CN112675810A - Amorphous high-efficiency phosphorus removal adsorption material, preparation method and water treatment application thereof - Google Patents
Amorphous high-efficiency phosphorus removal adsorption material, preparation method and water treatment application thereof Download PDFInfo
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Abstract
An amorphous high-efficiency dephosphorization adsorption material and a preparation method and application thereof, belonging to the technical field of water treatment material preparation. The invention mainly aims at the problems of limited removal amount, complex preparation and the like of the existing dephosphorization adsorbing material, and aims to construct the amorphous efficient dephosphorization adsorbing material which has high saturated adsorption capacity, stable pH and is not influenced by water quality by using a one-pot reaction and taking a natural clay mineral material as a substrate and co-loading amorphous cerium carbonate and ferrous carbonate nano particles on the surface of the structure. The preparation method mainly comprises the following steps: adding a natural clay mineral material, a cerium salt, an iron salt and urea into water, stirring for 0.5-10 h, and adding a reducing agent; and continuously stirring for 0.3-2 h to uniformly mix, continuously stirring at 60-100 ℃ for reaction for 2-24 h, after the reaction is finished, performing solid-liquid separation and cleaning on the product for several times, and then drying in an oven at 40-80 ℃. The preparation method has the advantages of simple preparation process, convenient operation, easily obtained raw materials and better application prospect.
Description
Technical Field
The invention belongs to the technical field of water treatment material preparation, and particularly relates to an amorphous high-efficiency phosphorus removal adsorption material, a preparation method thereof and water treatment application.
Background
It is well known that eutrophication of water bodies causes mass propagation of algae, depletion of oxygen in the water, death of biological organisms and disruption of aquatic ecological balance. Among them, excessive nitrogen and phosphorus are the main causes of water eutrophication. Research generally considers that the over-standard phosphorus content is a decisive factor for causing eutrophication of water bodies, so that the phosphorus removal of the water bodies is crucial to the control of the eutrophication. The adsorption-based dephosphorization method has the advantages of simple operation, high efficiency and the like, and is concerned in a plurality of dephosphorization methods.
Cerium is the element with the highest abundance in rare earth elements, has a unique 4f electronic structure, can form a complex with a Lewis base substance functional group, and has a special adsorption effect on phosphate ions. Because nanoparticles are easy to agglomerate, a large number of active sites are difficult to utilize, so in order to realize the maximum utilization of cerium-based active adsorption sites, at present, cerium nanoparticles are mainly loaded on various carriers to realize the dispersion of cerium nanomaterials and strengthen the contact and adsorption of the cerium nanoparticles on phosphate radicals. In general, the characteristics of the support material can affect the loading of the nanoparticles, which in turn affects the adsorption of contaminants by the composite adsorbent material. At present, documents report that orange peel, chitosan, lignin or biochar are used as carriers, and loaded cerium ions, cerium oxide or cerium hydroxide are used as phosphorus removal adsorption materials. However, most of them have the disadvantages of complicated preparation, low adsorption capacity, poor removal effect in low-concentration phosphorus environment, poor pH stability or easy interference of coexisting ions, and the like, and the application of the phosphorus removal catalyst in the aspect of actual water body phosphorus removal is severely limited.
Some natural clay mineral materials, such as sepiolite, attapulgite, halloysite, bentonite, diatomite, kaolin and the like, are abundant in reserves and low in price, have high cation exchange performance and large specific surface area, and are often used as high-quality catalyst carriers and adsorption materials. In water environment, the natural clay mineral material has very limited removal amount of phosphate because the surface of the natural clay mineral material has higher net negative charge, so that the natural clay mineral material is difficult to combine with phosphate anions with negative charges.
Disclosure of Invention
The invention aims to solve the problems of limited removal amount, complex preparation, high preparation cost, poor pH stability and the like of the existing phosphorus removal adsorbing material, and provides an amorphous high-efficiency phosphorus removal adsorbing material, a preparation method and water treatment application thereof. The cerium-iron nano particles loaded on the adsorbing material are in an amorphous structure, have more defect sites and larger specific surface area, and can provide a large number of active sites. The adsorbing material prepared by the method has excellent phosphorus removal performance, simple process steps, used equipment and specific implementation, environmental friendliness, low price of raw materials, easiness in obtaining and good application prospect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the phosphorus removal adsorption material is formed by compounding amorphous cerium carbonate and ferrous carbonate nanoparticles and a natural clay mineral material, wherein the amorphous cerium carbonate and ferrous carbonate nanoparticles are attached to the structural surface of the natural clay mineral material.
A preparation method of the amorphous high-efficiency phosphorus removal adsorption material comprises the following steps: adding untreated natural clay mineral material, cerium salt, ferric salt and urea into water, stirring for 0.5-10 h, and adding a reducing agent; and then, continuously stirring for 0.3-2 h to uniformly mix, stirring at 60-100 ℃ for reaction for 2-24 h, after the reaction is finished, performing solid-liquid separation and cleaning on a product, and drying at 40-80 ℃ to obtain the amorphous efficient phosphorus removal adsorbing material.
An application of the amorphous high-efficiency dephosphorization adsorption material prepared by the method in removing phosphorus in various water bodies.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method has the advantages of simple preparation process, convenient operation, easily obtained raw materials and better application prospect;
(2) the cerium-iron co-modified natural clay mineral efficient phosphorus removal adsorption material prepared by the invention has a large specific surface area, amorphous cerium-iron nano particles are uniformly distributed and have small sizes, and the surface has many defects, so that the adsorption is facilitated;
(3) the amorphous cerium-iron co-modified natural clay mineral efficient phosphorus removal adsorbing material prepared by the invention has the advantages of excellent phosphorus removal effect, stronger selectivity, higher adsorption capacity, higher adsorption rate, wide pH application range and better removal effect on low-concentration phosphorus.
(4) The invention takes untreated natural clay mineral material as a carrier, and the amorphous cerium-iron nano particles are loaded on the carrier together, thereby not only realizing the dispersion of the cerium nano particles, reasonably utilizing cerium active sites and reducing the dosage of cerium element, but also improving the defect of phosphorus removal performance of the original natural clay mineral material. The co-doping of the cheap iron element can further reduce the dosage of cerium in the composite adsorbing material and reduce the cost of the cerium-iron co-modified natural clay mineral efficient dephosphorization adsorbing material.
Drawings
FIG. 1 is an XRD (X-ray diffraction) diagram of raw sepiolite, the amorphous high-efficiency phosphorus removal adsorption material obtained in example 2 and example 3;
FIG. 2 is an SEM image of the efficient phosphorus removal adsorbent made of amorphous cerium-iron co-modified sepiolite obtained in example 3;
FIG. 3 is a FTIR chart of efficient dephosphorization adsorbent material of original sepiolite and amorphous cerium-iron co-modified sepiolite obtained in example 3;
FIG. 4 is a graph showing the kinetics of phosphorus adsorption of the phosphorus removal adsorbent obtained in example 3;
FIG. 5 is a graph showing isothermal adsorption for removing phosphorus from the phosphorus removal adsorbent obtained in example 3;
FIG. 6 is a graph showing the phosphorus removal effect of the phosphorus removal adsorbent obtained in example 3 at different pH values;
FIG. 7 is a graph showing the phosphorus removal effect of the phosphorus removal adsorbent obtained in example 3 under different coexisting ions;
Detailed Description
The technical solution of the present invention is further described below by the drawings and examples, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
According to the invention, a natural clay mineral material, a cerium salt, an iron salt, urea and an ascorbic acid solution are uniformly mixed according to a certain proportion, and the amorphous cerium carbonate and ferrous carbonate nanoparticle co-loaded natural clay mineral composite adsorbing material is successfully prepared through a simple one-pot reaction. The adsorbing material keeps the special framework structure of a natural clay mineral material, realizes the uniform dispersion of amorphous cerium carbonate and ferrous carbonate nanoparticles, greatly improves the phosphorus removal performance of the original natural clay mineral material, and has the saturated adsorption capacity of 50-73.68 mg-P/g for phosphate anions. Meanwhile, the preparation method has the advantages of low energy consumption, simple operation, no special equipment, good reproducibility and the like, and has good application prospect.
The first embodiment is as follows: the embodiment describes an amorphous high-efficiency phosphorus removal adsorption material, which is formed by compounding amorphous cerium carbonate and ferrous carbonate nanoparticles with a natural clay mineral material, wherein the amorphous cerium carbonate and ferrous carbonate nanoparticles are attached to the structural surface of the natural clay mineral material and can selectively adsorb phosphate in water, so that the high-efficiency removal of phosphorus in water is realized.
The second embodiment is as follows: in a specific embodiment of the amorphous high-efficiency phosphorus removal adsorption material, the natural clay mineral material is one or more of calcium-rich sepiolite, magnesium-rich sepiolite, halloysite, attapulgite, bentonite, diatomite and kaolin, and is preferably magnesium-rich sepiolite.
The third concrete implementation mode: a method for preparing an amorphous high efficiency phosphorus removal adsorbent material according to the first or second embodiment, the method comprises the following steps: adding untreated natural clay mineral material, cerium salt, ferric salt and urea into water, stirring for 0.5-10 h, and adding a reducing agent; and then, continuously stirring for 0.3-2 hours to uniformly mix the materials, stirring at 60-100 ℃ for reaction for 2-24 hours, carrying out solid-liquid separation and cleaning on a product after the reaction is finished, and drying at 40-80 ℃ to obtain the efficient dephosphorization adsorbing material with the functional component being the amorphous cerium-iron nano particles. The material obtained by the invention can effectively remove phosphorus with different concentrations in raw water, tail water and various surface waters of a sewage treatment plant, and has the following unique characteristics: (1) the pH application range is wide, and the pH-sensitive adhesive can be effectively applied under the pH value of 3-10; (2) the specific adsorption capacity of phosphate radical is stronger, and the saturated adsorption capacity of phosphorus can reach 73.68 mg-P/g; (3) faster phosphorus adsorption removal rate.
The fourth concrete implementation mode: in the preparation method of the amorphous high-efficiency phosphorus removal adsorption material according to the third embodiment, the cerium salt is one or more of cerium chloride, cerium nitrate or a hydrate thereof, and preferably cerium nitrate hexahydrate; the iron salt is one or more of ferric chloride, ferric nitrate, ferric sulfate and hydrate thereof, and ferric chloride hexahydrate is preferred.
The fifth concrete implementation mode: in the preparation method of the amorphous high-efficiency phosphorus removal adsorption material according to the third embodiment, the molar ratio of the cerium salt to the iron salt is 3: 1-6, preferably 1: 1; based on the content of cerium ions, the mass ratio of the cerium salt to the natural clay mineral material is 0.03-1: 1, preferably 0.15: 1; the molar ratio of urea to the total amount of cerium salt and iron salt is 5-50: 1, preferably 25: 1.
the sixth specific implementation mode: in the third specific embodiment, the stirring mode is magnetic stirring or mechanical stirring, and the stirring speed is 300-1000 r/min.
The seventh embodiment: in the preparation method of the amorphous high-efficiency phosphorus removal adsorbing material according to the third embodiment, the reducing agent is one or more of ascorbic acid, hydrazine hydrate or citric acid, and the molar ratio of the reducing agent to the iron salt is 1-5.
The specific implementation mode is eight: in the preparation method of the amorphous high-efficiency phosphorus removal adsorbing material according to the third embodiment, the water bath temperature is 65-90 ℃, preferably 85 ℃, and the water bath reaction time is 2-12 hours, preferably 4 hours.
The specific implementation method nine: in the preparation method of the amorphous high-efficiency phosphorus removal adsorbing material according to the third specific embodiment, the solid-liquid separation is one of centrifugal separation, gravity settling and filtration separation.
The detailed implementation mode is ten: an application of the amorphous high-efficiency phosphorus removal adsorption material prepared by any one of the third to ninth specific embodiments in removing phosphorus in various water bodies.
Example 1:
dissolving 2.0g of 400-mesh attapulgite, 1.31g of cerous nitrate hexahydrate, 0.82g of ferric chloride hexahydrate and 9g of urea in 100mL of water, and stirring for 5 hours on a magnetic stirrer; after the solution is uniformly mixed, adding 1g of ascorbic acid into the solution, and continuously stirring the solution for 1 hour; then heating and stirring the mixture at 85 ℃ for reaction for 4 hours, and controlling the rotating speed to be 500 r/min. After the reaction is finished, the product is subjected to solid-liquid separation and washing for a plurality of times, and is dried for 12 hours at 50 ℃ to obtain the modified attapulgite high-efficiency dephosphorization adsorbing material with the functional component of amorphous cerium-iron nano particles.
Example 2:
dissolving 4g of sepiolite, 1.31g of cerous nitrate hexahydrate, 0.82g of ferric chloride hexahydrate and 9g of urea in 100mL of water, and stirring for 1h on a magnetic stirrer; after the solution is uniformly mixed, 1g of ascorbic acid is added into the solution, and the solution is continuously stirred for 0.5 h; then heating and stirring the mixture at 85 ℃ for reaction for 4 hours, and controlling the rotating speed to be 500 r/min. After the reaction is finished, the product is subjected to solid-liquid separation and cleaning for a plurality of times, and is dried for 12 hours at 50 ℃ to obtain the modified sepiolite high-efficiency dephosphorization adsorbing material with the functional component of amorphous cerium-iron nano particles.
Example 3:
2g of sepiolite, 1.31g of cerous nitrate hexahydrate, 0.82g of ferric chloride hexahydrate and 9g of urea are dissolved in 100mL of water and placed on a magnetic stirrer to be stirred for 1 hour; after the solution is uniformly mixed, 1g of ascorbic acid is added into the solution, and the solution is continuously stirred for 0.4 h; then heating and stirring the mixture at 85 ℃ for reaction for 4 hours, and controlling the rotating speed to be 500 r/min. After the reaction is finished, the product is subjected to solid-liquid separation and cleaning for a plurality of times, and is dried for 12 hours at 50 ℃ to obtain the modified sepiolite high-efficiency dephosphorization adsorbing material with the functional component of amorphous cerium-iron nano particles.
Example 4:
dissolving 2g of halloysite, 1.74g of cerium nitrate hexahydrate, 0.56g of ferric chloride hexahydrate and 7.2g of urea in 100mL of water, and mechanically stirring for 2 hours; after the solution is uniformly mixed, 0.65g of ascorbic acid is added into the solution, and the solution is continuously stirred for 0.5 h; then heating and stirring the mixture at 85 ℃ for reaction for 6 hours, and controlling the rotating speed to be 600 r/min. And after the reaction is finished, performing solid-liquid separation on the product, washing the product for a plurality of times by using water, and drying the product for 12 hours at 50 ℃ to obtain the modified halloysite high-efficiency dephosphorization adsorbing material with the functional components of amorphous cerium-iron nano particles.
Example 5:
2g of bentonite, 0.87g of cerous nitrate hexahydrate, 1.08g of ferric chloride hexahydrate and 9g of urea are dissolved in 100mL of water and mechanically stirred for 2 hours; after the solution is uniformly mixed, adding 1.25g of ascorbic acid into the solution, and continuously stirring the solution for 1 hour; then heating and stirring the mixture at 85 ℃ for reaction for 6 hours, and controlling the rotating speed to be 600 r/min. And after the reaction is finished, carrying out solid-liquid separation on the product, washing the product for a plurality of times by using water, and drying the product for 12 hours at 50 ℃ to obtain the modified bentonite high-efficiency dephosphorization adsorbing material with the functional component of amorphous cerium-iron nano particles.
Example 6:
2g of bentonite, 1.74g of cerous nitrate hexahydrate, 1.08g of ferric chloride hexahydrate and 12g of urea are dissolved in 100mL of pure water and placed on a magnetic stirrer to be stirred for 2 hours; after the solution is uniformly mixed, adding 1.25g of ascorbic acid into the solution, and continuously stirring the solution for 1 hour; then heating and stirring the mixture at 85 ℃ for reaction for 6 hours, and controlling the rotating speed to be 600 r/min. And after the reaction is finished, carrying out solid-liquid separation on the product, washing the product for a plurality of times by using water, and drying the product for 12 hours at 50 ℃ to obtain the modified bentonite high-efficiency dephosphorization adsorbing material with the functional component of amorphous cerium-iron nano particles.
The technical solution of the present invention is not limited thereto, and other embodiments are not listed herein.
Fig. 1 is an XRD chart of the raw sepiolite, the amorphous cerium-iron co-modified sepiolite natural clay mineral high-efficiency phosphorus removal adsorption material prepared in example 2 and example 3, and it can be known that the crystal structure of the cerium-iron nanoparticle co-modified sepiolite natural clay mineral high-efficiency phosphorus removal adsorption material obtained in example 2 and example 3 is consistent with that of the raw sepiolite. This shows that the loaded cerium carbonate and ferrous carbonate particles are in an amorphous structure, and the co-loading of the cerium and iron nanoparticles only enables the intensity of each diffraction peak of the sepiolite to show a certain descending trend.
Fig. 2 is an SEM image of the cerium-iron co-modified sepiolite natural clay mineral high-efficiency phosphorus removal adsorbent material obtained in example 3, and it can be seen that the obtained phosphorus removal adsorbent material is composed of nanofiber rods and nanoparticles. The nano fiber rod is sepiolite carrier, the nano particles are amorphous cerium-iron nano particles, and the nano particles are unevenly attached to the surface of the fiber rod-shaped structure.
FIG. 3 is a comparison graph of infrared spectra of raw sepiolite and the cerium-iron co-modified sepiolite natural clay mineral high-efficiency dephosphorization adsorbing material obtained in example 3, and it can be seen that after loading cerium-iron nanoparticles, the concentration of cerium-iron nanoparticles is 1500cm-1In the vicinity, a triple characteristic absorption peak of carbonate appears in the obtained phosphorus removal material, which indicates that the loaded cerium and iron nanoparticles are metal carbonate compounds, and the loaded cerium and iron nanoparticles are a mixture of cerium carbonate and ferrous carbonate in combination with preparation conditions.
The invention aims to investigate the advantages and beneficial achievements of the cerium-iron co-modified natural clay mineral high-efficiency dephosphorization adsorbing material prepared by the embodiment through the following application examples:
application example 1:
the amorphous cerium-iron co-modified natural clay mineral materials prepared in the above examples 1, 2, 3, 4, 5 and 6 were added to 100ml of raw sewage which was filtered through a 0.45 μm glass fiber filter membrane in an amount of 0.5g/L, and the mixture was placed in a constant temperature shaking table and subjected to oscillatory adsorption at 25 ℃ and 200r/min for 2 hours to measure the concentration of the residual phosphate radical in the solution. The properties of the membrane-passing domestic sewage are shown in table 1, and the removal effect of the prepared amorphous cerium-iron co-modified natural clay mineral material on phosphorus is shown in table 2. As shown in the table, although the domestic sewage is complex in composition, more types of coexisting ions and higher in concentration, the prepared amorphous cerium-iron co-modified natural clay mineral material has stronger adsorption capacity on phosphate anions, after two-hour treatment, more than 91% of phosphate can be removed, and for the adsorption material with high cerium content, the removal rate of the phosphate can further reach 99.8%.
TABLE 1 quality characteristic table of raw domestic sewage (0.45 μm through glass fibre filter)
| Ion species | pH | TOC | Cl- | NO3 - | SO4 2- | PO4 3- | Na+ | K+ | Ca2+ | Mg2+ |
| Content (mg/L) | 7.32 | 189.2 | 154.3 | 26.27 | 541.2 | 4.87 | 153.2 | 42.6 | 49.8 | 61.2 |
TABLE 2 Table of the effect of the non-crystalline cerium-iron co-modified natural clay mineral highly effective phosphorus removal adsorption material on phosphorus removal
| Adsorbent material | Source | Phosphorus concentration in effluent (mg-P/L) | Removal Rate (%) |
| Cerium-iron co-modified attapulgite | Example 1 | <0.01 | 99.8 |
| Cerium-iron co-modified sepiolite | Example 2 | 0.34 | 93.0 |
| Cerium-iron co-modified sepiolite | Example 3 | <0.01 | 99.8 |
| Cerium-iron co-modified halloysite | Examples4 | <0.01 | 99.8 |
| Cerium-iron co-modified bentonite | Example 5 | 0.42 | 91.4 |
| Cerium-iron co-modified bentonite | Example 6 | <0.01 | 99.8 |
Application example 2:
the original sepiolite and the amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorbing material prepared in the example 3 are respectively added into two parts of initial phosphorus concentration C0KH of 10mg-P/L2PO4Adding 0.5g/L of phosphate into the aqueous solution, placing the aqueous solution in a constant-temperature shaking table, oscillating the aqueous solution at the temperature of 25 ℃ and the rotating speed of 200r/min, taking the solution at a certain time interval to measure the residual concentration of the phosphate, and drawing a relation graph between the concentration of the phosphate in the solution and the adsorption time.
As shown in fig. 4, the concentration of phosphate in the solution added with the amorphous cerium-iron co-modified sepiolite high efficiency phosphorus removal adsorbing material continuously decreases with the passage of time. After the cerium and iron are added to co-modify the high-efficiency phosphorus removal adsorption material for 10min, the removal rate of phosphorus in the solution can reach 75 percent; after 2h, the removal rate of phosphorus is almost 100%; in contrast, sepiolite has a very limited ability to remove phosphorus, and only 3% of the phosphorus is removed by 2 hours of adsorption.
Application example 3:
the original sepiolite and the amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorbing material prepared in the example 3 are respectively added into two parts of initial phosphorus concentration C0KH of 5-100 mg-P/L2PO4Adding 0.2g/L of water solution into the water solution, placing the water solution in a constant temperature shaking table, and oscillating and adsorbing for 24 hours at the temperature of 25 ℃ and the rotating speed of 200 r/min.
As shown in FIG. 5, with the increase of the equilibrium phosphorus concentration, the adsorption capacity of the amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorption material firstly increases remarkably and then gradually approaches equilibrium, and the saturated adsorption capacity is 50.23 mg-P/g. The ICP-OES measurement result shows that the content of cerium in the dephosphorization adsorbing material is 14.13 wt%. Through calculation, the adsorption capacity of the amorphous cerium-iron co-modified sepiolite dephosphorization adsorbing material on phosphorus can reach 355.48mg-P/g Ce, and cerium sites are fully applied. In comparison, the original sepiolite has obviously insufficient adsorption capacity to phosphorus, and the saturated adsorption capacity is only 5.74 mg-P/g. Therefore, the co-modification of the amorphous cerium-iron metal carbonate greatly improves the adsorption capacity of the original sepiolite.
Application example 4:
the amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorbing material prepared in example 3 is respectively added to the initial phosphorus concentration C0Multiple parts of KH with the pH value of 2.43-11 and the concentration of 20mg-P/L2PO4In the water solution, the adding amount of the adsorbing material is 0.2g/L, the adsorbing material is placed in a constant temperature shaking table and is subjected to oscillation adsorption reaction for 24 hours at the temperature of 25 ℃ and the rotating speed of 200 r/min.
As shown in fig. 6, the change of the solution pH value has a small influence on the phosphorus removal performance of the prepared amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorbing material. Within a wider pH value range (3-10), the phosphorus removal material has excellent phosphorus removal performance, and the saturated adsorption capacity of the phosphorus removal material is hardly influenced by pH. The prepared amorphous cerium-iron co-modified sepiolite natural clay mineral high-efficiency phosphorus removal adsorbing material is suitable for various different water bodies, and the removal effect of the water bodies on phosphorus is not influenced by the acidity and alkalinity of the water bodies.
Application example 5:
the amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorbing material prepared in example 3 is respectively added to the initial phosphorus concentration C010mg-P/L, Cl-、NO3 -、HCO3 -、SO4 2-And Ca2+Ion concentration of more than 100mg/LPart of KH2PO4In the water solution, the adding amount of the adsorbing material is 0.2g/L, the adsorbing material is placed in a constant temperature shaking table and is subjected to oscillation adsorption reaction for 24 hours at the temperature of 25 ℃ and the rotating speed of 200 r/min.
As shown in fig. 7, even if the concentration of the coexisting ions in the solution is 10 times of the concentration of the phosphate anions, the phosphorus removal performance of the prepared amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorbing material is hardly affected by the coexisting ions, which indicates that the prepared phosphorus removal adsorbing material has high selectivity and anti-ion interference capability for the phosphate anions, and thus, the application of the phosphorus removal adsorbing material in practical water is facilitated.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and guidance of the specification. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. An amorphous high-efficiency phosphorus removal adsorbing material is characterized in that: the dephosphorization adsorbing material is formed by compounding cerium carbonate and ferrous carbonate nanoparticles with a natural clay mineral material, wherein the amorphous cerium carbonate and ferrous carbonate nanoparticles are attached to the structural surface of the natural clay mineral material.
2. The amorphous high-efficiency phosphorus removal adsorption material of claim 1, wherein: the natural clay mineral material is one or more of calcium-rich sepiolite, magnesium-rich sepiolite, halloysite, attapulgite, bentonite, diatomite and kaolin.
3. A method for preparing the amorphous high-efficiency phosphorus removal adsorbing material as claimed in claim 1 or 2, which is characterized in that: the method comprises the following steps: adding untreated natural clay mineral material, cerium salt, ferric salt and urea into water, stirring for 0.5-10 h, and adding a reducing agent; and then, continuously stirring for 0.3-2 h to uniformly mix, continuously stirring at 60-100 ℃ for reaction for 2-24 h, after the reaction is finished, performing solid-liquid separation and cleaning on the product, and drying at 40-80 ℃ to obtain the amorphous efficient dephosphorization adsorbing material.
4. The method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 3, wherein the method comprises the following steps: the cerium salt is one or more of cerium chloride, cerium nitrate or hydrate thereof; the ferric salt is one or more of ferric chloride, ferric nitrate, ferric sulfate and hydrate thereof.
5. The method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 3, wherein the method comprises the following steps: the molar ratio of the cerium salt to the iron salt is 3: 1-6; based on the content of cerium ions, the mass ratio of the cerium salt to the natural clay mineral material is 0.03-1: 1; the molar ratio of urea to the total amount of cerium salt and iron salt is 5-50: 1.
6. the method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 3, wherein the method comprises the following steps: the stirring mode is magnetic stirring or mechanical stirring, and the stirring speed is 400-1000 r/min.
7. The method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 3, wherein the method comprises the following steps: the reducing agent is one or more of ascorbic acid, hydrazine hydrate or citric acid, and the molar ratio of the reducing agent to the iron salt is 1-5.
8. The method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 3, wherein the method comprises the following steps: the reaction temperature is 60-100 ℃, and the reaction time is 2-24 h.
9. The method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 3, wherein the method comprises the following steps: the solid-liquid separation is one of centrifugal separation, gravity settling and filtration separation.
10. The application of the amorphous high-efficiency phosphorus removal adsorbing material prepared by any one of claims 3 to 9 in removing phosphorus in various water bodies.
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| CN113996268A (en) * | 2021-11-16 | 2022-02-01 | 太原理工大学 | Supported nano zero-valent iron and cerium adsorbent and synchronous nitrogen and phosphorus removal method thereof |
| CN116281913A (en) * | 2022-11-28 | 2023-06-23 | 昆明理工大学 | Preparation method of transparent to semitransparent massive inorganic material |
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| CN116281913A (en) * | 2022-11-28 | 2023-06-23 | 昆明理工大学 | Preparation method of transparent to semitransparent massive inorganic material |
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