Preparation method and application of a kind of dull phosphorus composite material

Abstract

The application relates to a preparation method and application of a phosphorus passivation composite material, and belongs to the field of water treatment composite material preparation. Zirconium oxide is loaded on montmorillonite, and a mixed suspension is obtained by adding biochar and a sodium alginate solution. The mixed suspension is interchanged with calcium ions to form microspheres, and low-temperature drying is carried out to obtain a phosphorus passivation composite material. The method has simple steps, the material can efficiently passivate phosphorus, and the effect is stable. In particular, the method can effectively control phosphorus in high-organic-load sediment.

Description

Technical Field

[0001] This invention belongs to the field of water treatment composite material preparation, specifically relating to a method for preparing a porous passive phosphorus composite material and its application. Background Technology

[0002] In recent years, with increasing attention to the quality of the aquatic ecological environment, especially with the continuous and in-depth advancement of the "source control and pollution interception" project, the number of water pollution incidents caused by excessive discharge from external sources has been decreasing. Water pollution is beginning to shift towards endogenous source treatment, aquatic ecological restoration, and the construction and long-term guarantee of a healthy aquatic ecosystem, resulting in huge demand for related technologies and market prospects.

[0003] Among the endogenous pollution releases from sediments, phosphorus pollution is relatively prominent. This is because, compared to phosphorus, pollutants such as carbon and nitrogen can be mineralized and degraded in the aquatic environment through biochemical processes such as microorganisms, ultimately transforming into carbon dioxide and nitrogen gas that leave the water body. Phosphorus accumulates in the sediments of water bodies during exogenous pollution processes. When changes in the quality of the overlying water affect the sediments, the phosphorus accumulated in the sediments is easily released back into the overlying water bodies, leading to eutrophication again and thus making water body remediation long-term and complex.

[0004] Currently, commonly used methods for controlling endogenous phosphorus in sediments include in-situ aeration, sediment dredging, and the addition of phosphorus passivation materials. The addition of phosphorus passivation materials is simple to operate, has a significant phosphorus control effect, and is environmentally friendly, making it a focus of attention in the field of aquatic ecological restoration and treatment. Research and practical applications of existing phosphorus passivation materials have shown that they are effective for releasing simple endogenous phosphorus from sediments. However, when applied to heavily polluted sediments, especially when influenced by complex organic matter, the passivation materials are easily affected, leading to reduced passivation efficiency or even failure. Therefore, developing a phosphorus passivation composite material suitable for the synergistic release of complex organic matter and phosphorus is a current research hotspot.

[0005] In view of this, the present invention aims to solve the bottleneck problem of existing phosphorus passivation materials being intolerant to complex organic compounds. First, based on the idea of ​​combining the characteristic of zirconium, which is resistant to complex organic compounds, with the characteristics of montmorillonite, such as its large specific surface area and abundant adhesion sites, the present invention proposes to improve the resistance of phosphorus passivation materials to highly complex organic compounds by loading zirconium, thereby solving the problem of phosphorus passivation materials being intolerant to complex organic compounds. Summary of the Invention

[0006] This invention addresses the shortcomings of existing technologies by providing a method for preparing a phosphorus passivation composite material and its application. The aim is to obtain a composite product with high phosphorus passivation efficiency and resistance to impacts from complex organic matter, which will be used for the treatment of endogenous pollution in aquatic sediments.

[0007] To achieve the above objectives, one of the technical solutions of the present invention is the preparation of a porous zirconium-modified montmorillonite microsphere passivated phosphorus composite material, wherein the composite material is prepared by the following steps:

[0008] S1. Place 100-200 g of montmorillonite in deionized water and stir for 2 hours. Centrifuge to remove the upper liquid and impurities at the bottom, retain the solid material in the middle and upper layers, dry it at about 105℃ and grind it through a 200-mesh sieve. This is denoted as MT.

[0009] S2. Take an appropriate amount of MT from S1 into ZrOCl2•8H2O solution, stir continuously at 60-80℃ for 2-4 h, adjust the pH of the suspension to about 9 with 1 mol / L NaOH, continue the reaction for 2-4 h, then stop stirring and place in a water bath for 24 h.

[0010] S3. After the reaction is complete, the suspension in S2 is centrifuged, the solid part is washed several times with deionized water until neutral, dried at 100-110℃, ground and passed through a 200-mesh sieve to obtain zirconium-modified montmorillonite, denoted as ZrMT;

[0011] S4. Take an appropriate amount of carbon-based material and potassium carbonate in a mass ratio of 1:1 in deionized water, stir at room temperature for 1-2 h, centrifuge to remove the supernatant, dry the surface moisture of the solid material at 100-110℃ and place it in a quartz boat, keep it at 400-600℃ for 3 h, after cooling to room temperature, soak it in 1 mol / L hydrochloric acid for 1-2 h, centrifuge to separate, wash with water several times until neutral, dry and grind through a 200-mesh sieve to obtain biochar, denoted as BC;

[0012] S5. Take an appropriate amount of sodium alginate in a beaker, add an appropriate amount of deionized water, heat and stir at 50°C until it is completely dissolved to obtain a sodium alginate solution.

[0013] S6. Take ZrMT and BC obtained in a certain mass ratio of S3 and S4 into a beaker, add deionized water, and ultrasonically disperse them for 30-60 min to form a suspension;

[0014] S7. Slowly add the suspension from S6 to the solution in S5 and stir continuously for 2-4 hours to obtain a mixed suspension;

[0015] S8. Take an appropriate amount of CaCl2 in a beaker, add deionized water, and prepare a 2wt% CaCl2 solution for later use;

[0016] S9. Using a peristaltic pump, the mixed suspension in S6 is slowly added dropwise to the 2wt% CaCl2 solution in S7 to crosslink with calcium ions and form microspheres. After the addition of the mixed suspension is complete, the reaction continues for 12–24 h to allow the microspheres to crosslink and solidify.

[0017] S10. After repeatedly rinsing the microspheres obtained in S9 with deionized water to remove the CaCl2 on the surface, the microspheres were placed in a vacuum freeze dryer and dried at low temperature to obtain a porous zirconium-modified montmorillonite microsphere phosphite-passivated composite material, denoted as SA@ZrMT / BC.

[0018] Based on the above solutions, the second technical solution of the present invention provides a method for using porous zirconium montmorillonite microsphere passivated phosphorus composite material, wherein the steps of the method are as follows:

[0019] 1. Prepare a phosphate solution and adjust the pH to about 7. Take 50 mL of potassium dihydrogen phosphate solution in an Erlenmeyer flask and add the porous zirconium-modified montmorillonite composite material prepared in the above scheme.

[0020] 2. Place the conical flask from step 1 in a constant temperature shaker and shake it at a speed of 150-200 r / min and a temperature of 25℃.

[0021] 3. After shaking, solid-liquid separation was performed, and the concentration of phosphate in the remaining solution was determined using molybdate spectrophotometry. Detailed Implementation

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 In Examples 1-5, the concentration of phosphate in the remaining solution was determined by molybdate spectrophotometry, and the removal rate was calculated.

[0024] Figure 2 The porous zirconium-modified montmorillonite microsphere / phosphorus-doped composite material SA@ZrMT / BC prepared in Example 4 8:1 Performance tests were conducted at different pH values. The concentration of phosphate in the remaining solution was determined by molybdate spectrophotometry, and the removal rate was calculated.

[0025] Figure 3 The porous zirconium-modified montmorillonite microsphere / phosphorus-doped composite material SA@ZrMT / BC prepared in Example 4 8:1 Performance tests were conducted at different humic acid concentrations. The concentration of phosphate in the remaining solution was determined by molybdate spectrophotometry, and the removal rate was calculated. Attached Figure Description

[0026] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0027] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0028] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Furthermore, various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0029] Example 1

[0030] (1) Weigh 100 g of montmorillonite into 2 L of deionized water and stir for 2 h. Centrifuge to remove the upper liquid and impurities at the bottom, retain the solid material in the middle and upper layers, dry at about 105℃ and grind through a 200-mesh sieve, and record it as MT.

[0031] (2) Weigh 50 g of the purified montmorillonite from (1) into 500 g of 10wt% ZrOCl2•8H2O, adjust the pH of the suspension to about 9 using 1 mol / L NaOH, continue the reaction for 2 h, then stop stirring and place it in a water bath for 24 h.

[0032] (3) After the reaction is complete, the suspension in (2) is centrifuged, the solid part is washed several times with deionized water until neutral, dried at 105°C, ground through a 200-mesh sieve to obtain zirconium-modified montmorillonite, denoted as ZrMT;

[0033] (4) Remove the branches and leaves from the collected canna lilies, wash them several times with clean water to remove surface impurities, dry the remaining moisture in an oven, cut them into small pieces with a guillotine and crush them in a small pulverizer to obtain canna lily stalk powder.

[0034] (5) Weigh carbon-based material and potassium carbonate in a mass ratio of 1:1 into deionized water, stir at room temperature for 2 h, centrifuge to remove supernatant, dry the surface moisture of the solid material at 105℃ and place it in a quartz boat, keep it at 500℃ for 3 h, and after cooling to room temperature, soak it in 1 mol / L hydrochloric acid for 2 h, centrifuge to separate, wash with water several times until neutral, dry and grind through a 200 mesh sieve to obtain biochar, denoted as BC;

[0035] (6) Weigh 0.5 g sodium alginate into 50 mL of deionized water, heat and stir at 50°C for 2 h until it is completely dissolved, weigh 2.915 g ZrMT and 2.915 g BC into 100 mL of deionized water and ultrasonically disperse for 30 min, then slowly add them to the sodium alginate solution in (6) and stir continuously for 2 h to obtain a mixed suspension;

[0036] (7) Prepare 200 mL of 1 wt% CaCl2 solution. Slowly add the above mixed suspension to the CaCl2 solution using a peristaltic pump for cross-linking for 12 h to form microspheres. Wash the microspheres three times with deionized water to remove the CaCl2 on the surface. Then place the microspheres in a freeze dryer and dry for 12 h to obtain porous zirconium-modified montmorillonite microsphere phosphite-passivated composite material, denoted as SA@ZrMT / BC. 1:1 .

[0037] Example 2

[0038] (1) Weigh 100 g of montmorillonite into 2 L of deionized water and stir for 2 h. Centrifuge to remove the upper liquid and impurities at the bottom, retain the solid material in the middle and upper layers, dry at about 105℃ and grind through a 200-mesh sieve, and record it as MT.

[0039] (2) Weigh 50 g of the purified montmorillonite from (1) into 10wt% ZrOCl2•8H2O, adjust the pH of the suspension to about 9 using 1 mol / L NaOH, continue the reaction for 2 h, then stop stirring and place it in a water bath for 24 h.

[0040] (3) After the reaction is complete, the suspension in (3) is centrifuged, the solid part is washed several times with deionized water until neutral, dried at 105°C, ground through a 200-mesh sieve to obtain zirconium-modified montmorillonite, denoted as ZrMT;

[0041] (4) Remove the branches and leaves from the collected canna lilies, wash them several times with clean water to remove surface impurities, dry the remaining moisture in an oven, cut them into small pieces with a guillotine and crush them in a small pulverizer to obtain canna lily stalk powder.

[0042] (5) Weigh carbon-based material and potassium carbonate in a mass ratio of 1:1 into deionized water, stir at room temperature for 2 h, centrifuge to remove supernatant, dry the surface moisture of the solid material at 105℃ and place it in a quartz boat, keep it at 500℃ for 3 h, and after cooling to room temperature, soak it in 1 mol / L hydrochloric acid for 2 h, centrifuge to separate, wash with water several times until neutral, dry and grind through a 200 mesh sieve to obtain biochar, denoted as BC;

[0043] (6) Weigh 0.5 g sodium alginate into 50 mL of deionized water, heat and stir at 50°C for 2 h until it is completely dissolved, weigh 2.915 g ZrMT and 0.9716 g BC into 100 mL of deionized water and ultrasonically disperse for 30 min, then slowly add them to the above sodium alginate solution and stir continuously for 2 h to obtain a mixed suspension.

[0044] (7) Prepare 200 mL of 1 wt% CaCl2 solution. Slowly add the above mixed suspension to the CaCl2 solution using a peristaltic pump for cross-linking for 12 h to form microspheres. Wash the microspheres three times with deionized water to remove the CaCl2 on the surface. Then place the microspheres in a freeze dryer and dry for 12 h to obtain porous zirconium-modified montmorillonite microsphere phosphite-passivated composite material, denoted as SA@ZrMT / BC. 3:1 .

[0045] Example 3

[0046] (1) Weigh 100 g of montmorillonite into 2 L of deionized water and stir for 2 h. Centrifuge to remove the upper liquid and impurities at the bottom, retain the solid material in the middle and upper layers, dry at about 105℃ and grind through a 200-mesh sieve, and record it as MT.

[0047] (2) Weigh 50 g of the purified montmorillonite from (1) into 10wt% ZrOCl2•8H2O, adjust the pH of the suspension to about 9 using 1 mol / L NaOH, continue the reaction for 2 h, then stop stirring and place it in a water bath for 24 h.

[0048] (3) After the reaction is complete, the suspension in (2) is centrifuged, the solid part is washed several times with deionized water until neutral, dried at 105°C, ground through a 200-mesh sieve to obtain zirconium-modified montmorillonite, denoted as ZrMT;

[0049] (4) Remove the branches and leaves from the collected canna lilies, wash them several times with clean water to remove surface impurities, dry the remaining moisture in an oven, cut them into small pieces with a guillotine and crush them in a small pulverizer to obtain canna lily stalk powder.

[0050] (5) Weigh carbon-based material and potassium carbonate in a mass ratio of 1:1 into deionized water, stir at room temperature for 2 h, centrifuge to remove supernatant, dry the surface moisture of the solid material at 105℃ and place it in a quartz boat, keep it at 500℃ for 3 h, and after cooling to room temperature, soak it in 1 mol / L hydrochloric acid for 2 h, centrifuge to separate, wash with water several times until neutral, dry and grind through a 200 mesh sieve to obtain biochar, denoted as BC;

[0051] (6) Weigh 0.5 g sodium alginate into 50 mL of deionized water, heat and stir at 50 °C for 2 h until it is completely dissolved, weigh 2.915 g ZrMT and 0.583 g BC into 100 mL of deionized water and ultrasonically disperse for 30 min, then slowly add them to the above sodium alginate solution and stir continuously for 2 h to obtain a mixed suspension.

[0052] (7) Prepare 200 mL of 1 wt% CaCl2 solution. Slowly add the above mixed suspension to the CaCl2 solution using a peristaltic pump for cross-linking for 12 h to form microspheres. Wash the microspheres three times with deionized water to remove the CaCl2 on the surface. Then place the microspheres in a freeze dryer and dry for 12 h to obtain porous zirconium-modified montmorillonite microsphere phosphite-passivated composite material, denoted as SA@ZrMT / BC. 5:1 .

[0053] Example 4

[0054] (1) Weigh 100 g of montmorillonite into 2 L of deionized water and stir for 2 h. Centrifuge to remove the upper liquid and impurities at the bottom, retain the solid material in the middle and upper layers, dry at about 105℃ and grind through a 200-mesh sieve, and record it as MT.

[0055] (2) Weigh 50 g of the purified montmorillonite from (1) into 10wt% ZrOCl2•8H2O, adjust the pH of the suspension to about 9 using 1 mol / L NaOH, continue the reaction for 2 h, then stop stirring and place it in a water bath for 24 h.

[0056] (3) After the reaction is complete, the suspension in (2) is centrifuged, the solid part is washed several times with deionized water until neutral, dried at 105°C, ground through a 200-mesh sieve to obtain zirconium-modified montmorillonite, denoted as ZrMT;

[0057] (4) Remove the branches and leaves from the collected canna lilies, wash them several times with clean water to remove surface impurities, dry the remaining moisture in an oven, cut them into small pieces with a guillotine and crush them in a small pulverizer to obtain canna lily stalk powder.

[0058] (5) Weigh carbon-based material and potassium carbonate in a mass ratio of 1:1 into deionized water, stir at room temperature for 2 h, centrifuge to remove supernatant, dry the surface moisture of the solid material at 105℃ and place it in a quartz boat, keep it at 500℃ for 3 h, and after cooling to room temperature, soak it in 1 mol / L hydrochloric acid for 2 h, centrifuge to separate, wash with water several times until neutral, dry and grind through a 200 mesh sieve to obtain biochar, denoted as BC;

[0059] (6) Weigh 0.5 g sodium alginate into 50 mL of deionized water, heat and stir at 50 °C for 2 h until it is completely dissolved, weigh 2.915 g ZrMT and 0.3644 g BC into 100 mL of deionized water and ultrasonically disperse for 30 min, then slowly add them to the above sodium alginate solution and stir continuously for 2 h to obtain a mixed suspension.

[0060] (7) Prepare 200 mL of 1 wt% CaCl2 solution. Slowly add the above mixed suspension to the CaCl2 solution using a peristaltic pump for cross-linking for 12 h to form microspheres. Wash the microspheres three times with deionized water to remove the CaCl2 on the surface. Then place the microspheres in a freeze dryer and dry for 12 h to obtain porous zirconium-modified montmorillonite microsphere phosphite-passivated composite material, denoted as SA@ZrMT / BC. 8:1 .

[0061] Example 5

[0062] (1) Weigh 100 g of montmorillonite into 2 L of deionized water and stir for 2 h. Centrifuge to remove the upper liquid and impurities at the bottom, retain the solid material in the middle and upper layers, dry at about 105℃ and grind through a 200-mesh sieve, and record it as MT.

[0063] (2) Weigh 50 g of the purified montmorillonite from (1) into 10wt% ZrOCl2•8H2O, adjust the pH of the suspension to about 9 using 1 mol / L NaOH, continue the reaction for 2 h, then stop stirring and place it in a water bath for 24 h.

[0064] (3) After the reaction is complete, the suspension in (2) is centrifuged, the solid part is washed several times with deionized water until neutral, dried at 105°C, ground through a 200-mesh sieve to obtain zirconium-modified montmorillonite, denoted as ZrMT;

[0065] (4) Remove the branches and leaves from the collected canna lilies, wash them several times with clean water to remove surface impurities, dry the remaining moisture in an oven, cut them into small pieces with a guillotine and crush them in a small pulverizer to obtain canna lily stalk powder.

[0066] (5) Weigh carbon-based material and potassium carbonate in a mass ratio of 1:1 into deionized water, stir at room temperature for 2 h, centrifuge to remove supernatant, dry the surface moisture of the solid material at 105℃ and place it in a quartz boat, keep it at 500℃ for 3 h, and after cooling to room temperature, soak it in 1 mol / L hydrochloric acid for 2 h, centrifuge to separate, wash with water several times until neutral, dry and grind through a 200 mesh sieve to obtain biochar, denoted as BC;

[0067] (6) Weigh 0.5 g sodium alginate into 50 mL of deionized water, heat and stir at 50°C for 2 h until it is completely dissolved, weigh 2.915 g ZrMT and 0.2915 g BC into 100 mL of deionized water and ultrasonically disperse for 30 min, then slowly add them to the above sodium alginate solution and stir continuously for 2 h to obtain a mixed suspension.

[0068] (7) Prepare 200 mL of 1 wt% CaCl2 solution. Slowly add the above mixed suspension to the CaCl2 solution using a peristaltic pump for cross-linking for 12 h to form microspheres. Wash the microspheres three times with deionized water to remove the CaCl2 on the surface. Then place the microspheres in a freeze dryer and dry for 12 h to obtain porous zirconium-modified montmorillonite microsphere phosphite-passivated composite material, denoted as SA@ZrMT / BC. 10:1 .

[0069] Weigh 0.05 g of the porous zirconium-modified montmorillonite microsphere passivated phosphorus composite material prepared in Examples 1-5, place it in 50 mL of a 10 mg / L potassium dihydrogen phosphate solution, adjust the pH of the solution to approximately 7, and shake in a constant temperature shaker at 150 r / min for 24 h. Then, perform solid-liquid separation, determine the concentration of phosphate in the remaining solution using molybdate spectrophotometry, calculate the removal rate, and the results are shown below. Figure 1 As can be seen from the figure, SA@ZrMT / BC 8:1 It has the best phosphorus removal effect, reaching 96.29%.

[0070] The porous zirconium-modified montmorillonite microsphere passivated phosphorus composite material SA@ZrMT / BC prepared in Example 4 8:1 Perform performance testing. Weigh 0.05 g of SA@ZrMT / BC. 8:1 In 50 mL of a 10 mg / L potassium dihydrogen phosphate solution, the pH was adjusted to 5-9, and the solution was shaken in a constant temperature shaker at 150 r / min for 24 h. Solid-liquid separation was then performed, and the concentration of phosphate in the remaining solution was determined using molybdate spectrophotometry. The removal rate was calculated, and the results are shown below. Figure 2 .

[0071] Weigh 0.05 g SA@ZrMT / BC 8:1In 50 mL of a potassium dihydrogen phosphate solution containing 10 mg / L humic acid, the pH was adjusted to approximately 7. After shaking in a constant-temperature shaker at 50 r / min for 24 h, solid-liquid separation was performed. The concentration of phosphate in the remaining solution was determined using molybdate spectrophotometry, and the removal rate was calculated. The results are shown in Table 3. The humic acid concentrations in the potassium dihydrogen phosphate solutions were 1, 10, 20, 30, 40, 50, 80, and 100 mg / L, respectively. Figure 3 .

[0072] In summary, the porous zirconium-modified montmorillonite microsphere phosphorus-removing composite material provided by this invention exhibits good phosphate removal capabilities in water bodies, with minimal impact from pH and humic acid. When used in phosphorus-containing wastewater or natural water bodies, it achieves stable phosphorus removal without requiring pH adjustment. Furthermore, this material shows strong application potential for phosphorus-containing wastewater or natural water bodies with high organic loads.

[0073] The above description is merely a preferred embodiment and experimental example of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made on the basis of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for producing a passivation composite material, characterized by, Includes the following steps: Zirconium source is reacted with montmorillonite to load zirconium oxide into the montmorillonite interlayer to obtain zirconium-modified montmorillonite; The zirconium-modified montmorillonite and biochar were dispersed in a sodium alginate solution to obtain a mixed suspension; The mixed suspension was added dropwise to a solution containing CaCl2 to crosslink with calcium ions to form microspheres; the obtained microspheres were washed and dried at medium and low temperatures to obtain a porous zirconium-modified montmorillonite microsphere phosphite-passivated composite material.

2. The production method according to claim 1, characterized by, Includes the following steps: S1. Montmorillonite is placed in deionized water and stirred, centrifuged to purify, dried and ground through a fine sieve, and denoted as MT; S2. Take MT into ZrOCl2·8H2O solution, stir continuously under heating conditions, and adjust the pH of the suspension to neutral; S3. Centrifuge the suspension in S2, wash the solid part until neutral, dry, grind and pass through a sieve to obtain zirconium-modified montmorillonite, denoted as ZrMT; S4. Take carbon-based material and potassium carbonate in water, stir, centrifuge, dry, soak in hydrochloric acid, separate, wash until neutral, dry, grind and pass through a sieve to obtain biochar, denoted as BC; S5. Add sodium alginate to deionized water, heat and stir until it is completely dissolved to obtain sodium alginate solution; S6. Take a certain mass ratio of ZrMT and BC, add them to deionized water, and disperse them to form a suspension; S7. Add the suspension from S6 to the sodium alginate solution from S5 and stir to obtain a mixed suspension; S8. Add CaCl2 to deionized water to obtain a CaCl2 solution; S9. The mixed suspension in S7 is added dropwise to the CaCl2 solution in S8 to form microspheres, and the reaction continues to crosslink and solidify the microspheres; S10. After removing the CaCl2 from the surface of the microspheres obtained in S9, dry them at medium and low temperature to obtain porous zirconium-modified montmorillonite microspheres, denoted as SA@ZrMT / BC.

3. The preparation method according to claim 2, characterized in that, In step S1, the concentration ratio of montmorillonite to deionized water is 50 g / L.

4. The production method according to claim 2, characterized by, In step S2, the mass ratio of MT to ZrOCl2·8H2O is 1:1 to 1:

5.

5. The preparation method according to claim 2, characterized in that, The carbon-based material in step S4 is derived from the wetland plant Canna indica. The preparation of the carbon-based material includes: removing the branches and leaves from the Canna indica, washing, drying, cutting into sections and crushing to obtain Canna indica stem powder.

6. The preparation method according to claim 2, characterized in that, In step S5, the concentration of the sodium alginate solution is 0.05 g / L to 0.1 g / L.

7. The preparation method according to claim 2, characterized in that, In step S6, the mass ratio of ZrMT to BC is 1:1 to 10:

1.

8. The preparation method according to claim 2, characterized in that, In step S8, the mass fraction of the CaCl2 solution is 0.5% to 4%.

9. A porous zirconium-modified montmorillonite microsphere passivated phosphorus composite material, characterized in that: It is prepared by the preparation method described in claim 1.

10. A water treatment method, characterized in that: The porous zirconium-modified montmorillonite microsphere phosphorus-removing composite material of claim 9 is brought into contact with phosphorus-containing water to remove phosphate from the phosphorus-containing water.

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