CN115945160A - Porous lanthanum zirconium phosphate fluorine-removing material and preparation method and application thereof - Google Patents
Porous lanthanum zirconium phosphate fluorine-removing material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CCFBRYMTRHGJQH-UHFFFAOYSA-K lanthanum(3+) zirconium(4+) phosphate Chemical compound [Zr+4].P(=O)([O-])([O-])[O-].[La+3] CCFBRYMTRHGJQH-UHFFFAOYSA-K 0.000 title claims description 18
- -1 lanthanum zirconium phosphate fluorine Chemical compound 0.000 claims abstract description 77
- 239000011737 fluorine Substances 0.000 claims abstract description 41
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 31
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- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 10
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- 238000006115 defluorination reaction Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
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- 238000000034 method Methods 0.000 abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 18
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000223 arsonoyl group Chemical group [H][As](*)(*)=O 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a porous lanthanum zirconium phosphate fluorine removal material, a preparation method and application thereof, wherein the porous lanthanum zirconium phosphate fluorine removal material comprises the following raw material components in parts by weight: zirconium oxychloride, lanthanum nitrate, diammonium hydrogen phosphate, ammonium carbonate and a template agent, wherein the addition amounts of the zirconium oxychloride and the lanthanum nitrate are recorded in terms of mol ratio Zr 4+ :La 3+ And (0.3-3). The method mainly uses zirconium oxychloride as a zirconium source, lanthanum nitrate as a lanthanum source, diammonium hydrogen phosphate as a phosphorus source and hexadecyl trimethyl ammonium bromide as a template agent, and prepares the porous zirconium lanthanum phosphate fluorine removal material with high specific surface area through high-temperature precipitation, filtering, washing, drying and roasting, and the porous zirconium lanthanum phosphate fluorine removal material has a stable mesoporous structure and high specific surface area and can be used as an efficient fluorine removal agent. The method obtainsThe obtained porous zirconium lanthanum phosphate fluorine removal material has the advantages of uniform element distribution, high specific surface area, many active sites, strong adsorption capacity, high adsorption capacity for fluorine ions, cyclic utilization and great application value in the field of fluorine-containing water purification.
Description
Technical Field
The invention belongs to the technical field of synthesis of inorganic functional materials, and particularly relates to a porous lanthanum zirconium phosphate fluorine removal material as well as a preparation method and application thereof.
Background
The high fluoride concentration in groundwater is caused by the large volumes of wastewater generated by the aluminum processing industry, the semiconductor industry, the phosphating industry, the fertilizer industry and the like, as well as the geological characteristics of underground rock minerals and the weathering and leaching of certain fluorine-containing minerals such as amphiboles, apatites, micas and fluorites. The World Health Organization (WHO) stipulates that the optimal concentration of fluoride in drinking water is 0.5-1.5mg/L. The intake of trace amount of fluoride is beneficial to the healthy growth of human bones and teeth, but too high amount of fluoride causes various diseases such as thyroid diseases, nervous system diseases, fluorosis and the like.
The fluorine removal methods commonly used at present mainly comprise a chemical precipitation method, an adsorption method, an ion exchange method and the like. The traditional defluorination process mainly takes a limestone precipitation method as a main part, and the process mainly takes Ca 2+ And F - Formation of calcium fluoride precipitate reduces fluoride ion concentration, but CaF 2 Will be wrapped in Ca (OH) 2 The surface reduces the precipitation efficiency, and the concentration of the fluorine-containing wastewater is difficult to reduce to 1.5mg/L.
In recent years, researches show that certain metal oxides, hydroxides, phosphates and the like have high anion adsorption capacity, and the treated objects are mainly H 2 AsO 4 - 、HAsO 4 2- 、H 2 PO 4 - 、H 2 PO 4 2- 、F - Ions and the like, wherein zirconium and lanthanum oxides have good removal effect on fluorine. Zirconium salts have been developed and utilized in adsorption because of their large specific surface area, high thermal stability, water resistance and easy precipitation.Lanthanum salts are generally used as active materials for adsorbing fluoride ions because lanthanum metal has a low atomic potential and a high basicity, so that hydrated lanthanum oxide has a positive charge and a strong anion adsorption capacity, however, pure lanthanum oxide has the defects of difficult regeneration and dissolution of lanthanum ions.
Based on the method, zirconium and lanthanum metal are combined with phosphate ions to prepare the porous zirconium phosphate lanthanum fluorine removal material adsorption material, so that the fluorine removal efficiency is high, and the porous zirconium phosphate lanthanum fluorine removal material adsorption material has good chemical stability and cyclic regeneration performance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a porous zirconium lanthanum phosphate fluorine removal material and a preparation method and application thereof. The method mainly uses zirconium oxychloride as a zirconium source, lanthanum nitrate as a lanthanum source, diammonium hydrogen phosphate as a phosphorus source and hexadecyl trimethyl ammonium bromide as a template agent, and prepares the porous zirconium lanthanum phosphate fluorine removal material with high specific surface area through high-temperature precipitation, filtering, washing, drying and roasting, and the porous zirconium lanthanum phosphate fluorine removal material has a stable mesoporous structure and high specific surface area and can be used as an efficient fluorine removal agent. The porous lanthanum zirconium phosphate fluorine removal material obtained by the method has the advantages of uniform element distribution, high specific surface area, many active sites, strong adsorption capacity, high adsorption capacity for fluorine ions, cyclic use and great application value in the field of fluorine-containing water purification.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in one aspect, the invention provides a porous lanthanum zirconium phosphate fluorine removal material, which comprises the following raw material components in parts by weight: zirconium oxychloride, lanthanum nitrate, diammonium hydrogen phosphate, ammonium carbonate and a template agent, wherein the addition amounts of the zirconium oxychloride and the lanthanum nitrate are recorded in terms of mol ratio Zr 4+ :La 3+ ＝1:(0.3-3)。
Preferably, the addition amounts of the zirconium oxychloride and the lanthanum nitrate are expressed by mol ratio Zr 4+ :La 3+ ＝2:1。
Preferably, the specific surface area of the porous lanthanum zirconium phosphate fluorine removal material is 450-455 m 2 Per g, pore volume of 0.078cm 3 G, average pore size 1.5 ℃2.0nm。
Preferably, the templating agent is selected from cetyltrimethylammonium bromide.
On the other hand, the invention provides a preparation method of the porous lanthanum zirconium phosphate fluorine removal material, which comprises the following steps:
(1) Dissolving zirconium oxychloride and ammonium carbonate in deionized water to prepare a solution A, dissolving diammonium hydrogen phosphate in deionized water to prepare a solution B, and dissolving lanthanum nitrate in deionized water to prepare a solution C;
(2) Slowly dripping the solution B into the solution A, stirring for 10-30 minutes, dripping the solution C, and stirring for 10-30 minutes until the solution is clear; then adding a template agent, and stirring for 1-2 hours to obtain a mixed solution D;
(3) And pouring the mixed solution D into a sealed polyethylene bottle, placing the mixed solution D at the temperature of 80-90 ℃ for precipitation for 72-84 h, filtering, washing and drying a product after complete precipitation, and roasting the product at the temperature of 500-600 ℃ for 3-5 h to obtain the porous zirconium lanthanum phosphate fluorine removal material with high specific surface area.
Preferably, in the step (3), the temperature for heating and precipitating is 85 ℃, and the reaction time is 72h.
Preferably, in the step (3), the high-temperature calcination temperature is 550 ℃ and the calcination time is 3h.
In another aspect, the present invention provides an application of a porous lanthanum zirconium phosphate fluorine removal material in the treatment of fluorine ions in water, including: adding the porous lanthanum zirconium phosphate fluorine-removing material into a fluorine-containing water solution, and placing the fluorine-containing water solution in a constant-temperature shaking table to shake so as to remove fluorine ions.
Preferably, the shaking is carried out by adopting a constant-temperature constant-humidity gas bath shaking table, the shaking frequency is 160-180rpm, the shaking time is 2 hours, and the shaking temperature is 25 ℃.
Preferably, the fluorine-containing aqueous solution is an acidic or neutral system, and the addition amount of the porous zirconium lanthanum phosphate fluorine removal material is 0.2-2.0g/L. Further, the optimal dosage of the porous lanthanum zirconium phosphate fluorine removal material is 0.85g/L.
Preferably, the porous lanthanum zirconium phosphate fluorine removal material which is saturated after being used in an adsorption mode is added into a solution with the concentration of 0.01-0.5mol/LNaOH, the solution is vibrated at room temperature, the regeneration can be completed through desorption reaction for 24 hours, deionized water is used for cleaning the solution to be neutral after the desorption, and the porous lanthanum zirconium phosphate fluorine removal material after the desorption can be recycled.
Compared with the prior art, the invention has the following beneficial effects:
1. the concentration of fluorine-containing wastewater is difficult to reduce to 1.5mg/L by the traditional fluorine removal process at present, and the fluorine-containing wastewater cannot be recycled, the porous zirconium lanthanum phosphate fluorine removal material prepared by the invention has good regeneration cycle performance, and 78% removal rate can be still ensured after 6 times of cyclic adsorption in fluorine-containing solution with the initial concentration of 5mg/L.
2. The porous zirconium lanthanum phosphate fluorine removal material prepared by the invention has larger specific surface area, uniform and stable mesoporous structure and maximum specific surface area of 455.15m 2 The maximum adsorption capacity of the prepared porous lanthanum zirconium phosphate defluorination material reaches 95.15mg/g, and the adsorption can reach balance in 50 min.
3. The preparation method disclosed by the invention is simple in process and low in cost, and meets the environmental requirements.
Drawings
FIG. 1 is a scanning electron micrograph and an elemental mapping of a porous lanthanum zirconium phosphate fluorine removal material in example 2 of the present invention; wherein, fig. 1a is a scanning electron micrograph, and fig. 1b is an element mapping chart;
FIG. 2 is a transmission electron microscope of the porous lanthanum zirconium phosphate defluorination material in example 2 of the present invention;
FIG. 3 is a graph showing the fluorine removal performance of the porous lanthanum zirconium phosphate fluorine removal material with different ratios in example 3 of the present invention;
FIG. 4 is a graph showing the effect of contact time on the fluorine removal performance of the porous lanthanum zirconium phosphate fluorine removal material in example 4 of the present invention;
FIG. 5 is a graph showing the test of the influence of the initial concentration on the fluorine removal performance of the porous lanthanum zirconium phosphate fluorine removal material in example 5 of the present invention;
FIG. 6 is a graph showing the performance of the regeneration cycle of the porous lanthanum zirconium phosphate defluorination material in example 6 of the present invention; fig. 6a shows the influence of NaOH solutions with different concentrations as the desorption solution on the adsorption efficiency of the porous lanthanum zirconium phosphate fluorine removal material, and fig. 6b shows the influence of different recycling times on the adsorption efficiency of the porous lanthanum zirconium phosphate fluorine removal material;
FIG. 7 is a graph showing the application result of the porous lanthanum zirconium phosphate fluorine removal material in practical fluorine-containing water according to application example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with the specific examples, but the present invention should not be construed as being limited thereto, and only by way of example.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are either commercially available from conventional sources or are prepared in conventional manners.
Example 1
A preparation method of a porous zirconium lanthanum phosphate fluorine removal material adsorbent with a high specific surface area comprises the following steps:
respectively weighing 1.79g of zirconium oxychloride and 3.78g of ammonium carbonate to dissolve in 40ml of deionized water, then weighing 1.47g of diammonium hydrogen phosphate to dissolve in 30ml of deionized water, then weighing a certain amount of lanthanum nitrate to dissolve in 30ml of deionized water, respectively stirring on a constant-temperature magnetic stirrer for 20min until the solution is clear, then mixing and stirring the solution until the solution is clear, and adding 0.61g of hexadecyl trimethyl ammonium bromide to continuously stir for 2h until the solution is completely dissolved. The contents of zirconium oxychloride and lanthanum nitrate are expressed in terms of molar ratio Zr 4+ :La 3+ 0.3, 1, 0.5, 1, 2, 1. Covering the obtained solution with a cover, placing the solution in an oven at 85 ℃, keeping the temperature for 72 hours for complete precipitation and cooling, filtering, washing with deionized water, drying, and calcining at 550 ℃ for 3 hours to obtain the porous zirconium lanthanum phosphate defluorination material.
The BET specific surface area analysis was carried out on the porous lanthanum zirconium phosphate fluorine-removing material prepared as described above, and the obtained parameters are shown in Table 1.
Example 2
The structure and the performance of the porous lanthanum zirconium phosphate fluorine removal material are as follows:
on the basis of zirconium phosphate, porous lanthanum zirconium phosphate fluoride-removing materials with different specific surface areas can be obtained by changing the doping amount of lanthanum nitrate, so that the optimal proportion is further obtainedAnd a better adsorption effect is achieved. Zr obtained from example 1 4+ :La 3+ When the mixture ratio is 2 2 (iv) g. The scanning electron microscope picture of the porous zirconium lanthanum phosphate fluorine-removing material is shown in figure 1, and the transmission electron microscope picture is shown in figure 2, so that the porous zirconium lanthanum phosphate fluorine-removing material is spherical, rough in appearance and provided with gaps. Obviously, the porous structure can provide more adsorption sites, which is more beneficial to F - Bonded and reinforced porous lanthanum zirconium phosphate fluorine removal material pair F - Adsorption efficiency and adsorption capacity.
Example 3
The fluorine removal performance of the porous lanthanum zirconium phosphate fluorine removal material with different proportions is as follows:
weighing porous lanthanum zirconium phosphate fluorine-removing material (taking Zr according to molar ratio) with different proportions 4+ : La 3+ 1, 2, 1):
wherein q is t Is the equilibrium adsorption capacity of the adsorbent of unit mass in t time, mg/g; c 0 Initial fluoride ion concentration, mg/L; c t The concentration of the fluorinion after t time of adsorption is mg/L; v is the volume of the fluorine ion solution, mL; and m is the mass of the porous zirconium lanthanum fluoride removal material, and g.
The results are shown in FIG. 3, from which it can be seen that in Zr 4+ :La 3+ The adsorption capacity is maximized when the ratio is 2 4+ And La 3+ Form a stable structural framework with phosphate ions, but with La 3+ The increase in the content appears to be non-framework La 3+ The excess affects the formation of the porous structure.
Example 4
Influence of contact time on fluorine removal performance of the porous lanthanum zirconium phosphate fluorine removal material:
0.3g of porous lanthanum zirconium phosphate defluorination material (Zr) 4+ :La 3+ The formulation of (2) was added to 500mL of fluoride ion solution with pH =3 and different initial concentrations (5 and 10 mg/L), shaken at constant temperature at 25 ℃, 30mL of sample was taken every 10min, and the adsorbed amount was measured according to the formula (1), and the results are shown in fig. 4. As can be seen from the figure, the adsorption capacity gradually increased over time up to equilibrium. When the initial concentration is 5mg/L and 10mg/L, the equilibrium time of the porous zirconium lanthanum phosphate fluorine removal material is about 50min and 80min, and the corresponding adsorption capacity is 7.14 mg/g and 13.88mg/g respectively.
Example 5
Influence of initial concentration on fluorine removal performance of the porous lanthanum zirconium phosphate fluorine removal material:
in order to investigate the influence of different fluoride ion concentrations on the adsorption performance of the porous lanthanum zirconium phosphate fluoride removal material, 0.03g of lanthanum zirconium phosphate (Zr) 4+ :La 3+ The mixture ratio of (2). It can be seen from the figure that the adsorption capacity of the porous zirconium lanthanum phosphate fluorine removal material is increased along with the increase of the initial fluoride ion concentration, because the higher the concentration of fluoride ions, the higher the combination efficiency of the fluoride ions and the porous zirconium lanthanum phosphate fluorine removal material is, the higher the adsorption efficiency is.
Example 6
The regeneration cycle performance of the porous lanthanum zirconium phosphate fluorine removal material is as follows:
adopting NaOH solutions with different concentrations of 0.01, 0.05, 0.1, 0.2 and 0.5mol/L as analysis solutions to remove the fluoride (Zr) from the porous lanthanum zirconium phosphate which is saturated in adsorption 4+ :La 3+ The preparation ratio of (1) is 2), soaking for 12h, cleaning with deionized water, filtering, drying, then continuously adding into 50mL of a fluorine ion solution with pH =3 and concentration of 5mg/L, carrying out a re-adsorption experiment, shaking at a constant temperature of 25 ℃, adsorbing for 2h, then calculating according to the formula (1), and then repeating the experiment. The regeneration cycle performance of the porous lanthanum zirconium phosphate fluorine removal material is shown in figure 6. As can be seen from the figure, the adsorption performance is substantially unchanged even though 6After the secondary circulation, the adsorption efficiency can still maintain 78%.
Comparative example 1
Table 2 compares the performance of the zirconium-based oxide for adsorbing fluoride ions in water. As can be seen from the table, the prepared porous lanthanum zirconium phosphate fluorine removal material has relatively high adsorption performance on fluorine ions in water, which is probably due to Zr 4+ And La 3+ The porous lanthanum zirconium phosphate fluoride removal material has strong affinity for fluorine ions, and the internal porous structure provides more adsorption sites for the fluorine ions, so that the adsorption performance of the porous lanthanum zirconium phosphate fluoride removal material on fluorine is improved.
Application example 1
In order to test the application of the adsorption material in the actual fluorine-containing water, a water well in the high-fluorine area of phosphorite town of Zhongxiang city, jingmen, hubei province is selected. Due to the rapid development of the local phosphorus chemical industry, the problem of fluorine pollution of groundwater in the area has become more and more serious. Analysis of fluorine-containing groundwater using ICP-MS showed fluoride concentration in the groundwater sample (initial pH 7.6, fluoride concentration 2.94 mg/L) and the groundwater quality index is shown in table 3. Using porous lanthanum zirconium phosphate fluorine removal material (Zr) weighed in different doses of 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14 and 0.15g 4+ :La 3+ The ratio of (1) is 2), 50mL of actual fluorine-containing water is added, the mixture is shaken at constant temperature at 25 ℃, after 2 hours of adsorption, the adsorption quantity is measured according to the formula (1), and the result is shown in figure 7. As the adsorbent dosage increased, the fluoride concentration decreased and the residual fluoride concentration after adsorption equilibration decreased from 2.94mg/L to 0.33mg/L. When the dosage of the adsorbent is 0.05g, the concentration of residual fluoride after adsorption equilibrium is 0.74mg/L, the concentration of fluorine ions can be effectively reduced to be below 1.0mg/L, and an assistant is provided for the applicability and feasibility of the porous lanthanum zirconium phosphate fluorine removal material for removing fluoride in water.
The BET analysis and specific surface area parameters of the porous zirconium lanthanum phosphate fluorine removal material prepared by the method with different zirconium lanthanum ratios are shown in Table 1.
TABLE 1
TABLE 2
TABLE 3
It should be noted that the above-described embodiments are only preferred embodiments of the present invention, and it is apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, and that the present invention can be embodied in any other specific form without departing from the spirit or essential characteristics thereof. Thus, the present embodiments are merely exemplary and non-limiting. The scope of the invention is indicated by the appended claims rather than the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The porous zirconium lanthanum phosphate fluorine removal material is characterized by comprising the following raw material components: zirconium oxychloride, lanthanum nitrate, diammonium hydrogen phosphate, ammonium carbonate and a template agent, wherein the addition amounts of the zirconium oxychloride and the lanthanum nitrate are calculated by Zr according to molar ratio 4+ :La 3+ ＝1:(0.3-3)。
2. The preparation method of the porous lanthanum zirconium phosphate fluorine removal material according to claim 1, characterized in that: the addition amounts of the zirconium oxychloride and the lanthanum nitrate are based on the molar ratio of Zr 4+ :La 3+ ＝2:1。
3. The porous lanthanum zirconium phosphate fluorine removal material of claim 1, wherein: the specific surface area of the porous lanthanum zirconium phosphate fluorine removal material is 450-455 m 2 Per g, pore volume of 0.078cm 3 (g) the average pore diameter is 1.5-2.0 nm.
4. The porous lanthanum zirconium phosphate fluoride removal material of claim 1, wherein: the template agent is selected from cetyl trimethyl ammonium bromide.
5. The preparation method of the porous lanthanum zirconium phosphate fluorine-removing material as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
(1) Dissolving zirconium oxychloride and ammonium carbonate in deionized water to prepare a solution A, dissolving diammonium hydrogen phosphate in deionized water to prepare a solution B, and dissolving lanthanum nitrate in deionized water to prepare a solution C;
(2) Slowly dripping the solution B into the solution A, stirring for 10-30 minutes, dripping the solution C, and stirring for 10-30 minutes until the solution is clear; then adding a template agent, and stirring for 1-2 hours to obtain a mixed solution D;
(3) And pouring the mixed solution D into a sealed polyethylene bottle, placing the mixed solution D at the temperature of 80-90 ℃ for precipitation for 72-84 h, filtering, washing and drying a product after complete precipitation, and roasting the product at the temperature of 500-600 ℃ for 3-5 h to obtain the porous zirconium lanthanum phosphate fluorine removal material with high specific surface area.
6. The preparation method of the porous lanthanum zirconium phosphate fluorine removal material according to claim 5, characterized in that: in the step (3), the temperature for heating and precipitating is 85 ℃, and the reaction time is 72h.
7. The preparation method of the porous lanthanum zirconium phosphate fluorine removal material according to claim 5, characterized in that: in the step (3), the high-temperature roasting temperature is 550 ℃, and the roasting time is 3 hours.
8. The use of the porous lanthanum zirconium phosphate fluorine removal material of any one of claims 1 to 4 in the treatment of fluoride ions in water, comprising: adding the porous lanthanum zirconium phosphate fluorine-removing material into a fluorine-containing water solution, and placing the fluorine-containing water solution in a constant-temperature shaking table to shake so as to remove fluorine ions.
9. Use according to claim 8, characterized in that: the fluorine-containing aqueous solution is an acidic or neutral system, and the addition amount of the porous zirconium lanthanum phosphate fluorine removal material is 0.2-2.0g/L.
10. Use according to claim 8, characterized in that: adding the porous lanthanum zirconium phosphate defluorination material which is used and is saturated in adsorption into a solution with the concentration of 0.01-0.5mol/LNaOH, oscillating at room temperature, completing regeneration after 24h of desorption reaction, washing with deionized water to be neutral after desorption, and recycling the porous lanthanum zirconium phosphate defluorination material after desorption.
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| JP2011194335A (en) * | 2010-03-19 | 2011-10-06 | Toda Kogyo Corp | Method for treating fluorine ion-containing wastewater by fluorine adsorbent |
| CN102389769A (en) * | 2011-08-15 | 2012-03-28 | 武汉理工大学 | Preparation method of calcium-aluminum-lanthanum-based compound fluorine-removing material |
| CN111330550A (en) * | 2020-03-27 | 2020-06-26 | 神华神东煤炭集团有限责任公司 | Zr/La co-modified cross-linked chitosan, preparation method and application thereof |
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| JP2011194335A (en) * | 2010-03-19 | 2011-10-06 | Toda Kogyo Corp | Method for treating fluorine ion-containing wastewater by fluorine adsorbent |
| CN102389769A (en) * | 2011-08-15 | 2012-03-28 | 武汉理工大学 | Preparation method of calcium-aluminum-lanthanum-based compound fluorine-removing material |
| CN111330550A (en) * | 2020-03-27 | 2020-06-26 | 神华神东煤炭集团有限责任公司 | Zr/La co-modified cross-linked chitosan, preparation method and application thereof |
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