CN114950352A - Lanthanum carbonate modified Fe 3 O 4 @ C phosphorus removal adsorbent and preparation method and application thereof - Google Patents

Lanthanum carbonate modified Fe 3 O 4 @ C phosphorus removal adsorbent and preparation method and application thereof Download PDF

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CN114950352A
CN114950352A CN202110213537.6A CN202110213537A CN114950352A CN 114950352 A CN114950352 A CN 114950352A CN 202110213537 A CN202110213537 A CN 202110213537A CN 114950352 A CN114950352 A CN 114950352A
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lanthanum carbonate
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lanthanum
carbonate modified
phosphorus removal
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CN114950352B (en
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刘自力
练钊华
左建良
林璟
杨伟
郑文芝
王琪莹
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Guangzhou University
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Abstract

The invention belongs to the field of environmental wastewater treatment, and discloses lanthanum carbonate modified Fe 3 O 4 The @ C composite adsorbing material and the preparation method and the application thereof. The preparation method of the adsorbent comprises the following steps: preparation of Fe by solvothermal method 3 O 4 A nanoparticle; then adding Fe 3 O 4 Coating a carbon layer by a hydrothermal method; finally, the precipitation deposition method is utilized to deposit Fe 3 O 4 Loading on @ C CarrierAnd lanthanum carbonate to obtain the composite dephosphorizing adsorbent. The invention has strong magnetism, and the adsorbent can be externally added with a magnetic field for solid-liquid separation and recovery after adsorption. Carbon coating of Fe 3 O 4 The material is not easy to be oxidized, and the dispersibility of active substances of the material is improved; lanthanum carbonate has strong affinity to phosphate and can realize high-efficiency adsorption on acidic or neutral phosphorus-containing wastewater.

Description

Lanthanum carbonate modified Fe 3 O 4 @ C phosphorus removal adsorbent and preparation method and application thereof
Technical Field
The invention belongs to the field of environmental adsorption, and particularly relates to lanthanum carbonate modified Fe 3 O 4 A @ C phosphorus removal adsorbent and a preparation method and application thereof.
Background
Phosphorus is an important element for human beings, various animals, plants and bacteria, but the discharge of a large amount of phosphorus-containing wastewater can cause eutrophication of water bodies. The natural circulation of phosphorus is very slow, and eutrophic water bodies cause a series of environmental problems such as algae reproduction, water quality deterioration, aquatic organism death and the like. Therefore, it is necessary to treat the phosphorus-containing wastewater.
Many methods for removing phosphorus from water have been developed, including chemical precipitation, membrane separation, biological methods, and adsorption methods. Among the methods, the adsorption method has been widely noticed because of its advantages of simple operation, low cost, wide application range, no secondary pollution, etc.
Lanthanum is one of the relatively abundant and environmentally friendly rare earth elements on earth. Lanthanum and its compounds have specific adsorption properties for phosphorus, and even in trace amounts, have strong affinity. Currently, the active lanthanum compound commonly used in environmental phosphorus removal agents is lanthanum hydroxide or lanthanum oxide. For example, an expanded graphite supported lanthanum hydroxide dephosphorizing adsorbent disclosed in chinese patent publication CN 104722271A; chinese patent publication CN105214629A discloses a biomass-based nano lanthanum oxide phosphorus removal composite adsorbent. However, when the two lanthanum compounds are combined with phosphate, the pH of the solution is rapidly increased due to coordination exchange, so that the adsorption efficiency is obviously reduced. Therefore, changing anions in the lanthanum compound and reducing the influence of pH change on a system in the adsorption process are one of the methods for improving the phosphorus removal efficiency of the adsorbent.
Lanthanum carbonate is another compound form of lanthanum, which is highly insoluble and has less effect on the pH of the solution when exchanged with phosphate. Lanthanum carbonate, because of its relatively low toxicity to humans and living organisms, has been approved by the U.S. Food and Drug Administration (FDA) as a cohesive agent for the treatment of hyperphosphatemia. Although lanthanum carbonate has been well studied in the medical field, relatively few reports have been made on its application in the treatment of environmental phosphorus-containing wastewater.
The traditional adsorbent has the problem of difficult separation and regeneration in use, and the development of a magnetic composite material is a good solution. Fe 3 O 4 Has the advantages of strong magnetism, simple preparation process and the like, so the magnetic material is widely applied. Unfortunately, Fe 3 O 4 Oxidation easily occurs in the air, which leads to agglomeration of particles and reduction of magnetism. To overcome this, many researchers have attempted to work with Fe 3 O 4 The surface of the particles is covered with an inert shell layer, which is used to prevent Fe 3 O 4 And during oxidation, the material generates steric hindrance repulsion, and the dispersibility and the specific surface area of the composite adsorbent are improved. For example, Chinese patent publication CN103964538A discloses CeO 2 Modified SiO 2 Coated with Fe 3 O 4 A magnetic phosphorus adsorbent. However, the phosphate adsorption effect of this publication is significantly weaker than that of the lanthanum compound-modified adsorbents in other patents.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide lanthanum carbonate modified Fe 3 O 4 A preparation method of a @ C phosphorus removal adsorbent.
The invention also aims to provide lanthanum carbonate modified Fe prepared by the method 3 O 4 The @ C phosphorus removal adsorbent is strong in adsorption performance, strong in magnetism and convenient to separate and recycle.
It is still another object of the present invention to provide the above lanthanum carbonate-modified Fe 3 O 4 The application of the @ C phosphorus removal adsorbent in phosphate adsorption.
The purpose of the invention is realized by the following scheme:
lanthanum carbonate modified Fe 3 O 4 The preparation method of the @ C phosphorus removal adsorbent comprises the following steps:
(1) solvothermal method for preparing Fe 3 O 4 Nano-particles: adding ferric salt into glycol solvent for ultrasonic dissolution, adding anhydrous sodium acetate and polyethylene glycol, stirring for dissolution, transferring into a reaction kettle for reaction, and purifying the obtained product to obtain Fe 3 O 4 A nanoparticle;
(2) hydrothermal method for preparing Fe 3 O 4 Material @ C: fe prepared in the step (1) 3 O 4 Dispersing the nano particles in water uniformly, adding glucose or sucrose, stirring uniformly, transferring to a reaction kettle for hydrothermal reaction, and purifying the obtained product to obtain Fe 3 O 4 @C；
(3) Preparation of lanthanum carbonate modified Fe by precipitation deposition method 3 O 4 Material @ C: ultrasonically dissolving lanthanum salt in water, and then adding the Fe prepared in the step (2) 3 O 4 @ C, stirring and mixing uniformly by oscillation, dropwise adding a bicarbonate aqueous solution until the pH value is neutral, standing the obtained suspension for one night, and then washing and drying to obtain lanthanum carbonate modified Fe 3 O 4 @ C material.
The ferric salt in the step (1) is FeCl 3 ·6H 2 O，Fe(NO 3 ) 3 ·9H 2 O，Fe 2 (SO 4 ) 3 ·9H 2 At least one of O.
The dosage of the ferric salt and the ethylene glycol in the step (1) meets the condition that every 1-4 mmol of ferric salt is correspondingly added into 30-50ml of ethylene glycol; preferably, 40ml of ethylene glycol per 2mmol of iron salt.
The dosage of the ferric salt and the anhydrous sodium acetate in the step (1) meets the following requirements: adding 0.5-1 g of polyethylene glycol and 2.4-7.2g of anhydrous sodium acetate into every 1-4 mmol of iron salt; the polymerization degree of the polyethylene glycol in the step (1) is 500-10000.
The stirring and dissolving time in the step (1) is preferably 30-120 min.
The reaction in the step (1) is to place the reaction kettle in an oven at 150-220 ℃ for reaction, preferably in an oven at 200 ℃; the reaction time in the step (1) is 8-16h, and preferably 12 h.
The purification in the step (1) means that after the reaction is finished, the obtained product is naturally cooled, then is subjected to magnetic separation to obtain a solid product, and is washed three times respectively by deionized water and absolute ethyl alcohol and dried to obtain purified Fe 3 O 4 The drying is preferably vacuum drying, the drying temperature is 60-100 ℃, and the drying time is 8-12 hours.
Fe described in step (2) 3 O 4 The nanoparticles are preferably dispersed in HNO before dispersing in water 3 In the solution, then the solution is dispersed in water after magnetic separation and water washing, wherein HNO is contained in the solution 3 The concentration of the solution is preferably 1 mol/L. Fe 3 O 4 Is hydrophobic, with HNO 3 The treatment is for Fe 3 O 4 Introduction of hydrophilic functional groups to make Fe 3 O 4 Are easily coated with glucose or sucrose.
The dosage of the glucose or the sucrose in the step (2) meets the following requirements: per 1g of Fe 3 O 4 2-4 g of glucose or sucrose is correspondingly added into the nano particles.
The hydrothermal reaction in the step (2) is carried out in an oven at 150-220 ℃, preferably 200 ℃; the hydrothermal time in the step (2) is 8-16h, and preferably 12 h.
The purification in the step (2) means that the product after the reaction is naturally cooled and then is subjected to magnetic separation to obtain a solid product, the solid product is washed three times by deionized water and dried to obtain purified Fe 3 O 4 @ C, wherein the preferable drying is forced air drying, the drying temperature is 60-100 ℃, and the drying time is 8-12 h.
The lanthanum salt in the step (3) is LaCl 3 ·7H 2 O，La(NO 3 ) 3 ·6H 2 O，La 2 (SO 4 ) 3 ·9H 2 At least one of O.
Lanthanum salt and Fe in step (3) 3 O 4 The dosage of @ C satisfies: la in lanthanum salt 3+ Mass of and Fe 3 O 4 The mass ratio of @ C is 0.5-2: 1.
the bicarbonate in step (3) is preferably NaHCO 3 、KHCO 3 、NH 4 HCO 3 At least one of (a); the concentration of the bicarbonate aqueous solution in the step (3) is preferably 1 mol/L; the dropping speed is 0.2-1 ml/min, preferably 0.4 ml/min.
The drying in the step (3) is forced air drying, the drying temperature is 60-100 ℃, and the drying time is 8-12 hours.
Lanthanum carbonate modified Fe prepared by the method 3 O 4 @ C phosphorus removal adsorbent.
The lanthanum carbonate modified Fe 3 O 4 The application of the @ C phosphorus removal adsorbent in adsorbing phosphate under acidic or neutral conditions.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the prepared adsorbent has high adsorption capacity to phosphate in water. Referring to the attached figure 2, the adsorption of phosphate by the adsorbent of the invention is more consistent with a Langmuir model, which calculates that the maximum theoretical adsorption amount can reach 74.63mg-P/g under the adsorption conditions that the addition amount of the adsorbent is 0.4g/L, the pH value of the solution is 7 +/-0.1 and the adsorption temperature is 298K.
(2) Has good adsorption performance under acidic or neutral conditions, as shown in figure 3.
(3) The adsorbent has strong magnetism, and can be conveniently subjected to solid-liquid separation operation, as shown in figure 4.
(4) Compared with common lanthanum hydroxide or lanthanum oxide, the invention utilizes lanthanum carbonate with better adsorption property to phosphate for modification.
(5) The carbon coating layer effectively protects Fe 3 O 4 Nanoparticles, prevention of Fe 3 O 4 Oxidized in air or water. Fe 3 O 4 The @ C substrate has a certain dispersion effect, and agglomeration of the active material lanthanum carbonate is avoided.
Drawings
FIG. 1 is a graph comparing the adsorption performance of the adsorbents in examples 1 to 4 and comparative examples 1 to 3 with respect to phosphate.
FIG. 2 is a graph showing the adsorption isotherm of the corresponding material in example 2 (the amount of adsorbent added is 0.4g/L, the initial pH of the solution is 7. + -. 0.1, and the adsorption temperature is 298K)
FIG. 3 is a graph showing the adsorption amounts of the corresponding materials in example 2 at different initial pHs (adsorbent addition amount of 0.4g/L, initial solution concentration of 50mg-P/L, adsorption temperature of 298K)
FIG. 4 is a graph of the magnetic separation of the corresponding material in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. All the similar structures or similar changes adopted by the invention are included in the protection scope of the invention.
Example 1
La 3+ ：Fe 3 O 4 @ C mass ratio of 0.5: 1 lanthanum carbonate modified Fe 3 O 4 The preparation method of the @ C composite material comprises the following steps:
(1)2mmol FeCl 3 ·6H 2 adding O into 40ml of glycol solvent for ultrasonic dissolution, adding 1g of polyethylene glycol 4000 and 3.6g of anhydrous sodium acetate, magnetically stirring for 30min, transferring into a reaction kettle for reaction at 200 ℃ for 12h, naturally cooling, magnetically separating, washing solid products with deionized water and anhydrous ethanol for three times respectively, and vacuum drying at 60 ℃ for 12h to obtain Fe 3 O 4 And (3) nanoparticles.
(2) 1g of Fe prepared in step (1) 3 O 4 At 0.1mol/LHNO 3 After ultrasonic dispersion in the solution for 10min, magnetic separation and three times of deionized water washing, the particles are mechanically stirred and dispersed in 30ml of deionized water. Adding 2g glucose into the suspension, mechanically stirring for 10min, transferring the solution into a reaction kettle, reacting at 200 deg.C for 12 hr, naturally cooling, magnetically separating, and removing ions from the solid productWashing with water for three times, and drying at 60 ℃ for 12h to obtain Fe 3 O 4 @ C for use.
(3) 0.743g of LaCl 3 ·7H 2 O is dissolved in 50ml of deionized water by ultrasonic wave, and 0.556g of Fe prepared in step (2) is added 3 O 4 @ C, stirring with shaking in a constant temperature shaker for 4 h. While rapidly and mechanically stirring, 1mol/LNaHCO was added dropwise to the suspension at a rate of 0.4ml/min 3 The solution was allowed to stand overnight until the pH was neutral. The solid after magnetic separation is washed three times by deionized water and dried for 12h at 60 ℃.
Sorbent activity testing:
adding 50ml KH with concentration of 50mg-P/L and pH of 7.0 + -0.1 into a 100ml conical flask 2 PO 4 And (3) solution. With 0.02gLa 3+ ：Fe 3 O 4 @ C mass ratio of 0.5: 1 lanthanum carbonate modified Fe 3 O 4 The @ C composite material is adsorbed. The adsorption conditions were a temperature of 298K, constant temperature shaking at 200rpm for 24 h.
After the reaction, the ammonium molybdate spectrophotometry is used for analysis, and the result shows that the adsorption quantity of the phosphate is 50.90 mg-P/g.
Example 2
La 3+ ：Fe 3 O 4 @ C mass ratio of 1: 1 lanthanum carbonate modified Fe 3 O 4 The preparation method of the @ C composite material comprises the following steps:
(1)2mmolFeCl 3 ·6H 2 adding O into 40ml of glycol solvent for ultrasonic dissolution, adding 1g of polyethylene glycol 4000 and 3.6g of anhydrous sodium acetate, magnetically stirring for 30min, transferring into a reaction kettle for reaction at 200 ℃ for 12h, naturally cooling, magnetically separating, washing solid products with deionized water and anhydrous ethanol for three times respectively, and vacuum drying at 60 ℃ for 12h to obtain Fe 3 O 4 And (3) nanoparticles.
(2) 1g of Fe prepared in step (1) 3 O 4 At 0.1mol/LHNO 3 After ultrasonic dispersion in the solution for 10min, magnetic separation and three times of deionized water washing, the particles are mechanically stirred and dispersed in 30ml of deionized water. Adding 2g glucose into the suspension, mechanically stirring for 10min, transferring the solution into a reaction kettleReacting at 200 ℃ for 12 hours, naturally cooling, magnetically separating, washing a solid product with deionized water for three times, and drying at 60 ℃ for 12 hours to obtain Fe 3 O 4 @ C for use.
(3) 1.486g of LaCl 3 ·7H 2 O is dissolved in 50ml of deionized water by ultrasonic wave, and 0.556g of Fe prepared in step (2) is added 3 O 4 @ C, stirring with shaking in a constant temperature shaker for 4 h. While stirring rapidly, 1mol/L NaHCO was added dropwise to the suspension at a rate of 0.4ml/min 3 The solution was allowed to stand overnight until the pH was neutral. After magnetic separation, the solid is washed three times by deionized water and dried for 12h at 60 ℃.
Sorbent activity testing:
adding 50ml KH with concentration of 50mg-P/L and pH of 7.0 + -0.1 into a 100ml conical flask 2 PO 4 And (3) solution. With 0.02gLa 3+ ：Fe 3 O 4 @ C mass ratio of 1: 1 lanthanum carbonate modified Fe 3 O 4 The @ C composite is adsorbed. The adsorption conditions were a temperature of 298K, constant temperature shaking at 200rpm for 24 h.
After the reaction, the ammonium molybdate spectrophotometry was used for analysis, and the result showed that the phosphate adsorbed amount was 63.64 mg-P/g.
Example 3
La 3+ ：Fe 3 O 4 The mass ratio of @ C is 2: 1 lanthanum carbonate modified Fe 3 O 4 A preparation method of the @ C composite material comprises the following steps:
(1)2mmol FeCl 3 ·6H 2 adding O into 40ml of glycol solvent for ultrasonic dissolution, adding 1g of polyethylene glycol 4000 and 3.6g of anhydrous sodium acetate, magnetically stirring for 30min, transferring into a reaction kettle for reaction at 200 ℃ for 12h, naturally cooling, magnetically separating, washing solid products with deionized water and anhydrous ethanol for three times respectively, and vacuum drying at 60 ℃ for 12h to obtain Fe 3 O 4 And (3) nanoparticles.
(2) 1g of Fe prepared in step (1) 3 O 4 At 0.1mol/L HNO 3 After ultrasonic dispersion in the solution for 10min, magnetic separation and deionized water washing are carried out for three times, and then the particles are mechanically stirred and dispersed in 30ml of deionized water. In the above-mentioned suspensionAdding 2g of glucose into the turbid solution, mechanically stirring for 10min, transferring the solution into a reaction kettle, reacting for 12 hours at 200 ℃, naturally cooling, magnetically separating, washing a solid product with deionized water for three times, and drying for 12 hours at 60 ℃ to obtain Fe 3 O 4 @ C for use.
(3) 2.972gLaCl 3 ·7H 2 O is dissolved in 50ml of deionized water by ultrasonic wave, and 0.556g of Fe prepared in step (2) is added 3 O 4 @ C, stirring with shaking in a constant temperature shaker for 4 h. While rapidly and mechanically stirring, 1mol/LNaHCO was added dropwise to the suspension at a rate of 0.4ml/min 3 The solution was allowed to stand overnight until the pH was neutral. The solid after magnetic separation is washed three times by deionized water and dried for 12h at 60 ℃.
Sorbent activity testing:
adding 50ml of KH with the concentration of 50mg-P/L and the pH value of 7.0 +/-0.1 into a 100ml conical flask 2 PO 4 And (3) solution. With 0.02gLa 3+ ：Fe 3 O 4 @ C mass ratio of 2: 1 lanthanum carbonate modified Fe 3 O 4 The @ C composite material is adsorbed. The adsorption conditions were a temperature of 298K, constant temperature shaking at 200rpm for 24 h.
After the reaction, the ammonium molybdate spectrophotometry was used for analysis, and the result showed that the phosphate adsorption was 69.30 mg-P/g.
Example 4
Lanthanum carbonate modified Fe of this example 3 O 4 The preparation method of the @ C composite material is the same as that of example 2
Sorbent activity testing:
adding 50ml KH with concentration of 50mg-P/L and pH of 4.0 + -0.1 into a 100ml conical flask 2 PO 4 And (3) solution. With 0.02gLa 3+ ：Fe 3 O 4 @ C mass ratio of 1: 1 lanthanum carbonate modified Fe 3 O 4 The @ C composite material is adsorbed. The adsorption conditions were a temperature of 298K, constant temperature shaking at 200rpm for 24 h.
After the reaction, the amount of phosphate adsorbed was 74.25mg-P/g as determined by spectrophotometry using ammonium molybdate.
Comparative example 1
Fe 3 O 4 The material preparation method of @ C composite, this comparative example, differs from the corresponding material of example 2 above in that there is no lanthanum carbonate modification of step (3).
Sorbent activity testing:
adding 50ml of KH with the concentration of 50mg-P/L and the pH value of 7.0 +/-0.1 into a 100ml conical flask 2 PO 4 And (3) solution. With 0.02gFe 3 O 4 The @ C composite material is adsorbed. The adsorption conditions were a temperature of 298K, constant temperature shaking at 200rpm for 24 h.
After the reaction, the amount of adsorbed phosphate was 9.125mg-P/g as determined by spectrophotometric ammonium molybdate analysis.
Comparative example 2
The preparation method of the pure lanthanum carbonate comprises the following steps:
1.486g of LaCl 3 ·7H 2 Dissolving O in 50ml deionized water by ultrasonic, and dripping 1mol/LNaHCO at the speed of 0.4ml/min while stirring rapidly 3 The solution was allowed to stand overnight until the pH was neutral. After magnetic separation, the solid is washed three times by deionized water and dried for 12h at 60 ℃.
Sorbent activity testing:
adding 50ml of KH with the concentration of 50mg-P/L and the pH value of 7.0 +/-0.1 into a 100ml conical flask 2 PO 4 And (3) solution. 0.02g of pure lanthanum carbonate was used for the adsorption. The adsorption conditions were a temperature of 298K, constant temperature shaking at 200rpm for 24 h.
After the reaction is finished, the material is analyzed by ammonium molybdate spectrophotometry, and the result shows that the absorption amount of the material phosphate is 47.13 mg-P/g.
Comparative example 3
La 3+ ：Fe 3 O 4 @ C mass ratio of 1: 1 lanthanum hydroxide modified Fe 3 O 4 The preparation method of the @ C composite material comprises the following steps:
the steps (1) and (2) are the same as those in example 2.
Step (3) adding 1.486g of LaCl 3 ·7H 2 O is dissolved in 50ml of deionized water by ultrasonic wave, and 0.556g of Fe prepared in step (2) is added 3 O 4 @ C, stirring with shaking in a constant temperature shaker for 4 h. While stirring rapidly, 1mol/L NaOH solution was added dropwise to the suspension at a rate of 0.4ml/min until the pH was 11. + -. 0.1, and the suspension was allowed to stand overnight. The solid after magnetic separation is washed three times by deionized water and dried for 12h at 60 ℃.
Sorbent activity testing:
adding 50ml KH with concentration of 50mg-P/L and pH of 7.0 + -0.1 into a 100ml conical flask 2 PO 4 And (3) solution. With 0.02gLa 3+ ：Fe 3 O 4 @ C mass ratio of 1: 1 lanthanum hydroxide modified Fe 3 O 4 The @ C composite material is adsorbed. The adsorption conditions were a temperature of 298K, constant temperature shaking at 200rpm for 24 h.
After the reaction, the amount of adsorbed phosphate was 36.98mg-P/g as determined by spectrophotometric ammonium molybdate analysis.
The comparative graph of the adsorption performance of the adsorbents in examples 1 to 4 and comparative examples 1 to 3 on phosphate is shown in FIG. 1, and examples 1 to 3 show lanthanum carbonate modified Fe prepared according to different mass ratios 3 O 4 Examples of adsorption of @ C composites under simulated neutral conditions; example 4 is an example of adsorption under simulated acidic conditions. It can be seen that the adsorbent of the present invention has a very good adsorption capacity regardless of whether the phosphorus-containing simulated wastewater is acidic or neutral.
Comparative examples 1 to 3 are compared with example 2. Comparative example 1 illustrates Fe 3 O 4 The self adsorption capacity of the @ C substrate is extremely small; comparative example 2 adsorbed less than example 2, indicating Fe 3 O 4 The @ C substrate aids in the dispersion of the active material lanthanum carbonate; comparative example 3 adsorbed less than example 2, indicating that the modification with lanthanum carbonate was superior to the modification with lanthanum hydroxide.
Isothermal adsorption line graph (adsorbent dosage of 0.4g/L, initial pH of 7 + -0.1, adsorption temperature of 298K) of the corresponding material in example 2 is shown in FIG. 2, and lanthanum carbonate modified Fe that can be prepared by the present invention from FIG. 2 3 O 4 The @ C composite material has very high adsorption capacity, the adsorption of the adsorbent disclosed by the invention on phosphate better conforms to a Langmuir model, and the model is calculated and obtainedThe addition amount of the adsorbent is 0.4g/L, the pH value of the solution is 7 +/-0.1, and the maximum theoretical adsorption amount can reach 74.63mg-P/g under the adsorption condition of the adsorption temperature of 298K.
The graph of the adsorption amount of the corresponding material in example 2 under different initial pH (the addition amount of the adsorbent is 0.4g/L, the initial concentration of the solution is 50mg-P/L, and the adsorption temperature is 298K) is shown in FIG. 3, and it can be seen from FIG. 3 that the lanthanum carbonate modified Fe prepared by the invention 3 O 4 The @ C composite material has good adsorption performance under acidic or neutral conditions.
The magnetic separation diagram of the corresponding material in example 2 is shown in fig. 4, and it can be seen from fig. 4 that the lanthanum carbonate modified Fe3O4@ C composite material prepared by the invention has strong magnetism, and can be conveniently subjected to solid-liquid separation operation.
Comparing example 2 with comparative examples 1 and 2, lanthanum carbonate modified Fe when equal amount of adsorbent was used 3 O 4 @ C composite vs. lanthanum carbonate alone and Fe alone 3 O 4 The adsorption effect of @ C is good, which explains that lanthanum carbonate and Fe 3 O 4 @ C produces a synergistic effect.
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 (10)

1. Lanthanum carbonate modified Fe 3 O 4 A preparation method of the @ C phosphorus removal adsorbent is characterized by comprising the following steps:
(1) solvothermal method for preparing Fe 3 O 4 Nano-particles: adding ferric salt into glycol solvent for ultrasonic dissolution, adding anhydrous sodium acetate and polyethylene glycol, stirring for dissolution, transferring into a reaction kettle for reaction, and purifying the obtained product to obtain Fe 3 O 4 A nanoparticle;
(2) hydrothermal method for preparing Fe 3 O 4 Material @ C: fe prepared in the step (1) 3 O 4 Dispersing the nano particles in water uniformly, adding glucose or sucrose, stirring uniformly, transferring to a reaction kettle for hydrothermal reaction, and purifying the obtained product to obtain Fe 3 O 4 @C；
(3) Preparation of lanthanum carbonate modified Fe by precipitation deposition method 3 O 4 Material @ C: ultrasonically dissolving lanthanum salt in water, and then adding the Fe prepared in the step (2) 3 O 4 @ C, stirring and mixing uniformly by oscillation, dropwise adding a bicarbonate aqueous solution until the pH value is neutral, standing the obtained suspension for one night, and then washing and drying to obtain lanthanum carbonate modified Fe 3 O 4 @ C material.
2. Lanthanum carbonate modified Fe according to claim 1 3 O 4 A preparation method of the @ C phosphorus removal adsorbent is characterized by comprising the following steps:
the ferric salt in the step (1) is FeCl 3 ·6H 2 O，Fe(NO 3 ) 3 ·9H 2 O，Fe 2 (SO 4 ) 3 ·9H 2 At least one of O;
the dosage of the ferric salt and the ethylene glycol in the step (1) meets the condition that every 1-4 mmol of ferric salt is correspondingly added into 30-50ml of ethylene glycol; the dosage of the ferric salt and the anhydrous sodium acetate in the step (1) meets the following requirements: adding 0.5-1 g of polyethylene glycol and 2.4-7.2g of anhydrous sodium acetate into every 1-4 mmol of iron salt;
the reaction in the step (1) is to place the reaction kettle in an oven at 150-220 ℃ for reaction for 8-16 h.
3. Lanthanum carbonate modified Fe according to claim 1 3 O 4 The preparation method of the @ C phosphorus removal adsorbent is characterized by comprising the following steps:
the dosage of the glucose or the sucrose in the step (2) meets the following requirements: per 1g of Fe 3 O 4 2-4 g of glucose or sucrose is correspondingly added into the nano particles.
4. Lanthanum carbonate modified Fe according to claim 1 3 O 4 Preparation of @ C phosphorus removal adsorbentThe preparation method is characterized by comprising the following steps:
the hydrothermal reaction in the step (2) is carried out in an oven at the temperature of 150-220 ℃, and the hydrothermal time in the step (2) is 8-16 h.
5. Lanthanum carbonate modified Fe according to claim 1 3 O 4 The preparation method of the @ C phosphorus removal adsorbent is characterized by comprising the following steps:
fe described in step (2) 3 O 4 The nanoparticles are dispersed in HNO before being dispersed in water 3 Then the solution is separated magnetically, washed by water and then dispersed in water.
6. Lanthanum carbonate modified Fe according to claim 1 3 O 4 The preparation method of the @ C phosphorus removal adsorbent is characterized by comprising the following steps:
the lanthanum salt in the step (3) is LaCl 3 ·7H 2 O，La(NO 3 ) 3 ·6H 2 O，La 2 (SO 4 ) 3 ·9H 2 At least one of O;
lanthanum salt and Fe in step (3) 3 O 4 The amount of @ C satisfies: la in lanthanum salt 3+ Mass of and Fe 3 O 4 The mass ratio of @ C is 0.5-2: 1.
7. lanthanum carbonate modified Fe according to claim 1 3 O 4 A preparation method of the @ C phosphorus removal adsorbent is characterized by comprising the following steps:
the bicarbonate salt solution in the step (3) is NaHCO 3 、KHCO 3 、NH 4 HCO 3 At least one of (a);
the concentration of the bicarbonate water solution in the step (3) is 1 mol/L; the dropping speed is 0.2-1 ml/min;
the drying in the step (3) is blast drying, the drying temperature is 60-100 ℃, and the drying time is 8-12 h.
8. A process according to any one of claims 1 to 7Obtained lanthanum carbonate modified Fe 3 O 4 @ C phosphorus removal adsorbent.
9. Lanthanum carbonate modified Fe according to claim 8 3 O 4 The application of the @ C phosphorus removal adsorbent in adsorption of phosphate.
10. Lanthanum carbonate modified Fe according to claim 8 3 O 4 The application of the @ C phosphorus removal adsorbent in adsorbing phosphate under acidic or neutral conditions.
CN202110213537.6A 2021-02-26 2021-02-26 Lanthanum carbonate modified Fe 3 O 4 Dephosphorization adsorbent at@C and preparation method and application thereof Active CN114950352B (en)

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CN103406108A (en) * 2013-07-10 2013-11-27 江苏大学 Preparation method of carbon-based magnetic temperature-sensitive surface imprinted adsorbent
CN103906523A (en) * 2011-09-08 2014-07-02 柏林夏洛蒂医科大学 Nanoparticulate phosphate adsorbent on the basis of maghemite or maghemite/magnetite, production and uses thereof
CN109569552A (en) * 2018-12-13 2019-04-05 北京林业大学 A kind of magnetic/non magnetic lanthanum carbonate sodium dephosphorization adsorbent and its synthetic method
CN110652963A (en) * 2019-11-01 2020-01-07 广州大学 Lanthanum carbonate modified co-pyrolysis sludge biochar and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103906523A (en) * 2011-09-08 2014-07-02 柏林夏洛蒂医科大学 Nanoparticulate phosphate adsorbent on the basis of maghemite or maghemite/magnetite, production and uses thereof
CN103406108A (en) * 2013-07-10 2013-11-27 江苏大学 Preparation method of carbon-based magnetic temperature-sensitive surface imprinted adsorbent
CN109569552A (en) * 2018-12-13 2019-04-05 北京林业大学 A kind of magnetic/non magnetic lanthanum carbonate sodium dephosphorization adsorbent and its synthetic method
CN110652963A (en) * 2019-11-01 2020-01-07 广州大学 Lanthanum carbonate modified co-pyrolysis sludge biochar and preparation method and application thereof

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