Fluorine ion visual adsorption material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of wastewater treatment, and particularly discloses a fluorine ion visual adsorption material and a preparation method and application thereof.The preparation method comprises the following steps that organic aluminum salt and organic lanthanum salt are dispersed in an organic polar solvent, and a precursor solution is obtained; and under stirring, adding an initiator into the precursor solution, carrying out ultraviolet irradiation, and then carrying out high-pressure solvothermal reaction and post-treatment to obtain a lanthanum-aluminum binary polymer, namely the fluorine ion visual adsorption material. The fluorine ion visual adsorption material prepared by the invention not only has an adsorption treatment function on fluorine ions, but also has an excellent fluorescence detection effect, can realize high-sensitivity quantitative analysis detection and visual treatment of the fluorine ions, can judge whether the concentration of the fluorine ions in the effluent reaches the standard or not according to the change of the color of the effluent under ultraviolet light, and has a good application prospect. And whether the adsorption material reaches adsorption saturation or not can be judged, so that fluorine ion treatment and monitoring can be accurately and effectively realized.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater treatment, and in particular to a fluorine ion visual adsorption material and a preparation method and application thereof. Background Art

[0002] Under normal circumstances, the main way for humans to ingest fluoride is through drinking water. The amount of fluoride intake depends on the average daily amount of water consumed and the level of fluoride pollution in the water. Trace amounts of fluoride are necessary for the normal development of the human body. However, with the development of modern industry, a large amount of fluoride-containing industrial wastewater is generated during the production process of the fluoride-related industry. Currently, many companies do not have complete water treatment facilities to treat fluoride-containing industrial wastewater and can only discharge it into natural water bodies, resulting in a sharp increase in the content of fluoride ions in natural water bodies. If people ingest high doses of fluoride for a long time, it will lead to problems such as fluorosis and bone deformation, and even cause fluoride poisoning, posing a great threat to human health.

[0003] In addition, since fluorine-containing industrial wastewater usually has the characteristics of complex fluoride ion forms, large concentration differences, wide distribution range, and high difficulty in removal, and industrial production wastewater contains other pollutants such as inorganic salts or organic matter in addition to fluorine elements, its treatment difficulty is further increased, which seriously restricts the further development of fluorine-related industries.

[0004] At present, the technology of using adsorbent materials to purify drinking water has attracted more and more attention due to its low cost and simple operation. There are many adsorbent materials currently used in water treatment, including clay, zeolite, diatomaceous earth, molecular sieves, activated carbon, resins and some nano-composite adsorbent materials, and when the adsorbent materials are used for adsorption and purification of fluoride-containing wastewater in a flowing state, they have the advantages of high purification efficiency, simplified operation and low cost. However, conventional adsorbent materials still have the following problems: after the conventional adsorbent material is adsorbed, it is difficult to monitor the residual fluoride ion concentration in real time in situ, and it is impossible to achieve visual processing; after the conventional adsorbent material is adsorbed, it is difficult to visually judge the adsorption saturation of the material, which limits the rapid and deep purification performance of fluoride ions. Summary of the invention

[0005] Based on this, the purpose of the present invention is to provide a fluoride ion visual adsorption material and a preparation method and application thereof. The fluoride ion visual adsorption material can not only remove fluoride ions in water, but also perform in-situ real-time detection of the fluoride ion concentration in the treated water and whether the material is adsorbed saturated, thereby realizing visual processing, overcoming the deficiency that existing fluoride ion adsorption materials cannot simultaneously have both fluoride ion detection and visual processing functions.

[0006] To achieve the above object, the present invention adopts the following technical solutions: The first object of the present invention is to provide a fluoride ion visual adsorption material, which comprises the following steps: dispersing an organic aluminum salt and an organic lanthanum salt in an organic polar solvent to obtain a precursor solution; adding an initiator to the precursor solution under stirring and irradiating it with ultraviolet light, then performing a high-pressure solvent thermal reaction, and post-treating to obtain a lanthanum-aluminum binary polymer, which is the fluoride ion visual adsorption material.

[0007] As a further improvement of the above scheme of the present invention, the molar ratio of the organic aluminum salt to the organic lanthanum salt is 1-10:1; the mass of the organic polar solvent is 5-10 times the total mass of the organic aluminum salt and the organic lanthanum salt.

[0008] As a further improvement of the above scheme of the present invention, the organic aluminum salt is at least one of aluminum acetate, aluminum oxalate, aluminum citrate, aluminum isopropoxide, aluminum sec-butoxide, aluminum stearate, and aluminum acetylacetonate; And / or, the organic lanthanum salt is at least one of lanthanum acetate, lanthanum oxalate, lanthanum isopropoxide, lanthanum ethoxide, and lanthanum acetylacetonate; And / or, the organic polar solvent is at least one of ethanol, acetone, chloroform, ether, acetic acid, acetonitrile, isopropanol, and N,N-dimethylformamide; And / or, the initiator is at least one of benzophenone, benzoyl peroxide, and ammonium persulfate.

[0009] As a further improvement of the above solution of the present invention, the added amount of the initiator is 0.1%-1.5% of the mass of the organic polar solvent.

[0010] As a further improvement of the above scheme of the present invention, the stirring speed is 200-300 rpm, and the time is 5-10 min; the wavelength of the ultraviolet light is 254 nm, and the ultraviolet light irradiation time is 10-30 min.

[0011] As a further improvement of the above scheme of the present invention, the pressure of the high-pressure solvent thermal reaction is 5-8 MPa, the temperature is 180-220° C., and the time is 12-24 h.

[0012] As a further improvement of the above scheme of the present invention, the post-treatment includes separation, cleaning and drying in sequence, the separation is carried out by vacuum filtration, the cleaning is carried out by ethanol and ultrapure water continuously for at least 3 times, and the drying temperature is 60-80°C.

[0013] The second object of the present invention is to provide a fluoride ion visual adsorption material, which is a lanthanum-aluminum binary polymer prepared by the preparation method as described above.

[0014] The third object of the present invention is to provide an application of the fluoride ion visual adsorption material as described above, which is used for the adsorption treatment of fluoride ions in fluoride-containing wastewater.

[0015] As a further improvement of the above scheme of the present invention, in fluoride-containing wastewater with a fluoride ion concentration of 200 mg / L, the maximum adsorption capacity of fluoride ions by the fluoride ion visualization adsorption material is 194.82 mg / g.

[0016] The fourth object of the present invention is to provide an application of the fluoride ion visualization adsorption material as described above, which is used for the fluorescence detection of fluoride ions in fluoride-containing wastewater.

[0017] The fifth object of the present invention is to provide an application of the fluoride ion visual adsorption material as described above, which is used for visual removal of fluoride ions in fluoride-containing wastewater.

[0018] As a further improvement of the above scheme of the present invention, the visual removal of fluoride ions in the fluoride-containing wastewater comprises the following steps: filling the fluoride ion visualization adsorption material into an adsorption column; allowing the fluorine-containing wastewater to flow through the adsorption column; Under ultraviolet light: observe the color of the water outlet of the adsorption column to determine the fluoride ion concentration in the water; and observe the water inlet color and water outlet color of the adsorption column to determine whether the fluoride ion visualization adsorption material has reached saturation in adsorbing fluoride ions. Specifically, when the water outlet color is red, it indicates that the fluoride ion concentration in the water outlet is lower than 1 mg / L; when the water outlet color is the same as the water inlet color, it indicates that the fluoride ion visualization adsorption material has reached saturation in adsorbing fluoride ions.

[0019] As a further improvement of the above scheme of the present invention, the adsorption column is a tubular structure made of transparent material, and the fluoride ion visualization adsorption material is filled in the middle of the adsorption column to form an adsorption material layer, and a cavity is left between the two ends of the adsorption material layer and the water inlet and outlet of the adsorption column; the reserved cavity is for the convenience of observing the fluorescent color development of the inlet and outlet water.

[0020] As a further improvement of the above scheme of the present invention, the concentration of fluoride ions in the fluoride-containing wastewater is 1-10 mg / L; the fluoride-containing wastewater is introduced into the adsorption column by a peristaltic pump and stays in the adsorption column for 10-30 minutes.

[0021] Compared with the prior art, the present invention has the following beneficial effects: The present invention combines the excellent fluoride ion adsorption performance of aluminum-based materials with the fluoride ion fluorescence response performance of lanthanum-based materials, and obtains a lanthanum-aluminum binary polymer fluoride ion visualization adsorption material through polymerization regulation, thereby realizing the dual functions of fluorescence detection and adsorption treatment of fluoride ions, and can realize rapid adsorption, highly sensitive quantitative analysis detection and visualization treatment of fluoride ions, solving the bottleneck problems of difficulty in real-time in-situ monitoring of the remaining fluoride ion concentration and the adsorption saturation of the material after the adsorption of conventional adsorption materials is completed, and the inability to achieve visualization treatment.

[0022] The present invention selects organic aluminum salts and organic lanthanum salts with rich surfaces of hydroxyl groups, carboxyl groups and carbon chains, and under the action of high temperature and high pressure and an initiator, the hydroxyl groups and carboxyl groups on the surfaces of the organic aluminum salts and organic lanthanum salts undergo polymerization reaction, thereby obtaining a lanthanum-aluminum binary polymer, so that the active groups such as hydroxyl groups and carboxyl groups on the surface of the material are greatly increased, which is beneficial to improving the adsorption rate and efficiency of fluoride ions, can realize the rapid adsorption and removal of fluoride ions, and overcomes the defect of slow adsorption rate of fluoride ions by conventional adsorption materials.

[0023] The fluoride ion visualization adsorption material prepared by the present invention has the functions of fluorescence detection (lanthanum-based part) and adsorption treatment (aluminum-based part) of fluoride ions. Its excellent fluorescence detection effect can realize highly sensitive quantitative analysis detection and visualization treatment of fluoride ions, that is, under ultraviolet light, it can be judged whether the fluoride ion concentration in the effluent water meets the standard (lower than 1 mg / L) and whether the adsorption material has reached adsorption saturation based on the change in the effluent color. It can accurately and effectively realize fluoride ion treatment and monitoring, which has important scientific significance and application value for ensuring the accurate acquisition and efficient removal of fluoride pollution information. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a SEM image of the fluoride ion visual adsorption material prepared in Example 1; Figure 2 The adsorption performance curve of the fluoride ion visual adsorption material prepared in Example 1 to fluoride ions; Figure 3 The fluorescence detection performance curve of the fluoride ion visual adsorption material prepared in Example 1 for fluoride ions; Figure 4 It is a schematic diagram of the structure of the visual removal device in Experimental Example 3; Figure numerals: 1. peristaltic pump; 2. protective cover; 3. ultraviolet lamp; 4. observation window; 5. adsorption column; 6. sponge; 7. adsorption material layer. DETAILED DESCRIPTION

[0025] For ease of understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0027] Example 1 This embodiment provides a fluorine ion visual adsorption material, and the preparation method thereof comprises the following steps: S1. Disperse 20.41 g of aluminum acetate and 3.16 g of lanthanum isopropoxide in 200 mL of ethanol solution to obtain a precursor solution; S2. Under stirring at a speed of 200 rpm, 1.82 g of initiator benzophenone was added to the precursor solution and stirred for 10 min, and then irradiated with ultraviolet light at a wavelength of 254 nm for 10 min to generate free radicals; S3. The solution obtained in S2 was added to the reactor for high-pressure solvent thermal reaction, the pressure of the high-pressure solvent thermal reaction was 5MPa, the temperature was 180 ° C, the time was 12h, and the organic aluminum salt and the organic lanthanum salt were polymerized; S4. After the reactants are cooled to room temperature, they are separated by vacuum filtration to obtain a solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven to dry at 60°C to obtain a lanthanum-aluminum binary polymer, which is a fluoride ion visual adsorption material.

[0028] The fluoride ion visual adsorption material prepared in this example was characterized by scanning electron microscopy, and the following Figure 1 The SEM images shown are from Figure 1 It can be seen that the lanthanum-aluminum binary polymer prepared in this example is a block structure with uniform particles and a particle size of 200-300 nm.

[0029] Test Example 1 The fluoride ion visual adsorption material prepared in Example 1 was subjected to an adsorption capacity measurement test in fluoride-containing wastewater at different temperatures and different fluoride ion concentrations, specifically: Three groups of fluoride-containing wastewater were prepared, each group containing 12 portions of fluoride-containing wastewater with a volume of 1 L, and the initial concentrations of fluoride ions (C0) in the 12 portions of fluoride-containing wastewater were 1 mg / L, 2 mg / L, 3 mg / L, 5 mg / L, 10 mg / L, 20 mg / L, 30 mg / L, 50 mg / L, 80 mg / L, 100 mg / L, 150 mg / L, and 200 mg / L, respectively; 0.5 g of the fluoride ion visualization adsorption material prepared in Example 1 was added to each fluoride-containing wastewater; The three groups of fluoride-containing wastewater were stirred at 25℃, 35℃, and 45℃ for 30 minutes respectively. After standing, the supernatant was taken and the fluoride ion concentration C1 in each solution was detected by ion selective electrode method. The test results are as follows: Figure 2 As shown (the equilibrium concentration on the horizontal axis in the figure is C1, which is the fluoride ion concentration of the above-mentioned fluoride-containing wastewater after being adsorbed by the fluoride ion visual adsorption material).

[0030] from Figure 2 It can be seen that with the increase of fluoride ion concentration in fluoride-containing wastewater, the adsorption capacity of fluoride ion visualization adsorption material for fluoride ions gradually increases; and with the increase of temperature, the adsorption capacity of fluoride ion visualization adsorption material for fluoride ions also increases slightly. When the fluoride ion concentration in fluoride-containing wastewater is 200 mg / L and the temperature is 45°C, the equilibrium concentration of fluoride ions after adsorption by the fluoride ion visualization adsorption material is 102.59 mg / L. According to the formula: (C0-C1) / m, the maximum adsorption capacity of fluoride ions by the fluoride ion visualization adsorption material prepared in Example 1 reaches 194.82 mg / g, where m is the mass of the fluoride ion visualization adsorption material.

[0031] Test Example 2 10 mg of the fluoride ion visualization adsorption material prepared in Example 1 was added to 50 mL of deionized water and ultrasonically dispersed for 30 min to form a uniform suspension (0.2 mg / mL), which was stored in a refrigerator at 277 K for subsequent use.

[0032] 2.0 mL of the suspension prepared above was placed in a quartz test tube; then 0-220 μL of a 30 mg / L fluoride solution was gradually added to the quartz test tube for mixing, so that the fluoride ion concentration in the mixed solution was 0-3 mg / L; the fluorescence spectrum was immediately recorded at room temperature using an American Cary Eclipse fluorescence spectrophotometer, as shown in FIG. Figure 3 As shown. Figure 3 It can be seen that in the process of fluorescence detection of fluoride ions, fluoride ions have a good fluorescence quenching performance on the fluoride ion visualization adsorption material, and as F - As the concentration gradually increases (from 0 to 3 mg / L), the fluorescence intensity of the visualized adsorption material decays rapidly; -When the concentration was 3 mg / L, the fluorescence intensity quenching efficiency of the visualized adsorption material at the 605 nm emission peak reached 63%, indicating that the fluorescence intensity was closely related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0033] At the same time, the mixed solution with different fluoride ion concentrations (the suspension prepared above was mixed with the fluoride solution) was subjected to fluorescence colorimetric analysis. The results are as follows: Figure 3 As shown in the illustration, it was found that: when the fluoride ion concentration in the mixed solution is lower than 1 mg / L, the solution fluorescence color is red; when the fluoride ion concentration is 1-3 mg / L, the solution fluorescence color is light blue; when the fluoride ion concentration is higher than 3 mg / L, the solution fluorescence color is dark blue. Therefore, by observing the fluorescence color, the fluoride ion concentration in the solution and whether the fluoride ion visualization adsorption material has reached adsorption saturation can be judged, and the fluoride ion visualization adsorption and removal can be achieved.

[0034] Test Example 3 The fluoride ion visual adsorption material prepared in Example 1 was used in a visual removal test of fluoride-containing wastewater, specifically: S1. First build Figure 4 The visual removal test device shown is as follows: 200g of fluoride ion visual adsorption material is filled into an adsorption column 5 (transparent glass material) to form an adsorption material layer 7, and sponges 6 are respectively filled at both ends of the adsorption material layer 7. The adsorption column 5 is built into a protective cover 2, and an ultraviolet lamp 3 is installed above the adsorption column 5 inside the protective cover 2; an observation window 4 is opened on the protective cover 2; the water inlet of the adsorption column 5 is connected to a fluoride-containing wastewater tank through a peristaltic pump 1, and the water outlet is connected to a treated water tank, and the fluoride-containing wastewater tank contains fluoride-containing wastewater with a fluoride ion concentration of 5mg / L; S2. Use a peristaltic pump 1 to introduce fluoride-containing wastewater having a fluoride ion concentration of 5 mg / L into the adsorption column 5 and allow it to remain in the adsorption column 5 for 10 min; S3. Under the light of the ultraviolet lamp 3, through the observation window 4, in the initial stage, it is observed that the color of the water entering the adsorption column 5 is blue and the color of the water leaving is red, indicating that the fluoride ion concentration in the water leaving is lower than 1 mg / L at this time; when the water leaving is blue, the fluoride ion visualization adsorption material has reached adsorption saturation.

[0035] Example 2 This embodiment provides a fluorine ion visual adsorption material, and the preparation method thereof comprises the following steps: S1. Dispersing 21.61 g of aluminum citrate and 3.16 g of lanthanum isopropoxide in 200 mL of ethanol solution to obtain a precursor solution; S2. Under stirring at a speed of 200 rpm, 1.82 g of initiator benzophenone was added to the precursor solution and stirred for 10 min, and then irradiated with ultraviolet light at a wavelength of 254 nm for 20 min to generate free radicals; S3. The solution obtained in S2 was added to a reactor for high-pressure solvent thermal reaction, the pressure of the high-pressure solvent thermal reaction was 5MPa, the temperature was 200 ° C, the time was 16h, and the organic aluminum salt and the organic lanthanum salt were polymerized; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven to dry at 80°C to obtain a lanthanum-aluminum binary polymer, which is a fluoride ion visual adsorption material.

[0036] According to the test method of Test Example 1, the fluoride ion visualization adsorption material prepared in Example 2 was subjected to an adsorption capacity measurement test on fluoride-containing wastewater with different fluoride ion concentrations at 45°C. After testing, it was found that when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption capacity of the fluoride ion visualization adsorption material prepared in Example 2 reached 191.59 mg / g.

[0037] According to the test method of Test Example 2, the fluoride ion visualization adsorption material prepared in Example 2 was used for fluorescence detection of fluoride ions in fluoride-containing wastewater. The fluoride ion visualization adsorption material prepared in Example 2 was tested to have excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity decayed rapidly, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0038] Test Example 4 The fluoride ion visual adsorption material prepared in Example 2 was used in a visual removal test of fluoride-containing wastewater, specifically: S1. First build a visual removal test device (same as Experiment 3); S2. Use a peristaltic pump to introduce fluoride-containing wastewater with a fluoride ion concentration of 8 mg / L into the adsorption column and keep it in the adsorption column for 20 minutes; S3. Under the light of ultraviolet lamp, it is observed that the color of the water entering the adsorption column is blue, while the color of the water leaving the column is red, indicating that the fluoride ion concentration in the water leaving the column is lower than 1 mg / L. When the water leaving the column is blue, the fluoride ion visualization adsorption material has reached adsorption saturation.

[0039] Example 3 This embodiment provides a fluorine ion visual adsorption material, and the preparation method thereof comprises the following steps: S1. Disperse 20.42 g of aluminum isopropoxide and 11.18 g of lanthanum oxalate in 200 mL of acetone solution to obtain a precursor solution; S2. Under stirring at a speed of 300 rpm, 2.28 g of initiator ammonium persulfate was added to the precursor solution and stirred for 5 min, and irradiated with ultraviolet light at a wavelength of 254 nm for 30 min to generate free radicals; S3. The solution obtained in S2 was added to a reactor for high-pressure solvent thermal reaction, the pressure of the high-pressure solvent thermal reaction was 5MPa, the temperature was 220°C, the time was 24h, and the organic aluminum salt and the organic lanthanum salt were polymerized; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven to dry at 80°C to obtain a lanthanum-aluminum binary polymer, which is a fluoride ion visual adsorption material.

[0040] According to the test method of Test Example 1, the fluoride ion visualization adsorption material prepared in Example 3 was subjected to an adsorption capacity measurement test on fluoride-containing wastewater with different fluoride ion concentrations at 45°C. After testing, it was found that when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption capacity of the fluoride ion visualization adsorption material prepared in Example 3 reached 186.75 mg / g.

[0041] According to the test method of Test Example 2, the fluoride ion visualization adsorption material prepared in Example 3 was used for fluorescence detection of fluoride ions in fluoride-containing wastewater. The fluoride ion visualization adsorption material prepared in Example 3 was tested to have excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity decayed rapidly, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0042] Test Example 5 The fluoride ion visual adsorption material prepared in Example 3 was used in a visual removal test of fluoride-containing wastewater, specifically: S1. First build a visual removal test device (same as Experiment 3); S2. Use a peristaltic pump to introduce fluoride-containing wastewater with a fluoride ion concentration of 10 mg / L into the adsorption column and keep it in the adsorption column for 30 minutes; S3. Under the light of ultraviolet lamp, it is observed that the color of the water entering the adsorption column is blue, while the color of the water leaving the column is red, indicating that the fluoride ion concentration in the water leaving the column is lower than 1 mg / L. When the water leaving the column is blue, the fluoride ion visualization adsorption material has reached adsorption saturation.

[0043] Example 4 This embodiment provides a fluorine ion visual adsorption material, and the preparation method thereof comprises the following steps: S1. Disperse 43.87 g of aluminum stearate and 11.18 g of lanthanum oxalate in 200 mL of chloroform solution to obtain a precursor solution; S2. Under stirring at a speed of 200 rpm, 4.56 g of initiator ammonium persulfate was added to the precursor solution and stirred for 10 min, and irradiated with ultraviolet light at a wavelength of 254 nm for 30 min to generate free radicals; S3. The solution obtained in S2 was added to a reactor for high-pressure solvent thermal reaction, the pressure of the high-pressure solvent thermal reaction was 5MPa, the temperature was 200 ° C, the time was 20h, and the organic aluminum salt and the organic lanthanum salt were polymerized; S4. After the reactants are cooled to room temperature, they are separated by vacuum filtration to obtain a solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven to dry at 60°C to obtain a lanthanum-aluminum binary polymer, which is a fluoride ion visual adsorption material.

[0044] According to the test method of Test Example 1, the fluoride ion visualization adsorption material prepared in Example 4 was subjected to an adsorption capacity measurement test on fluoride-containing wastewater with different fluoride ion concentrations at 45°C. After testing, it was found that when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption capacity of the fluoride ion visualization adsorption material prepared in Example 4 reached 188.24 mg / g.

[0045] According to the test method of Test Example 2, the fluoride ion visualization adsorption material prepared in Example 4 was used for fluorescence detection of fluoride ions in fluoride-containing wastewater. The fluoride ion visualization adsorption material prepared in Example 4 was tested to have excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity decayed rapidly, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0046] Example 5 This embodiment provides a fluorine ion visual adsorption material, and the preparation method thereof comprises the following steps: S1. 31.80 g of aluminum oxalate and 4.36 g of lanthanum acetylacetonate were dispersed in 200 mL of isopropanol solution to obtain a precursor solution; S2. Under stirring at a speed of 200 rpm, 2.42 g of initiator ammonium persulfate was added to the precursor solution and stirred for 10 min, and irradiated with ultraviolet light at a wavelength of 254 nm for 20 min to generate free radicals; S3. The solution obtained in S2 was added to a reactor for high-pressure solvent thermal reaction, the pressure of the high-pressure solvent thermal reaction was 8MPa, the temperature was 180°C, the time was 12h, and the organic aluminum salt and the organic lanthanum salt were polymerized; S4. After the reactants are cooled to room temperature, they are separated by vacuum filtration to obtain a solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven to dry at 60°C to obtain a lanthanum-aluminum binary polymer, which is a fluoride ion visual adsorption material.

[0047] According to the test method of Test Example 1, the fluoride ion visualization adsorption material prepared in Example 5 was subjected to an adsorption capacity measurement test on fluoride-containing wastewater with different fluoride ion concentrations at 45°C. After testing, when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption capacity of the fluoride ion visualization adsorption material prepared in Example 5 reached 186.73 mg / g.

[0048] According to the test method of Test Example 2, the fluoride ion visualization adsorption material prepared in Example 5 was used for fluorescence detection of fluoride ions in fluoride-containing wastewater. The fluoride ion visualization adsorption material prepared in Example 5 was tested to have excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity decayed rapidly, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0049] Example 6 This embodiment provides a fluorine ion visual adsorption material, and the preparation method thereof comprises the following steps: S1. Disperse 20.42 g of aluminum isopropoxide and 3.16 g of lanthanum isopropoxide in 200 mL of N,N-dimethylformamide solution to obtain a precursor solution; S2. Under stirring at a speed of 200 rpm, 2.42 g of initiator benzoyl peroxide was added to the precursor solution and stirred for 10 min, and irradiated with ultraviolet light at a wavelength of 254 nm for 10 min to generate free radicals; S3. The solution obtained in S2 was added to a reactor for high-pressure solvent thermal reaction, the pressure of the high-pressure solvent thermal reaction was 6MPa, the temperature was 200 ° C, the time was 16h, and the organic aluminum salt and the organic lanthanum salt were polymerized; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven to dry at 80°C to obtain a lanthanum-aluminum binary polymer, which is a fluoride ion visual adsorption material.

[0050] According to the test method of Test Example 1, the fluoride ion visualization adsorption material prepared in Example 6 was subjected to an adsorption capacity measurement test on fluoride-containing wastewater with different fluoride ion concentrations at 45°C. After testing, it was found that when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption capacity of the fluoride ion visualization adsorption material prepared in Example 6 reached 190.32 mg / g.

[0051] According to the test method of Test Example 2, the fluoride ion visualization adsorption material prepared in Example 6 was used for fluorescence detection of fluoride ions in fluoride-containing wastewater. The fluoride ion visualization adsorption material prepared in Example 6 was tested to have excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity of the material rapidly decayed, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0052] Comparative Example 1 This comparative example proposes a fluoride ion adsorbent material, and its preparation method comprises the following steps: S1. Dispersing 20.42 g of aluminum isopropoxide in 200 mL of N,N-dimethylformamide solution to obtain a precursor solution; S2. Under stirring at a speed of 200 rpm, 2.42 g of initiator benzoyl peroxide was added to the precursor solution and stirred for 10 min, and irradiated with ultraviolet light at a wavelength of 254 nm for 10 min to generate free radicals; S3. The solution obtained in S2 was added to a reactor for high-pressure solvent thermal reaction, the pressure of the high-pressure solvent thermal reaction was 6MPa, the temperature was 200 ° C, the time was 16h, and the polymerization reaction was carried out between the organic aluminum salts; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven at 80° C. to obtain a polyaluminum fluoride ion adsorption material.

[0053] According to the test method of Test Example 1, the fluoride ion adsorption material prepared in Comparative Example 1 was subjected to an adsorption capacity measurement test on fluoride-containing wastewater with different fluoride ion concentrations at 45°C. After testing, it was found that when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption capacity of the fluoride ion adsorption material prepared in Comparative Example 1 reached 168.72 mg / g.

[0054] According to the test method of Test Example 2, the fluoride ion adsorbent material prepared in Comparative Example 1 was used for fluorescence detection of fluoride ions in fluoride-containing wastewater. After testing, the fluoride ion adsorbent material prepared in Comparative Example 1 had no fluorescence detection performance. - With the gradual increase of concentration (0-3 mg / L), the fluorescence intensity of the material did not change.

[0055] Comparative Example 2 This comparative example proposes a fluoride ion fluorescent adsorption material, and the preparation method thereof comprises the following steps: S1. 3.16 g of lanthanum isopropoxide was dispersed in 200 mL of N, N-dimethylformamide solution to obtain a precursor solution; S2. Under stirring at a speed of 200 rpm, 2.42 g of initiator benzoyl peroxide was added to the precursor solution and stirred for 10 min, and irradiated with ultraviolet light at a wavelength of 254 nm for 10 min to generate free radicals; S3. The solution obtained in S2 was added to a reactor for high-pressure solvent thermal reaction, the pressure of the high-pressure solvent thermal reaction was 6MPa, the temperature was 200 ° C, the time was 16h, and the organic lanthanum salt was polymerized; S4. After cooling the reactants to room temperature, vacuum filtration is performed to separate the solid product, which is then washed three times with ethanol and ultrapure water, and then placed in an oven at 80° C. to obtain a polymerized lanthanum fluoride ion fluorescent adsorption material.

[0056] According to the test method of Test Example 1, the fluoride ion fluorescent adsorption material prepared in Comparative Example 2 was subjected to an adsorption capacity measurement test on fluoride-containing wastewater with different fluoride ion concentrations at 45°C. After testing, it was found that when the initial fluoride ion concentration was 200 mg / L, the maximum adsorption capacity of the fluoride ion fluorescent adsorption material prepared in Comparative Example 2 was only 53.68 mg / g, and the adsorption performance was poor.

[0057] According to the test method of Test Example 2, the fluoride ion fluorescent adsorption material prepared in Comparative Example 2 was used for the fluorescence detection of fluoride ions in fluoride-containing wastewater. After testing, the fluoride ion fluorescent adsorption material prepared in Comparative Example 2 had excellent fluorescence detection performance. - As the concentration gradually increased (0-3 mg / L), the fluorescence intensity of the material rapidly decayed, indicating that the fluorescence intensity was related to F - The concentrations show a good linear relationship and can be used for highly sensitive quantitative analysis and detection of fluoride ions.

[0058] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0059] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a fluoride ion visual adsorption material, characterized in that: It includes the following steps: An organic aluminum salt and an organic lanthanum salt are dispersed in an organic polar solvent to obtain a precursor solution; under stirring, an initiator is added to the precursor solution and irradiated with ultraviolet light, and then a high-pressure solvent thermal reaction is carried out, and post-treatment is performed to obtain a lanthanum-aluminum binary polymer, which is a fluoride ion visual adsorption material.

2. The method for preparing the fluorine ion visual adsorption material according to claim 1, characterized in that: The molar ratio of the organic aluminum salt to the organic lanthanum salt is 1-10:1; the mass of the organic polar solvent is 5-10 times the total mass of the organic aluminum salt and the organic lanthanum salt.

3. The method for preparing the fluorine ion visual adsorption material according to claim 1, characterized in that: The organic aluminum salt is at least one of aluminum acetate, aluminum oxalate, aluminum citrate, aluminum isopropoxide, aluminum sec-butoxide, aluminum stearate, and aluminum acetylacetonate; And / or, the organic lanthanum salt is at least one of lanthanum acetate, lanthanum oxalate, lanthanum isopropoxide, lanthanum ethoxide, and lanthanum acetylacetonate; And / or, the organic polar solvent is at least one of ethanol, acetone, chloroform, ether, acetic acid, acetonitrile, isopropanol, and N,N-dimethylformamide; And / or, the initiator is at least one of benzophenone, benzoyl peroxide, and ammonium persulfate.

4. The method for preparing the fluorine ion visual adsorption material according to claim 1, characterized in that: The mass of the initiator is 0.1%-1.5% of the mass of the organic polar solvent.

5. The method for preparing the fluorine ion visual adsorption material according to claim 1, characterized in that: The stirring speed is 200-300 rpm, and the time is 5-10 min; the wavelength of the ultraviolet light is 254 nm, and the ultraviolet light irradiation time is 10-30 min.

6. The method for preparing the fluorine ion visual adsorption material according to claim 1, characterized in that: The high-pressure solvent thermal reaction has a pressure of 5-8 MPa, a temperature of 180-220° C., and a time of 12-24 h.

7. The method for preparing the fluorine ion visual adsorption material according to claim 1, characterized in that: The post-treatment includes separation, washing and drying in sequence. The separation is performed by vacuum filtration. The washing is performed by ethanol and ultrapure water for at least 3 consecutive times. The drying temperature is 60-80°C.

8. A fluoride ion visual adsorption material, characterized in that: The lanthanum-aluminum binary polymer is prepared by the preparation method described in any one of claims 1 to 7.

9. An application of the fluorine ion visual adsorption material as claimed in claim 8, characterized in that: It is used for the adsorption treatment of fluoride ions in fluoride-containing wastewater.

10. The use according to claim 9, characterized in that: In fluoride-containing wastewater with a fluoride ion concentration of 200 mg / L, the maximum adsorption capacity of fluoride ions by the fluoride ion visualization adsorption material is 194.82 mg / g.

11. A use of the fluorine ion visual adsorption material as claimed in claim 8, characterized in that: It is used for fluorescence detection of fluoride ions in fluoride-containing wastewater.

12. An application of the fluorine ion visual adsorption material as claimed in claim 8, characterized in that: It is used for visual removal of fluoride ions in fluoride-containing wastewater.

13. The use according to claim 12, characterized in that: The visual removal of fluoride ions in the fluoride-containing wastewater comprises the following steps: filling the fluoride ion visualization adsorption material into an adsorption column; allowing the fluorine-containing wastewater to flow through the adsorption column; Under ultraviolet light: observe the color of the water outlet from the adsorption column to determine the fluoride ion concentration in the water; and by observing the color of the water inlet and outlet from the adsorption column, determine whether the adsorption of fluoride ions by the fluoride ion visualization adsorption material has reached saturation.

14. The use according to claim 13, characterized in that The adsorption column is a tubular structure made of transparent material. The fluorine ion visualization adsorption material is filled in the middle of the adsorption column to form an adsorption material layer. A cavity is left between the two ends of the adsorption material layer and the water inlet and outlet of the adsorption column.

15. The use according to claim 13, characterized in that: The concentration of fluoride ions in the fluoride-containing wastewater is 1-10 mg / L; the fluoride-containing wastewater is introduced into the adsorption column by a peristaltic pump and stays in the adsorption column for 10-30 minutes.

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