | 2012-07-04 | 广西工业职业技术学院 | Preparation method of stable-state chlorine dioxide solution of food additive |
| CN108782552A (en) * | 2018-08-09 | 2018-11-13 | 中昊(大连)化工研究设计院有限公司 | The new process for producing of chlorine dioxide slow-release piece |
| CN111771907A (en) * | 2020-08-03 | 2020-10-16 | 中山大学 | Antivirus nano material for slowly releasing chlorine dioxide and preparation method and application thereof |
| CN113207904A (en) * | 2021-04-30 | 2021-08-06 | 深圳市安保医疗感控科技股份有限公司 | Chlorine dioxide slow-release material, manufacturing method of related fabric and foot product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1053427C (en) | 2000-06-14 |
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