CN109865502B - Oyster shell powder modified water treatment agent and preparation method and application thereof - Google Patents
Oyster shell powder modified water treatment agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an oyster shell powder modified water treatment agent and a preparation method and application thereof. The preparation method comprises the following steps: evenly mixing oyster shell powder, Polyacrylamide (PAM) and a solvent, and adding a pH regulator to regulate the pH; ultrasonic emulsification, stirring and heating at 50-90 ℃ for 30-150 min, cooling to room temperature, centrifuging, drying, crushing and sieving to obtain modified oyster shell powder; and (3) uniformly mixing the modified oyster shell powder with sodium carboxymethylcellulose, naturally airing, calcining at a medium-low temperature, and cooling to obtain the oyster shell powder modified water treatment agent. The oyster shell powder modified water treatment agent of the invention is Ni2+、Co2+、Cu2+The heavy metal ions have a faster and more efficient adsorption effect, and excellent stability and durability, effectively realize the treatment of wastes with processes of wastes against one another, are efficient environment-friendly adsorption separation materials, and have good application value.
Description
Technical Field
The invention belongs to the technical field of biological medicines. More particularly relates to an oyster shell powder modified water treatment agent and a preparation method and application thereof.
Background
The oysters are economic shellfishes with the largest culture yield in China, and a large amount of waste oyster shells are generated while people enjoy the delicious taste. At present, the oyster shells are processed relatively less in China, most of the oyster shells are discarded or buried, and some organic matters in the oyster shells are putrefactive due to long-term stacking, so that the environmental pollution and the resource waste are caused. The oyster has two shells, the right shell is also called the upper shell and the left shell is also called the lower shell. Oyster shell divide into 3 layers according to the mode of formation and organizational structure's difference: the outermost layer is cuticle or cortex (periodoracum) which contains conchiolin and has stronger resistance to corrosion of external chemical articles; the middle layer is a prism layer (prism layer) which is formed by lime sediment of polygonal prism crystals and contains a large number of micropores with the diameter of 2-10 mu m; the inner layer is a pearl layer (pearl layer), which is mainly composed of calcite and can be gradually thickened, and the pearl layer is more layered with the age of the oyster. The oyster shell contains calcium carbonate, calcium phosphate and other compounds, and the content of calcium element is more than 95%. The oyster shell has a special physical structure, and a plurality of mutually communicated pore channels are arranged in the oyster shell, so that after the oyster shell is processed by a special process, a plurality of hole structures with different functions can be generated, and the oyster shell has higher application value in the aspects of medicine, food, chemical industry and the like. About 100 million tons of waste oyster shells are produced in China coastal every year, and the raw materials which are accumulated to cause disasters cause low cost and developability of product cost, thus having strong market competitiveness.
Oyster shell can be used as an adsorbent in water treatment. In the process of water treatment, oyster shell has both adsorbed certain pollutant, has also taken place some chemical reaction: on one hand, the oyster shell has certain adsorption capacity due to the special physical structure, and a plurality of pollutants are attached to the hole structure; on the other hand, the oyster shell mainly contains calcium carbonate which is slightly soluble in water and reacts with certain pollutants in water to produce complex or precipitate. In general, physical adsorption and chemical precipitation occur simultaneously, but the water treatment efficiency of a water treatment agent of single oyster shell is low, the adsorption capacity is slow, the adsorption efficiency is low, the adsorption capacity is poor, and modification is needed.
In order to improve the water treatment efficiency, oyster shells are often modified by high-temperature calcination at present; or modifying oyster shell with organic substance widely used, such as clay and kaolin, to obtain easily-usable granular material; or modifying oyster shell with sodium dodecyl sulfate (CN107126931A), sodium hexadecyl sulfonate (CN103551119A), sodium dodecyl sulfate (CN106423085A), hexadecyl trimethyl ammonium bromide, octadecyl amine and other surfactant to raise the adsorption efficiency. But the adopted modifier has not obvious modification effect on oyster shells, has not obvious improvement on the water body treatment capability and has not obvious effect on Ni in the water body2+、Co2+The removal rate is low, the adsorption selectivity is poor, and the interference of other high-content substances is easy to occur; in addition, the cost of calcination and surfactant is high, and if the surfactant cannot be recycled, the treatment cost is obviously increased, and the application prospect of the surfactant as an excellent adsorbent is limited; in addition, the modified oyster shell material is difficult to adsorb and then treat, and secondary pollution is easily caused. Therefore, the development of the oyster shell powder modified water treatment agent which is efficient, reusable and cheap has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provide a preparation method of an oyster shell powder modified water treatment agent, which is convenient to prepare, high in efficiency, reusable and low in cost.
The invention also aims to provide the oyster shell powder modified water treatment agent prepared by the preparation method, which has the advantages of quick and efficient adsorption effect and excellent reusability.
The invention also aims to provide application of the oyster shell powder modified water treatment agent in serving as or preparing a sewage treatment agent, in particular to application in adsorption and removal of heavy metal Ni2+、Co2+、Cu2+The use of (1).
The purpose of the invention is realized by the following technical scheme:
a preparation method of an oyster shell powder modified water treatment agent comprises the following steps:
s1, uniformly mixing oyster shell powder, Polyacrylamide (PAM) and a solvent to obtain a suspension, and adding a pH regulator to regulate the pH of the suspension to 5-9; wherein, the addition amount of the polyacrylamide is 1 to 20 percent of the weight of the oyster shell powder;
s2, ultrasonically emulsifying the suspension, stirring and heating at 50-90 ℃ for 30-150 min, cooling to room temperature, centrifugally separating for 4-8 times, drying, crushing and sieving to obtain modified oyster shell powder;
and S3, mixing the modified oyster shell powder with sodium carboxymethylcellulose, uniformly stirring, adding water to condense the mixture to prepare a hollow ring adsorbent, naturally drying the hollow ring adsorbent, calcining the hollow ring adsorbent at a medium-low temperature of 250-300 ℃ for 10-15 hours, and cooling to obtain the oyster shell powder modified water treatment agent.
Further, in a preferred embodiment of the present invention, in step S1, the solvent is water.
Further, in the preferred embodiment of the present invention, in step S1, the addition amount of polyacrylamide is 10% to 20% by weight of oyster shell powder.
Further, in a preferred embodiment of the present invention, in step S1, the amount of polyacrylamide added is 15% to 20% by weight of oyster shell powder.
Further, in the preferred embodiment of the present invention, in step S1, the pH is adjusted to 7-9.
Furthermore, in the preferred embodiment of the present invention, in step S1, the pH is adjusted to 7.5-8.
Further, in the preferred embodiment of the present invention, in step S2, the stirring is constant temperature magnetic stirring.
Further, in a preferred embodiment of the present invention, in step S2, the temperature of stirring and heating is 70 to 90 ℃.
Further, in the preferred embodiment of the present invention, in step S2, the stirring and heating temperature is 80 ℃.
Further, in the preferred embodiment of the present invention, in step S2, the stirring and heating time is 90-150 min.
Furthermore, in the preferred embodiment of the present invention, in step S2, the stirring and heating time is 120-150 min.
Further, in the preferred embodiment of the present invention, in step S2, the drying is performed at 60-70 ℃.
Further, in a preferred embodiment of the present invention, in step S2, the sieving is performed by 80-100 mesh sieving.
Further, in a preferred embodiment of the present invention, in step S3, the mass ratio of the modified oyster shell powder to the sodium carboxymethyl cellulose is 30-35: 1.
oyster shell powder modified water treatment agent prepared by using method and application of oyster shell powder modified water treatment agent as or in preparation of Ni2+、Co2+、Cu2+The application of the adsorbent is also in the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention fully utilizes the unique physical and chemical characteristics of the modified oyster shell powder material, modifies the modified oyster shell powder material by a specific modifier Polyacrylamide (PAM) and a modification method, and modifies Ni2+、Co2+、Cu2+The heavy metal ions have a faster and more efficient adsorption effect, effectively realize the treatment of wastes with processes of wastes against one another, and are efficient environment-friendly adsorption separation materials.
2. The oyster shell powder modified water treatment agent disclosed by the invention has excellent stability and durability, after adsorption and degradation are completed and the water treatment agent is recycled for 3 times, a certain adsorption removal rate can still be kept for heavy metal ions, the reusability of the water treatment agent is excellent, and the recovery method of the modified oyster shell powder modified water treatment agent is simple and does not cause secondary pollution. In addition, the preparation process is simple, the conditions are easy to control, the modification cost is greatly reduced, and the method is suitable for batch production.
Drawings
FIG. 1 is a standard curve of nickel ions.
FIG. 2 is a standard curve of copper ions.
FIG. 3 is a standard curve for cobalt ion.
Fig. 4 shows the effect of the addition amount of Polyacrylamide (PAM) on the removal rate of cobalt ions.
FIG. 5 shows the effect of the amount of Polyacrylamide (PAM) added on the copper ion removal rate.
FIG. 6 shows the effect of the amount of Polyacrylamide (PAM) added on the removal rate of nickel ions.
Fig. 7 is a graph showing the influence of the stirring heating time on the cobalt ion removal rate in step S2.
Fig. 8 is a graph showing the effect of the stirring heating time on the copper ion removal rate in step S2.
Fig. 9 is a graph showing the influence of the stirring heating time on the nickel ion removal rate in step S2.
Fig. 10 is a graph showing the effect of the stirring heating temperature on the cobalt ion removal rate in step S2.
Fig. 11 shows the effect of the stirring heating temperature on the copper ion removal rate in step S2.
Fig. 12 is a graph showing the influence of the agitation heating temperature on the nickel ion removal rate in step S2.
Fig. 13 is a graph showing the effect of the pH of the mixed solution on the removal rate of cobalt ions in step S1.
Fig. 14 is a graph showing the effect of the pH of the mixed solution on the removal rate of copper ions in step S1.
Fig. 15 is a graph showing the effect of the pH of the mixed solution on the removal rate of nickel ions in step S1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1 preparation of oyster Shell powder-modified Water treatment agent
A preparation method of an oyster shell powder modified water treatment agent comprises the following steps:
s1, evenly mixing oyster shell powder, polyacrylamide and solvent water to obtain a suspension, and adding a pH regulator to regulate the pH of the suspension to 7.5; wherein the addition amount of the polyacrylamide is 15 percent of the weight of the oyster shell powder;
s2, ultrasonically emulsifying the suspension, magnetically stirring and heating at the constant temperature of 80 ℃ for 120min, cooling to room temperature, centrifugally separating for 4-8 times, drying and crushing at 70 ℃, and sieving with a 100-mesh sieve to obtain modified oyster shell powder;
s3, mixing the modified oyster shell powder with sodium carboxymethylcellulose (the mass ratio of the modified oyster shell powder to the sodium carboxymethylcellulose is 30: 1), uniformly stirring, adding water to coagulate the mixture to prepare a hollow ring adsorbent, naturally drying the hollow ring adsorbent, calcining the hollow ring adsorbent at 250 ℃ for 11 hours, and cooling the hollow ring adsorbent to obtain the oyster shell powder modified water treatment agent.
Example 2 preparation of oyster Shell powder-modified Water treatment agent
A preparation method of an oyster shell powder modified water treatment agent comprises the following steps:
s1, uniformly mixing oyster shell powder, polyacrylamide and solvent water to obtain a suspension, and adding a pH regulator to regulate the pH of the suspension to 8; wherein the addition amount of the polyacrylamide is 20 percent of the weight of the oyster shell powder;
s2, ultrasonically emulsifying the suspension, magnetically stirring and heating at the constant temperature of 70 ℃ for 150min, cooling to room temperature, centrifugally separating for 4-5 times, drying and crushing at the temperature of 70 ℃, and sieving with a 100-mesh sieve to obtain modified oyster shell powder;
s3, mixing the modified oyster shell powder with sodium carboxymethylcellulose (the mass ratio of the modified oyster shell powder to the sodium carboxymethylcellulose is 35: 1), uniformly stirring, adding water to coagulate the mixture to prepare a hollow ring adsorbent, naturally drying the hollow ring adsorbent, calcining the hollow ring adsorbent at 260 ℃ for 12 hours, and cooling the hollow ring adsorbent to obtain the oyster shell powder modified water treatment agent.
Example 3 preparation of oyster Shell powder-modified Water treatment agent
A preparation method of an oyster shell powder modified water treatment agent comprises the following steps:
s1, uniformly mixing oyster shell powder, polyacrylamide and solvent water to obtain a suspension, and adding a pH regulator to regulate the pH of the suspension to 7; wherein the addition amount of the polyacrylamide is 20 percent of the weight of the oyster shell powder;
s2, ultrasonically emulsifying the suspension, magnetically stirring and heating at the constant temperature of 90 ℃ for 90min, cooling to room temperature, centrifugally separating for 4-5 times, drying and crushing at 70 ℃, and sieving with a 100-mesh sieve to obtain modified oyster shell powder;
s3, mixing the modified oyster shell powder with sodium carboxymethylcellulose (the mass ratio of the modified oyster shell powder to the sodium carboxymethylcellulose is 30: 1), uniformly stirring, adding water to coagulate the mixture to prepare a hollow ring adsorbent, naturally drying the hollow ring adsorbent, calcining the hollow ring adsorbent at 270 ℃ for 13 hours, and cooling the hollow ring adsorbent to obtain the oyster shell powder modified water treatment agent.
Example 4 preparation of oyster Shell powder-modified Water treatment agent
A preparation method of an oyster shell powder modified water treatment agent comprises the following steps:
s1, uniformly mixing oyster shell powder, polyacrylamide and solvent water to obtain a suspension, and adding a pH regulator to regulate the pH of the suspension to 9; wherein the addition amount of the polyacrylamide is 10 percent of the weight of the oyster shell powder;
s2, ultrasonically emulsifying the suspension, magnetically stirring and heating at the constant temperature of 50 ℃ for 30min, cooling to room temperature, centrifugally separating for 4-5 times, drying and crushing at 70 ℃, and sieving with a 100-mesh sieve to obtain modified oyster shell powder;
s3, mixing the modified oyster shell powder with sodium carboxymethylcellulose (the mass ratio of the modified oyster shell powder to the sodium carboxymethylcellulose is 30: 1), uniformly stirring, adding water to coagulate the mixture to prepare a hollow ring adsorbent, naturally drying the hollow ring adsorbent, calcining the hollow ring adsorbent at 280 ℃ for 14 hours, and cooling the hollow ring adsorbent to obtain the oyster shell powder modified water treatment agent.
Example 5 preparation of oyster Shell powder-modified Water treatment agent
A preparation method of an oyster shell powder modified water treatment agent comprises the following steps:
s1, uniformly mixing oyster shell powder, polyacrylamide and solvent water to obtain a suspension, and adding a pH regulator to regulate the pH of the suspension to 5; wherein the addition amount of the polyacrylamide is 20 percent of the weight of the oyster shell powder;
s2, ultrasonically emulsifying the suspension, magnetically stirring and heating at the constant temperature of 50 ℃ for 30min, cooling to room temperature, centrifugally separating for 4-5 times, drying and crushing at 70 ℃, and sieving with a 100-mesh sieve to obtain modified oyster shell powder;
s3, mixing the modified oyster shell powder with sodium carboxymethylcellulose (the mass ratio of the modified oyster shell powder to the sodium carboxymethylcellulose is 30: 1), uniformly stirring, adding water to coagulate the mixture to prepare a hollow ring adsorbent, naturally drying the hollow ring adsorbent, calcining the hollow ring adsorbent at 300 ℃ for 15 hours, and cooling the hollow ring adsorbent to obtain the oyster shell powder modified water treatment agent.
Oyster shells are modified by adopting the water treatment preparations prepared in examples 1 to 5 and the prior art (CN107126931A) as a surfactant, 6 parts of sample water are respectively treated, and the recycling rate is compared.
The test method comprises the following steps: the water treatment preparations prepared in examples 1 to 5 and the water treatment preparation prepared by using sodium lauryl sulfate as a surfactant according to the prior art (CN107126931A) were treated with 6 samples of the water treatment preparation containing Co2+Ionized water adsorbing Co2+The desorption of the ionic water treatment preparation adopts deionized water, synthetic (artificial) zeolite and the water treatment preparation according to the ratio of 100: 1: 20, slightly vibrating a layered container for 2-4 hours for the synthetic (artificial) zeolite and the water treatment preparation, taking out the water treatment preparation, and drying to complete desorption. The results are shown in Table 1.
TABLE 1 Water treatment formulations prepared in examples 1-5
The oyster shell powder modified water treatment agent has excellent stability and durability, and can be recycled for 2-3 times after adsorption and degradation are finished, so that Co can be treated2+The adsorption efficiency of the composite adsorbent is still more than 65%, the heavy metal ions still can keep higher adsorption removal rate, after the composite adsorbent is recycled for 3 times, the heavy metal ions still can keep certain adsorption removal rate, and the reusability of the composite adsorbent is excellent.
Example 6 measurement of adsorption Capacity of Water treatment agent to heavy Metal ions
1. Preparation of Standard solutions
(1) Preparing a nickel ion standard solution: weighing NiSO 0.2g, 0.5g, 0.8g, 1.0g and 1.5g respectively4·6H2And adding 100mL of purified water into the O to prepare standard nickel ion solutions with the concentrations of 0.4466g/L, 1.1165g/L, 1.7864g/L, 2.233g/L and 3.3495g/L to prepare a standard nickel ion curve, which is shown in figure 1.
(2) Preparing a copper ion standard solution: 0.5g, 0.75g, 1.0g, 1.25g and 1.5g of CuSO are respectively weighed4100mL of purified water was added to prepare standard solutions of copper ions at concentrations of 1.991g/L, 2.919g/L, 3.892g/L, 4.865g/L and 5.973g/L, to obtain a standard curve of copper ions, as shown in FIG. 2.
(3) Preparing a cobalt ion standard solution: 0.125g, 0.25g, 0.5g, 0.75g and 1.0g of cobalt acetate tetrahydrate are respectively weighed and added into 100mL of purified water to prepare cobalt ion standard solutions with the concentrations of 0.2957g/L, 0.5914g/L, 1.1827g/L, 1.7741g/L and 2.3654g/L, and a standard curve of cobalt ions is prepared, and is shown in figure 3.
50mL of each of a nickel ion solution with the concentration of 1.7864g/L, a copper ion solution with the concentration of 3.892g/L and a cobalt ion solution with the concentration of 1.7741g/L is respectively prepared and placed in a conical flask, 0.1g of the oyster shell powder modified water treatment agent is respectively added, standing is carried out for 24 hours at normal temperature, supernatant is taken to measure the absorbance, the average value is measured for three times, and the removal rate of heavy metal ions is calculated.
2. Optimization test of water treatment agent preparation process
The following absorbances were measured by an ultraviolet spectrophotometer, and 0.05g of the prepared water treatment agent was placed in a metal ion solution and left to stand for 22 hours, respectively.
(1) Effect of Polyacrylamide (PAM) addition amount on modification Effect
Examination of the amount of Polyacrylamide (PAM) added to Ni2+、Co2+、Cu2+The removal rate of (c). It is found that the removal rate of different heavy metal ions is affected differently by the addition amount of polyacrylamide.
1) The effect on the removal rate of cobalt ions is shown in table 2 and fig. 4.
TABLE 2 influence of the amount of PAM added on the removal rate of cobalt ions
As can be seen from table 2 and fig. 4, the removal rate of cobalt ions in a certain range tends to increase with the amount of the modifier Polyacrylamide (PAM).
2) The effect on the copper ion removal rate is shown in table 3 and fig. 5.
TABLE 3 influence of the amount of PAM added on the copper ion removal rate
As can be seen from table 3 and fig. 5, the removal rate of copper ions in a certain range tends to increase with the amount of the modifier Polyacrylamide (PAM). .
3) The effect on the removal rate of nickel ions is shown in table 4 and fig. 6.
TABLE 4 influence of PAM addition amount on Nickel ion removal Rate
As can be seen from table 4 and fig. 6, the removal rate of nickel ions in a certain range tends to increase with the amount of the modifier Polyacrylamide (PAM).
(2) Effect of modification time on modification Effect
Considering the stirring heating time in step S2 for Ni2+、Co2+、Cu2+The removal rate of (c). It was found that the removal rates of different heavy metal ions were not affected the same by the time factor of the stirring heating in step S2.
1) The effect on the removal rate of cobalt ions is shown in table 5 and fig. 7.
TABLE 5 Effect of modification time on cobalt ion removal Rate
As can be seen from table 5 and fig. 7, the cobalt ion removal rate increases with the increase in the stirring heating time in step S2 within a certain range.
2) The effect on the copper ion removal rate is shown in table 6 and fig. 8.
TABLE 6 Effect of modification time on copper ion removal Rate
As can be seen from table 6 and fig. 8, the copper ion removal rate increased with the increase in the stirring heating time in step S2 between 30min and 90 min.
3) The effect on the removal rate of nickel ions is shown in table 7 and fig. 9.
TABLE 7 influence of modification time on Nickel ion removal Rate
As can be seen from Table 7 and FIG. 9, the oyster shell powder-modified water treatment agent of the present invention has a good removal rate of nickel ions.
(3) Influence of modification temperature on modification Effect
With Ni2+、Co2+、Cu2+The removal rate of (2) was used as an index, and the influence of the stirring heating temperature in step S2 on the modification effect of oyster shell powder was examined.
1) The effect on the removal rate of cobalt ions is shown in table 8 and fig. 10.
TABLE 8 Effect of modification temperature on cobalt ion removal Rate
As can be seen from table 8 and fig. 10, the removal rate of cobalt ions in a certain range tends to increase as the stirring heating temperature in step S2 increases.
2) The effect on the copper ion removal rate is shown in table 9 and fig. 11.
TABLE 9 Effect of modification temperature on copper ion removal Rate
As can be seen from table 9 and fig. 11, the removal rate of copper ions in a certain range tends to increase as the stirring heating temperature in step S2 increases.
3) The effect on the removal rate of nickel ions is shown in table 10 and fig. 12.
TABLE 10 influence of modification temperature on Nickel ion removal Rate
As can be seen from table 10 and fig. 12, in a certain range, the removal rate of nickel ions did not change much as the heating temperature of the constant temperature magnetic stirring was increased in step S2, but at 80 ℃, the removal rate of nickel ions reached the maximum.
(4) Influence of pH value of modified solution on modification effect
With Ni2+、Co2+、Cu2+The removal rate of (D) was used as an index, and the influence of the pH value of the mixed solution in step S1 on the modification effect of oyster shell powder was examined.
1) The effect on the removal rate of cobalt ions is shown in table 11 and fig. 13.
TABLE 11 influence of pH of the modified solution on the removal rate of cobalt ions
As can be seen from table 11 and fig. 13, the removal rate of cobalt ions in a certain range shows a tendency to increase as the pH value of the mixed solution increases in step S1.
2) The effect on the copper ion removal rate is shown in table 12 and fig. 14.
TABLE 12 influence of pH of modified solution on copper ion removal
As can be seen from table 12 and fig. 14, the removal rate of copper ions in a certain range shows a tendency to increase as the pH value of the mixed solution increases in step S1.
3) The effect on the nickel ion removal rate is shown in table 13 and fig. 15.
TABLE 13 influence of pH of modified solution on removal of Nickel ions
As can be seen from table 13 and fig. 15, the removal rate of nickel ions in a certain range shows a tendency to increase as the pH value of the mixed solution increases in step S1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. Application of oyster shell powder modified water treatment agent in preparation of Ni2+、Co2+The application of the adsorbent is characterized in that the preparation method of the oyster shell powder modified water treatment agent comprises the following steps:
s1, uniformly mixing oyster shell powder, polyacrylamide and a solvent to obtain a suspension, and adding a pH regulator to regulate the pH of the suspension to 5-9; wherein the addition amount of the polyacrylamide is 10-20% of the weight of the oyster shell powder;
s2, ultrasonically emulsifying the suspension, stirring and heating at 50-90 ℃ for 30-150 min, cooling to room temperature, centrifugally separating for 4-8 times, drying, crushing and sieving to obtain modified oyster shell powder;
s3, mixing the modified oyster shell powder with sodium carboxymethylcellulose, uniformly stirring, adding water to coagulate the mixture to prepare a hollow ring adsorbent, naturally drying the hollow ring adsorbent, calcining the hollow ring adsorbent at a medium-low temperature of 250-300 ℃ for 10-15 hours, and cooling to obtain the oyster shell powder modified water treatment agent;
wherein the mass ratio of the modified oyster shell powder and the sodium carboxymethyl cellulose in the step S3 is 30-35: 1.
2. the use according to claim 1, wherein in step S1, the polyacrylamide is added in an amount of 15-20% by weight based on the weight of oyster shell powder.
3. The use according to claim 2, wherein in step S1, the pH is adjusted to 7-9.
4. The use according to claim 3, wherein the temperature of stirring and heating in step S2 is 70-90 ℃.
5. The use according to claim 4, wherein in step S2, the stirring and heating time is 90-150 min.
6. The use according to claim 5, wherein in step S2, the drying is carried out at 60-70 ℃; and the sieving is to sieve the mixture by a sieve of 80-100 meshes.
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