CN112675810B - Amorphous high-efficiency phosphorus removal adsorption material and preparation method thereof and water treatment application - Google Patents

Abstract

An amorphous high-efficiency phosphorus removal adsorption material and a preparation method and application thereof belong to the technical field of water treatment material preparation. The invention mainly aims at the problems of limited removal amount and complicated preparation of the existing phosphorus removal adsorption materials. It is planned to use a natural clay mineral material as a substrate through a "one-pot method" reaction, and the amorphous cerium carbonate and ferrous carbonate nanoparticles are mixed together. It is loaded on the surface of its structure to construct an amorphous high-efficiency phosphorus removal adsorption material with high saturated adsorption capacity, stable pH and not affected by water quality. The main preparation steps are as follows: adding natural clay mineral materials, cerium salts, iron salts and urea into water, stirring for 0.5-10 hours and then adding a reducing agent; continuing to stir for 0.3-2 hours to make them evenly mixed, and then continuing at 60-100° C. Stir bar reaction for 2 to 24 hours. After the reaction, the product is separated from solid and liquid, washed several times, and then placed in an oven at 40 to 80 °C for drying. The preparation process of the invention is simple, the operation is convenient, the raw materials are easily obtained, and the invention has a good application prospect.

Description

Amorphous high-efficiency phosphorus removal adsorption material and preparation method thereof and water treatment application

technical field

The invention belongs to the technical field of water treatment material preparation, in particular to an amorphous ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorption material and a preparation method and application thereof.

Background technique

It is well known that eutrophication of water bodies can cause algal blooms, depletion of oxygen in water, death of biological organisms, and disruption of aquatic ecological balance. Among them, excess nitrogen and phosphorus are the main causes of water eutrophication. However, studies generally believe that excessive phosphorus content is the decisive factor for eutrophication in water bodies, so phosphorus removal from water bodies is very important to control eutrophication. Phosphorus removal by adsorption has attracted much attention among many phosphorus removal methods due to its advantages of simple operation and high efficiency.

Cerium is the most abundant element among rare earth elements, and has a unique 4f electronic structure, which can form complexes with functional groups of Lewis bases, and has an exclusive adsorption effect on phosphate ions. Due to the easy agglomeration of nanoparticles, it is difficult to utilize a large number of active sites. Therefore, in order to maximize the utilization of cerium-based active adsorption sites, the current main method is to load each cerium nanoparticle on various supports to realize the cerium nanomaterials. disperse, strengthen its contact and adsorption to phosphate. In general, the properties of the support material can affect the loading of nanoparticles, which in turn affects the adsorption of pollutants by composite adsorbents. At present, it has been reported in the literature that orange peel, chitosan, lignin or biochar are used as carriers, and cerium ions, cerium oxide or cerium hydroxide are supported as phosphorus removal adsorption materials. However, most of them have shortcomings such as complex preparation, low adsorption capacity, poor removal effect in low-concentration phosphorus environment, poor pH stability, or easy interference from coexisting ions, which seriously limit their application in practical water phosphorus removal.

Some natural clay mineral materials, such as sepiolite, attapulgite, halloysite, bentonite, diatomite, kaolin, etc., are not only abundant in reserves and low in price, but also often have higher cation exchange performance and larger ratio. surface area, and is often used as a high-quality catalyst carrier and adsorption material. In the water environment, due to the high net negative charge on the surface of these natural clay minerals, it is difficult for them to combine with the negatively charged phosphate anions. Therefore, the removal of phosphate by the original natural clay minerals is very limited.

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the problems of limited removal amount of existing phosphorus removal adsorption materials, complicated preparation, high preparation cost, poor pH stability, etc. Its preparation method and application. Since the loaded cerium iron nanoparticles have an amorphous structure, they have more defect sites and a larger specific surface area, which can provide a large number of active sites. The adsorption material prepared by the method has excellent phosphorus removal performance, and the process steps, the equipment used and the specific implementation are relatively simple, green and environmentally friendly, and the raw materials are cheap and easy to obtain, and has a good application prospect.

To achieve the above object, the technical scheme adopted by the present invention is as follows:

An amorphous high-efficiency phosphorus removal adsorbent, which specifically relates to an amorphous cerium-iron co-modified natural clay mineral high-efficiency phosphorus-removing adsorption material. The particles are composited with natural clay mineral materials, wherein amorphous cerium carbonate and ferrous carbonate nanoparticles are attached to the structural surface of the natural clay mineral materials.

A preparation method of the above-mentioned amorphous cerium-iron co-modified natural clay mineral high-efficiency phosphorus removal adsorption material, the method steps are as follows: adding untreated natural clay mineral material, cerium salt, iron salt and urea into water , stirring for a total of 0.5~10 h, and then adding the reducing agent; then continue stirring for 0.3~2 h to make it evenly mixed, and stirring for 2~24 h at 60~100 °C. The high-efficiency phosphorus removal adsorption material whose functional component is amorphous cerium iron nanoparticles can be obtained by drying.

An application of the above-prepared amorphous ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorption material in removing phosphorus in various water bodies.

The beneficial effects of the present invention relative to the prior art are:

(1) The preparation process of the present invention is simple, the operation is convenient, the raw materials are easily obtained, and the invention has a good application prospect;

(2) The ferric cerium co-modified natural clay mineral high-efficiency phosphorus removal adsorption material prepared by the present invention has a large specific surface area, and the amorphous ferric cerium nanoparticles are uniformly distributed, small in size, and have many defects on the surface, which is conducive to adsorption ;

(3) The amorphous cerium-iron co-modified natural clay mineral high-efficiency phosphorus removal adsorption material prepared by the present invention has excellent phosphorus removal effect, strong selectivity, high adsorption capacity and fast adsorption rate, and a wide range of pH adaptability , and has a good removal effect on low-concentration phosphorus.

(4) The present invention uses untreated natural clay mineral material as a carrier, and co-loads amorphous cerium iron nanoparticles on it, which can realize the dispersion of cerium nanoparticles, rationally utilize cerium active sites, and reduce cerium elements. It can also improve the deficiency of the phosphorus removal performance of the original natural clay mineral material. The co-doping of cheap iron elements can further reduce the amount of cerium in the composite adsorption material, and reduce the cost of the invented high-efficiency phosphorus removal adsorption material of cerium-iron co-modified natural clay minerals.

Description of drawings

Fig. 1 is the XRD pattern of the amorphous high-efficiency phosphorus removal adsorption material obtained from the original sepiolite, Example 2 and Example 3;

Fig. 2 is the SEM image of the high-efficiency phosphorus removal adsorption material of amorphous cerium-iron co-modified sepiolite obtained in Example 3;

Fig. 3 is the FTIR image of original sepiolite and amorphous cerium iron co-modified sepiolite high-efficiency phosphorus removal adsorption material obtained in Example 3;

Fig. 4 is the phosphorus adsorption kinetic curve diagram of the phosphorus removal adsorption material obtained in Example 3;

Fig. 5 is the phosphorus removal isothermal adsorption curve diagram of the phosphorus removal adsorption material obtained in Example 3;

Fig. 6 is the phosphorus removal effect diagram of the phosphorus removal adsorption material obtained in Example 3 at different pH;

Fig. 7 is the phosphorus removal effect diagram of the phosphorus removal adsorption material obtained in Example 3 under different coexisting ions;

Detailed ways

The technical solutions of the present invention will be further described below through the accompanying drawings and examples, but are not limited thereto. Any modification or equivalent replacement of the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention shall cover within the scope of the present invention.

In the invention, the natural clay mineral material is uniformly mixed with cerium salt, iron salt, urea and ascorbic acid solution in a certain proportion, and the co-loading of amorphous cerium carbonate and ferrous carbonate nanoparticles is successfully prepared through a simple "one-pot method" reaction. Natural clay mineral composite adsorption material. The adsorption material retains the special skeleton structure of the natural clay mineral material, realizes the uniform dispersion of the amorphous cerium carbonate and ferrous carbonate nanoparticles, and greatly improves the phosphorus removal performance of the original natural clay mineral material. The saturated adsorption capacity can reach 50~73.68 mg-P/g. At the same time, the preparation method of the present invention has the advantages of low energy consumption, simple operation, no special equipment, good reproducibility and the like, and has a good application prospect.

Embodiment 1: This embodiment describes a high-efficiency phosphorus removal adsorption material of amorphous cerium and iron co-modified natural clay minerals. The phosphorus removal adsorption material is composed of amorphous cerium carbonate, ferrous carbonate nanoparticles and natural It is composed of clay mineral materials. Among them, amorphous cerium carbonate and ferrous carbonate nanoparticles are attached to the structural surface of natural clay mineral materials, which can selectively adsorb with phosphate in water, so as to achieve efficient removal of phosphorus in water. .

Embodiment 2: A kind of amorphous ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorption material described in Embodiment 1, the natural clay mineral material is calcium-rich sepiolite, magnesium-rich sepiolite, One or more of halloysite, attapulgite, bentonite, diatomite, and kaolin, preferably magnesium-rich sepiolite.

Embodiment 3: A method for preparing an amorphous ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorption material according to Embodiment 1 or 2, the method steps are as follows: Clay mineral materials, cerium salts, iron salts and urea are added to the water, stirred for a total of 0.5~10 h, and then the reducing agent is added; then continue to stir for 0.3~2 h to make it evenly mixed, and the reaction is stirred at 60~100 °C for 2~24 h. After the reaction, the product is separated from solid and liquid, washed, and dried at 40-80° C. to obtain an efficient phosphorus removal adsorption material whose functional component is amorphous cerium iron nanoparticles. The material obtained by the invention can effectively remove phosphorus of different concentrations in the raw water, tail water and various surface waters of sewage treatment plants, and has the following unique characteristics: (1) Wide pH applicable range, effective at pH 3-10 (2) Strong phosphate specific adsorption capacity, the saturated phosphorus adsorption capacity can reach 73.68 mg-P/g; (3) Fast phosphorus adsorption and removal rate.

Embodiment 4: The preparation method of an amorphous ferric cerium co-modified natural clay mineral high-efficiency phosphorus removal adsorption material described in Embodiment 3, the cerium salt is cerium chloride, cerium nitrate and hydrates thereof. One or more of ferric nitrate hexahydrate, preferably cerium nitrate hexahydrate; the iron salt is one or more of ferric chloride, ferric nitrate, ferric sulfate and its hydrate, preferably ferric chloride hexahydrate.

Embodiment 5: The preparation method of a kind of amorphous cerium-iron co-modified natural clay mineral high-efficiency phosphorus removal adsorption material described in Embodiment 3, the molar ratio of cerium salt and iron salt is 3:1~6, preferably is 1:1; in terms of cerium ion content, the mass ratio between cerium salt and natural clay mineral material is 0.03~1:1, preferably 0.15:1; the molar ratio of urea to the sum of cerium salt and iron salt It is 5~50:1, preferably 25:1.

Specific embodiment 6: The preparation method of a kind of amorphous ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorption material described in specific embodiment 3, the stirring mode is magnetic stirring or mechanical stirring, and the stirring speed is 400~1000 r /min.

Embodiment 7: The preparation method of an amorphous cerium-iron co-modified natural clay mineral high-efficiency phosphorus removal adsorption material according to Embodiment 3, wherein the reducing agent is one of ascorbic acid, hydrazine hydrate and citric acid Or more, the molar dosage ratio of it and iron salt is 1~5.

Specific embodiment 8: The preparation method of an amorphous cerium iron co-modified natural clay mineral high-efficiency phosphorus removal adsorption material according to the specific embodiment 3, the water bath temperature is 60~100 ℃, preferably 85 ℃, so The reaction time is 2~24h, preferably 4h.

Embodiment 9: The method for preparing an amorphous ferric ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorption material according to Embodiment 3, the solid-liquid separation is centrifugal separation, gravity sedimentation and filtration separation. A sort of.

Specific embodiment ten: a kind of adsorption material obtained according to the preparation method of amorphous ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorption material according to any one of specific embodiments three to nine in the removal of various water bodies Application of Phosphorus.

Example 1:

Dissolve 2.0 g of 400-mesh attapulgite, 1.31 g of cerium nitrate hexahydrate, 0.82 g of ferric chloride hexahydrate, and 9 g of urea in 100 mL of water, and stir on a magnetic stirrer for 5 h; after the solution is uniformly mixed, add it to the solution. 1 g of ascorbic acid was added, and stirring was continued for 1 h; then, the reaction was heated and stirred at 85 °C for 4 h, and the speed was controlled at 500 r/min. At the end of the reaction, the product was subjected to solid-liquid separation, washing several times, and drying at 50 °C for 12 h to obtain the modified attapulgite high-efficiency phosphorus removal adsorption material whose functional component was amorphous cerium iron nanoparticles.

Example 2:

Dissolve 4 g of sepiolite, 1.31 g of cerium nitrate hexahydrate, 0.82 g of ferric chloride hexahydrate, and 9 g of urea in 100 mL of water, and stir on a magnetic stirrer for 1 h; after the solution is uniformly mixed, add 1 g of urea to it. ascorbic acid, and continued stirring for 0.5 h; then, the reaction was heated and stirred at 85 °C for 4 h, and the speed was controlled at 500 r/min. At the end of the reaction, the product was subjected to solid-liquid separation, washing several times, and drying at 50 °C for 12 h to obtain a modified sepiolite high-efficiency phosphorus removal adsorption material whose functional component was amorphous cerium iron nanoparticles.

Example 3:

Dissolve 2 g of sepiolite, 1.31 g of cerium nitrate hexahydrate, 0.82 g of ferric chloride hexahydrate, and 9 g of urea in 100 mL of water, and stir on a magnetic stirrer for 1 h; after the solution is uniformly mixed, add 1 g of urea to it. ascorbic acid, and continued stirring for 0.4 h; then, the reaction was heated and stirred at 85 °C for 4 h, and the rotational speed was controlled at 500 r/min. At the end of the reaction, the product was subjected to solid-liquid separation, washing several times, and drying at 50 °C for 12 h to obtain a modified sepiolite high-efficiency phosphorus removal adsorption material whose functional component was amorphous cerium iron nanoparticles.

Example 4:

Dissolve 2 g of halloysite, 1.74 g of cerium nitrate hexahydrate, 0.56 g of ferric chloride hexahydrate, and 7.2 g of urea in 100 mL of water, and stir mechanically for 2 h; after the solution is uniformly mixed, add 0.65 g of ascorbic acid to it, and continue to stir for 0.5 h; then heated and stirred at 85 °C for 6 h, and the control speed was 600 r/min. At the end of the reaction, the product was separated from solid and liquid, washed with water for several times, and dried at 50 °C for 12 h to obtain a modified halloysite high-efficiency phosphorus removal adsorption material whose functional component was amorphous cerium iron nanoparticles.

Example 5:

Dissolve 2 g bentonite, 0.87 g cerium nitrate hexahydrate, 1.08 g ferric chloride hexahydrate, and 9 g urea in 100 mL of water, and stir mechanically for 2 h; after the solution is uniformly mixed, add 1.25 g ascorbic acid to it, and continue stirring for 1 h ; The reaction was heated and stirred at 85 °C for 6 h, and the control speed was 600 r/min. At the end of the reaction, the product was separated from solid and liquid, washed with water for several times, and dried at 50 °C for 12 h to obtain a modified bentonite high-efficiency phosphorus removal adsorption material whose functional component was amorphous cerium iron nanoparticles.

Example 6:

Dissolve 2 g of bentonite, 1.74 g of cerium nitrate hexahydrate, 1.08 g of ferric chloride hexahydrate, and 12 g of urea in 100 mL of pure water, and stir on a magnetic stirrer for 2 h; after the solution is uniformly mixed, add 1.25 g of urea to it. g ascorbic acid, continue to stir for 1 h; then heat and stir at 85 °C for 6 h, and control the rotation speed to 600 r/min. At the end of the reaction, the product was separated from solid and liquid, washed with water for several times, and dried at 50 °C for 12 h to obtain a modified bentonite high-efficiency phosphorus removal adsorption material whose functional component was amorphous cerium iron nanoparticles.

The technical solutions of the present invention are not limited thereto, and other embodiments are not listed one by one here.

Fig. 1 is the XRD pattern of original sepiolite, amorphous ceria co-modified sepiolite natural clay mineral high-efficiency phosphorus removal adsorption material prepared in Example 2 and Example 3. It can be seen from the figure that Example 2 and Example 3 The crystal structure of the obtained ferric cerium nanoparticles co-modified sepiolite natural clay mineral high-efficiency phosphorus removal adsorption material is consistent with the original sepiolite. This shows that the supported cerium carbonate and ferrous carbonate particles are amorphous structures, and the co-loading of cerium and iron nanoparticles only makes the intensity of each diffraction peak of sepiolite show a certain downward trend.

Fig. 2 is the SEM image of the high-efficiency phosphorus removal adsorption material of cerium-iron co-modified sepiolite natural clay mineral obtained in Example 3. It can be seen that the obtained phosphorus removal adsorption material is composed of nanofiber rods and nanoparticles. The nanofiber rods are sepiolite carriers, the nanoparticles are amorphous cerium iron nanoparticles, and the nanoparticles are unevenly attached to the surface of the fiber rod-like structure.

Figure 3 is a comparison chart of the infrared spectra of the original sepiolite and the ferric cerium co-modified natural clay mineral high-efficiency phosphorus removal adsorption material obtained in Example 3. It can be seen that after the ferric cerium nanoparticles are loaded, at 1500 cm ^-1 Nearby, triple characteristic absorption peaks of carbonate appeared in the obtained phosphorus removal material, indicating that the loaded cerium and iron nanoparticles were metal carbonate compounds, and combined with the preparation conditions, they should be a mixture of cerium carbonate and ferrous carbonate.

The present invention intends to investigate the advantages and beneficial results of the amorphous ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorption material prepared by the above-mentioned embodiment through the following application examples:

Application example 1:

The amorphous ferric ceria co-modified natural clay mineral materials prepared in the above examples 1, 2, 3, 4, 5 and 6 were added to 100 ml of the original domestic sewage filtered through a 0.45 μm glass fiber membrane. , the dosage is 0.5 g/L, placed in a constant temperature shaker, 25 ℃, under the conditions of 200 r/min vibration and adsorption for 2 h, and the remaining phosphate concentration in the solution was determined. Table 1 shows the properties of domestic sewage after membrane passing, and Table 2 shows the phosphorus removal effect of the prepared amorphous ceria co-modified natural clay mineral material. It can be seen from the table that although the composition of domestic sewage is complex, the coexisting ions are more species and the concentration is higher, the prepared amorphous ceria co-modified natural clay mineral materials have strong adsorption capacity for phosphate anions in them. After two hours of treatment, more than 91% of phosphate can be removed, and for adsorbents with high cerium content, the removal rate of phosphate can further reach 99.8%.

Table 1 Water quality characteristics of original domestic sewage (passed through 0.45 μm glass fiber membrane)

Table 2 Phosphorus removal effect of amorphous ceria co-modified natural clay mineral high-efficiency phosphorus removal adsorbents

Application example 2:

The original sepiolite and the amorphous ferric cerium co-modified sepiolite high-efficiency phosphorus removal adsorption material prepared in Example 3 were respectively added to two parts of KH ₂ PO ₄ with an initial phosphorus concentration C ₀ of 10 mg-P/L. In the aqueous solution, the dosage is 0.5 g/L, placed in a constant temperature shaker, shaken at a temperature of 25 °C and a rotation speed of 200 r/min, and the solution is taken within a certain time interval to measure the remaining concentration of phosphate radicals , plot the relationship between the phosphate concentration in solution and the adsorption time.

As shown in Figure 4, the concentration of phosphate radicals in the solution added with amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorbent material decreased continuously over time. After adding cerium-iron co-modified high-efficiency phosphorus removal adsorbent for 10 min, the phosphorus removal rate in the solution can reach 75%; after 2 h, the phosphorus removal rate is almost 100%; The removal capacity of phosphate was very limited, and only 3% of phosphorus was removed after 2 h of adsorption.

Application example 3:

The original sepiolite and the amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorption material prepared in Example 3 were respectively added to two parts of KH ₂ PO with an initial phosphorus concentration C ₀ of 5-100 mg-P/L. ₄ in the aqueous solution, the dosage is 0.2 g/L, placed in a constant temperature shaker, 25 ℃, under the conditions of 200 r/min vibration and adsorption for 24 h.

As shown in Figure 5, with the increase of the equilibrium phosphorus concentration, the adsorption capacity of the prepared amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorption material first increased significantly, and then gradually tended to balance, and its saturated adsorption capacity was 50.23 mg-P/g. ICP-OES measurement results show that the content of cerium in the phosphorus removal adsorption material is 14.13wt%. It is calculated that the adsorption capacity of the amorphous sepiolite co-modified sepiolite for phosphorus removal can reach 355.48 mg-P/g Ce, and the cerium site has been fully used. In comparison, the original sepiolite has a significantly insufficient adsorption capacity for phosphorus, and its saturated adsorption capacity is only 5.74 mg-P/g. It can be seen that the co-modification of amorphous cerium iron carbonate greatly improves the adsorption capacity of the original sepiolite.

Application example 4:

The amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorption materials prepared in Example 3 were respectively added to multiple parts of KH ₂ PO with an initial phosphorus concentration C ₀ of 20 mg-P/L and a pH of 2.43-11. ₄ In the aqueous solution, the dosage of the adsorbent material was 0.2 g/L, and the adsorption reaction was shaken for 24 h at 25 °C and a rotating speed of 200 r/min in a constant temperature shaker.

As shown in Figure 6, the change of pH value of the solution has little effect on the phosphorus removal performance of the prepared amorphous ceria co-modified sepiolite high-efficiency phosphorus removal adsorption material. In a wide pH range (3~10), the phosphorus removal material has excellent phosphorus removal performance, and its saturated adsorption capacity is hardly affected by pH. This shows that the prepared amorphous ceria co-modified sepiolite natural clay mineral high-efficiency phosphorus removal adsorption material can be applied to a variety of different water bodies, and the acidity and alkalinity of the water body does not affect its phosphorus removal effect.

Application example 5:

The amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorption material prepared in Example 3 was respectively added to the initial phosphorus concentration C ₀ of 10 mg-P/L, Cl ^- , NO ₃ ^- , HCO ₃ ^- , The SO ₄ ^2- and Ca ²⁺ ion concentrations were respectively 100 mg/L in several KH ₂ PO ₄ aqueous solutions, the dosage of adsorbent material was 0.2 g/L, and placed in a constant temperature shaker at 25 °C and a rotating speed of 200 r The adsorption reaction was shaken under the condition of /min for 24 h.

As shown in Figure 7, even if the concentration of coexisting ions in the solution is 10 times that of phosphate anions, the phosphorus removal performance of the prepared amorphous cerium-iron co-modified sepiolite high-efficiency phosphorus removal adsorbent is hardly affected by these coexisting ions The effect of phosphorus removal adsorption material showed that the prepared phosphorus removal adsorption material has high selectivity for phosphate anion and anti-ion interference ability, which is beneficial to its application in practical water bodies.

Based on the disclosure and guidance of the above specification, those skilled in the art to which the present invention pertains can also make appropriate changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention.

Claims (8)

1. A preparation method of an amorphous high-efficiency dephosphorization adsorption material is characterized by comprising the following steps: the dephosphorization adsorption material is formed by compounding cerium carbonate and ferrous carbonate nanoparticles with a natural clay mineral material, wherein amorphous cerium carbonate and ferrous carbonate nanoparticles are attached to the structural surface of the natural clay mineral material, the natural clay mineral material is one or more of calcium-rich sepiolite, magnesium-rich sepiolite, halloysite, attapulgite, bentonite, diatomite and kaolin, and the preparation method comprises the following steps: adding untreated natural clay mineral material, cerium salt, ferric salt and urea into water, stirring for 0.5 to 10 hours, and adding a reducing agent; and continuously stirring for 0.3 to 2 hours to uniformly mix, then continuously heating and stirring at 60 to 100 ℃ to react for 2 to 24 hours, after the reaction is finished, carrying out solid-liquid separation on the product, cleaning, and drying at 40 to 80 ℃ to obtain the amorphous efficient phosphorus removal adsorbing material.

2. The preparation method of the amorphous high-efficiency phosphorus removal adsorbing material according to claim 1, characterized by comprising the following steps: the cerium salt is one or more of cerium chloride, cerium nitrate and hydrates thereof; the ferric salt is one or more of ferric chloride, ferric nitrate, ferric sulfate and hydrate thereof.

3. According to claim 1The preparation method of the amorphous high-efficiency dephosphorization adsorption material is characterized by comprising the following steps: the molar ratio of the added cerium salt to the added iron salt is 3:1 to 6; with trivalent cerium ions (Ce) ³⁺ ) The mass ratio of the cerium salt to the natural clay mineral material is 0.03 to 1:1; the molar ratio of urea to the sum of the total amount of cerium salt and ferric salt is 5-50: 1.

4. the method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 1, wherein the method comprises the following steps: stirring is needed in the synthesis process, the stirring mode is magnetic stirring or mechanical stirring, and the stirring speed is 400-1000 r/min.

5. The method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 1, wherein the method comprises the following steps: the reducing agent is one or more of ascorbic acid, hydrazine hydrate and citric acid, and the molar usage ratio of the reducing agent to the ferric salt is 1-5.

6. The method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 1, wherein the method comprises the following steps: the reaction temperature is 60 to 100 ℃ during synthesis, and the reaction time is 2 to 24 hours.

7. The method for preparing the amorphous high-efficiency phosphorus removal adsorbing material according to claim 1, wherein the method comprises the following steps: the solid-liquid separation is one of centrifugal separation, gravity settling and filtration separation.

8. The application of the adsorbing material obtained by the preparation method of the amorphous high-efficiency phosphorus removal adsorbing material according to any one of claims 1 to 7 in removing phosphorus in various water bodies.

Images