CN1128096C - Process for preparing stable ClO2 solution based on hydrochloric acid - Google Patents
Process for preparing stable ClO2 solution based on hydrochloric acid Download PDFInfo
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- CN1128096C CN1128096C CN 99112023 CN99112023A CN1128096C CN 1128096 C CN1128096 C CN 1128096C CN 99112023 CN99112023 CN 99112023 CN 99112023 A CN99112023 A CN 99112023A CN 1128096 C CN1128096 C CN 1128096C
- Authority
- CN
- China
- Prior art keywords
- chlorine dioxide
- sodium
- hydrochloric acid
- gas
- generator
- 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.)
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 title 1
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000498 cooling water Substances 0.000 claims description 2
- 229910001902 chlorine oxide Inorganic materials 0.000 claims 1
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012629 purifying agent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treating Waste Gases (AREA)
Abstract
本发明涉及一种基于盐酸的稳定性二氧化氯溶液生产方法。它以氯酸钠为氧化剂，以盐酸为还原剂进行反应，生成二氧化氯和氯气的混合气体，再经亚氯酸钠溶液进行纯化，生成纯二氧化氯气体，用氢氧化钠或碳酸钠与双氧水进行稳定和吸收，即可制取稳定性二氧化氯溶液。该方法在负压条件下进行，负压由水射器产生，操作为连续加料，与同类技术相比，该方法具有操作简单、设备投资少、二氧化氯纯度高等优点。The invention relates to a method for producing a stable chlorine dioxide solution based on hydrochloric acid. It reacts with sodium chlorate as oxidant and hydrochloric acid as reducing agent to generate a mixed gas of chlorine dioxide and chlorine gas, and then purifies it with sodium chlorite solution to generate pure chlorine dioxide gas, and then uses sodium hydroxide or sodium carbonate Stable chlorine dioxide solution can be prepared by stabilizing and absorbing with hydrogen peroxide. The method is carried out under negative pressure, the negative pressure is generated by a water ejector, and the operation is continuous feeding. Compared with similar technologies, the method has the advantages of simple operation, less investment in equipment, and high purity of chlorine dioxide.
Description
(I) technical field
The invention relates to a method for producing stable chlorine dioxide solution.
(II) background of the invention
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 wasteliquid 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. Regarding the production method of stable chlorine dioxide, the chinese patent office discloses CN1075298A a method for producing high-concentration stable chlorine dioxide, which uses sodium chlorate, sulfuric acid and methanol as reaction raw materials, and sodium percarbonate solution as an absorption stabilizer. The disadvantages are that: the reaction is not stable and difficult to operate.
Disclosure of the invention
The invention aims to provide a method for producing high-purity stable chlorine dioxide solution with simple operation.
The present invention is achieved as follows. The production method comprises a chlorine dioxide generator, a purifier, an absorption tower, a water ejector and a residual liquid tank. Preparing 25-40% aqueous solution of sodium chlorate, and continuously adding sodium chlorate and hydrochloric acid into the negative pressure aeration chlorine dioxide generator through a charging titration valve according to the proportion of 1: 0.7-1.4 to generate mixed gas of chlorine dioxide and chlorine. The reaction is as follows:
and purifying the generated chlorine dioxide and chlorine gas mixed gas by using a 20-40% sodium chlorite aqueous solution to convert chlorine gas into chlorine dioxide, thereby generating pure chlorine dioxide gas. The reaction is as follows:
the purified pure chlorine dioxide gas is subjected to stable and repeated absorption by taking 1-3% of sodium hydroxide or 5-8% of sodium carbonate and 0.5-1.5% of hydrogen peroxide as circulating absorption liquid, and then the stable chlorine dioxide solution can be prepared. The sodium hydroxide or sodium carbonate and hydrogen peroxide can be added at one time or added continuously in batches. The residual liquid generated by the chlorine dioxide generator is led out from the generator and neutralized by sodium hydroxide solution, and disinfectant by-products can be produced for other uses. The negative pressure of the system is generated by a water ejector, so that the chlorine dioxide generator and the purifier operate under the negative pressure condition.
The invention is provided with the explosion-proof plugs at the top of the residual liquid tank and the purifier to ensure the safety of the production process. In order to ensure the continuous operation of the production process, the residual liquid tank, the purifier and the chlorine dioxide generator are connected in a two-stage parallel mode.
Compared with the prior art, the invention has the following advantages: continuous production, no residual liquid discharge, no environmental pollution, less equipment investment, small occupied area and high purity of chlorine dioxide.
(IV) detailed description of the preferred embodiments
The present invention is described in detail below:
the chlorine dioxide generator takes sodium chlorate as an oxidant and hydrochloric acid as a reducing agent to react, the sodium chlorate is prepared into 25-40% aqueous solution, and the aqueous solution and the hydrochloric acid are continuously added into the chlorine dioxide generator under the condition of negative pressure according to the proportion of 1: 0.7-1.4; the raffinate produced in the generator automatically flows into a raffinate tank, which may be neutralized with aqueous sodium hydroxide. And purifying the mixed gas of chlorine dioxide and chlorine generated in the generator by a 20-40% sodium chlorite aqueous solution after flowing through a purifier to generate pure chlorine dioxide gas. And (3) introducing the purified pure chlorine dioxide gas to an absorption device, and taking 1-3% of sodium hydroxide or 5-8% of sodium carbonate and 0.5-1.5% of hydrogen peroxide as circulating absorption liquid to perform stable and repeated absorption so as to prepare stable chlorine dioxide solution. The circulating absorption liquid repeatedly absorbs chlorine dioxide gas in the water ejector, the absorption tower and the circulating pump, 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. If the system pressure is too high, the explosion-proof plug is started, and the safety of the production process is ensured. In the repeated absorption process, if the temperature of the circulating absorption liquid is too high, the circulating absorption liquid can be cooled by cooling water, and the temperature of the circulating absorption liquid is preferably controlled to be below 30 ℃.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99112023 CN1128096C (en) | 1999-01-15 | 1999-01-15 | Process for preparing stable ClO2 solution based on hydrochloric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99112023 CN1128096C (en) | 1999-01-15 | 1999-01-15 | Process for preparing stable ClO2 solution based on hydrochloric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1261051A CN1261051A (en) | 2000-07-26 |
| CN1128096C true CN1128096C (en) | 2003-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99112023 Expired - Fee Related CN1128096C (en) | 1999-01-15 | 1999-01-15 | Process for preparing stable ClO2 solution based on hydrochloric acid |
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| Country | Link |
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| CN (1) | CN1128096C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530875B (en) * | 2012-01-04 | 2014-06-25 | 安庆五宁精细化工有限责任公司 | Production method of 4% stable chlorine dioxide solution |
| CN103159178A (en) * | 2013-04-11 | 2013-06-19 | 常州和方环保科技有限公司 | Preparation method of sodium chlorite |
| CN105417497B (en) * | 2015-12-15 | 2017-12-08 | 刘学思 | A kind of process units and technique of high concentration of chlorine dioxide stable state liquid |
| CN108975276B (en) * | 2018-08-20 | 2020-06-30 | 广西大学 | A kind of method for separating chlorine gas from chlorine dioxide solution |
| 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 |
| CN115461304A (en) * | 2020-04-27 | 2022-12-09 | 阿莱西亚生命科学公司 | Chlorine dioxide aqueous solution and preparation method thereof |
| CN112209345A (en) * | 2020-11-10 | 2021-01-12 | 深圳市加德圣环保科技有限公司 | Method and device for producing chlorine dioxide disinfectant |
| CN114158566A (en) * | 2021-08-09 | 2022-03-11 | 山东大学 | Single-component gel slow-release chlorine dioxide disinfectant and preparation method and application thereof |
| CN113800472A (en) * | 2021-08-13 | 2021-12-17 | 湖北金汉江精制棉有限公司 | Preparation method of stable chlorine dioxide bleaching solution |
| CN115159463A (en) * | 2022-08-03 | 2022-10-11 | 北京大凡创软技术有限公司 | Long-term storage method of chlorine dioxide disinfectant |
-
1999
- 1999-01-15 CN CN 99112023 patent/CN1128096C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1261051A (en) | 2000-07-26 |
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Granted publication date: 20031119 Termination date: 20120115 |