CN114053992B - Composite material for deeply removing fluoride ions in wastewater, preparation method and application - Google Patents
Composite material for deeply removing fluoride ions in wastewater, preparation method and application Download PDFInfo
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention belongs to the field of sewage treatment, and discloses a composite material for deeply removing fluoride ions in wastewater, a preparation method and application thereof. The invention utilizes the layered composite metal hydroxide to adsorb and remove the fluoride ions and other high-valence anions in the wastewater, and simultaneously utilizes the strong complexation of the aluminum hydroxide, the zirconium hydroxide and the fluoride ions to remove the fluoride ions, thereby achieving the purpose of deeply removing the fluoride ions in the wastewater by the cooperation of the components, solving the problems of high cost, slow sedimentation rate and large solid waste generation amount of the existing method, and the material can endure a wider pH range when being applied, does not need to lower the pH of the wastewater to below 4, greatly widens the application range, reduces the treatment cost and is beneficial to popularization.
Description
Technical Field
The invention belongs to the field of water treatment, and in particular relates to a composite material for deeply removing fluoride ions in wastewater, and preparation and application thereof.
Background
Fluoride is a common contaminant in water and prolonged fluorine exposure can lead to fluorosis [ Jadhav S.V., bringas E, yadav G.D., rathod V.K., ortiz I., marath K.V. arc and fluoride contaminated ground waters: a review of current technologies for contaminants remote. Journal of Environmental management 2015,162,306-325; mohaptra m., anand s., mishara b.k., giles d.e., singh p.review of fluoride removal from drinking water journal of Environmental management 2009,91,67-77]. The world health organization prescribes that fluorine in drinking water must be below 1.5mg L -1 [World Health Organization(WHO),2011.Guidelines for Drinking Water Quality,fourth ed]. Various methods have been developed to remove fluorine from water, such as chemical precipitation, coagulation, electrocoagulation, adsorption, ion exchange and membrane filtration. Many metal oxides and hydroxides, such as aluminum and zirconium oxides, are reported to be effective adsorbents of fluoride ions. For better engineering applications, zirconium hydroxide/oxide is supported on different carriers such as collagen fibers, carboxymethyl cellulose, beta-cyclodextrin and hollow fiber membranes. One common disadvantage of these zirconium-based adsorbents is poor pH adaptability. For efficient removal of F, acidic conditions (pH of about 3.0) [ Gan y., wang x., zhang l., wu b., zhang g., zhang s.coagnication removal of fluoride by zirconium tetrachloride: performance evaluation and mechanism analysis.chemosphere.2019,218, 860-868 are generally used.]。
The decrease in solution pH is a natural result of hydrolysis of the metal salt coagulant. Thus, coagulation can better meet the pH requirements for fluorine removal. Aluminum-based coagulants are reported to have strong fluorine removal capacity [ Ingallinella A.M., pacini V.A., fernandez R.G., vidoni R.M., sanguinetti G.Simulineaneous removal of arsenic and fluoride from groundwater by coagulation-adsorption with polyaluminum chloride. Journal of Environmental Science and Health Part A,2011,46,1288-1296 ]. However, the formation of aluminum-fluorine complexes significantly inhibited the hydrolysis of aluminum salts [ Liu r.p., liu b., zhu l.j., he z., ju j.w., lan h.c., liu h.j.effects of fluoride on the removal of cadmium and phosphate by aluminum coagnment. Journal of Environmental sciences 2015,32,118-125]. As a result, the residual concentrations of aluminum and fluorine were not able to reach the prescribed limits [ Yu W.Z., gregory J., graham N.Regrowth of broken hydroxide flocs: effect of added fluoride.environmental Science and technology.2016.50, 1828-1833]. Further measures are required to remove the residual aluminum. In addition, aluminum salts coagulate to produce hazardous sludge that is difficult to dispose of [ Gan y, wang x, zhang l, wu b, zhang g, zhang s.coagulation removal of fluoride by zirconium tetrachloride: performance evaluation and mechanism analysis.chemosphere.2019,218, 860-868].
Zirconium salts have been widely used as coagulants for water treatment in recent decades, and inorganic zirconium salt coagulants have been effective in removing organics, thereby minimizing the production of disinfection byproducts [ Jarvis p., sharp e., pidou m., moliner., parsons s.a., jefferson b.2012, comprison of coagulation performance and floc properties using a novel zirconium coagulant against traditional ferric and alum coagulants.water research.2012,46, 4179-4187; aftab B., hur J.Fast tracking the molecular weight changes of humic substances in coagulation/flocculation processes via fluorescence EEM-PARAFAC. Chemosphere.2017,178, 317-324]. In addition, the zirconium salt flocs are larger than the aluminum coagulant, more conducive to subsequent membrane filtration [ Su z.y., li x., yang y.l., fan y.r. probing the application of a zirconium coagulant in a coagulation-ultrafiltration process: observations on organics removal and membrane shaping.rsc advances.2017,7, 42329-42338]. Gan et al applied zirconium tetrachloride to remove fluoride ions from wastewater found that fluoride ions could be efficiently removed and flocculated to precipitate, but the optimal reaction conditions were ph=4, with applicable conditions being pH limited.
Based on the defects of the prior art, a new material and a new method capable of deeply removing fluorine ions are needed.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem of poor effect of deep removal of fluoride ions in water, the invention prepares the layered composite metal hydroxide containing 3 or more metal types of zirconium hydroxide by a hydrothermal method, utilizes the layered composite metal hydroxide to remove fluoride ions and other high valence anions in wastewater by ion exchange adsorption, and simultaneously utilizes the strong complexation of the zirconium hydroxide doped in a composite structure and the fluoride ions to remove the fluoride ions in a targeted manner, and in the treatment process, the layered composite metal hydroxide removes the other high valence anions to reduce the competition of complexation between the fluoride ions and the zirconium hydroxide, thereby achieving the purpose of deep removal of the fluoride ions in the wastewater.
Further, aiming at the problems that the zirconium hydroxide/oxide is supported on different carriers and has poor pH adaptability, acidic conditions (the pH value is about 3.0) are generally needed, and the zirconium salt is used for defluorination and has the problem of being limited by low pH (the pH is less than or equal to 4), the material of the invention is not limited by low pH environment in the application process, and has wide application range.
Furthermore, aiming at the problem that the aluminum-based coagulant is easy to pollute, the composite material prepared by the invention can not dissolve into water to cause secondary pollution by stably fixing zirconium hydroxide and other metal hydroxides in crystal lattices of synthetic minerals, so that the composite material has better environmental friendliness.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a composite material for deeply removing fluoride ions in wastewater, which is a layered composite metal hydroxide prepared by a hydrothermal method and containing at least 3 metal hydroxides, wherein the layered composite metal hydroxide contains zirconium hydroxide.
As a further improvement of the present invention, the layered double hydroxide contains zirconium hydroxide and aluminum hydroxide.
As a further improvement of the present invention, the layered double hydroxide contains zirconium hydroxide, magnesium hydroxide and aluminum hydroxide.
As a further improvement of the invention, the preparation method of the composite material for deeply removing the fluoride ions in the wastewater comprises the following steps:
1) Preparing a mixed solution containing at least 3 metal ions, wherein the mixed solution contains zirconium ions;
2) Dropwise adding sodium hydroxide solution into the mixed solution to obtain slurry-like substances;
3) Centrifuging the slurry material, washing with pure water, and centrifuging again to obtain a solid material;
4) And (3) carrying out hydrothermal treatment, freeze drying, grinding into powder, and sieving on the solid obtained in the step (3) to obtain the composite material.
As a further improvement of the invention, the preparation process of the step 1) is as follows: mixing magnesium salt, aluminum salt and zirconium salt to obtain a mixture, and adding water for dissolution to obtain a mixed solution; the adding mass of the zirconium salt is not less than 5% of the total mass of the mixture.
As a further improvement of the invention, the added mass of the zirconium salt in the step 1) accounts for 5 to 30 percent of the total mass of the mixture.
As a further improvement of the invention, the content of the sodium hydroxide substance is not less than 3 times of the total content of magnesium, aluminum and zirconium.
As a further improvement of the present invention, the centrifugation rate in step 3) is 5000 to 10000rpm.
As a further improvement of the invention, the temperature of the hydrothermal treatment in the step 4) is not lower than 60 ℃ and the treatment time is not less than 60 minutes.
As a further improvement of the invention, the temperature of the hydrothermal treatment is 105 ℃ and the time is 240 minutes.
As a further improvement of the invention, the invention provides an application method of the composite material for deeply removing the fluoride ions in the wastewater, wherein the composite material is added into the wastewater containing the fluoride to remove the fluoride ions in the wastewater.
As a further improvement of the invention, the concentration of the composite material in the wastewater is not lower than 5mg/L.
As a further improvement of the invention, the concentration of the composite material in the wastewater is not lower than 25mg/L.
As a further improvement of the invention, the pH value of the wastewater is less than or equal to 6.
In the preferred scheme, in the process of removing the fluoride ions in the wastewater, the rapid stirring is firstly carried out, and then the slow stirring is carried out to remove the fluoride ions by sedimentation.
In a preferred scheme, during the process of removing the fluoride ions in the wastewater, the wastewater is firstly stirred rapidly for 2 minutes, then stirred slowly for 15 minutes, and then settled and removed for 15 minutes.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention utilizes the characteristic that the interlayer of the layered composite metal hydroxide in the composite material has positive charges, anions are adsorbed in the middle of the layer to keep electric neutrality, the anions in the wastewater can be removed through the ion exchange effect, fluoride ions and other anions (such as phosphate and carbonate commonly exist in tap water) in the water body are removed, meanwhile, the selective complexing fluoride ions of the zirconium hydroxide in the material are utilized, the competition of the complexing effect between the fluoride ions and the zirconium hydroxide is greatly reduced in the process of removing the layered composite metal hydroxide, thereby remarkably improving the selective complexing effect of the zirconium hydroxide and the fluoride ions, and the synergistic effect of the zirconium hydroxide and the fluoride ions remarkably improves the removing effect of the composite material on the fluoride ions.
(2) The composite material for efficiently removing the fluoride ions in the wastewater also contains the aluminum hydroxide, and has strong complexation with the fluoride ions, so that the competition of complexation between the fluoride ions and the zirconium hydroxide is reduced by removing other high-valence anions by the layered composite metal hydroxide in the treatment process, and the purpose of deeply removing the fluoride ions in the wastewater is achieved.
(3) The composite material for efficiently removing the fluoride ions in the wastewater, disclosed by the invention, has the advantages that the prepared layered composite metal hydroxide containing 3 or more metal types of zirconium hydroxide is structured into regular cubes or hexagons, and has larger specific surface area, larger adsorption capacity and more favorable for removing the fluoride ions compared with the layered double hydroxide with the original cuboid structure.
(4) The composite material for efficiently removing the fluoride ions in the wastewater has the advantages of environmental friendliness, small influence on the physicochemical properties of the wastewater, obvious economic benefit and application value, and the composite material can stably fix the zirconium hydroxide in the crystal lattice of the synthetic mineral and can not dissolve into water to cause secondary pollution.
(5) The method for deeply removing the fluoride ions in the water body by the composite material widens the application range of the material, the application process of the material is not limited by the condition of low pH, the composite is better in use in the water body with the pH less than or equal to 6, the hydrolysis degree of the water body with the pH less than or equal to 6 is relatively lower, and the competition effect of anions is reduced, so that zirconium hydroxide in the composite material has more fluoride ion coordination sites, and further, the more excellent fluoride removal effect is realized.
Drawings
FIG. 1 is a schematic structural diagram of a zirconium doped layered composite metal hydroxide;
FIG. 2 is a transmission electron microscope characterization comparison of the zirconium doped layered double hydroxide of example 1 with the layered double hydroxide alone;
FIG. 3 is a graph showing the effect of the composite material containing 5% zirconium on the removal of fluoride ions at different concentrations in example 2;
FIG. 4 is a graph showing the effect of 20% zirconium-containing composite in example 3 on fluoride ion removal at different concentrations;
FIG. 5 is a graph showing the effect of the composite material containing 30% zirconium on fluoride ion removal at different concentrations in example 4;
FIG. 6 is a graph showing the effect of 30% zirconium-containing composite material of example 5 on the fluoride ion depth removal of actual photovoltaic wastewater;
FIG. 7 is a graph showing the effect of the layered double hydroxide prepared in comparative example A on the removal of fluoride ions at different concentrations;
FIG. 8 is a graph showing the effect of zirconium salt added in comparative example B on the removal of fluorine ions at different concentrations.
Detailed Description
The invention is further described below in connection with specific embodiments.
The terms such as "upper", "lower", "left", "right", "middle" and the like are also used in the present specification for convenience of description, and are not intended to limit the scope of the present invention, but rather to change or adjust the relative relationship thereof, and are also considered to be within the scope of the present invention without substantial change of technical content.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, metric or value. The degree of flexibility of a particular variable can be readily determined by one skilled in the art.
As used herein, the term "is intended to be synonymous with" one or more of ". For example, "at least one of A, B and C" expressly includes a only, B only, C only, and respective combinations thereof.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limits of 1 to about 4.5, but also include individual numbers (such as 2,3, 4) and subranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed to include all such values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.
Any steps recited in any method or process claims may be performed in any order and are not limited to the order set forth in the claims.
The invention is further described below in connection with specific embodiments.
Example 1
The synthesis method of the zirconium doped layered composite hydroxide for deeply removing fluoride ions in wastewater comprises the following steps:
1) Respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; the zirconium chloride accounts for 5-30% of the total mass of the mixture, water is added, the mixture is stirred on a stirrer until the mixture is completely dissolved, and the mixed solution is formed, wherein the concentration of magnesium chloride, aluminum chloride and zirconium chloride in the mixed solution is 285mg/L, 133mg/L and 21mg/L respectively.
2) And dissolving sodium hydroxide in water to obtain a sodium hydroxide solution with the concentration of 6g/L, dropwise adding the sodium hydroxide solution into the mixed solution of the magnesium salt, the aluminum salt and the zirconium salt to obtain a slurry substance, wherein the adding amount of the sodium hydroxide substance is not less than 3 times of the sum of the amounts of the magnesium, aluminum and zirconium substances.
3) Centrifuging the slurry material at 5000-10000 rpm, and washing with pure water three times. And after the washing is finished, carrying out hydrothermal treatment, wherein the time of the hydrothermal treatment is not less than 60 ℃, and the treatment time is not less than 60 minutes. And freeze-drying the sample subjected to the hydrothermal treatment, grinding the sample into powder, sieving, sealing and storing the composite material. FIG. 1 is a schematic structural diagram of a finally prepared zirconium-doped layered composite metal hydroxide.
While the layered double hydroxide (zirconium undoped) was synthesized alone as a comparison, the procedure for the individual synthesis was essentially the same as that described above, except that: no zirconium salt is added in step 1).
FIG. 2 is a graph of a transmission electron microscope characterization comparison of zirconium doped layered double hydroxide (LDH-Zr) with Layered Double Hydroxide (LDH) alone in example 1; as can be seen from comparison of fig. 2, the layered double hydroxide prepared alone is in a regular cuboid, while the zirconium-doped layered double hydroxide is in a regular square or hexagonal structure.
Example 2
In the embodiment, a composite material is firstly prepared, and then fluoride ions in wastewater are deeply removed by adopting the composite material, and the method comprises the following steps:
1) Respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; wherein the added mass of zirconium chloride accounts for 5% of the total mass of the mixture, water is added and stirred uniformly, and then the mixture is placed on a stirrer to be stirred until the mixture is completely dissolved, so as to obtain a mixed solution; the concentration of magnesium chloride, aluminum chloride and zirconium chloride in the mixed solution is 285mg/L, 133mg/L and 21mg/L respectively.
2) And (3) weighing sodium hydroxide, dissolving in water to obtain a sodium hydroxide solution, dropwise adding 6g/L of the sodium hydroxide solution into a mixed solution containing magnesium salt, aluminum salt and zirconium salt, wherein the amount of sodium hydroxide substances is not less than 3 times of the sum of the amounts of magnesium, aluminum and zirconium substances, and obtaining a slurry substance. Centrifuging the slurry material at 5000-10000 rpm, and washing with pure water three times. After the washing, a hydrothermal treatment (treatment temperature 105 ℃ C., treatment time 240 minutes) was performed. And freeze-drying the sample subjected to the hydrothermal treatment, grinding the sample into powder, sieving, sealing and storing the composite material.
3) Potassium fluoride was dissolved in Nanjing tap water at pH 7.6, and the anion species and concentrations are shown in Table 1.
TABLE 1 tap water anion concentration
| Cl - (mg/L) | SO 4 2- (mg/L) | NO 3 - (mg/L) | PO 4 3- (mg/L) |
| 1.52 | 1.90 | 0.29 | 1.32 |
Fluoride ion solutions having initial concentrations of 2.5, 5.0, 10.0 and 15.0mg/L were prepared as described above. Hydrochloric acid is added to adjust the pH of the fluorine-containing tap water to be less than 6, 50mg/L of the composite material is added, the mixture is rapidly stirred for 2 minutes, then slowly stirred for 15 minutes, flocculation sedimentation is carried out for 15 minutes, and then the concentration of fluorine ions in the supernatant is measured by using a fluorine ion selective electrode.
As shown in the figure 3, the fluorine ion removal rate of the composite material is more than 60% when three groups of the composite material are parallel, wherein the fluorine ion removal rates of the composite material are 65%,64%,63% and 65% for different concentrations respectively.
The larger the adding amount of the zirconium doped layered composite metal hydroxide is, the better the fluoride ion deep removal effect is.
Example 3
In the embodiment, a composite material is firstly prepared, and then fluoride ions in wastewater are deeply removed by adopting the composite material, and the method comprises the following steps:
1) Respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; the zirconium chloride accounts for 20% of the total mass of the mixture, water is added, the mixture is stirred on a stirrer until the mixture is completely dissolved, and the mixed solution is obtained, wherein the concentration of magnesium chloride, aluminum chloride and zirconium chloride in the mixed solution is 285mg/L, 133mg/L and 105mg/L respectively.
2) And (3) weighing sodium hydroxide, dissolving in water to obtain a sodium hydroxide solution, dropwise adding 6g/L of the sodium hydroxide solution into a mixed solution of magnesium salt, aluminum salt and zirconium salt, wherein the mass of the sodium hydroxide is not less than 3 times of the sum of the mass of magnesium, aluminum and zirconium, and obtaining a slurry-like substance. Centrifuging the slurry material at 5000-10000 rpm, and washing with pure water three times. After the washing, a hydrothermal treatment (105 ℃ C., 240 minutes) was performed. And freeze-drying the sample subjected to the hydrothermal treatment, grinding the sample into powder, sieving, sealing and storing the composite material.
(2) Potassium fluoride was dissolved in Nanjing tap water at pH 7.6, and the anion species and concentrations are shown in Table 1. Fluoride ion solutions were prepared at initial concentrations of 2.5, 5.0, 10.0 and 15.0 mg/L. Hydrochloric acid is added to adjust the pH of the fluorine-containing tap water to be less than 6, 50mg/L of the composite material is added, the mixture is rapidly stirred for 2 minutes, then slowly stirred for 15 minutes, flocculation sedimentation is carried out for 15 minutes, and then the concentration of fluorine ions in the supernatant is measured by using a fluorine ion selective electrode.
As shown in the figure 4, the fluorine ion removal rate of the composite material is over 70% when three groups of the composite material are parallel, wherein the fluorine ion removal rates of the composite material are 77%,78%,77% and 73% for different concentrations respectively.
The larger the adding amount of the zirconium doped layered composite metal hydroxide is, the better the fluoride ion deep removal effect is.
Example 4
In the embodiment, a composite material is firstly prepared, and then fluoride ions in wastewater are deeply removed by adopting the composite material, and the method comprises the following steps:
1) Respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; the zirconium chloride accounts for 30% of the total mass of the mixture, water is added, the mixture is stirred on a stirrer until the mixture is completely dissolved, and the mixed solution is obtained, wherein the concentration of magnesium chloride, aluminum chloride and zirconium chloride in the mixed solution is 285mg/L, 133mg/L and 179mg/L respectively.
2) And (3) weighing sodium hydroxide, dissolving in water to obtain a sodium hydroxide solution, dropwise adding 6g/L of the sodium hydroxide solution into a mixed solution of magnesium salt, aluminum salt and zirconium salt, wherein the mass of the sodium hydroxide is not less than 3 times of the sum of the mass of magnesium, aluminum and zirconium, and obtaining a slurry-like substance. Centrifuging the slurry material at 5000-10000 rpm, and washing with pure water three times. After the washing, a hydrothermal treatment (105 ℃ C., 240 minutes) was performed. And freeze-drying the sample subjected to the hydrothermal treatment, grinding the sample into powder, sieving, sealing and storing the composite material.
3) Potassium fluoride was dissolved in Nanjing tap water at pH 7.6, and the anion species and concentrations are shown in Table 1. Fluoride ion solutions were prepared at initial concentrations of 2.5, 5.0, 10.0 and 15.0 mg/L. Hydrochloric acid is added to adjust the pH of the fluorine-containing tap water to be less than 6, 50mg/L of the composite material is added, the mixture is rapidly stirred for 2 minutes, then slowly stirred for 15 minutes, flocculation sedimentation is carried out for 15 minutes, and then the concentration of fluorine ions in the supernatant is measured by using a fluorine ion selective electrode.
As shown in FIG. 5, the fluorine ion removal rate of the composite material is over 78% when three groups of the composite material are parallel, wherein the fluorine ion removal rates of the composite material are respectively 84%,85%,83% and 78% for different concentrations.
Example 5
In the embodiment, a composite material is firstly prepared, and then fluoride ions in wastewater are deeply removed by adopting the composite material, and the method comprises the following steps:
1) Respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; the zirconium chloride accounts for 30% of the total mass of the mixture, water is added, the mixture is stirred on a stirrer until the mixture is completely dissolved, and the mixed solution is obtained, wherein the concentration of magnesium chloride, aluminum chloride and zirconium chloride in the mixed solution is 285mg/L, 133mg/L and 179mg/L respectively.
2) And (3) weighing sodium hydroxide, dissolving in water to obtain a sodium hydroxide solution, dropwise adding 6g/L of the sodium hydroxide solution into a mixed solution of magnesium salt, aluminum salt and zirconium salt, wherein the mass of the sodium hydroxide is not less than 3 times of the sum of the mass of magnesium, aluminum and zirconium, and obtaining a slurry-like substance. Centrifuging the slurry material at 5000-10000 rpm, and washing with pure water three times. After the washing, a hydrothermal treatment (105 ℃ C., 240 minutes) was performed. And freeze-drying the sample subjected to the hydrothermal treatment, grinding the sample into powder, sieving, sealing and storing the composite material.
(2) And collecting the photovoltaic wastewater, and determining the concentration of fluoride ions to be 3.2mg/L and the pH of the water body to be 8.5. The pH of the wastewater is firstly regulated to be less than 6, zirconium doped layered composite metal hydroxides (10, 25, 50, 75 and 100 mg/L) with different concentrations are added, the rapid stirring is carried out for 2 minutes, then the slow stirring is carried out for 15 minutes, the flocculation sedimentation is carried out for 15 minutes, and then the concentration of fluoride ions in the supernatant fluid is measured by using a fluoride ion selective electrode. As shown in FIG. 6, the fluorine ion removal results of the three groups are shown in parallel, and the removal rates are 41%,58%,79%,87% and 92%, respectively. When the zirconium doped layered composite metal hydroxide with concentration of more than or equal to 50mg/L is added, the concentration of fluoride ions can be reduced to below 1.0 mg/L, and the emission standard of the world health organization is met.
Comparative example A
This comparative example is a result of the preparation of a layered double hydroxide alone and the removal of fluoride ion adsorption, and the layered double hydroxide preparation procedure is substantially the same as in example 1, except that: step 1) does not introduce zirconium chloride, and is specifically as follows:
(1) Adding magnesium chloride and aluminum chloride into a beaker respectively, adding water, stirring uniformly, and then placing the mixture on a stirrer to be completely dissolved to obtain a mixed solution, wherein the concentration of the magnesium chloride and the aluminum chloride in the mixed solution is 285mg/L and 133mg/L respectively. And (3) weighing sodium hydroxide, dissolving in water, and dropwise adding 6g/L sodium hydroxide solution into the mixed solution of the magnesium salt and the aluminum salt to obtain a slurry substance. Centrifuging the slurry material at 5000-10000 rpm, and washing with pure water for three times. After the washing, a hydrothermal treatment (105 ℃ C., 240 minutes) was performed. And freeze-drying the sample subjected to the hydrothermal treatment, grinding the sample into powder, sieving, sealing and storing the composite material.
(2) Potassium fluoride was dissolved in Nanjing tap water at pH 7.6, and the anion species and concentrations are shown in Table 1. Fluoride ion solutions with initial concentrations of 2.5, 5.0, 10.0 and 15.0mg/L are prepared, hydrochloric acid is added to adjust the pH of fluorine-containing tap water to be less than 6, 50mg/L of layered double hydroxide is added, rapid stirring is carried out for 2 minutes, then slow stirring is carried out for 15 minutes, flocculation and sedimentation are carried out for 15 minutes, then the concentration of fluoride ions in the supernatant is measured by using a fluoride ion selective electrode, and the removal result is shown in figure 7. The fluoride ion removal rates were 42%,44%,35%,40%, respectively.
Comparative example B
This comparative example is the result of fluoride ion adsorption removal by zirconium salt alone, potassium fluoride was dissolved in tap water in Nanjing, where Nanjing tap water had a pH of 7.6, and the anion species and their concentrations are shown in Table 1.
Preparing fluoride ion solutions with initial concentrations of 2.5, 5.0, 10.0 and 15.0mg/L, adding hydrochloric acid to adjust pH of fluorine-containing tap water to be less than 6, respectively adding zirconium chloride with concentration of 50mg/L into the fluoride ion solutions, rapidly stirring for 2 minutes, slowly stirring for 15 minutes, flocculating and settling for 15 minutes, and measuring the concentration of fluoride ions in the supernatant by using a fluoride ion selective electrode, wherein the removal result is shown in figure 8. The fluoride ion removal rates were 58%,60%,54%,65%, respectively.
As can be seen from the comparison results of the comparative examples A and B and the examples 2 to 5, the components in the composite material structure of the invention exert synergistic effect in the process of removing the fluoride ions in the water body, thereby greatly enhancing the targeted removal of the fluoride ions.
Claims (4)
1. A composite material for deeply removing fluoride ions in wastewater is characterized in that: the composite material is a layered composite metal hydroxide prepared by a hydrothermal method and containing at least 3 metal hydroxides, wherein the layered composite metal hydroxide contains zirconium hydroxide, magnesium hydroxide and aluminum hydroxide;
the preparation method of the composite material comprises the following steps:
1) Preparing a mixed solution containing at least 3 metal ions, wherein the mixed solution contains zirconium ions;
2) Dropwise adding sodium hydroxide solution into the mixed solution to obtain slurry-like substances;
3) Centrifuging the slurry material, washing with pure water, and centrifuging again to obtain a solid material;
4) Carrying out hydrothermal treatment, freeze drying, grinding into powder and sieving on the solid obtained in the step 3) to obtain a composite material;
the preparation process of the step 1) comprises the following steps: mixing magnesium salt, aluminum salt and zirconium salt to obtain a mixture, and adding water to dissolve the mixture to obtain a mixed solution; the adding mass of the zirconium salt is not less than 5% of the total mass of the mixture;
the content of the sodium hydroxide is not less than 3 times of the total content of magnesium, aluminum and zirconium;
the centrifugation speed in the step 3) is 5000-10000 rpm, and/or the temperature of the hydrothermal treatment in the step 4) is not lower than 60 ℃, and the treatment time is not less than 60 minutes.
2. The method for applying the composite material for deeply removing fluoride ions in wastewater, as claimed in claim 1, wherein the method comprises the following steps: and adding the composite material into the fluorine-containing wastewater to remove fluorine ions in the wastewater.
3. The application method for deeply removing fluoride ions in wastewater according to claim 2, wherein: the concentration of the composite material in the wastewater is not lower than 25mg/L.
4. The method for deeply removing fluoride ions from wastewater according to claim 3, wherein: the pH value of the wastewater is less than or equal to 6.
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