CN111036167A - Use of boroaluminates as fluorine adsorbents - Google Patents
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Abstract
The invention provides application of boroaluminate as a fluorine adsorbent, and relates to the technical field of wastewater treatment. The chemical composition of the boroaluminate comprises B, Al and Cl, wherein n (B/Al) is 0.45-0.65, and n (Cl/Al) is 0.17-0.27, and the boroaluminate is a cation framework material with a lamellar morphology. The boron aluminate is used for adsorbing fluoride ions, the fluorine removal effect is excellent, the wastewater containing fluoride ions and with the pH value of 3-11 can be effectively treated, and the wastewater is acid-resistant, wide in application range and low in cost. The boron aluminate is utilized, so that the content of the fluoride exceeding the standard in water can be treated to be lower than the fluoride limit value specified by the national drinking water standard; and has excellent selective adsorption performance to fluoride ions even under the interference of other competitive ions.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to application of boroaluminate as a fluorine adsorbent.
Background
The fluorine content of underground water in partial areas of China is seriously overproof, and drinking high-fluorine water for a long time can cause dental fluorosis, fluorosis and the like, thereby seriously affecting the physical health of residents. The concentration of fluoride in drinking water recommended by the world health organization does not exceed 1.5mg/L, and the concentration of fluoride cannot exceed 1.0mg/L according to the current drinking water standard in China.
Patent CN107282022A discloses an inorganic defluorination adsorbent with a layered crystal structure, which is composed of lithium hydroxide, aluminum hydroxide and lanthanum hydroxide, and the adsorbent is deposited in an anion exchange resin pore channel, so that the material has a good defluorination effect and is also suitable for the defluorination application of an industrial fixed bed, but rare earth metal lanthanum is needed for synthesis, the adsorbent has high cost, the pH range is 5-9, and the adsorbent cannot be used in a strong acid environment.
Disclosure of Invention
In view of the above, the present invention aims to provide the use of boroaluminates as fluorine adsorbents. The method can effectively treat the fluorine-containing ion water body with the pH value of 3-11 by using the boron aluminate, and has the advantages of good acid resistance, wide application range and low cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an application of boron aluminate as a fluorine adsorbent, wherein the chemical composition of the boron aluminate comprises B, Al and Cl, wherein n (B/Al) is 0.45-0.65, n (Cl/Al) is 0.17-0.27, and the boron aluminate is a cation framework material with a lamellar morphology.
Preferably, the method is applied to the treatment of the water body containing the fluoride ions.
Preferably, the fluorine-containing ionic water body also comprises Cl-And/or NO3 -。
Preferably, the pH value of the fluorine ion-containing water body is 3-11.
Preferably, the mass concentration of the fluorine ions in the fluorine ion-containing water body is less than or equal to 20 mg/L.
Preferably, the method of application is:
adding the boron aluminate into the fluoride ion-containing wastewater for adsorption.
Preferably, the adsorption is stirring adsorption, standing adsorption or circulating adsorption.
Preferably, the adding amount of the boron aluminate in the fluorine-containing ion water body is 0.3-2.0 g/L.
The invention provides an application of boron aluminate as a fluorine adsorbent, wherein the chemical composition of the boron aluminate comprises B, Al and Cl, wherein n (B/Al) is 0.45-0.65, n (Cl/Al) is 0.17-0.27, and the boron aluminate is a cation framework material with a lamellar morphology. In the invention, the chloride ions in the boroaluminate framework can exchange ions with the fluoride ions in the solution, so that the fluoride ions in the solution enter the framework, and the layered structure of the boroaluminate has a larger specific surface area and a larger contact area in the adsorption process, so that higher adsorption capacity can be obtained. Therefore, the boron aluminate is used for adsorbing fluoride ions, the adsorption effect is strong, the fluoride removal effect is excellent, the water body containing fluoride ions and with the pH value of 3-11 can be effectively treated, and the water body is acid-resistant, wide in application range and low in cost. The boron aluminate is utilized to treat the content of the fluoride exceeding the standard in the water quality to be lower than the limit value of the fluoride specified in the national drinking water standard (GB 5749-2006); and has excellent selective adsorption performance to fluoride ions even under the interference of other competitive ions.
The results of the examples show that the invention makes use of the boron aluminate in a concentration of 20mg/L initially for F-Adsorbing the solution to F-The adsorption rate is 95.05-95.7%, and the adsorption capacity is 38.02-38.28 mg/g; f-F of groundwater with excessive concentration after treatment of boron aluminate-Is lower than the limit of fluoride in the national drinking water standard (GB 5749-; other competing ions, e.g. Cl-、NO3 -Adsorbing F to said boroaluminate-The ability of (a) has no significant effect; the boron aluminate contains F under strong acid environment-The adsorption performance of the water body is not obviousAnd (4) descending.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the boroaluminate salt obtained in example 1;
FIG. 2 is a scanning electron micrograph of the boroaluminate obtained in example 1.
Detailed Description
The invention provides an application of boron aluminate as a fluorine adsorbent, wherein the chemical composition of the boron aluminate comprises B, Al and Cl, wherein n (B/Al) is 0.45-0.65, n (Cl/Al) is 0.17-0.27, and the boron aluminate is a cation framework material with a lamellar morphology.
In the present invention, the method for producing the boroaluminate preferably comprises the steps of:
(1) mixing boric acid, aluminum chloride, ammonia water and water under a heating condition, cooling to room temperature, and adjusting the pH value of the mixed solution to 3.0-3.5 by using hydrochloric acid to obtain gel;
the mass ratio of the boric acid to the aluminum chloride is 25-35: 15-25;
(2) and carrying out hydrothermal crystallization on the gel to obtain the boroaluminate.
Mixing boric acid, aluminum chloride, ammonia water and water under the heating condition, cooling to room temperature, and adjusting the pH value of the mixed solution to 3.0-3.5 by using hydrochloric acid to obtain gel. In the present invention, the mass ratio of boric acid to aluminum chloride is preferably 29: 18. in the present invention, the water is preferably deionized water; the mass ratio of the boric acid to the water is preferably 25-30: 200 to 250, more preferably 29: 240. in the invention, the mass concentration of the ammonia water is preferably 25-28%; the mass ratio of the ammonia water to the boric acid is preferably 7-13: 10-20, and more preferably 10: 15. In the invention, the heating temperature is preferably 40-100 ℃, and more preferably 70 ℃; the heating is preferably carried out by a water bath method.
According to the invention, preferably, boric acid is added into water, and then the temperature is raised to the heating temperature to dissolve the boric acid, so as to obtain a boric acid solution; and then sequentially adding aluminum chloride and ammonia water into the boric acid solution for mixing. In the present invention, the mixing is preferably performed under a closed condition; the method of mixing is not particularly required in the present invention, and a mixing method well known in the art can be adopted, specifically stirring and mixing, in the specific embodiment of the present invention, stirring is preferably performed for 30min after adding aluminum chloride, and stirring is preferably performed for 1.5h after adding ammonia water. The invention mixes boric acid, aluminum chloride, ammonia water and water under the condition of heating, and the boric acid and the aluminum chloride form a liquid mixture under the alkaline environment.
After mixing boric acid, aluminum chloride, ammonia water and water, cooling the mixed solution to room temperature, and adjusting the pH value of the mixed solution to 3.0-3.5 by using hydrochloric acid to obtain gel. In the present invention, the pH is preferably 3.1; the concentration of the hydrochloric acid is preferably 12 mol/L. The present invention strictly controls the pH of the mixed liquor, otherwise no gel can be formed.
After the gel is obtained, the invention carries out hydrothermal crystallization on the gel to obtain the boron aluminate. In the invention, the temperature of the hydrothermal crystallization is preferably 140-200 ℃, and more preferably 150-180 ℃; the time for the hydrothermal crystallization is preferably 1 to 3 days, and more preferably 2 days.
The reaction apparatus for hydrothermal crystallization in the present invention is not particularly required, and a reaction apparatus well known to those skilled in the art may be used. In the hydrothermal crystallization process, boron-oxygen tetrahedron and aluminum-oxygen tetrahedron formed by dissolving boric acid and aluminum chloride are directionally connected according to a certain rule to form a long-range ordered cation framework.
After the hydrothermal crystallization, the obtained hydrothermal crystallization reaction liquid is preferably cooled to room temperature, and then solid-liquid separation is carried out; the solid obtained by separation is then washed and dried in sequence. In the present invention, the method of solid-liquid separation is preferably centrifugal separation, and the present invention does not require any particular method for the operation of the centrifugal separation, and may employ a method known to those skilled in the art. The invention preferably adopts distilled water to wash the solid obtained by solid-liquid separation, has no special requirement on the washing times, and can clean the obtained solid. In the invention, the drying temperature is preferably 60-100 ℃, and the drying time is preferably 2-12 h. Drying to obtain the boroaluminate.
In the present invention, the application is preferably in the treatment of a fluoride ion-containing water body; the pH value of the fluorine ion-containing water body is preferably 3-11; the mass concentration of the fluorine ions in the fluorine ion-containing water body is preferably less than or equal to 20 mg/L. In the present invention, the fluorine-containing ionic water body preferably further comprises Cl-And/or NO3 -. In the present invention, the fluoride ion-containing water body preferably includes fluoride ion-containing wastewater or fluoride ion-containing groundwater.
In the present invention, the method of application is preferably:
adding the boroaluminate into a fluorine-containing ion water body for adsorption.
In the present invention, the adsorption is preferably stirring adsorption, standing adsorption or circulating adsorption. The invention has no special requirements on the specific operation methods of stirring adsorption, standing adsorption and circulating adsorption, and corresponding operations well known in the field can be adopted.
In the invention, the adding amount of the boroaluminate in the water body containing the fluoride ions is preferably 0.3-2.0 g/L, and the specific adding amount can be adjusted according to the concentration of the fluoride ions in the water body.
In the invention, the chloride ions in the boroaluminate framework can exchange ions with the fluoride ions in the solution, so that the fluoride ions in the solution enter the framework, and the layered structure of the boroaluminate has a larger specific surface area and a larger contact area in the adsorption process, so that higher adsorption capacity can be obtained. Therefore, the boron aluminate is used for adsorbing fluoride ions, the adsorption effect is strong, the fluoride removal effect is excellent, the water body containing fluoride ions and with the pH value of 3-11 can be effectively treated, and the water body is acid-resistant, wide in application range and low in cost. The invention utilizes the boron aluminate to treat the content of the fluoride exceeding the standard in the water quality to be lower than the limit value of the fluoride specified in the national drinking water standard (GB 5749-; and has excellent selective adsorption performance to fluoride ions even under the interference of other competitive ions.
The application of the boroaluminate provided by the present invention as a defluorination adsorbent is described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Adding 15g of boric acid into 120g of deionized water, and dissolving in a water bath at 70 ℃ to obtain a clear solution;
(2) adding 9g of aluminum chloride into the solution obtained in the step (1), stirring for 30 minutes, then adding 12mL of ammonia water with the mass concentration of 28%, stirring for 1.5 hours, and cooling to room temperature;
(3) adjusting the pH value of the solution obtained in the step (2) to 3.1 by adopting hydrochloric acid with the concentration of 12mol/L to obtain gel;
(4) putting the gel obtained in the step (3) into a reaction kettle, and putting the reaction kettle into a 160 ℃ oven for hydrothermal crystallization for 1 day; and cooling the crystallized product to room temperature, centrifuging the crystallized product, washing the obtained solid with distilled water, and drying to obtain the boron aluminate.
The boroaluminate obtained in example 1 was characterized and tested for its adsorption effect on fluoride ions, as follows:
characterization of the boroaluminate obtained in example 1
Fig. 1 is an X-ray powder diffraction pattern of the boroaluminate obtained in example 1, and it can be seen from fig. 1 that the obtained boroaluminate is a long-range ordered crystalline material and has a cationic skeleton structure. Fig. 2 is a scanning electron microscope image of the boroaluminate obtained in example 1, and it can be seen from fig. 2 that the obtained boroaluminate has a lamellar microstructure morphology.
(II) test of the adsorption Effect of boroaluminate obtained in example 1 on fluoride ion
(A) The adsorption capacity of the boroaluminate obtained in example 1 was tested
The common commercial defluorinating agent active alumina material on the market is used as a comparison, and the test method comprises the following steps: 0.5g of adsorbent was added to 1L of an artificially prepared F-containing solution-In solution, F-The initial concentration was 20mg/L, the pH of the system was adjusted to 6.8, and the mixture was stirred at 25 ℃ for 24h at 300 rpm. After adsorption, the filtrate was centrifuged (9000rpm, 10min) and filtered (22 μm microporous membrane) to detect F in the filtrate-Concentration, calculating adsorbent pair F-The adsorption rate of (3). The test results are shown in table 1:
TABLE 1 adsorption rate and adsorption amount of fluorine ions by activated alumina material and boroaluminate obtained in example 1
| Adsorbent and process for producing the same | Adsorption rate | Amount of adsorption |
| Boron aluminate | 95.05％ | 38.02mg/g |
| Activated alumina | 14.45％ | 5.78mg/g |
As can be seen from table 1, the adsorption rate and adsorption amount of the boroaluminate obtained in example 1 to fluoride ions are significantly higher than those of the conventional defluorinating agent activated alumina material.
(B) Testing the influence of other competitive ions on the adsorption of fluoride ions by boroaluminate
Test 1: the adsorption experiment conditions are the same as the process (A) above, except that F is contained-The solution was further mixed with 10mmol/L Cl-Under these conditions, the boroaluminate couple F obtained in example 1-The adsorption rate of (D) was 93.87%.
And (3) testing 2: the adsorption experiment conditions are the same as the process (A) above, except that F is contained-The solution is mixed with 10mmol/L NO3 -Under these conditions, the boroaluminate couple F obtained in example 1-The adsorption rate of (D) was 93.98%.
As can be seen from the results of tests 1 and 2, the boroaluminate pair F obtained in example 1 is present even in the presence of a certain amount of negative monovalent anions-The adsorption capacity is not obviously reduced, which shows that the boron aluminate of the invention is used for F-Has good selective adsorption capacity.
(C) The treatment effect of the boroaluminate obtained in example 1 on the fluoride ion-containing wastewater was tested
The common commercial defluorinating agent active alumina material on the market is used as a comparison, and the test method comprises the following steps: from a place F-Groundwater of excessive concentration, F-The concentration is 2.84mg/L, and the pH is 8.7; respectively putting 0.025g of boron aluminate and active alumina material into 50mL of the water sample, stirring at room temperature for 24h at the rotating speed of 300r/min, centrifuging (9000rpm, 10min) and filtering (0.22 mu m microporous filter membrane), and detecting F in the filtrate-The concentration was 0.399 mg/L. The test results are shown in table 2:
TABLE 2 treatment Effect of boroaluminate obtained in example 1 on fluoride ion-containing wastewater
| Adsorbent and process for producing the same | Adsorption rate | After adsorption F-Concentration of |
| Boron aluminate | 85.95％ | 0.399mg/L |
| Activated alumina | 11.16％ | 2.523mg/L |
Watch with watch2 it can be seen that F-After groundwater with excessive concentration is treated by the boroaluminate obtained in example 1, F in the filtrate is detected-The concentration is 0.399mg/L, which is lower than the limit of fluoride in the national drinking water standard (GB 5749-2006).
(D) The boroaluminate obtained in example 1 was tested for acid resistance
The test method comprises the following steps: 0.5g of adsorbent was added to a prepared 1L of F-containing adsorbent-In solution, F-The initial concentration was 20mg/L, the pH of the system was adjusted to 3.92, and the mixture was stirred at 25 ℃ for 24h at 300 rpm. After adsorption, the filtrate was centrifuged (9000rpm, 10min) and filtered (22 μm microporous membrane) to detect F in the filtrate-Concentration, calculating adsorbent pair F-The adsorption rate of (3). The remaining fluoride ion concentration in the solution after adsorption was measured to be 1.68mg/g, and the adsorption rate was 91.6%. It can be seen that the adsorption performance is not obviously reduced under the strong acid environment.
Example 2
The temperature for hydrothermal crystallization in the step (4) of example 1 was changed to 150 ℃ and the same procedure as in example 1 was repeated to obtain boroaluminate.
The X-ray powder diffraction pattern and the scanning electron microscope image of the boroaluminate obtained in example 2 are respectively similar to those in fig. 1 and fig. 2, that is, the boroaluminate obtained in example 2 is a cationic framework material with lamellar morphology.
The adsorption capacity of the boroaluminate obtained in example 2 was measured by the method of the above-mentioned procedure (A), and F was measured-The adsorption rate of (2) was 95.7%, and the adsorption amount was 38.28 mg/g.
Testing of other competitor ions (Cl) Using the procedure (B) above-、NO3 -) Influence of adsorption of fluoride ion on the boroaluminate of example 2, resulting in the boroaluminate of example 2 on F even if a certain amount of negative monovalent anion is present-The adsorption capacity is not obviously reduced, which shows that the boron aluminate of the invention is used for F-Has good selective adsorption capacity.
The treatment effect of the boroaluminate obtained in example 2 on the fluorine-containing ion-containing wastewater was tested by the method of the process (C), and the result F-The groundwater with excessive concentration is implementedExample 2 boroaluminate treated F-The concentration of the concentration is lower than the limit of fluoride in the national drinking water standard (GB 5749-.
The acid resistance of the boroaluminate obtained in example 2 was tested by the method of the process (D) above, and it was found that the remaining fluoride ion concentration in the solution after adsorption was 1.84mg/g and the adsorption rate was 90.8%. It can be seen that the adsorption performance is not obviously reduced under the strong acid environment.
Example 3
The temperature for heating the water bath in the step (1) of example 1 was changed to 75 ℃ and the same procedure as in example 1 was repeated to obtain boroaluminate.
The X-ray powder diffraction pattern and the scanning electron microscope image of the boroaluminate obtained in example 3 are similar to those in fig. 1 and fig. 2, respectively, that is, the boroaluminate obtained in example 3 is a cationic framework material with a lamellar morphology.
The adsorption capacity of the boroaluminate obtained in example 3 was measured by the method of the above-mentioned procedure (A), and F was measured-The adsorption rate of (D) was 95.65% and the adsorption amount was 38.26 mg/g.
Testing of other competitor ions (Cl) Using the procedure (B) above-、NO3 -) Influence of adsorption of fluoride ion on the boroaluminate of example 3, with the result that the boroaluminate obtained in example 3 is responsible for F even if a certain amount of negative monovalent anions is present-The adsorption capacity is not obviously reduced, which shows that the boron aluminate of the invention is used for F-Has good selective adsorption capacity.
The acid resistance of the boroaluminate obtained in example 3 was tested by the method of the process (D) above, and it was found that the remaining fluoride ion concentration in the solution after adsorption was 1.35mg/g and the adsorption rate was 93.25%. It can be seen that the adsorption performance is not obviously reduced under the strong acid environment.
The treatment effect of the boroaluminate obtained in example 2 on the fluorine-containing ion-containing wastewater was tested by the method of the process (C), and the result F-After groundwater with excessive concentration is treated with boroaluminate obtained in example 3, F-The concentration of the concentration is lower than the limit of fluoride in the national drinking water standard (GB 5749-.
Example 4
The boric acid in step (1) of example 1 was changed to 16g, water was changed to 130g, aluminum chloride was changed to 10g, and the rest was the same as in example 1 to obtain boroaluminate.
The X-ray powder diffraction pattern and the scanning electron microscope image of the boroaluminate obtained in example 4 are respectively similar to those in fig. 1 and fig. 2, that is, the boroaluminate obtained in example 4 is a cationic framework material with lamellar morphology.
The adsorption capacity of the boroaluminate obtained in example 4 was measured by the method of the above-mentioned procedure (A), and F was measured-The adsorption rate of (2) was 95.53%, and the adsorption amount was 38.21 mg/g.
Testing of other competitor ions (Cl) Using the procedure (B) above-、NO3 -) The influence of fluoride ion adsorption on the boroaluminate of example 4, results that the boroaluminate obtained in example 4 is responsible for F even if a certain amount of negative monovalent anions is present-The adsorption capacity is not obviously reduced, which shows that the boron aluminate of the invention is used for F-Has good selective adsorption capacity.
The treatment effect of the boroaluminate obtained in example 4 on the fluorine-containing ion-containing wastewater was tested by the method of the process (C) described above, and the result F-After groundwater with excessive concentration is treated with boroaluminate obtained in example 4, F-The concentration of the concentration is lower than the limit of fluoride in the national drinking water standard (GB 5749-.
The acid resistance of the boroaluminate obtained in example 4 was tested by the method of the procedure (D) above, and the remaining fluoride ion concentration in the solution after adsorption was 2.05mg/g, and the adsorption rate was 89.75%. It can be seen that the adsorption performance is not obviously reduced under the strong acid environment.
The embodiments show that the invention utilizes boron aluminate to adsorb fluoride ions, has stronger selective adsorption capacity, excellent fluoride removal effect and good acid resistance, and can effectively treat fluoride ion-containing wastewater.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The boron aluminate is used as a fluorine adsorbent, the chemical composition of the boron aluminate comprises B, Al and Cl, wherein n (B/Al) is 0.45-0.65, n (Cl/Al) is 0.17-0.27, and the boron aluminate is a cationic framework material with lamellar morphology.
2. Use according to claim 1, in the treatment of a body of water containing fluoride ions.
3. The use of claim 2, wherein the fluoride ion-containing water body further comprises Cl-And/or NO3 -。
4. The use according to claim 2, wherein the pH value of the fluoride ion-containing water body is 3 to 11.
5. The use according to claim 2, wherein the mass concentration of fluoride ions in the fluoride ion-containing water body is less than or equal to 20 mg/L.
6. The application according to claim 2, 3, 4 or 5, wherein the method of application is:
adding the boroaluminate into a fluorine-containing ion water body for adsorption.
7. Use according to claim 6, wherein the adsorption is stirred adsorption, standing adsorption or cyclic adsorption.
8. The use of claim 6, wherein the amount of the boroaluminate added to the fluoride ion-containing water is 0.3-2.0 g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116116374A (en) * | 2023-03-09 | 2023-05-16 | 河北工业大学 | La (La) 2 O 3 Preparation method and application of BNNFs composite adsorbent |
| CN116116374B (en) * | 2023-03-09 | 2024-05-17 | 河北工业大学 | La (La)2O3Preparation method and application of BNNFs composite adsorbent |
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