CN113952934B - Internal load control material for water body mud source - Google Patents
Internal load control material for water body mud source Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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Abstract
The invention provides a load control material in a water body mud source, which is prepared by the following method: (1) Crushing and grinding sediments taken from a water body to obtain sediment powder; (2) Mixing the sediment powder prepared in the step (1) with natural zeolite powder, and stirring to obtain a uniform mixture; adding solid polyaluminium oxide powder into the mixture, adding distilled water, and stirring to form paste, wherein the adding amount of the solid polyaluminium oxide powder accounts for 1-10 wt% of the mixture by mass; (3) And (3) after the paste is formed and dried, roasting the paste at 400-600 ℃ to prepare the control material. According to the load control material in the water body mud source, the sediment/natural zeolite material is modified by the polymeric alumina, so that the material has good adsorption effect on nitrogen and phosphorus.
Description
Technical Field
The invention belongs to the technical field of load control in a water body sludge source, and particularly relates to a load control material in a water body sludge source for controlling the release of nitrogen and phosphorus in bottom sludge.
Background
Water eutrophication is a water pollution phenomenon widely existing in the global scope. In more than 30 years, due to the development of social economy and the influence of human activities, a large amount of exogenous pollutants enter lakes and are deposited in bottom mud, so that most of lake bottoms in countries all over the world are seriously polluted. Recent survey results show that due to the prevalence and severity of lake sediment contamination, sediment contamination is released as an important endogenous source in many lakes. Among the control techniques for the load in the mud source, the sediment covering technique is one of the more common techniques.
The sediment covering technology is a control technology for covering one or more layers of cleaning matters on the surface of the polluted sediment to physically isolate the polluted sediment from an upper water body, so that the release of lake sediment pollutants to the water body is limited. The effects brought by the original bottom mud covering technology comprise the following points: 1. physically separating the lake polluted bottom sediment and the overlying water body; 2. the bottom mud is firmly polluted, and suspension and migration are avoided; 3. under the anaerobic environment condition caused by the covering layer, some anaerobic bacteria can accelerate the degradation of organic matters in the bottom sediment and reduce the diffusion of the organic matters in the overlying water body. In the prior art, common bed mud covering materials comprise calcite, fly ash, calcium bentonite, ash, sand, gravel, various mineral composite geotechnical materials and the like. However, the covering materials are all from the outside of the lake, and the hidden danger of introducing new pollutants is always existed when the covering materials are added into a water body in a large amount. In addition, although the material can play a role in physical isolation, the adsorption capacity of the material on nitrogen and phosphorus pollutants is relatively limited, and a remarkable control effect is often difficult to achieve.
In order to solve these problems, those skilled in the art have recently searched for control materials based on in-situ sediments, which are used as a covering material for bottom sediment by separating and calcining sediments taken from a water body and then throwing the sediments into the water body. Compared with the traditional covering material, the in-situ covering technology does not introduce a large amount of foreign substances, and can achieve the purpose of controlling the release of the nitrogen and the phosphorus of the bottom mud by utilizing the adsorption performance of the roasted material. However, even the control material using the sediment as the main raw material in the prior art still has the problem that the adsorption capacity of the control material to nitrogen and phosphorus is not balanced, so that the prior control material is difficult to achieve the effect of efficiently controlling nitrogen and phosphorus at the same time, and ideal control is difficult to achieve for water areas with high nitrogen and phosphorus pollutant contents, which undoubtedly limits the application of the control material in polluted water bodies.
Disclosure of Invention
The invention solves the technical problem that the existing in-situ control material is difficult to simultaneously have the effect of efficiently controlling nitrogen and phosphorus, and further provides a load control material in a water body mud source for controlling the release of bottom mud nitrogen and phosphorus.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a load control material in a water body mud source is prepared by the following method:
(1) Taking water body bottom mud, and carrying out vacuum freeze drying, grinding and sieving to obtain sediment powder;
(2) Mixing the sediment powder prepared in the step (1) with natural zeolite powder, and stirring to obtain a uniform mixture; adding polymeric alumina solid powder and water into the mixture, and stirring the mixture into paste, wherein the addition amount of the natural zeolite powder accounts for 30-70 wt% of the mixture by mass, and the addition amount of the polymeric alumina solid powder accounts for 1-10 wt% of the mixture by mass;
(3) Molding and drying the paste, and then roasting at 400-600 ℃;
(4) And (4) placing the roasted product obtained in the step (3) into an aqueous solution of a hydrophilic organic matter for modification treatment, and taking out the roasted product after the modification treatment is finished to prepare the control material.
The particle size range of the natural zeolite powder is 2-200 mu m.
And (3) forming the paste into particles with the particle size of 0.5-5 cm.
The method for performing modification treatment in the step (3) comprises the following steps: freeze-drying the water body bottom mud, and mixing the freeze-dried sediment with distilled water to form a mixed solution; vibrating the mixed solution and then passing through a membrane to obtain an organic matter solution, and treating the organic matter solution by XAD-8 resin to obtain the hydrophilic organic matter solution; and soaking the roasted product in the hydrophilic organic matter solution to prepare the control material.
The total organic carbon concentration of the hydrophilic organic matter solution is not less than 25mg/L.
When modification treatment is carried out, the mixed solution is placed in a constant-temperature oscillation box to oscillate for 16h, and the rotating speed is 200r/min; and filtering by using a 0.45 mu m mixed fiber membrane to obtain an organic matter solution.
And when modification treatment is carried out, placing the roasted product in the hydrophilic organic matter solution for soaking for 24 hours to prepare the control material.
The addition amount of the polymeric aluminum oxide solid powder accounts for 6-10 wt% of the mixture by mass.
And (4) molding and drying the paste in the step (3), and roasting at 400-600 ℃.
The load control material in the water body mud source has good adsorption effect on nitrogen and phosphorus after the sediment powder after high-temperature roasting is modified by natural zeolite, polymeric alumina and hydrophilic organic matters. The existing sediment/natural zeolite adsorbing material can only be used for denitrification, but has poor phosphorus adsorbing effect, and the adsorbing material modified by polymeric alumina has improved phosphorus adsorbing performance but poor nitrogen adsorbing effect. And the inventor of the application discovers through long-term research that the adsorption material has higher requirements on the roasting temperature, and particularly the adsorption rate of the adsorption material prepared under the high-temperature roasting condition of more than 500 ℃ is usually inhibited aiming at ammonia nitrogen, so that the balance of nitrogen and phosphorus adsorption is influenced. The problem is effectively improved by modifying with hydrophilic organic matters, and the control material prepared under the high-temperature condition of 600 ℃ still has good adsorption effect on nitrogen and phosphorus. Compared with low-temperature roasting, high-temperature roasting can improve the stability of the product structure, so that the product can be soaked in water for a long time without loosening, and the service life of the control material can be prolonged.
The invention utilizes hydrophilic organic matter to modify the control material. In the dissolving process of the soluble DOM, besides hydrophilic organic matters, a large amount of hydrophobic organic matters and other impurities can be adsorbed and dissolved due to the existence of the similar and compatible phenomenon. However, the inventors of the present application have long studied that each component in the soluble DOM is not favorable for the adsorption removal of nitrogen and phosphorus. The organic matter solution is treated with XAD-8 resin in a specific extraction method, which results in a hydrophilic organic matter with a structural composition substantially different from that of the dissolved organic matter, and with higher H/C and O/C ratios. The result shows that the hydrophilic organic matter contains more functional group structures such as carboxyl, phenolic group or amino, nitro and the like, is beneficial to modifying materials, and improves the adsorption performance and removal efficiency of nitrogen and phosphorus.
In order to make the technical scheme of the load control material in the water body mud source more clear and obvious, the invention is further described in detail by combining with specific embodiments.
Detailed Description
Bottom mud sampling and air drying
In the Dian lake region (24.908056 degrees N;102.690278 degrees E), a Petersen mud sampler is used for collecting bottom mud with the surface layer of 5-10cm, the bottom mud is put into an insulation box and taken back to a laboratory, the bottom mud is laid in a relatively open and ventilated place to be dried in air, and the dried bottom mud is used as a raw material for preparing the load control material in the water body mud source in the following examples.
Preparation of hydrophilic organic matter solution
The following examples 1-8 were conducted using XAD-8 resin to treat the organic solution to obtain a hydrophilic organic solution: adding the organic matter solution at a rate of 1 mL/min -1 Passing through an XAD-8 resin column, and collecting the fraction passing through the resin column; washing the resin column with 1.5 times of ultrapure water (BV), collecting the fraction passing through the resin column, and reusing the fraction at a concentration of 6 mol. L -1 Adjusting the pH to 2 with HCl; then the concentration of the mixture is 0.01 mol.L according to 1 time of column volume -1 The HCl solution is used for leaching the resin column, the part passing through the resin column is collected, and the three collected parts are mixed to obtain the hydrophilic organic matter solution.
The XAD-8 resin used in the embodiment has a column height of 50cm, a diameter of 4.5cm and a resin particle size of 50-250 μm, and the resin is pretreated before use, and the pretreatment method specifically comprises the following steps: XAD-8 resin at a concentration of 0.1 mol. L -1 Soaking in NaOH for 24 hr, extracting with acetone and hexane for 12 hr respectively to remove organic substances, soaking in methanol, loading into column, washing with methanol to remove acetone and hexane, and washing with ultrapure water until the DOC concentration of effluent is less than 1mol -1 。
Natural zeolite powder
The particle size range of the natural zeolite powder used in examples 1 to 8 below was 2 to 200 μm.
Example 1
The embodiment provides a load control material in a water body mud source, which is prepared by the following method: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain deposit powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 3. Adding polymeric alumina solid powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the polymeric alumina solid powder accounts for 1wt% of the mixture by mass. (3) Forming the paste into particles with the particle size range of 0.5-1cm, drying, and roasting at 400 ℃ for 3h; (4) Modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying the sediment taken from the water body, and mixing the freeze-dried sediment with distilled water to form a mixed solution, wherein the mass percentage of the sediment in the mixed solution is 10wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45 mu m microporous filter membrane to obtain an organic matter solution; and treating the organic matter solution by using XAD-8 resin to obtain a hydrophilic organic matter solution. The total organic carbon concentration in the hydrophilic organic matter solution is 42mg/L; and placing the roasted product in the hydrophilic organic matter solution for soaking for 24 hours, and taking out the roasted product after finishing the modification treatment to prepare the control material.
Example 2
The load control material in the water body mud source provided by the embodiment is prepared by the following method: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain sediment powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 7. Adding polymeric alumina solid powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the polymeric alumina solid powder accounts for 2wt% of the mixture by mass. (3) Forming the paste into particles with the particle size range of 0.5-1cm, drying, and roasting at 400 ℃ for 2h; (4) Modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying the sediment taken from the water body, and mixing the freeze-dried sediment with distilled water to form a mixed solution, wherein the mass percentage of the sediment in the mixed solution is 15wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45 mu m mixed fiber membrane to obtain an organic matter solution; and (3) treating the organic matter solution by using XAD-8 resin to obtain a hydrophilic organic matter solution. And (3) setting the total organic carbon concentration in the hydrophilic organic matter solution to be 51mg/L, placing the roasted product in the hydrophilic organic matter solution for soaking for 24 hours, taking out the roasted product after modification treatment is finished, and preparing the control material.
Example 3
The preparation method of the load control material in the water body mud source in the embodiment comprises the following steps: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain deposit powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 6. Adding polymeric alumina solid powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the polymeric alumina solid powder accounts for 3wt% of the mixture by mass; (3) Forming the paste into particles with the particle size range of 0.5-1cm, drying, and roasting at 400 ℃ for 1h; (4) Modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying the sediment taken from the water body, and mixing the freeze-dried sediment with distilled water to form a mixed solution, wherein the mass percentage of the sediment in the mixed solution is 15wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45 mu m mixed fiber membrane to obtain an organic matter solution; and treating the organic matter solution by using XAD-8 resin to obtain a hydrophilic organic matter solution. And (3) setting the total organic carbon concentration in the hydrophilic organic matter solution to be 51mg/L, placing the roasted product in the hydrophilic organic matter solution for soaking for 24 hours, taking out the roasted product after modification treatment is finished, and preparing the control material.
Example 4
The preparation method of the load control material in the water body sludge source in the embodiment comprises the following steps: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain sediment powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 6. Adding polymeric alumina solid powder into the mixture, adding distilled water, and stirring to form paste, wherein the addition amount of the polymeric alumina solid powder accounts for 4wt% of the mixture by mass; (3) Forming the paste into particles with the particle size range of 0.5-1cm, drying, and roasting at 400 ℃ for 2h; (4) Modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying sediments taken from a water body, and mixing the freeze-dried sediments with distilled water to form a mixed solution, wherein the mass percent of the sediments in the mixed solution is 15wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45 mu m mixed fiber membrane to obtain an organic matter solution; and treating the organic matter solution by using XAD-8 resin to obtain a hydrophilic organic matter solution. And the total organic carbon concentration in the hydrophilic organic matter solution is 51mg/L, the roasted product is placed in the hydrophilic organic matter solution to be soaked for 24 hours, and the roasted product is taken out after modification treatment is finished, so that the control material is prepared.
Example 5
In this embodiment, the preparation method of the load control material in the cement source includes: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain sediment powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 6. Adding solid polyaluminium oxide powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the solid polyaluminium oxide powder accounts for 4wt% of the mixture by mass; (3) Forming the paste into particles with the particle size range of 0.5-1cm, drying, and roasting at 600 ℃ for 2h; (4) Modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying the sediment taken from the water body, and mixing the freeze-dried sediment with distilled water to form a mixed solution, wherein the mass percentage of the sediment in the mixed solution is 15wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45 mu m mixed fiber membrane to obtain an organic matter solution; and treating the organic matter solution by using XAD-8 resin to obtain a hydrophilic organic matter solution. And the total organic carbon concentration in the hydrophilic organic matter solution is 51mg/L, the roasted product is placed in the hydrophilic organic matter solution to be soaked for 24 hours, and the roasted product is taken out after modification treatment is finished, so that the control material is prepared.
Example 6
In the present embodiment, the preparation method of the load control material in the cement source is as follows: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain deposit powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 6. Adding solid polyaluminium oxide powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the solid polyaluminium oxide powder accounts for 6wt% of the mixture by mass; (3) Forming the paste into particles with the particle size range of 0.5-1cm, drying, and roasting at 600 ℃ for 2h; (4) Modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying sediments taken from a water body, and mixing the freeze-dried sediments with distilled water to form a mixed solution, wherein the mass percent of the sediments in the mixed solution is 15wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45-micron mixed fiber membrane to obtain an organic matter solution, and treating the organic matter solution sequentially through XAD-8 resin and anion-cation exchange resin to obtain the hydrophilic organic matter solution; and treating the organic matter solution by using XAD-8 resin to obtain a hydrophilic organic matter solution. And (3) setting the total organic carbon concentration in the hydrophilic organic matter solution to be 51mg/L, placing the roasted product in the hydrophilic organic matter solution for soaking for 24 hours, taking out the roasted product after modification treatment is finished, and preparing the control material.
Example 7
In this embodiment, the preparation method of the load control material in the cement source includes: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain sediment powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 6. Adding solid polyaluminium oxide powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the solid polyaluminium oxide powder accounts for 10wt% of the mixture by mass; (3) Forming the paste into particles with the particle size range of 0.5-1cm, drying, and roasting at 600 ℃ for 2h; (4) Modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying sediments taken from a water body, and mixing the freeze-dried sediments with distilled water to form a mixed solution, wherein the mass percent of the sediments in the mixed solution is 15wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45 mu m mixed fiber membrane to obtain an organic matter solution; and treating the organic matter solution by using XAD-8 resin to obtain a hydrophilic organic matter solution. And the total organic carbon concentration in the hydrophilic organic matter solution is 51mg/L, the roasted product is placed in the hydrophilic organic matter solution to be soaked for 24 hours, and the roasted product is taken out after modification treatment is finished, so that the control material is prepared.
Example 8
In this embodiment, the preparation method of the load control material in the cement source includes: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain sediment powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 6. Adding solid polyaluminium oxide powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the solid polyaluminium oxide powder accounts for 10wt% of the mixture by mass; (3) Molding the paste into particles with the particle size range of 0.5-1cm, drying, and roasting at 400 ℃ for 2h; (4) Modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying sediments taken from a water body, and mixing the freeze-dried sediments with distilled water to form a mixed solution, wherein the mass percent of the sediments in the mixed solution is 15wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45 mu m mixed fiber membrane to obtain an organic matter solution; and treating the organic matter solution by using XAD-8 resin to obtain a hydrophilic organic matter solution. And the total organic carbon concentration in the hydrophilic organic matter solution is 51mg/L, the roasted product is placed in the hydrophilic organic matter solution to be soaked for 24 hours, and the roasted product is taken out after modification treatment is finished, so that the control material is prepared.
Examples of the experiments
In order to verify the technical effect of the load control material in the water body sludge source, the experimental example is arranged to carry out experimental tests on the control material prepared in the embodiments 1-8, and the experimental method is as follows:
the concentration ranges of the sediment interstitial water nitrogen and phosphorus of the Dian pond of the bottom mud sampling plot are respectively as follows: the ammonia nitrogen concentration is 2-20 mg/L, the phosphorus concentration is 0.2-2.0 mg/L, so the preparation of the mixed solution of ammonia nitrogen and phosphate with different concentrations adopts the following steps: the ammonia nitrogen concentration is 2, 5, 10, 15, 20mg/L, and the phosphate concentration is 0.2, 0.5, 1, 1.5, 2.0mg/L. Accurately weighing 0.5g of adsorbing material of the control material in a 100mL centrifuge tube, respectively adding ammonia nitrogen and phosphate mixed solution with different concentrations, placing the centrifuge tube in a constant temperature oscillation box for oscillation for 24h, T =25 ℃, and carrying out nitrogen and phosphorus adsorption experiments at the rotating speed of 200 r/min. The average values of the experimental results of ammonia nitrogen and phosphorus at the above concentrations are shown in the following table:
| ammonia nitrogen removal (%) | Phosphorus removal (%) | |
| Example 1 | 86.14 | 69.8 |
| Example 2 | 76.28 | 68.41 |
| Example 3 | 84.29 | 75.09 |
| Example 4 | 83.835 | 76.07 |
| Example 5 | 72.885 | 70.99 |
| Example 6 | 77.6 | 66.55 |
| Example 7 | 75.25 | 79.39 |
| Example 8 | 75.665 | 82.34 |
From the above experimental results, it can be seen that the sediment/natural zeolite material of the load control material in the water body sludge source prepared in examples 1-8 has good adsorption effect on nitrogen and phosphorus after being modified by the polymeric alumina, and the control material modified by the hydrophilic organic matter also has very excellent adsorption effect on nitrogen and phosphorus under the high temperature calcination condition of 600 ℃.
Comparative example
In order to further verify the technical effect of the load control material in the water body mud source, a comparative example is arranged for carrying out a comparative experiment.
Comparative example 1
The preparation method of the control material in the comparative example was: (1) Crushing and grinding the air-dried bottom mud by using a crusher, and sieving by using a 100-mesh sieve to obtain sediment powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 6. Adding solid polyaluminium oxide powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the solid polyaluminium oxide powder accounts for 10wt% of the mixture by mass; (3) Forming the paste into granules, drying, and roasting at 600 ℃ for 2h; modifying the roasted product, wherein the modifying method comprises the following steps: freeze-drying sediments taken from a water body, and mixing the freeze-dried sediments with distilled water to form a mixed solution, wherein the mass percent of the sediments in the mixed solution is 15wt%; placing the mixed solution in a constant-temperature oscillation box for oscillation for 16h, wherein the rotating speed is 200r/min; then passing through a 0.45 mu m mixed fiber membrane to obtain an organic matter solution; and placing the roasted product in the organic matter solution to be soaked for 24 hours, taking out the roasted product after modification treatment is finished, and preparing to obtain the control material. The control material prepared in the comparative example is subjected to an adsorption experiment of nitrogen and phosphorus, the steps of the adsorption experiment are the same as those of the experimental example, and the result shows that the removal rate of ammonia nitrogen is 52.1% and the removal rate of phosphorus is 60.6%.
According to the comparative example, compared with the method for modifying the hydrophilic organic matter, the method for modifying the control material by using the soluble DOM has the advantage that the removal rate of nitrogen and phosphorus is lower.
Comparative example 2
The preparation method of the control material in this comparative example was: (1) Crushing and grinding the air-dried bottom mud by using a crusher, sieving by using a 100-mesh sieve, and roasting at 800 ℃ for 2 hours to obtain deposit powder; (2) And (2) mixing the sediment powder prepared in the step (1) with natural zeolite powder according to the mass ratio of 6. Adding solid polyaluminium oxide powder into the mixture, adding distilled water, and stirring to obtain paste, wherein the addition amount of the solid polyaluminium oxide powder accounts for 10wt% of the mixture by mass; (3) And forming the paste into particles, drying, and roasting at 600 ℃ for 2 hours to obtain the control material. The control material prepared by the comparative example is subjected to an adsorption experiment of nitrogen and phosphorus, the adsorption experiment steps are the same as those of the experimental example, and the result shows that the removal rate of phosphorus is as high as 98.72%, and the removal rate of ammonia nitrogen is only 31.01%. Compared with the control material in the embodiment 8, the removal rate of nitrogen and phosphorus can reach more than 75%, and the removal rate of ammonia and nitrogen in the comparative example is only 31.01%, so that the control material prepared in the invention has better balance for controlling the adsorption of nitrogen and phosphorus, and is more suitable for being used in water body spaces with serious nitrogen and phosphorus pollution.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the claims.
Claims (7)
1. The application of a load control material in a water body mud source in controlling the release of nitrogen and phosphorus in bottom mud is characterized in that the control material is prepared by the following method:
(1) Taking water body bottom mud, and carrying out vacuum freeze drying, grinding and sieving to obtain sediment powder;
(2) Mixing the sediment powder prepared in the step (1) with natural zeolite powder, and stirring to obtain a uniform mixture; adding polymeric alumina solid powder and water into the mixture, and stirring the mixture into paste, wherein the addition amount of the natural zeolite powder accounts for 30-70 wt% of the mixture by mass, and the addition amount of the polymeric alumina solid powder accounts for 1-10 wt% of the mixture by mass;
(3) Molding and drying the paste, and then roasting at 400-600 ℃;
(4) Placing the roasted product obtained in the step (3) in an aqueous solution of a hydrophilic organic matter for modification treatment, and taking out the roasted product after the modification treatment is finished to prepare the control material;
the method for performing modification treatment in the step (4) comprises the following steps: freeze-drying the water body bottom mud, and mixing the freeze-dried sediment with distilled water to form a mixed solution; oscillating the mixed solution, and then passing through a membrane to obtain an organic matter solution, wherein the organic matter solution is treated by XAD-8 resin to obtain a hydrophilic organic matter aqueous solution; and soaking the roasted product in the aqueous solution of the hydrophilic organic matter to prepare the control material.
2. Use according to claim 1, wherein the natural zeolite powder has a particle size in the range of 2-200 μm.
3. Use according to claim 1 or 2, wherein in step (3) the paste is shaped into granules having a particle size of 0.5-5 cm.
4. Use according to claim 3, wherein the aqueous solution of hydrophilic organic matter has a total organic carbon concentration of not less than 25mg/L.
5. The application of the modified liquid of claim 4, wherein in the modification treatment, the mixed liquid is put in a constant temperature oscillation box to oscillate for 16h, and the rotating speed is 200r/min; and filtering by using a 0.45 mu m mixed fiber membrane to obtain an organic matter solution.
6. The use of claim 5, wherein the modification treatment is carried out by soaking the roasted product in the aqueous solution of the hydrophilic organic matter for 24h to prepare the control material.
7. The use according to claim 6, wherein the polyaluminium oxide solid powder is added in an amount of 6 to 10wt% by mass of the mixture.
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