阅读说明：本技术 一种高纯二氧化氯溶液的制备装置及方法 (preparation device and method of high-purity chlorine dioxide solution ) 是由 李玲 吴明松 袁雯雯 王琼梅 葛平 苗鑫壮 于 2019-10-25 设计创作，主要内容包括：本发明的一种高纯二氧化氯溶液的制备装置及方法,装置包括CO<Sub>2</Sub>存储装置,反应装置、洗气装置和吸收装置,所述的各装置之间通过管路依次连接。制备时,采用相应装置,将二氧化碳控制压力,通入反应器内的质量浓度为3～10％的亚氯酸钠溶液中；随着二氧化碳持续通入亚氯酸钠溶液中,30～50℃下进行加热反应,制得二氧化氯气体,经洗气瓶内固体亚氯酸钠洗气后,获得高纯二氧化氯气体,纯水吸收制得高纯二氧化氯溶液。该发明方法绿色环保,能够解决现有制备方法必须使用归属危险品的液体酸或固体酸、能耗大、产生危废残液的问题,且制得二氧化氯溶液具有较高纯度。(the invention relates to a preparation device and a preparation method of high-purity chlorine dioxide solution, wherein the device comprises CO 2 The device comprises a storage device, a reaction device, a gas washing device and an absorption device, wherein the devices are sequentially connected through pipelines. During preparation, a corresponding device is adopted, the pressure of carbon dioxide is controlled, and the carbon dioxide is introduced into a sodium chlorite solution with the mass concentration of 3-10% in a reactor; and continuously introducing carbon dioxide into the sodium chlorite solution, heating and reacting at 30-50 ℃ to obtain chlorine dioxide gas, washing the gas with solid sodium chlorite in a gas washing cylinder to obtain high-purity chlorine dioxide gas, and absorbing the high-purity chlorine dioxide gas with pure water to obtain the high-purity chlorine dioxide solution. The method is green and environment-friendly, can solve the problems that the existing preparation method needs to use liquid acid or solid acid belonging to dangerous goods, has large energy consumption and generates dangerous waste residual liquid, and the prepared chlorine dioxide solution has higher purity.)

1. the preparation device of the high-purity chlorine dioxide solution is characterized by comprising CO₂the device comprises a storage device, a reaction device, a gas washing device and an absorption device, wherein all the devices are sequentially connected through pipelines; the reaction device comprises a reactor and a heating device, wherein the reactor is internally provided with a reaction liquid-sodium chlorite solution, and the gas washing device is internally provided with a sodium chlorite solid.

2. A method for preparing a high purity chlorine dioxide solution using the apparatus of claim 1, comprising the steps of:

Step 1, the carbon dioxide is separated from CO₂The storage device is introduced into a sodium chlorite solution in the reactor, the introduction pressure of carbon dioxide is 0.05-2 MPa, and the sodium chlorite is dissolvedThe mass fraction of the liquid solute is 3-10%;

And 2, continuously introducing carbon dioxide into the sodium chlorite solution, and carrying out heating reaction to obtain chlorine dioxide gas, wherein the heating temperature is 30-50 ℃, and the chlorine dioxide gas is subjected to gas washing by solid sodium chlorite in a gas washing bottle to obtain high-purity chlorine dioxide gas, and the high-purity chlorine dioxide gas is absorbed by pure water to obtain the high-purity chlorine dioxide solution.

3. the method for preparing high purity chlorine dioxide solution as claimed in claim 2, wherein CO is used in step 1₂The purity is more than or equal to 99.98 percent.

4. The method for preparing a highly pure chlorine dioxide solution as claimed in claim 2, wherein the introduction pressure of carbon dioxide in step 1 is 0.1 to 1.5 Mpa.

5. The method for preparing high purity chlorine dioxide solution as claimed in claim 2, wherein in step 1, the sodium chlorite solution contains FeCl₃And/or CoCl₂When containing FeCl₃Or CoCl₂In the sodium chlorite solution, FeCl is added₃Or CoCl₂3 to 10 percent of FeCl when the material contains₃And CoCl₂In the sodium chlorite solution, FeCl is added₃And CoCl₂The mass ratio of the mixture is 3-10%, and the mixing ratio of the mixture and the mixture is any ratio.

6. The method for preparing a high purity chlorine dioxide solution according to claim 2, wherein the heating time in step 2 is 15 to 30 min.

7. The method for preparing a high purity chlorine dioxide solution as claimed in claim 2, wherein in step 2, the concentration of the chlorine dioxide solution is 1000 to 1500 mg/L.

8. The method for preparing high-purity chlorine dioxide solution according to claim 2, wherein in the step 2, the purity of the high-purity chlorine dioxide solution is not less than 98%, and the yield of chlorine dioxide in the obtained high-purity chlorine dioxide solution is 25-30%.

The technical field is as follows:

The invention belongs to the technical field of chemical industry, and particularly relates to a preparation device and method of a high-purity chlorine dioxide solution.

Background art:

Chlorine dioxide has strong reactivity and oxidation capacity, so that the chlorine dioxide shows excellent disinfection effect and oxidation effect in water treatment. The chlorine dioxide hardly forms organic halides such as chloroform and the like in the disinfection of drinking water, the effect of killing bacteria, viruses, algae and zooplankton is better than that of liquid chlorine, mutagenic substances are not generated in the water disinfection process, and the Ames test and the mouse bone marrow pleochromocyte micronucleus test both show negative. Since chlorine dioxide has been widely used as a disinfectant in water treatment processes in europe and the united states, its overall index is far better than that of other disinfectants.

The current chlorine dioxide preparation methods mainly use sodium chlorite and sodium chlorate as raw materials, and are divided into a sodium chlorite method and a sodium chlorate method. The former sodium chlorite is used as raw material and is acidified by hydrochloric acid (CN 105399054), sodium bisulfate (CN105692559A) and the like to obtain high-purity chlorine dioxide. Is a method which is earlier and mature. The latter requires methanol (CN102803131), sucrose (CN 107352512) or hydrogen peroxide (CN105439091) as a reducing agent, and prepares high-purity chlorine dioxide in the environment of concentrated sulfuric acid. However, the method does not use liquid concentrated hydrochloric acid, concentrated sulfuric acid or sodium bisulfate, and the dangerous chemicals are purchased and used dangerously.

The invention content is as follows:

The invention aims to overcome the problem of using a large amount of dangerous acid in the preparation method of chlorine dioxide in the prior art, and provides a preparation device and a preparation method of a high-purity chlorine dioxide solution.

In order to achieve the purpose, the invention adopts the following technical scheme:

a device for preparing high-purity chlorine dioxide solution comprises CO₂the device comprises a storage device, a reaction device, a gas washing device and an absorption device, wherein all the devices are sequentially connected through pipelines; the reaction device comprises a reactor and a heating device, wherein the reactor is internally provided with a reaction liquid-sodium chlorite solution, and the gas washing device is internally provided with a sodium chlorite solid.

Said CO₂The storage means comprising CO₂Steel cylinder, said CO₂The steel cylinder outlet is provided with a steel cylinder valve, a two-stage pressure reducing valve and a switch valve, and the CO is₂A flowmeter is arranged on a connecting pipe of the storage device and the reaction device and used for monitoring CO₂And (4) flow rate.

The heating device is a water bath heating device.

The air washing device is n absorption bottles which are connected in sequence, and n is more than or equal to 2.

The preparation method of the high-purity chlorine dioxide solution comprises the following steps:

step 1, the carbon dioxide is separated from CO₂The storage device is introduced into a sodium chlorite solution in the reactor, the introduction pressure of carbon dioxide is 0.05-2 MPa, and the mass fraction of solute in the sodium chlorite solution is 3-10%;

And 2, continuously introducing carbon dioxide into the sodium chlorite solution, and carrying out heating reaction to obtain chlorine dioxide gas, wherein the heating temperature is 30-50 ℃, and the chlorine dioxide gas is subjected to gas washing by solid sodium chlorite in a gas washing bottle to obtain high-purity chlorine dioxide gas, and the high-purity chlorine dioxide gas is absorbed by pure water to obtain the high-purity chlorine dioxide solution.

CO used in step 1₂the purity is more than or equal to 99.98 percent, and the grade is higher than industrial purity.

In the step 1, the introduction pressure of the carbon dioxide is 0.1-1.5 Mpa.

in the step 1, the sodium chlorite solution contains FeCl₃And/or CoCl₂When containing FeCl₃Or CoCl₂in the sodium chlorite solution, FeCl is added₃Or CoCl₂3 to 10 percent of FeCl when the material contains₃And CoCl₂(preferably 5%) FeCl in said sodium chlorite solution₃And CoCl₂the mass ratio of the mixture is 3-10%, and the mixing ratio of the mixture and the mixture is any ratio.

In the step 1, FeCl₃And CoCl₂As catalyst, sodium chlorite solution and CO₂Has the catalytic action, accelerates the reaction rate and improves the yield. By analysis, Fe³⁺The activation energy of sodium chlorite can be reduced, the activation energy of sodium chlorite is 109.35kJ/mol, and Fe is added³⁺the activation energy of the substrate was 107.81 kJ/mol. The magnitude of the activation energy may characterize the ease of chemical reaction. Thus, Fe is added³⁺the sodium chlorite solution reacts more readily and more rapidly.

In the step 2, the solute mass fraction of the sodium chlorite solution is 5 percent, and CO is₂The pressure was 0.1 MPa.

In the step 2, CO₂Continuously introducing into sodium chlorite solution to provide acid condition to make reaction quickly proceed.

In the step 2, the reaction is as follows: 5NaClO₂+2H₂CO₃＝NaCl+4ClO₂+2Na₂CO₃+2H₂O。

In the step 2, the concentration of the chlorine dioxide solution is 1000-1500 mg/L.

In the step 2, the heating mode is water bath heating, so that the preparation process of the chlorine dioxide is carried out at 30-50 ℃.

In the step 2, the heating time is 15-30 min, namely CO₂The introducing time is 15-30 min.

In the step 2, the purity of the high-purity chlorine dioxide solution is more than or equal to 98%, the yield of chlorine dioxide in the obtained high-purity chlorine dioxide solution is 25-30%, and the purity calculation mode is as follows: the mass ratio of chlorine dioxide to all chlorine-containing substances in the solution is; the yield calculation mode is as follows: the ratio of the actual production of chlorine dioxide to the theoretical production of chlorine dioxide.

The invention has the beneficial effects that:

in the method, high-purity chlorine dioxide is prepared by introducing a certain flow of carbon dioxide into a sodium chlorite solution with a catalyst, so that the problems that the conventional chlorine dioxide preparation method needs to use liquid acid or solid acid belonging to dangerous goods, has high energy consumption and generates dangerous waste residual liquid are solved. The defects of excessive strong acid addition, high energy consumption and generation of hazardous waste residual liquid in the traditional process are avoided. Provides scientific basis for the development of a new high-purity chlorine dioxide preparation process and also provides a new way for the recycling of carbon dioxide.

description of the drawings:

FIG. 1 is a schematic view showing the construction of an apparatus for producing a high-purity chlorine dioxide solution according to example 1; wherein, 1-CO₂The method comprises the following steps of steel cylinder, 2-steel cylinder valve, 3-two-stage pressure reducing valve, 4-switch valve, 5-flowmeter, 6-water bath water tank, 7-reactor, 8-gas washing bottle, 9-absorption bottle and A-reaction liquid.

The specific implementation mode is as follows:

The present invention will be described in further detail with reference to examples.