CN113145063A - Magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent and preparation and application methods thereof - Google Patents
Magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent and preparation and application methods thereof Download PDFInfo
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Abstract
The invention provides a magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent, which comprises an attapulgite clay carrier, wherein lanthanum and ferroferric oxide are loaded on the attapulgite clay carrier. The attapulgite clay carrier in the application provides an ideal structure without additional structural modification, and can ensure the uniform distribution of lanthanum loaded in the surface and the internal reticular pores, thereby improving the adsorption capacity of the adsorbent. Simultaneously solves the problem of lanthanum modified adsorptionThe material is easy to block in the modification process. The invention adds Fe3O4The method adds magnetism to the attapulgite clay, and the magnetic material is easy to separate from the water body, thereby realizing the effective recovery of phosphate and the reutilization of the material. Therefore, the magnetic lanthanum hydroxide modified attapulgite clay adsorbent (La-ATP @ Fe) provided by the invention3O4) Can achieve the high-efficiency adsorption and recovery of the phosphorus in the water body.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent, and a preparation method and an application method thereof.
Background
Phosphorus is one of the key nutrients in most aquatic and terrestrial ecosystems, and excessive phosphorus input into water can lead to eutrophication of the water body, with potentially devastating consequences for aquatic ecosystems, including excessive growth of harmful algal blooms and the spread of dead zones in coastal marine ecosystems. In order to avoid eutrophication and ensure the biological stability of water, the phosphorus concentration in the discharged wastewater is required to be less than 0.5mg/L in China. Therefore, the removal of phosphorus from water is a major concern for controlling eutrophication of water.
Several methods for removing phosphate from water exist in the prior art, including chemical precipitation, biological treatment, membrane technology and adsorption methods. Among them, the chemical precipitation method is widely used because of its low cost, but its performance is easily affected by pH and redox conditions, and a large amount of sludge is generated and secondary pollution is caused. Bioprocessing can provide high efficiency, but requires highly skilled operations and relatively high costs. The membrane technology for phosphorus removal has excellent efficiency, but may have the disadvantages of high investment and high energy cost, and is also not suitable for large-scale popularization and use.
Compared with other methods, the adsorption process has the advantages of low cost, simple operation, low energy consumption and high efficiency (especially at low phosphorus concentration), so the adsorption process is considered to be an effective and practical choice for removing phosphorus, and the key point of the method is how to select a proper adsorbent. However, the adsorbing material in the prior art generally has the disadvantages of low saturated adsorption capacity, easily influenced phosphorus removal efficiency by pH and the like, so that the adsorption capacity of the adsorbent needs to be improved, and the anti-interference capability of the adsorbent is enhanced. In addition, many adsorption materials do not work after being saturated, so that the preparation of an appropriate adsorption material with high adsorption capacity and good regeneration performance is particularly important to achieve the dual purposes of eliminating phosphorus pollution and recovering phosphorus resources.
Disclosure of Invention
What this application solved is how to improve the adsorption capacity of removing phosphorus adsorbent, reinforcing adsorbent interference killing feature and can realize the problem of recycle, and then provide a adsorption capacity height, interference killing feature strong, and the magnetic lanthanum load attapulgite clay that easily recycles removes phosphorus adsorbent, this application provides this method of preparing and application method that removes phosphorus adsorbent simultaneously.
The technical scheme adopted by the application for solving the technical problems is as follows:
the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent comprises an attapulgite clay carrier, wherein lanthanum and ferroferric oxide are loaded on the attapulgite clay carrier.
The BET specific surface area of the phosphorus removal adsorbent is 64-83m2(ii)/g; pore volume of 0.16-0.21 cc/g; the average pore diameter is 6.9-9.1 nm.
The preparation method of the magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent comprises the following steps: (1) calcining attapulgite clay to obtain an attapulgite clay carrier; (2) putting the attapulgite clay carrier prepared in the step (1) into deionized water, and adding solid FeSO in a nitrogen atmosphere4·7H2O and solid FeCl3Stirring uniformly; (3) rapidly adding ammonia water, fully stirring at 60-80 ℃ for reaction, and cooling to room temperature to obtain the attapulgite clay carrier loaded with ferroferric oxide; (4) separating the attapulgite clay carrier loaded with ferroferric oxide from the liquid, and washing, freezing and drying to obtain magnetic attapulgite clay; (5) mixing the magnetic attapulgite clay with LaCl3Mixing the solutions, adjusting the pH of the solution to 10.0-11.0 under stirring, and separating to obtain magnetic attapulgite clay loaded with lanthanum; (6) washing the magnetic attapulgite clay loaded with lanthanum to be neutral, and drying to obtain the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent.
In the step (1), the attapulgite clay is calcined for 2 to 3 hours at the temperature of between 400 and 500 ℃.
In the step (2), when the attapulgite clay carrier is placed in deionized water, the addition amount of the attapulgite clay carrier is 30-35 g/L; in step (2), FeSO4·7H2O and FeCl3In a molar ratio of 1: 2-1: 2.5; the FeSO4·7H2The addition amount of O in the deionized water is 1-1.2 mol/L.
The mass concentration of the ammonia water added in the step (3) is 25-28%; the volume ratio of the added ammonia water to the deionized water in the step (2) is 0.4-0.5.
In the step (5), the LaCl3The concentration of the solution is 0.02-0.03 mol/L; mixing the magnetic attapulgite clay with LaCl3When the solution is mixed, the magnetic attapulgite clay is in LaCl3The addition amount of the solution is 30-33 g/L.
In the step (5), after the pH value of the solution is adjusted to 10-11 under the stirring state, the mixed solution is vibrated for 24-26h under the conditions of 60-70 ℃ and 150-.
The application method of the magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent prepared by the preparation method comprises the following steps: the magnetic lanthanum-loaded attapulgite clay dephosphorization adsorbent is uniformly sprayed on the surface of a water body to adsorb phosphate in the water body.
And after the dosing is finished for 1-2h, sucking out the dephosphorized dephosphorizing adsorbent by using a magnet, washing the separated dephosphorizing adsorbent by using water, desorbing for 2-3h by using a 1-1.5M NaOH solution at room temperature, washing and drying to finish the regeneration of the dephosphorizing adsorbent.
The magnetic lanthanum-loaded attapulgite clay dephosphorization adsorbent has the advantages that:
the magnetic lanthanum-loaded attapulgite clay dephosphorization adsorbent provided by the invention adopts attapulgite clay as a carrier, and the calcined attapulgite clay carrier has internal mesopores/macropores formed by a cross-linked crystalline fiber network, so that an ideal structure is provided for lanthanum loading without additional structural modification, and the uniform distribution of lanthanum loaded in surface and internal reticular pores can be ensured, thereby improving the adsorption capacity of the adsorbent. Meanwhile, the macroporous structure of the attapulgite clay allows phosphate to enter, so that the attapulgite clay can be used for full crystallization of phosphate without triggering pore blockage, and the problem that the lanthanum modified adsorption material is easy to block in the modification process is solvedThe problem of the plug. In the case of the difficulty in recovering and separating the adsorbent, the present invention adds Fe3O4The method adds magnetism to the attapulgite clay, and the magnetic material is easy to separate from the water body, thereby realizing the effective recovery of phosphate and the reutilization of the material. Therefore, the magnetic lanthanum hydroxide modified attapulgite clay adsorbent (La-ATP @ Fe) provided by the invention3O4) Can achieve the high-efficiency adsorption and recovery of the phosphorus in the water body.
The magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent provided by the invention has the advantages that the base material is attapulgite clay, the raw materials are economical and easy to obtain, the cost of the adsorbent is low, meanwhile, the safety of the adsorbent material is also good, and the influence on the environment is small. The adsorbent is prepared by a hydrothermal and precipitation method, and the process is simple and easy to operate; the adsorbent has high removal rate of phosphorus in the water body, and can reduce the phosphorus content in the water body to the level of I and II class water in lakes and reservoirs; the phosphorus removal speed is high, and 80% of phosphorus content in the water body can be removed within 1 hour; the adsorbent has magnetism, and can be separated by using a magnet, so that the secondary pollution to a water body is avoided while the cyclic utilization is realized.
In order to make the technical scheme of the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent, the preparation method thereof and the evaluation method of the application method thereof more clear, the invention is further described with reference to specific examples.
Detailed Description
Example 1
The embodiment provides a magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent, which comprises an attapulgite clay carrier on which lanthanum and ferroferric oxide are loaded. The preparation method of the magnetic lanthanum-loaded attapulgite clay dephosphorization adsorbent in the embodiment comprises the following steps:
(1) calcining attapulgite clay for 2h at 400 ℃ to obtain the attapulgite clay carrier.
(2) Pouring 100mL of deionized water into a 250mL three-neck flask, and adding 3.0g of the attapulgite clay carrier calcined in the step (1); under nitrogen gasStirring under the protection of atmosphere, and adding 2.78g of FeSO4·7H2O and 3.25g FeCl3Stirring for 15min, FeSO4·7H2O and FeCl3The ratio of the amounts of the substances of (a) to (b) is 1:2.
(3) And quickly adding 40mL of ammonia water with the mass concentration of 25 wt% into the three-neck flask, fully stirring and reacting for 1h at the temperature of 60 ℃, and cooling to room temperature to obtain the attapulgite clay carrier loaded with ferroferric oxide.
(4) Separating the attapulgite clay carrier loaded with the ferroferric oxide from liquid, and washing with deionized water for three times, wherein the amount of the deionized water used each time is 500 mL; then washing with absolute ethyl alcohol for 2 times, wherein the amount of the waste ethyl alcohol used each time is 200 mL; after the washing, the mixture is freeze-dried overnight for standby, and the magnetic attapulgite clay (ATP @ Fe) is obtained3O4)。
(5) Preparing LaCl with the concentration of 0.02mol/L3Weighing 3.0g of the dried magnetic attapulgite clay and 90ml of 0.02mol/L lanthanum chloride solution, mixing and stirring in a 250ml conical flask, adjusting and controlling the pH value of the solution to be 10-11, and shaking the mixed solution at 60 ℃ under the condition of 150r/min for 24 h. In the step, NaOH or HCl solution with the mass concentration of 1mol/L is adopted for adjusting the pH value of the solution. And after the oscillation operation is finished, separating the solid to obtain the magnetic attapulgite clay loaded with lanthanum.
(6) Washing the magnetic attapulgite clay loaded with lanthanum to be neutral by using deionized water, and drying to obtain the magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent (La-ATP @ Fe)3O4)。
Example 2
The embodiment provides a magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent, which comprises an attapulgite clay carrier on which lanthanum and ferroferric oxide are loaded. The preparation method of the magnetic lanthanum-loaded attapulgite clay dephosphorization adsorbent in the embodiment comprises the following steps:
(1) calcining attapulgite clay for 3h at 500 ℃ to obtain the attapulgite clay carrier.
(2) Pouring 100mL of deionized water into a 250mL three-neck flask, and adding 3.5g of the attapulgite clay carrier calcined in the step (1); stirring under the protection of nitrogen atmosphere, and adding 3.34g of FeSO4·7H2O and 4.86g FeCl3Stirring for 15min, FeSO4·7H2O and FeCl3The ratio of the amounts of the substances of (a) to (b) is 1: 2.5.
(3) And quickly adding 40mL of ammonia water with the mass concentration of 28 wt% into the three-neck flask, fully stirring and reacting for 1h at the temperature of 60 ℃, and cooling to room temperature to obtain the attapulgite clay carrier loaded with ferroferric oxide.
(4) Separating the attapulgite clay carrier loaded with the ferroferric oxide from liquid, and washing with deionized water for three times, wherein the amount of the deionized water used each time is 500 mL; then washing with absolute ethyl alcohol for 2 times, wherein the amount of the waste ethyl alcohol used each time is 200 mL; after the washing, the mixture is freeze-dried overnight for standby, and the magnetic attapulgite clay (ATP @ Fe) is obtained3O4)。
(5) Preparing LaCl with the concentration of 0.03mol/L3Then weighing 3g of the dried magnetic attapulgite clay and 90ml of 0.03mol/L LaCl3The solution is mixed and stirred in a 250ml conical flask, the pH value of the solution is adjusted and controlled to be 10-11, and the mixed solution is shaken for 26 hours at 70 ℃ under the condition of 200 r/min. In the step, NaOH or HCl solution with the mass concentration of 1.5mol/L is adopted for adjusting the pH value of the solution. And after the oscillation operation is finished, separating the solid to obtain the magnetic attapulgite clay loaded with lanthanum.
(6) Washing the magnetic attapulgite clay loaded with lanthanum to be neutral by using deionized water, and drying to obtain the magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent (La-ATP @ Fe)3O4)。
The application method of the phosphorus removal adsorbent prepared in the example 1-2 comprises the following steps: the magnetic lanthanum-loaded attapulgite clay dephosphorization adsorbent is uniformly sprayed on the surface of a water body to adsorb phosphate in the water body. 1h-2h after the feeding is finished, La-ATP @ Fe3O4Adsorbing with adsorbent saturated and removing phosphorus with magnetAnd sucking out the adsorbent. After a sample is separated by a magnet, the separated adsorbent is firstly washed by water for 2-3 times, and is desorbed for 2-3h by using 1M-1.5M NaOH solution at room temperature, and is washed and dried, so that the phosphorus removal adsorbent can be reused after being regenerated.
Examples of the experiments
Phosphorus removal capability test experiment
Phosphate solution was prepared using La-ATP @ Fe prepared as described in example 1-2 above3O4The adsorbent was subjected to adsorption experiments, and the conclusion was as follows:
(1) La-ATP @ Fe prepared in example 1-2 above3O4The adsorbent prepared in example 1 has a large adsorption capacity for phosphate, and when the addition amount of the adsorbent is 2g/L, the initial concentration of phosphate is 100mg/L, and the adsorption time is 12 hours, the theoretical saturated adsorption capacities at 25 ℃, 30 ℃ and 35 ℃ are 42.95mg/g, 57.04mg/g and 73.06mg/g, respectively.
(2) La-ATP @ Fe prepared in examples 1 and 2 at 30 ℃ and an initial phosphate concentration (in terms of P) of less than 60mg/L, an adsorbent dosage of 2g/L, and an adsorption time of 12h3O4The removal efficiency of the adsorbent to phosphate is more than 95%. La-ATP @ Fe prepared in examples 1 and 2 at an initial phosphate concentration (in terms of P) of 100mg/L3O4The removal efficiency of the adsorbent to phosphate is more than 87%.
(3) La-ATP @ Fe prepared in examples 1 and 2 at an initial phosphorus concentration of 100mg/L in the initial stage of adsorption (first 1h)3O4The adsorption capacity of the adsorbent is rapidly improved, the removal rate of the phosphorus solution is more than 83 percent, and the adsorbent has obvious removal effect.
(4) La-ATP @ Fe prepared in example 1-23O4The adsorbent has a phosphorus removal rate of more than 88% in a wide range of pH 2-10, and shows more excellent pH stability.
(5)Cl-，SO4 2-And NO3 -、HCO3 -For La-ATP @ Fe at molar ratios of 1:1, 1:5, 1:10 and 1:15 to phosphate, respectively3O4The phosphate of the adsorbent hardly produces an inhibitory effect (change in adsorption capacity)<3%) showed a directional selectivity towards phosphate.
Cyclic utilization capacity test experiment
La-ATP @ Fe prepared in example 13O4The desorption rate of the adsorbent in each cycle is more than 92% in the 5-time cycle adsorption-desorption process, and the phosphorus resource can be effectively recovered. Wherein the adsorption amount of the phosphate is not obviously reduced in the first three recycling processes; the adsorption capacity is reduced after the fourth and fifth times of circulation, and La-ATP @ Fe3O4The adsorption amount of the phosphate on the surface is slightly reduced to 82.2 percent and 77.9 percent of the original value respectively, but the phosphate still has better phosphorus adsorption capacity (38.36 mg/g and 36.32mg/g respectively) and shows good recycling performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent is characterized by comprising an attapulgite clay carrier, wherein lanthanum and ferroferric oxide are loaded on the attapulgite clay carrier.
2. The magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent of claim 1, wherein the BET specific surface area of the phosphorus removal adsorbent is 64-83m2(ii)/g; pore volume of 0.16-0.21 cc/g; the average pore diameter is 6.9-9.1 nm.
3. The preparation method of the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent of claim 1, which is characterized by comprising the following steps:
(1) calcining attapulgite clay to obtain an attapulgite clay carrier;
(2) putting the attapulgite clay carrier prepared in the step (1) into deionized water, and adding solid FeSO in a nitrogen atmosphere4·7H2O and solid FeCl3Stirring uniformly;
(3) rapidly adding ammonia water, fully stirring at 60-80 ℃ for reaction, and cooling to room temperature to obtain the attapulgite clay carrier loaded with ferroferric oxide;
(4) separating the attapulgite clay carrier loaded with ferroferric oxide from the liquid, and washing, freezing and drying to obtain magnetic attapulgite clay;
(5) mixing the magnetic attapulgite clay with LaCl3Mixing the solutions, adjusting the pH of the solution to 10.0-11.0 under stirring, and separating to obtain magnetic attapulgite clay loaded with lanthanum;
(6) washing the magnetic attapulgite clay loaded with lanthanum to be neutral, and drying to obtain the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent.
4. The preparation method of the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent according to claim 3, wherein in the step (1), the attapulgite clay is calcined at 400-500 ℃ for 2-3 h.
5. The preparation method of the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent according to claim 4, wherein in the step (2), when the attapulgite clay carrier is placed in deionized water, the addition amount of the attapulgite clay carrier is 30-35 g/L; in step (2), FeSO4·7H2O and FeCl3In a molar ratio of 1: 2-1: 2.5; the FeSO4·7H2The addition amount of O in the deionized water is 1-1.2 mol/L.
6. The preparation method of the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent according to claim 5, wherein the mass concentration of the ammonia water added in the step (3) is 25-28%; the volume ratio of the added ammonia water to the deionized water in the step (2) is 0.4-0.5.
7. The method for preparing the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent according to claim 6, wherein in the step (5), the LaCl is added3The concentration of the solution is 0.02-0.03 mol/L; mixing the magnetic attapulgite clay with LaCl3When the solution is mixed, the magnetic attapulgite clay is in LaCl3The addition amount of the solution is 30-33 g/L.
8. The preparation method of the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent according to claim 7, wherein in the step (5), after the pH of the solution is adjusted to 10-11 under the stirring state, the mixed solution is shaken for 24-26h under the conditions of 60-70 ℃ and 200r/min of 150-.
9. The use method of the magnetic lanthanum-loaded attapulgite clay dephosphorizing adsorbent prepared by the preparation method of claims 3-8 is characterized by comprising the following steps: the magnetic lanthanum-loaded attapulgite clay dephosphorization adsorbent is uniformly sprayed on the surface of a water body to adsorb phosphate in the water body.
10. The use method of the magnetic lanthanum-loaded attapulgite clay phosphorus removal adsorbent prepared by the preparation method according to claim 9, characterized in that after the completion of the feeding for 1-2h, the phosphorus removal adsorbent after phosphorus removal is sucked out by a magnet, the separated phosphorus removal adsorbent is washed by water, then desorbed at room temperature for 2-3h by using 1-1.5M NaOH solution, and washed and dried to complete the regeneration of the phosphorus removal adsorbent.
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| CN114907058A (en) * | 2022-04-15 | 2022-08-16 | 浙江碧水量子科技有限公司 | Water purification component for reducing total phosphorus and preparation method and application thereof |
| CN115041132A (en) * | 2022-05-30 | 2022-09-13 | 中南大学 | Modified attapulgite, preparation method, application and recovery device thereof |
| CN115920828A (en) * | 2023-01-05 | 2023-04-07 | 中国科学院生态环境研究中心 | Magnetic lanthanum-based adsorbent, preparation method thereof and method for enriching phosphorus in water body |
| CN116371353A (en) * | 2023-04-06 | 2023-07-04 | 广东工业大学 | Lanthanum magnetic iron modified attapulgite phosphorus removal adsorbent and application thereof |
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Cited By (4)
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| CN114907058A (en) * | 2022-04-15 | 2022-08-16 | 浙江碧水量子科技有限公司 | Water purification component for reducing total phosphorus and preparation method and application thereof |
| CN115041132A (en) * | 2022-05-30 | 2022-09-13 | 中南大学 | Modified attapulgite, preparation method, application and recovery device thereof |
| CN115920828A (en) * | 2023-01-05 | 2023-04-07 | 中国科学院生态环境研究中心 | Magnetic lanthanum-based adsorbent, preparation method thereof and method for enriching phosphorus in water body |
| CN116371353A (en) * | 2023-04-06 | 2023-07-04 | 广东工业大学 | Lanthanum magnetic iron modified attapulgite phosphorus removal adsorbent and application thereof |
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