CN1128095C - Large high-purity chlorine dioxide generator and its production process - Google Patents
Large high-purity chlorine dioxide generator and its production process Download PDFInfo
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- CN1128095C CN1128095C CN 00129317 CN00129317A CN1128095C CN 1128095 C CN1128095 C CN 1128095C CN 00129317 CN00129317 CN 00129317 CN 00129317 A CN00129317 A CN 00129317A CN 1128095 C CN1128095 C CN 1128095C
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Abstract
The present invention relates to a large-sized high-purity chlorine dioxide generator and a production method thereof. Aluminum hydride solution is used as an oxydant, hydrogen peroxide or methanol is used as a reductant, the oxydant and the reductant react in sulfate medium to generate pure chlorine dioxide gas, and refrigerated water at 5 to 10DEGC is used for absorption and preparing the water solution of free high-concentration chlorine dioxide in an absorption tower. The production method adopts a process technology of negative-pressure aeration, in a multistage reactor, charge and reaction are continuously carried out under a negative-pressure condition. The method has the advantages of large productivity, simple operation, low production cost, high raw material utilization factor, high chlorine dioxide purity, etc. The high-purity chlorine dioxide can be applied to pulp bleaching, the sterilization of a large-sized water plant and the sterilization of a sewage treatment plant.
Description
(I) technical field
The invention relates to a large-scale high-purity chlorine dioxide production method.
(II) background of the invention
Chlorine dioxide is a broad-spectrum disinfectant, and can be widely applied to the sterilization and disinfection treatment of drinking water, swimming pool water and hospital sewage; sterilizing and algae-removing treatment of industrial circulating cooling water; sterilizing industrial cyanide-containing and phenol-containing wastewater; the disinfection of food pipelines, the fresh-keeping of fruits and vegetables and the like. Currently, disinfection for large waterworks; sterilizing, decoloring and deodorizing in an urban sewage treatment plant; in the fields of application such as fiber bleaching in the textile printing and dyeing industry, paper pulp bleaching in the paper making industry and the like, China mainly depends on liquid chlorine for treatment. In these application fields, the chlorine dioxide generator is required to have high production capacity and high concentration and purity of chlorine dioxide in the effective components of the disinfectant so as to meet the use requirements.
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 will produce a large amount of waste liquid containing sulfuric acid and sodium sulfate, which is complicated to recover. 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 raw materials used in the R8 method are the same as those used in the Solvey method, and because a reaction-evaporation-crystallization unit reactor is adopted, the production capacity is improved, and the conversion rate of the reacted sodium chlorate is improved to more than 90 percent. The process has the advantages of simple operation, easy control, high production efficiency and the like, but the process needs to evaporate water and consumes a large amount of steam. Chinese patent ZL93111202.8 and Chinese patent ZL97233737.7 disclose a novel technology of a production process of a negative-pressure aeration chlorine dioxide generator, and the technology uses sodium chlorate as an oxidant and hydrochloric acid as a reducing agent to produce a composite disinfectant of chlorine dioxide and chlorine, and belongs to a small chlorine dioxide generator.
Disclosure of the invention
The invention aims to provide a large-scale chlorine dioxide production method with high raw material utilization rate and high chlorine dioxide purity.
The present invention is achieved as follows. The production method comprises a reactor, an absorption device, a negative pressure generation device and a waste liquid treatment device. Sodium chlorate is used as an oxidant, hydrogen peroxide or methanol is used as a reducing agent, and the reaction is carried out in a sulfuric acid medium, wherein the reaction comprises the following steps:
the reactor adopts a multi-stage device, the reaction temperature in the multi-stage reactor is increased from 40 ℃ to 70 ℃, a fan generates negative pressure, and the continuous feeding reaction is carried out under the condition of the negative pressure. Sodium chlorate, concentrated sulfuric acid and mother liquor are continuously added into a main reactor at a certain flow rate, and hydrogen peroxide or methanol is continuously added into the main reactor and a secondary reactor at a certain flow rate respectively. Compressed air is introduced from the lower part of the reaction liquid of the multistage reactor to carry out chlorine dioxide gas generated by the reaction. The material ratio of the sodium chlorate to the hydrogen peroxide is 1: 0.15-0.32; the material ratio of the sodium chlorate to the methanol is 1: 0.05-0.1, and the mass percentage of the sulfuric acid in the reaction medium is 23-33%. The fan generates negative pressure, so that the multistage reactor and the absorption device are ensured to operate under the negative pressure condition, and the system pressure is 99325-100525 Pa.
The chlorine dioxide gas generated in the multistage reactor is absorbed by chilled water with the temperature of 5-10 ℃ in an absorption tower to prepare free high-concentration chlorine dioxide aqueoussolution, and the chlorine dioxide aqueous solution can be directly applied to sterilization and disinfection of large-scale water plants and sewage treatment plants and can also be used for bleaching paper pulp.
The waste liquid treatment device comprises an evaporative crystallizer, a condenser, a centrifuge, a mother liquid tank and a hydraulic ejector, wherein the hydraulic ejector generates negative pressure to ensure that the evaporative crystallizer is evaporated and concentrated under reduced pressure, crystalline sodium bisulfate is obtained through cooling and centrifugal separation, the mother liquid flows into the mother liquid tank and is pumped into a main reactor through a pump for cyclic utilization, and three wastes are not generated.
Compared with the prior art, the invention has the following advantages: large capacity of producing chlorine dioxide, continuous production, low production cost, high utilization rate of raw materials, less equipment investment, high purity of chlorine dioxide, no generation of three wastes and the like.
(IV) description of the drawings
The attached figure 1 shows a process flow schematic diagram of the production method of the invention. In the figure, 1 is a hydrogen peroxide or methanol feeding pipe, 2 is a sodium chlorate feeding pipe, 3 is a concentrated sulfuric acid feeding pipe, 4 is a mother liquor feeding pipe, 5 is a compressed air inlet pipe, 6, 8 and 9 are explosion-proof ports, 7 is a pressure gauge, 10 is a main reactor, 11 is a secondary reactor, 12 is a third-stage reactor, 13 is a mother liquor pump, 14 is a mother liquor tank, 15 is a centrifugal machine, 16 is a hydraulic ejector, 17 is an evaporation crystallizer, 18 is a condenser, 19 is an evacuation port, 20 is a fan, 21 is a chilled water inlet, 22 is an absorption tower, 23 is a high-concentration chlorine dioxide aqueous solution outlet, and 24 is a chlorine dioxide gas pipeline.
(V) detailed description of the preferred embodiments
The invention is described in detail below with reference to the accompanying drawings:
sodium chlorate is used as oxidant, hydrogen peroxide or methanol is used as reductant, and the reaction is carried out in sulfuric acid medium, and the temperature of the whole reaction process in the multistage reactor is controlled to be increased from 40 ℃ to 70 ℃. Sodium chlorate aqueous solution, concentrated sulfuric acid and mother liquor are continuously added into the main reactor 10 at a certain flow rate, and hydrogen peroxide or methanol is continuously added into the main reactor 10 and the secondary reactor 11 at a certain flow rate. Compressed air is introduced from the lower parts of the main reactor 10, the secondary reactor 11 and the third reactor 12 to take out chlorine dioxide gas generated by the reaction. The material ratio of the sodium chlorate to the hydrogen peroxide is 1: 0.15-0.32; the material ratio of the sodium chlorate to the methanol is 1: 0.05-0.1, and the mass percentage of the sulfuric acid in the reaction medium is 23-33%. The main reactor 10, the secondary reactor 11, the third-stage reactor 12 and the absorption tower 22 operate under the condition of negative pressure, the negative pressure is generated by a fan 20, the system pressure is 99325-100525 Pa, and air is exhausted through an exhaust port 19.
The chlorine dioxide gas 24 generated in the main reactor 10, the secondary reactor 11 and the third reactor 12 is absorbed by the chilled water 21 at 5-10 ℃ in the absorption tower 22 to prepare the free high-concentration chlorine dioxide aqueous solution 23.
The waste liquid of the reactor is decompressed and evaporated by an evaporation crystallizer 17, secondary steam is condensed by a condenser 18, the evaporated waste liquid is cooled and crystallized, and is centrifugally filtered by a centrifuge 15 to prepare a crystal sodium bisulfate, mother liquid flows into a mother liquid tank 14, and the mother liquid is circulated into a main reactor 10 by a mother liquid pump 13 to be recycled without generating three wastes. The evaporative crystallizer 17 operates under reduced pressure, and negative pressure is generated by the hydraulic ejector 16, so that the evaporative crystallizer 17 is ensured to be evaporated and concentrated under reduced pressure.
Example (b): 22.5kg/h pure chlorine dioxide production process, 44% of sodium chlorate aqueous solution, concentrated sulfuric acid, hydrogen peroxide and returned mother liquor are respectively added into a main reactor 10 at feeding amounts of 58.4L/h, 26.6L/h, 20.0L/h and 12.0L/h, hydrogen peroxide is added into a secondary reactor 11 at a feeding amount of 2.2L/h, the reaction temperature in the multi-stage reactor is increased from 40 ℃ to 70 ℃, 5-10 ℃ chilled water 21 is added to the upper part of an absorption tower 22 at a flow rate of 2.65T/h for absorbing chlorine dioxide gas 24 generated by the reactor, the production capacity of 22.5kg/h pure chlorine dioxide gas can be achieved, the purity of chlorine dioxide in the aqueous solution is more than 98%, and the conversion rate of sodium chlorate is 94.5%.
Claims (2)
1. A large-scale high-purity chlorine dioxide production method is characterized in that sodium chlorate is used as an oxidant, hydrogen peroxide or methanol is used as a reducing agent, the material ratio of the sodium chlorate to the methanol is 1: 0.05-0.1, the material ratio of the sodium chlorate to the hydrogenperoxide is 1: 0.15-0.32, and the sodium chlorate to the hydrogen peroxide reacts in a sulfuric acid medium, the production method adopts a negative pressure aeration process technology, the system pressure is 99325-100525 Pa, the sodium chlorate and concentrated sulfuric acid are added from a main reactor, the hydrogen peroxide or the methanol are respectively added into the main reactor and a secondary reactor, the reaction temperature is increased from 40 ℃ to 70 ℃, the mass percent of the sulfuric acid in the reaction medium is 23-33%, the chlorine dioxide generated in a reaction solution is taken out by introduced compressed air, and the generated pure chlorine dioxide gas is absorbed in an absorption tower by chilled water at the temperature of 5-10 ℃ to prepare a free high-.
2. A large scale high purity chlorine dioxide production process according to claim 1, characterized in that compressed air is introduced from the bottom of the reaction liquid, the upper part of the reactor is provided with an explosion-proof port, and the negative pressure in the reactor and the absorption tower is generated by a fan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129317 CN1128095C (en) | 2000-11-13 | 2000-11-13 | Large high-purity chlorine dioxide generator and its production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129317 CN1128095C (en) | 2000-11-13 | 2000-11-13 | Large high-purity chlorine dioxide generator and its production process |
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| CN1347841A CN1347841A (en) | 2002-05-08 |
| CN1128095C true CN1128095C (en) | 2003-11-19 |
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| CN 00129317 Expired - Fee Related CN1128095C (en) | 2000-11-13 | 2000-11-13 | Large high-purity chlorine dioxide generator and its production process |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387511C (en) * | 2005-08-26 | 2008-05-14 | 南京工业大学 | Chlorine dioxide generator |
| CN100445198C (en) * | 2006-08-25 | 2008-12-24 | 南京工业大学 | Graded chlorine dioxide generator |
| CN100430324C (en) * | 2006-09-30 | 2008-11-05 | 广东工业大学 | Fast process of sterilizing water in swimming pool |
| CN101880029B (en) * | 2010-07-14 | 2011-09-28 | 章艺 | Continuous production device of composite chlorine dioxide and technology |
| CN102502507A (en) * | 2011-11-04 | 2012-06-20 | 成都齐力水处理科技有限公司 | Preparation device and technology for chlorine dioxide |
| CN103482576B (en) * | 2013-08-23 | 2015-06-24 | 深圳欧泰华工程设备有限公司 | Method for efficiently preparing high-purity chlorine dioxide and special device thereof |
| CN106145044A (en) * | 2015-04-16 | 2016-11-23 | 湖南源生环保设备有限公司 | A kind of chlorine dioxide generator |
| CN105941603B (en) * | 2016-05-30 | 2019-10-25 | 陕西师范大学 | A kind of Kiwi fresh fruit storage period gray mold control method |
| CN107117581A (en) * | 2017-06-06 | 2017-09-01 | 广西大学 | A kind of preparation of chlorine dioxide with high purity and control decomposition method |
| CN109205563A (en) * | 2017-07-05 | 2019-01-15 | 冠亚腾达（北京）科技有限公司 | A kind of chlorine dioxide generator with reaction of high order and raffinate separator |
| CN108439341A (en) * | 2018-05-18 | 2018-08-24 | 广西大学 | A kind of method and device producing chlorine dioxide with high purity gas |
| CN111167299B (en) * | 2020-03-02 | 2024-02-27 | 中晶环境科技股份有限公司 | Flue gas denitration device based on liquid oxidizing ions and application method thereof |
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