Aerial fog type degradation device and method for degrading fluorine-containing pollutants by virtue of aerial fog type degradation device

Abstract

The invention provides an aerial fog type degradation device and a method for degrading fluorine-containing pollutants by using the aerial fog type degradation device, and belongs to the technical field of pollutant treatment. The aerial fog type degradation device provided by the invention has the characteristics of efficient degradation, flexibility, adjustability, good air tightness, safety, reliability, wide application and the like, and can show huge application potential and value in multiple fields of laboratory research, industrial production and the like. The degradation method provided by the invention can realize rapid and effective degradation of fluorides, reduces the treatment cost and the risk of byproducts, and provides a new strategy for treatment of persistent organic pollutants.

Description

Technical Field

[0001] The present invention relates to the technical field of pollutant treatment, and in particular to an aerosol type degradation device and a method for degrading fluorine-containing pollutants using the device. Background Art

[0002] Fluorinated pollutants such as perfluorooctanoic acid (fluoride) are widely used in many industries due to their stability and water and oil resistance, but they pose a significant potential threat to human and biological health. Advanced oxidation technology (AOT) as a water treatment method can effectively degrade a variety of organic pollutants, but it faces challenges when faced with the high chemical stability of fluoride and may produce toxic intermediates.

[0003] Although other degradation schemes in the prior art attempt to improve the efficiency of fluoride degradation by combining physical adsorption, photocatalysis and other methods, there are still problems such as difficulty in adsorbent recovery, high cost and health risks of by-products.

[0004] For example, Chinese utility model patent CN217103192U discloses an electrocoagulation device, which includes an electrolytic cell, multiple groups of anodes and multiple groups of cathodes; the anodes and cathodes are arranged in parallel at intervals in the electrolytic cell, and the outermost anodes and the outermost cathodes are respectively connected to an external power supply; the adjacent cathodes and anodes on the middle side are connected in series in groups of two, and the anodes and cathodes arranged in parallel at intervals and in a specific connection relationship are used as electrodes, and the electrolyte is used to achieve efficient degradation of perfluorinated organic pollutants, simple operation, and has the advantages of small flocculent volume, simple and efficient degradation process, low energy consumption, and stable degradation. Summary of the invention

[0005] The object of the present invention is to provide an aerosol type degradation device and a method for degrading fluorine-containing pollutants thereof, which has better degradation efficiency.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The invention provides an aerosol type degradation device, comprising a light source system, a reactor system, an atomization system, a cooling system and a control system.

[0008] Preferably, the reactor system comprises a cold trap and a housing made of transparent material;

[0009] The light source system is arranged inside the cold trap made of the transparent material.

[0010] Preferably, the transparent material is selected from one or more of borosilicate glass, quartz glass or transparent plastic;

[0011] The light source system is provided with one or more light sources;

[0012] The light source is in the shape of a column;

[0013] The light source has high temperature resistance and corrosion resistance.

[0014] Preferably, the light source is one or more of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an amalgam ultraviolet lamp, an excimer-excited ultraviolet lamp, a xenon lamp or a halogen lamp.

[0015] Preferably, the atomization system is provided with one or more atomizers;

[0016] The spray direction and mist range of the atomizer correspond to the arrangement of the light source, so that the light and the mist are fully in contact;

[0017] The atomizer has an automatic adjustment function and can adjust the droplet size and density according to the reaction requirements.

[0018] Preferably, the cooling system is provided with a water chiller, which can control the temperature inside the reactor system through circulating water flow;

[0019] The chiller has an intelligent temperature control function and can automatically adjust the cooling water flow and temperature according to the reaction conditions.

[0020] Preferably, the control system is provided with an electric control box, which integrates the control function and safety monitoring mechanism of the system;

[0021] The electric control box is provided with a touch screen or a computer interface, which can display real-time data or set reaction parameters;

[0022] The control system has fault alarm and automatic shutdown protection functions.

[0023] The present invention also provides the use of the above-mentioned aerosol type degradation device in degrading fluorine-containing pollutants;

[0024] Preferably, the fluorine-containing pollutants include perfluorooctane sulfonic acid and its salts, perfluorooctane sulfonyl fluoride (PFOS), perfluorooctanoic acid (PFOA) and its salts and related compounds or perfluorohexane sulfonic acid and its salts and related compounds (PFHxS).

[0025] The present invention also provides an aerosol degradation method for fluorine-containing pollutants, comprising the following steps:

[0026] The fluorine-containing pollutant sample is filtered using a filter membrane, and degraded using the aerosol type degradation device according to claim 1;

[0027] The sample is placed in a reactor system, and a light source system, an atomization system and a cooling system are operated to complete degradation.

[0028] Preferably, the filter membrane is a polycarbonate membrane, a quartz fiber membrane or a glass fiber membrane;

[0029] The filter membrane has a filtration particle size of less than 0.45 μm.

[0030] Beneficial effects of the present invention:

[0031] The aerosol degradation device provided by the present invention has the characteristics of efficient degradation, flexible adjustability, good air tightness, safety and reliability, and wide application, and can show great application potential and value in many fields such as laboratory research and industrial production.

[0032] The degradation method provided by the invention can realize rapid and effective degradation of fluoride, while reducing treatment costs and by-product risks, and provides a new strategy for the treatment of persistent organic pollutants. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a schematic diagram of the structure of the micro-droplet degradation device, including: 1. light source, 2. reactor, 3. atomizer, 4. chiller, 5. electric control box;

[0034] Figure 2 is the HPLC chromatogram of fluoride;

[0035] Figure 3 F - Ion chromatogram of

[0036] Figure 4 is the calibration curve of fluoride concentration;

[0037] Figure 5 F - Concentration calibration curve of

[0038] Figure 6 is the concentration-time dependence diagram of fluoride degradation;

[0039] Figure 7 Pseudo-first-order kinetic fitting for fluoride degradation;

[0040] Figure 8 is the response intensity-time dependence diagram of the fluoride degradation intermediates in the droplet;

[0041] Fig. 9 is the defluorination rate-time dependence diagram; DETAILED DESCRIPTION

[0042] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0043] Example 1

[0044] This embodiment provides an aerosol degradation device for fluorine-containing pollutants, including a light source system, a reactor system, an atomization system, a cooling system and a control system.

[0045] Specific as Figure 1 As shown in the figure: light source 1, reactor 2, atomizer 3, chiller 4, and electric control box 5.

[0046] As the core of the catalytic reaction of the device, the light source 1 system adopts a columnar design and is embedded in a transparent cold trap inside the reactor 2. It can withstand high temperatures and corrosive environments and emit light of multiple spectra to meet the degradation needs of different pollutants. By fine-tuning the power and spectral characteristics of the light source 1, the efficiency and effect of the photocatalytic reaction can be optimized.

[0047] The reactor 2 system is where the photocatalytic reaction takes place. The carefully designed reaction chamber inside is located in the annular columnar area between the cold trap and the borosilicate glass shell. This layout ensures that the columnar light source 1 can fully radiate to the droplet dispersion area in the chamber, while the borosilicate glass shell, with its excellent light transmittance and pressure and high temperature resistance, ensures the stability and safety of the reaction process.

[0048] The atomization system is the key to generating micro droplets. Its atomizer 3 has excellent atomization capabilities and can reach a height of 100 to 200 mm, meeting the needs of experiments and production of different scales. The built-in liquid placeholder can be flexibly adjusted according to the liquid volume (50-1500ml) to ensure uniform distribution of droplets and efficient atomization. In addition, the atomizer 3 also has an automatic adjustment function to adjust the droplet size and density according to the reaction requirements.

[0049] The cooling system consists of a chiller 4, which effectively controls the temperature in the reactor 2 through circulating water flow to ensure that the photocatalytic reaction is carried out within the optimal temperature range. The chiller 4 is equipped with an intelligent temperature control function that can automatically adjust the cooling water flow and temperature according to the reaction conditions, further improving the stability and efficiency of the system.

[0050] Finally, the control system, which serves as the command center of the entire device, is the electric control box 5, which integrates the control functions of the light source 1, atomizer 3, chiller 4, and the safety monitoring mechanism. Users can easily set reaction parameters, monitor the reaction process, and receive real-time data feedback through the touch screen or computer interface. At the same time, the control system also has fault alarm and automatic shutdown protection functions to ensure the safe and stable operation of the device under abnormal conditions.

[0051] This embodiment also provides a method for aerosol degradation and verification of fluorine-containing pollutants, comprising the following steps:

[0052] S1: Configure pollutants:

[0053] preparing a certain concentration of fluorine-containing pollutants as simulated fluorine-containing pollutants;

[0054] S2: Inject into reactor and start reaction:

[0055] Inject the configured fluorine-containing pollutant into the reactor, turn on the chiller, and wait for 10 minutes to ensure that the temperature in the reactor reaches the preset cooling temperature. This is to control the temperature during the reaction and avoid overheating that has an adverse effect on the reaction. Then, turn on the ultrasonic spray switch to spray the fluorine-containing pollutant in the form of micro-droplets, and after the droplets are generated and stabilized, turn on the light source (ultraviolet lamp is used in this embodiment) to carry out photocatalytic reaction;

[0056] S3: Sampling and sample processing:

[0057] During the reaction, samples are taken at regular intervals, and the sampling volume should be controlled between 0.1% and 1% of the total volume to avoid significant impact on the reaction system. The samples taken out need to be quantitatively diluted with a solution containing 5% isopropanol and 0.01M hydrochloric acid to adjust the pH value and solvent environment of the samples; before analysis, the samples need to be filtered with a 0.45μm polycarbonate membrane to remove impurities and particulate matter.

[0058] S4: Concentration determination:

[0059] The concentration of fluoride in the sample was determined using a high performance liquid chromatograph (HPLC) to assess its degradation degree. At the same time, an ion chromatograph (IC) was used to measure the concentration of fluoride ions (F-) removed from the sample to further confirm the degradation effect of fluoride; and the correlation coefficients of the two calibration curves were ensured to be above 99% to ensure the accuracy and reliability of the measurement results;

[0060] The HPLC chromatogram of the obtained fluoride is as follows Figure 2 As shown; the obtained F - The ion chromatogram of Figure 3 As shown; the concentration calibration curve of fluoride obtained is shown Figure 4 As shown; the obtained F - The concentration calibration curve is shown in Figure 5 shown.

[0061] S5: Semi-quantitative analysis of degradation intermediates:

[0062] High performance liquid chromatography-triple quadrupole time-of-flight mass spectrometry (HPLC-MS / MS) was used to semi-quantitatively analyze the degradation intermediates of fluoride. This method can identify and quantify the various intermediates produced during the reaction, thereby providing a more comprehensive understanding of the degradation mechanism and pathway of fluoride. Based on the measured fluoride ion concentration and the initial fluoride concentration, the defluorination rate was calculated to evaluate the degradation effect.

[0063] S6: Control experiment:

[0064] In order to verify the effectiveness of the aerosol degradation device, a control experiment is required. In the control experiment, the atomizer is turned off, all other conditions are the same as in the experiments in steps one to five, and the relevant data information is recorded; this can eliminate the influence of other factors on the experimental results and more accurately evaluate the degradation effect of the aerosol degradation device on fluoride.

[0065] S7: Comparative experimental results:

[0066] Compare the degradation effects and defluorination rates of the two experiments (i.e., the experiments of steps one to five and the control experiment of step six); through comparative analysis, evaluate whether the aerosol degradation device has a significant degradation effect on fluoride, as well as the feasibility and effectiveness of the device in practical applications.

[0067] Table 1 summarizes the degradation of fluoride:

[0068] Table 1 Degradation of fluoride

[0069]

[0070] Combining Table 1 and Figure 6 It can be found that the degradation efficiency of fluoride is greatly enhanced in the droplet experiment (nebulizer is turned on), and the complete degradation of fluoride is basically achieved within 80 minutes, with a degradation rate of up to 98.00%; while in the bulk experiment (nebulizer is not turned on), fluoride is only degraded by 10.42% after 4 hours.

[0071] Figure 7 The degradation process of fluoride was fitted by pseudo-first-order kinetics, and the reaction rate constant k of the droplet experiment was obtained to be 2.964h -1 , is the reaction rate constant of the bulk experiment (0.0334h -1 ), indicating that the droplets can significantly improve the degradation kinetics of fluoride.

[0072] Figure 8 It shows that the concentration of short-chain perfluoroalkane intermediates in the droplet experiment first increases and then decreases, and approaches 0 after the reaction is completed, indicating that toxic by-products are effectively controlled in the droplet experiment.

[0073] Since the stability and toxicity of fluoride mainly come from its stable CF bond, this example further uses the defluorination rate as an indicator to evaluate the overall mineralization degree of fluoride. The results are as follows: Fig. 9As shown in the figure, after 280 minutes of reaction, the defluorination rate in the bulk experiment was only 0.82%, indicating that the CF bonds in the fluoride molecules were only partially destroyed. The defluorination rate in the droplet experiment reached 99.05%, which is 105 times that of the bulk experiment, that is, the droplet basically converted all the organic CF bonds into harmless inorganic F - , achieving complete mineralization of fluoride.

[0074] It can be seen from the above embodiments that the spray droplet photoreaction device provided by the present invention has great application potential and value in many fields such as laboratory research and industrial production due to its characteristics of efficient degradation, flexible adjustability, good airtightness, safety and reliability, and wide application.

[0075] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An aerosol type degradation device, characterized in that: It includes a light source system, a reactor system, an atomization system, a cooling system and a control system.

2. The aerosol type degradation device according to claim 1, characterized in that: The reactor system includes a cold trap and a shell made of transparent material; The light source system is arranged inside the cold trap made of the transparent material.

3. The aerosol type degradation device according to claim 2, characterized in that: The transparent material is selected from one or more of borosilicate glass, quartz glass or transparent plastic; The light source system is provided with one or more light sources; The light source is in the shape of a column; The light source has high temperature resistance and corrosion resistance.

4. The aerosol type degradation device according to claim 3, characterized in that: The light source is one or more of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an amalgam ultraviolet lamp, an excimer-excited ultraviolet lamp, a xenon lamp or a halogen lamp.

5. The aerosol type degradation device according to claim 3, characterized in that: The atomization system is provided with one or more atomizers; The spray direction and mist range of the atomizer correspond to the arrangement of the light source, so that the light and the mist are fully in contact; The atomizer has an automatic adjustment function and can adjust the droplet size and density according to the reaction requirements.

6. The aerosol type degradation device according to claim 1, characterized in that: The cooling system is provided with a water chiller, which can control the temperature inside the reactor system through circulating water flow; The chiller has an intelligent temperature control function and can automatically adjust the cooling water flow and temperature according to the reaction conditions.

7. The aerosol type degradation device according to claim 1, characterized in that: The control system is provided with an electric control box, which integrates the control function and safety monitoring mechanism of the system; The electric control box is provided with a touch screen or a computer interface, which can display real-time data or set reaction parameters; The control system has fault alarm and automatic shutdown protection functions.

8. Use of the aerosol type degradation device according to any one of claims 1 to 7 in the degradation of fluorine-containing pollutants; Preferably, the fluorine-containing pollutants include perfluorooctane sulfonic acid and its salts, perfluorooctane sulfonyl fluoride, perfluorooctanoic acid and its salts and related compounds or perfluorohexane sulfonic acid and its salts and related compounds.

9. An aerosol degradation method for fluorine-containing pollutants, characterized in that: The following steps are involved: The fluorine-containing pollutant sample is filtered using a filter membrane, and degraded using the aerosol type degradation device according to claim 1; The sample is placed in a reactor system, and a light source system, an atomization system and a cooling system are operated to complete degradation.

10. The aerosol degradation method for fluorine-containing pollutants according to claim 9, characterized in that: The filter membrane is a polycarbonate membrane, a quartz fiber membrane or a glass fiber membrane; The filter membrane has a filtration particle size of less than 0.45 μm.

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