CN1261050A - Process for preparing stable ClO2 solution based on methanol - Google Patents
Process for preparing stable ClO2 solution based on methanol Download PDFInfo
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- CN1261050A CN1261050A CN 99112022 CN99112022A CN1261050A CN 1261050 A CN1261050 A CN 1261050A CN 99112022 CN99112022 CN 99112022 CN 99112022 A CN99112022 A CN 99112022A CN 1261050 A CN1261050 A CN 1261050A
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Abstract
A process for preparing stable ClO2 solution based on methanol includes the steps of reaction in sulfuric medium to generate ClO2 gas using sodium chlorate as oxidant and methanol as reducer, stabilizing and adsorption with sodium hydroxide or sodium carbonate and H2O2. Said reaction takes place in condition of negative pressure generated by hydraulic water sprayer and the methanol is continually feeded. Its advantages are simple operation, low production cost, high utilization rate of raw materials and high purity of ClO2.
Description
The invention relates to a method for producing stable chlorine dioxide solution.
Chlorine dioxide is a broad-spectrum disinfectant, but is not suitable for small and dispersive users because the chlorine dioxide is unstable in property, difficult to store and needs to be prepared and used on site. The stable chlorine dioxide solution can overcome the defect, so the development of the stable chlorine dioxide solution production method with simple process equipment and less investment is imperative. The generation method of chlorine dioxide is more, and the main raw material used is sodium chlorate. According to the difference of the reducing agent, the method can be divided into the following steps: the Mathieson method, which uses sulfur dioxide as a reducing agent and sulfuric acid as a medium, has the disadvantages of low yield and much waste acid. The R2 method uses sodium chlorate, sodium chloride and sulfuric acid as raw materials, wherein the sodium chloride is used as a reducing agent. The sodium chloride reacts with sulfuric acid to generate hydrogen chloride, and then sodium chlorate is further reduced to obtain chlorine dioxide. This process generates a large amount of waste liquid containing sulfuric acid and sodium sulfate, and the recovery and disposal thereof are troublesome. The Solvey method uses sodium chlorate, sulfuric acid and methanol as raw materials, wherein the methanol is used as a reducing agent. The yield of the chlorine dioxide is 85-90%. The R8 method has been put into operation in 1985 in the United states, the used raw materials are the same as those of the Solvey method, the production capacity is improved due to the adoption of a unit reactor of reaction, namely evaporation and crystallization, and the conversion rate of the reaction is improved to more than 95 percent. The process has the advantages of simple operation, easy control, high production efficiency and the like. However, this process requires evaporation of water and consumes a large amount of steam. Chinese patent ZL93111202.8 and Chinese patent ZL97233737.7 disclose a novel technology of a negative-pressure aeration chlorine dioxide generator production process, and the technology takes sodium chlorate as an oxidant and hydrochloric acid as a reducing agent. The Chinese patent office discloses CN1075298A a method for producing high-concentration stable chlorine dioxide, which takes sodium chlorate, sulfuric acid and methanol as raw materials, uniformly mixes all reactants in a reactor, heats the reactants to react at 75-80 ℃, and then uses a vacuumizing method to make the reaction product chlorine dioxide pass through an absorption tower filled with sodium percarbonate solution from an outlet on the reactor to form solution. The disadvantages are that: the reaction is not stable and is difficult to operate, and the material ratio of sodium chlorate to methanol is as high as 1: 0.6.
The invention aims to provide a method for producing stable chlorine dioxide solution with high raw material utilization rate and high chlorine dioxide purity.
The present invention is achieved as follows. The production method comprises a reactor, a condenser, an absorption device and a negative pressure generation device. Sodium chlorate is used as an oxidant, methanol is used as a reducing agent, and the reaction is carried out in a sulfuric acid medium, and the reaction is as follows:
the reaction temperature is raised to 80 ℃ at normal temperature, the methanol operation mode is continuous feeding, the material ratio of sodium chlorate to methanol is 1: 0.05-0.1, the acidity of a reaction medium is 26-33%, chlorine dioxide gas generated by reaction raw materials in a reactor is stabilized and absorbed by 1-3% of sodium hydroxide or 5-8% of sodium carbonate and 0.5-1.5% of hydrogen peroxide in an absorption device, and then the stable chlorine dioxide solution can be prepared. The sodium hydroxide or sodium carbonate and hydrogen peroxide can be added once or continuously dropwise. The circulating absorption liquid is cooled by cooling water under the necessary conditions, and the reaction temperature of the absorption liquid is controlled below 30 ℃. Negative pressure is generated by a hydraulic ejector or a draught fan, so that the reactor and the absorption device are ensured to operate under the condition of negative pressure, and the system pressure is 745-754 mmHg.
Compared with the prior art, the invention has the following advantages: continuous methanol feeding, low production cost, high raw material utilization rate, less equipment investment, high chlorine dioxide purity and the like.
FIG. 1 is a schematic process flow diagram of the present invention. In the figure, 1 is a reactor, 2 is a condenser, 3 is an absorption tower, 4 is a hydraulic ejector, 5 is a circulating water pool, and 6 is a circulating pump.
The invention is described in detail below with reference to the accompanying drawings:
sodium chlorate is used as oxidant, methanol is used as reducer, and reaction is carried out in sulfuric acid medium, and the temperature in the whole reaction process is controlled to be raised to 80 ℃ at normal temperature. Sodium chlorate, water and concentrated sulfuric acid are sequentially added into a reactor [1], the operation mode of methanol is continuous feeding, the material ratio of the sodium chlorate to the methanol is 1: 0.05-0.1, the acidity of a reaction medium is 26-33%, chlorine dioxide gas generated by reaction raw materials in the reactor [1]is condensed by a condenser [2], and is stabilized and absorbed by 1-3% of sodium hydroxide or 5-8% of sodium carbonate and 0.5-1.5% of hydrogen peroxide in an absorption tower [3]. The sodium hydroxide or sodium carbonate and hydrogen peroxide can be added once or continuously dropwise. The absorption liquid repeatedly absorbs chlorine dioxide gas in the absorption tower [3], and finally stable chlorine dioxide solution with the pH value of 8.2-9.2, the chlorine dioxide content of more than 2.0 percent and the chlorine dioxide purity of more than 98 percent can be prepared. The absorption liquid in the absorption tower [3]is cooled by cooling water under the necessary conditions, and the reaction temperature of the absorption liquid is controlled below 30 ℃. The negative pressure generating system consists of a hydraulic ejector [4], a circulating water pool [5]and a circulating pump [6], so that the reactor [1]and the absorption tower [3]are ensured to operate under the negative pressure condition, and the system pressure is 745-754 mmHg.
Claims (4)
1. The production method of the stable chlorine dioxide solution based on the methanol is characterized in that sodium chlorate is used as an oxidant, the methanol is used as a reducing agent, and the reaction is carried out in a sulfuric acid medium, the production method is under the condition of negative pressure, the reaction temperature is increased to 80 ℃ at normal temperature, the acidity of the reaction medium is 26-33%, and the generated chlorine dioxide gas is stabilized and absorbed by 1-3% of sodium hydroxide and 0.5-1.5% of hydrogen peroxide.
2. A stable chlorine dioxide production process as claimed in claim 1, characterized in that the sodium hydroxide used can be replaced by 5-8% sodium carbonate.
3. The method for producing stable chlorine dioxide according to claim 1, wherein the material ratio of sodium chlorate to methanol is 1: 0.05-0.1.
4. A stable chlorine dioxide production process as claimed in claim 1, characterized in that methanol is continuously fed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991120221A CN1146523C (en) | 1999-01-15 | 1999-01-15 | Process for preparing stable ClO2 solution based on methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991120221A CN1146523C (en) | 1999-01-15 | 1999-01-15 | Process for preparing stable ClO2 solution based on methanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1261050A true CN1261050A (en) | 2000-07-26 |
| CN1146523C CN1146523C (en) | 2004-04-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991120221A Expired - Fee Related CN1146523C (en) | 1999-01-15 | 1999-01-15 | Process for preparing stable ClO2 solution based on methanol |
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| Country | Link |
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| CN (1) | CN1146523C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441499C (en) * | 2003-04-22 | 2008-12-10 | 贵州大学 | Method of preparing stable chloride dioxide |
| CN101301997B (en) * | 2007-05-10 | 2010-07-07 | 淄博华润科贸有限责任公司 | Method for producing stable chlorine dioxide by bi-reduction method |
| CN102173386A (en) * | 2011-01-24 | 2011-09-07 | 陆清 | Preparation method of stable-state chlorine dioxide solution of food additive |
| CN102180446A (en) * | 2011-02-24 | 2011-09-14 | 苏州久泰集团公司 | Production method of food-grade stabilized chlorine dioxide disinfectant |
| CN109678116A (en) * | 2019-01-30 | 2019-04-26 | 广东至诚紫光新材料有限公司 | ClO 2 solution for sewage treatment and preparation method thereof, application |
| CN109704282A (en) * | 2019-01-30 | 2019-05-03 | 广东至诚紫光新材料有限公司 | ClO 2 solution for removing formaldehyde and preparation method thereof, application |
-
1999
- 1999-01-15 CN CNB991120221A patent/CN1146523C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441499C (en) * | 2003-04-22 | 2008-12-10 | 贵州大学 | Method of preparing stable chloride dioxide |
| CN101301997B (en) * | 2007-05-10 | 2010-07-07 | 淄博华润科贸有限责任公司 | Method for producing stable chlorine dioxide by bi-reduction method |
| 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 |
| CN102180446A (en) * | 2011-02-24 | 2011-09-14 | 苏州久泰集团公司 | Production method of food-grade stabilized chlorine dioxide disinfectant |
| CN109678116A (en) * | 2019-01-30 | 2019-04-26 | 广东至诚紫光新材料有限公司 | ClO 2 solution for sewage treatment and preparation method thereof, application |
| CN109704282A (en) * | 2019-01-30 | 2019-05-03 | 广东至诚紫光新材料有限公司 | ClO 2 solution for removing formaldehyde and preparation method thereof, application |
| CN109678116B (en) * | 2019-01-30 | 2022-05-27 | 广东至诚紫光新材料有限公司 | Chlorine dioxide solution for sewage treatment and preparation method and application thereof |
| CN109704282B (en) * | 2019-01-30 | 2022-05-27 | 广东至诚紫光新材料有限公司 | Chlorine dioxide solution for removing formaldehyde and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1146523C (en) | 2004-04-21 |
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Granted publication date: 20040421 Termination date: 20120115 |