CN115041152B - Resin-based neodymium-loaded nanocomposite, preparation method thereof and application thereof in deep removal of phosphate in water - Google Patents

Resin-based neodymium-loaded nanocomposite, preparation method thereof and application thereof in deep removal of phosphate in water Download PDF

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CN115041152B
CN115041152B CN202210767471.XA CN202210767471A CN115041152B CN 115041152 B CN115041152 B CN 115041152B CN 202210767471 A CN202210767471 A CN 202210767471A CN 115041152 B CN115041152 B CN 115041152B
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water
neodymium
resin
phosphate
nanocomposite
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CN115041152A (en
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潘丙军
倪臣浩
陈宁怡
吴双
王贤桦
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Zhejiang University of Technology ZJUT
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/18—PO4-P
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention discloses a resin-based neodymium-carrying nanocomposite material, a preparation method thereof and application thereof in deep removal of phosphate in water, wherein the application method comprises the following steps: filtering the waste water containing phosphate radical to remove suspended particles, and regulating the pH value of the filtrate; passing the phosphate-containing wastewater filtrate through an adsorption tower filled with a resin-based nanocomposite material to obtain a deeply purified water body; stopping adsorption when the concentration of phosphate ions in the effluent of the middle adsorption tower reaches a penetration point, and carrying out desorption regeneration and transformation on the composite material; and finally, cleaning the composite material until the water outlet of the adsorption tower is nearly neutral, and recycling. The adsorption material obtained by taking the quaternary ammonium polystyrene-divinylbenzene copolymer spheres as the matrix and loading neodymium hydroxide nano particles can deeply remove phosphate radical in water, and experiments show that when the pH value of the water is 2.0-12.0, high-concentration Cl coexist ‑ 、NO 3 ‑ 、SO 4 2‑ 、HCO 3 ‑ And under the condition of natural organic matters, the phosphate radical content of the effluent is reduced from less than 0.05-30 mg/L to less than 0.01 mg/L (calculated by P), and the material can be reused.

Description

Resin-based neodymium-loaded nanocomposite, preparation method thereof and application thereof in deep removal of phosphate in water
Technical Field
The invention relates to the technical field of sewage treatment and tap water treatment, in particular to a resin-based neodymium-carrying nanocomposite, a preparation method thereof and application thereof in deep removal of phosphate in water.
Background
Phosphorus is a basic nutrient element required by the terrestrial organisms. However, excessive phosphorus in water causes serious eutrophication problems of aquatic environment, such as excessive algae propagation, water quality deterioration and anoxic death of aquatic organisms, which threatens ecological safety and economic, social and health development. Thus, the phosphorus discharge of each country is strictly limited, for example, the maximum allowable concentration value of phosphorus in the comprehensive wastewater is set to be 0.5 mg P/L by the China ecological environment department; in Europe, phosphorus emission levels are recommended to be controlled between 0.1-0.5 mg P/L according to the water frame instructions. Therefore, the deep phosphorus removal technology research is always a hot research topic in the field of domestic and foreign environmental protection.
Various water treatment methods have been developed for removing phosphate from wastewater, including biological treatment, chemical precipitation, membrane separation, adsorption, and the like. Biological treatment is the most widely used technology in sewage treatment, but the dephosphorization efficiency of the technology often cannot meet the requirement of direct discharge. The chemical precipitation is carried out by adding alum, lime and the like, but excessive medicament is easy to cause secondary pollution and a large amount of sludge. Membrane separation is a promising technique for removing phosphorus, but the influence of membrane pollution caused by soluble organic matters in water is not negligible. In recent years, adsorption methods are becoming more and more important because of simple process operation, low energy and material consumption and potential for recycling pollutants. However, considering that contaminated water generally contains more various inorganic substances (e.g., sulfate, chloride, nitrate, bicarbonate, etc.) than phosphate and natural organic substances (e.g., humic acid), the adsorbent used is required to have a high adsorption selectivity for phosphate in a complex water quality background.
Conventional adsorbent materials include zeolites, activated carbon, anion exchange resins and the like,wherein zeolite and active carbon mainly remove phosphate radical through physical adsorption process, adsorption capacity is low; the adsorbent having a strongly basic anion exchange group is only electrostatically attracted to negatively charged phosphate, and thus causes a decrease in the adsorption removal rate of phosphate when a large amount of competing anions are present. Adsorbents having rich amine functionality have been demonstrated to have higher adsorption capacities for phosphate than the first few adsorbents. Chen et al prepared EDA@CMPS adsorbent by grafting Ethylenediamine (EDA) onto chloromethylated polystyrene microspheres (CMPS) and adsorbed trace amounts of phosphate in water (Chen, D.; yu, H.; pan, M.; pan, B.; hydrogen bonding-orientated selectivity of phosphate adsorption by imine-functional added solvent. Chemical Engineering Journal 2021.). The Chen et al study utilized the effect of quaternary ammonium-based polystyrene-divinylbenzene copolymer spheres (D201) on phosphate removal from water (Chen, l.; zhao, x.; pan, b.; zhang, w.; hua, m.; lv, l.; zhang, w.; preferable removal of phosphate from water using hydrous zirconium oxide-based nanocomposite of high stability, journal of Hazardous Materials, 2015, 284, 35-42). The above-mentioned several adsorbents show different degrees of reduction in adsorption removal capacity for phosphate under co-existing ion interference. Taking D201 as an example, when the initial concentration of phosphate is 10 mg P/L, 20 mmol/L Cl is coexistent in the solution - 、20 mmol/L NO 3 - 20 mmol/L SO 4 2- In the process, the removal rate of the D201 to the phosphate is respectively reduced from 71% to 7%, 5% and 4%, which indicates that the adsorption selectivity of the D201 to the phosphate is poor, and the technical application and popularization of the D201 to the actual water body are limited. Meanwhile, although the adsorption capacity of the adsorbent to phosphate radical can be improved, the desorption regeneration condition is more severe. Therefore, how to improve the adsorption selectivity and realize the balance between adsorption capacity and desorption regeneration is a main problem facing us.
Studies have shown that metal hydrous oxides can form stable compounds with phosphates by internal sphere complexation or ligand exchange specific adsorption. Research by Yao et al reports that the use of neodymium modified chitosan materials for deep removal of fluoride ions in water bodies effectively overcomes the disadvantages of low mechanical strength and easy loss by loading powdered metal hydrous oxides onto high strength adsorption materials (such as highly crosslinked resins), and improves the applicability of the materials in actual water treatment (Yao, r.; meng, f.; zhang, l.; ma, d.; wang, m.; defluoridation of water using neodymium-modified chitosan Journal of Hazardous Materials 2009, 165 (1-3), 454-60). At present, literature retrieval shows that no method for deeply removing phosphate radical in water body by adopting resin-based neodymium-carrying nano composite material is reported. In view of the foregoing, there is a need to develop a method for treating wastewater with high adsorption capacity and strong selectivity for phosphate.
Disclosure of Invention
Aiming at the problem that the metal oxide supported by the cation exchange resin is difficult to be used for deeply removing phosphate radical in the prior art, the invention provides a resin-based neodymium-supported nanocomposite, a preparation method thereof and application thereof in deeply removing phosphate radical in water. The invention adopts the nano composite material formed by compositing the macroporous anion exchange resin and the nano neodymium hydroxide as the adsorbent, combines the advantages of strong binding capacity of the macroporous anion exchange resin for selectively adsorbing phosphate ions and the nano neodymium hydroxide and the phosphate ions, good selectivity and large specific surface area, overcomes the defects of weak adsorption performance, low repeated utilization rate, poor adsorption selectivity and the like of the traditional adsorption material, and can compete for anion Cl in water coexistence - 、NO 3 - 、SO 4 2- 、HCO 3 - And under the condition that the concentration of natural organic matters is far higher than that of the phosphate radical of the target ion, the high-efficiency adsorption of the phosphate radical in the water body is realized in a wider pH range, the adsorption capacity of the phosphate radical in the wastewater is high, the adsorption selectivity is strong, and the content of the phosphate radical of the effluent reaches the standard after the wastewater passes through an adsorption tower filled with the material; meanwhile, the adsorption saturation can be realized by NaOH-NaCl mixed solution for regeneration and repeated utilization.
The invention adopts the following technical scheme:
the resin-based neodymium-loaded nanocomposite is characterized in that a substrate of the composite is a quaternary ammonium-based polystyrene-divinylbenzene copolymerized sphere, nano pore channels are uniformly distributed on the substrate, nano hydrated neodymium oxide particles are uniformly distributed in the pore channels, the particle size of the nano hydrated neodymium oxide particles is 15-50 nm, and the load of the nano hydrated neodymium oxide on the composite is 6.5-20.3% based on neodymium elements.
Further, the particle size of the quaternary ammonium polystyrene-divinylbenzene copolymerized sphere is 0.6-0.9 mm, and the average pore diameter of the nano pore canal on the copolymerized sphere is 10-80nm.
The preparation method of the resin-based neodymium-loaded nanocomposite comprises the following steps:
1) Washing the quaternary ammonium group polystyrene-divinylbenzene copolymerized sphere with ethanol, soaking the sphere in a strong alkali solution and a strong acid solution in sequence, washing the sphere with ultrapure water until the pH is neutral, and drying the sphere in an incubator to obtain the pretreated quaternary ammonium group polystyrene-divinylbenzene copolymerized sphere;
2) Adding the quaternary ammonium group polystyrene-divinylbenzene copolymer spheres pretreated in the step 1) into a solution containing neodymium salt, and dipping under the condition of water bath heating;
3) After the step 2) is completed, taking out the copolymer spheres, naturally airing, and then transferring the copolymer spheres to NaOH solution for heating and stirring in a water bath;
4) Finally filtering out the copolymer spheres, washing with water to neutrality, then rinsing with saturated sodium chloride solution, then washing with ultrapure water until the pH is neutral, and drying in a constant temperature box to obtain the resin-based neodymium-carrying nanocomposite.
Further, in the step 1), the strong alkali solution is NaOH solution with the pH value of 13-14, the strong acid solution is HCl solution with the pH value of 1-2, the soaking time in the strong alkali solution and the soaking time in the strong acid solution are respectively 4-6 hours, and the drying temperature is 50-60 ℃.
In step 2), the neodymium salt is neodymium chloride hexahydrate, the mass ratio of the copolymer spheres to the neodymium salt is 1 (1-1.5), the water bath heating temperature is 50-60 ℃, stirring is continuously carried out at the speed of 150-200 rpm at the water bath heating temperature, the soaking time is 20-30 hours, and the soaking time is preferably 24 hours.
Further, in the step 3), the mass concentration of the NaOH solution is 10-20%, the mass ratio of the copolymer spheres to the NaOH solution is 1 (20-30), the water bath heating temperature is 50-60 ℃, and the water bath heating reaction time is 10-15 hours.
Further, in the step 4), the saturated sodium chloride solution is used for rinsing for 6-10 hours, the drying temperature is 50-60 ℃, and the drying time is 20-30 hours.
The resin-based neodymium-carrying nanocomposite provided by the invention can be well applied to deep removal of phosphate in water, and the application method comprises the following steps:
s1: filling the resin-based neodymium-loaded nanocomposite material according to claim 1 or 2 into an adsorption tower;
s2: filtering the waste water containing phosphate radical to remove suspended particles, and regulating the pH value of the filtrate to be 2-12;
s3: passing the filtrate of the waste water containing phosphate radical in the step S2 through the adsorption tower filled with the resin matrix nanocomposite in the step S1;
s4: stopping adsorption when the concentration of phosphate radicals in the effluent of the adsorption tower reaches a penetration point in the step S3, and carrying out desorption regeneration and transformation on the composite material;
s5: after the composite material is regenerated and transformed in the step S4, the composite material is washed by water until the water discharged from the adsorption tower is neutral, and then the composite material is re-entered into the step S3 for recycling.
The resin-based neodymium-loaded nanocomposite adopted by the invention is prepared by loading nano neodymium hydroxide particles on the basis of the polymer skeleton of the quaternary ammonium polystyrene-divinylbenzene copolymer sphere D201, and can specifically adsorb phosphate radical through inner sphere complexation besides electrostatic attraction, so that the resin-based neodymium-loaded nanocomposite has excellent anti-interference capability; meanwhile, the resin skeleton can effectively fix nano neodymium hydroxide particles, thereby effectively reducing loss and avoiding secondary pollution.
Further, the mass concentration of phosphate radical in the water body in the phosphate radical-containing wastewater in the step S2 is 0.05-30 mg/L (calculated by P), and the mass concentration of other coexisting anions and natural organic substances in the water body is less than 500 times of the mass concentration of phosphate radical ions; the natural organic matter in the water body can be Humic Acid (HA), and the mass concentration is calculated by total organic carbon TOC.
Further, in the step S3, the operation temperature of the adsorption tower is 5-45 ℃, preferably 20-30 ℃, and the water outlet flow rate of the adsorption tower is 10-20 BV/h.
In the step S4, the composite material is desorbed and regenerated by adopting a NaOH-NaCl mixed solution, wherein the mass fraction of NaOH in the NaOH-NaCl mixed solution is 7-13%, the mass fraction of NaCl is 3-8%, the flow rate is 1-5 BV/h, the volume consumption of the NaOH-NaCl mixed solution is 5-15 times of the filling volume of the composite material in an adsorption tower, and the mass concentration of phosphate radical in effluent water is more than 0.01 mg/L (calculated by P); in the step S5, the flow rate of the cleaning water is 20-30 BV/h.
Further, in the steps S2 and S3, the operation mode of single-tower adsorption-desorption or multi-tower serial adsorption-single-tower desorption is adopted by the adsorption towers.
Because the quaternary amine group of the amine functional group contained in the macroporous anion exchange resin is easy to generate protonisation in aqueous solution and is converted into a quaternary ammonium group with positive electricity, the quaternary ammonium group can be combined with phosphate radical with negative electricity, and the phosphate radical is adsorbed through electrostatic interaction. However, in the presence of coexisting ions, the macroporous anion exchange resin is subjected to competing ions such as SO due to its protonated quaternary ammonium group adsorption sites 4 2- 、NO 3 - Occupancy, failure to sufficiently bind to phosphate, causes a decrease in the amount of adsorption to phosphate, and thus exhibits poor adsorption selectivity. While neodymium hydroxide can coordinate with phosphate radical in metal-ligand, and coexistent ions such as SO in solution 4 2- 、NO 3 - Can not be combined with neodymium hydroxide hydrate, thus showing adsorption selectivity under the condition of coexisting ions and realizing the selective adsorption of phosphate radicals.
The invention adopts the nano composite material formed by compositing macroporous anion exchange resin and nano neodymium hydroxide as an adsorbent, combines the advantages of large adsorption capacity of the macroporous anion exchange resin on phosphate and strong combination capacity, good selectivity and large specific surface area of the nano neodymium hydroxide and phosphate ions, and has high adsorption capacity, strong adsorption selectivity and easy desorption and regeneration on phosphate in wastewater under the synergistic effect of the macroporous anion exchange resin and the nano neodymium hydroxide.
3. Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
(1) The macroporous anion exchange resin-based neodymium-loaded nanocomposite adopted by the method can be used as an adsorption material to efficiently remove phosphate radical in water, and experiments show that when the pH value of the water is 2.0-12.0, high-concentration Cl coexist - 、NO 3 - 、SO 4 2- 、HCO 3 - And under the condition of natural organic matters, the concentration of phosphate in the effluent can be well reduced from 0.05-30 mg/L to below 0.01 mg/L (calculated by P).
(2) The macroporous anion exchange resin-based neodymium-carrying nanocomposite adopted by the method has large adsorption treatment on phosphate, high stability and repeated use, and can be regenerated by NaOH-NaCl mixed solution after adsorption saturation.
(3) According to the macroporous anion exchange resin-based neodymium-loaded nanocomposite material adopted by the method, nano neodymium hydroxide is loaded on a resin carrier, so that secondary pollution caused by release of metal nano particles into a water body is effectively avoided.
Drawings
FIG. 1 is a TEM image of the resin-based nanocomposite of examples 1 to 10 of the present invention;
FIG. 2a is a schematic diagram showing the effect of different pH on the removal of phosphate groups from water in a resin-based nanocomposite used in the present invention;
FIG. 2b is a schematic diagram showing the effect of different competing anions on the removal of phosphate groups from water at different molar ratios (0, 1, 5, 10 and 20) of the resin-based nanocomposite used in the present invention;
FIG. 2c is a schematic diagram showing the effect of different Humic Acid (HA) concentrations on the removal of phosphate from water by resin-based nanocomposites used in the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
The quaternized polystyrene-divinylbenzene copolymer spheres used in the examples of the present invention were purchased from Hangzhou light resin Co., ltd, and the degree of crosslinking of the polystyrene-divinylbenzene was about 8%.
Blank example 1
The resin-based neodymium-loaded nanocomposite related in the following examples is specifically prepared by:
(1) Washing the quaternary ammonium polystyrene-divinylbenzene copolymer spheres (with the particle size of 0.6-0.9 mm) with ethanol, soaking the spheres in a NaOH solution with the pH value of 13 for 6 h, filtering, soaking the spheres in a HCl solution with the pH value of 1 for 6 h, washing the spheres with ultrapure water until the pH value is neutral, and drying the spheres at the temperature of 60 ℃ to obtain the pretreated quaternary ammonium polystyrene-divinylbenzene copolymer spheres;
(2) Dissolving 5.0 g neodymium chloride hexahydrate into 50 mL of mixed aqueous solution containing 20% (v/v) ethanol, adding 5.0 g of the quaternary ammonium-based polystyrene-divinylbenzene copolymer spheres pretreated in the step (1), and soaking in a water bath at 60 ℃ for 24 hours under stirring at 180 rpm;
(3) Filtering the neodymium-saturated quaternary ammonium polystyrene-divinylbenzene copolymerized spheres obtained in the step (2), naturally air-drying, transferring into a 100 mL NaOH solution with the mass fraction of 15%, and carrying out heat treatment reaction on the obtained mixture at the water bath of 60 ℃ for 12 h so as to ensure that the loaded neodymium is converted into neodymium hydroxide;
(4) Filtering the composite material in the step (3), and then adding the filtered composite material into a saturated NaCl solution for rinsing 8 h; finally, the composite material is washed by ultra-pure water until the pH value is neutral, and is dried at 60 ℃ after being filtered, so as to obtain the resin-based neodymium-carrying nano composite material.
In the prepared resin-based neodymium-carrying nanocomposite, the load of neodymium element is 18.3%. TEM images show that neodymium is immobilized and dispersed in the form of nanoclusters in the framework of D201 (fig. 1), with a size diameter of 15-50 nm; BET characterization showed that the composite had an average pore size of 10.46.+ -. 1.21 nm and a specific surface area of 23.19.+ -. 2.13 m 2 /g。
The depth removal performance of the resin-based neodymium-supported nanocomposite of blank example 1 on phosphate in water was measured, wherein the measurement method of the phosphate adsorption test is as follows:
i) Phosphate adsorption test
100 mL phosphate concentration of 30 mg/L (calculated as P) was taken (the cation is Na + ) And adjusting the pH value of the solution to 6.0, adding 0.0500. 0.0500 g of the prepared resin-based neodymium-carrying nanocomposite, and oscillating and adsorbing at 25 ℃ for 24 h to achieve adsorption balance. And then the concentration of free phosphate radical in the solution is measured, and the adsorption capacity of the resin-based neodymium-carrying nano composite material to the phosphate radical is calculated to be 56.24 mg P/g.
Blank example 2
In blank example 2, the phosphate adsorption test of the resin matrix neodymium-supported nanocomposite was repeated for blank example 1, except that: the pH of the phosphate-containing solution was adjusted to 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, respectively, with the corresponding adsorption capacities shown in fig. 2a.
Blank example 3
In blank example 3, the phosphate adsorption test of the resin matrix neodymium-supported nanocomposite was repeated for blank example 1, except that: in the phosphate-containing solution, the solution was adjusted to contain different molar ratios (0, 1, 5, 10 and 20) of competing anions (HCO) 3 - 、Cl - 、NO 3 - Or SO 4 2- ) The corresponding adsorption capacity is shown in fig. 2b. Wherein, the molar ratio refers to the molar ratio of the concentration of the competing ions to the concentration of the phosphate. The 5 bar graphs corresponding to each competing anion in fig. 2b correspond to the experimental results of the molar ratios (0, 1, 5, 10 and 20), respectively. Wherein the cations competing for anion binding are all Na + 。
Blank example 4
In blank example 4, the phosphate adsorption test of the resin matrix neodymium-supported nanocomposite was repeated for blank example 1, except that: the phosphate-containing solutions were adjusted to contain 10, 30, 60, 100 and 150 mg/L Humic Acid (HA), respectively, with the corresponding adsorption capacities as shown in FIG. 2c.
The composite adsorbents used in examples 1 to 10 below were all strong alkaline resin-based neodymium-supported nanocomposites prepared by the method of blank example 1.
Example 1
A method for deeply removing phosphate radical in water by utilizing resin-based neodymium-carrying nano composite material comprises the following specific steps:
(1) 50 mL (about 30 g) resin-based neodymium-loaded nanocomposite material was loaded into a jacketed glass adsorption column (Φ32×360 mm);
(2) Phosphate-containing wastewater (concentration of 2 mg/L (calculated as P), cl - 、NO 3 - 、SO 4 2- 、HCO 3 - The concentration of (2) is 100 mg/L and the HA concentration is 10 mg/L), filtering to remove suspended particles, and adjusting the pH of the filtrate to 6;
(3) Passing the filtrate obtained in the step (2) through an adsorption column filled with a resin-based neodymium-carrying nanocomposite bed layer at the temperature of 25+/-5 ℃ at the flow rate of 15 BV/h, and reducing the phosphate concentration of the effluent to below 0.01 mg/L (calculated by P);
(4) Stopping operation when reaching a leakage point (the concentration of phosphate radical of outlet water is more than 0.01 mg/L (calculated by P)), wherein the treatment capacity of the phosphate radical-containing wastewater is about 8200 BV, and carrying out desorption regeneration and transformation by using a mixed solution of 500 mL mass fraction of 10% NaOH and 5% NaCl at the temperature of 25+/-5 ℃ and the flow of 1BV/h through a resin bed layer;
(5) After the composite material in the step (4) is regenerated and transformed, the composite material is cleaned until the water output from the adsorption tower is nearly neutral, and then the composite material is re-entered into the step (3) for recycling, wherein the total regeneration rate of the composite material is more than 90 percent (namely, when the regenerated composite material is treated by repeating the steps (1) - (3), the treatment capacity of a leakage point is more than 7380 and BV).
Example 2
The same method as in example 1 is adopted to carry out the deep removal of phosphate radical in water body, and the difference is that: the adsorption material filled in the adsorption column in the step (1) is replaced by a quaternary ammonium polystyrene-divinylbenzene copolymerized sphere D201, and the experimental result is that: when reaching the leakage point (the phosphate concentration of the outlet water is more than 0.01 mg/L (calculated by P)), the operation is stopped, and the treatment capacity of the phosphate-containing wastewater is 30 BV.
Example 3
The same method as in example 1 is adopted to carry out the deep removal of phosphate radical in water body, and the difference is that: in the step (3), the temperature of the filtrate passing through the bed layer filled with the adsorption material is controlled to be 10+/-2 ℃, and the experimental result is as follows: when reaching the leakage point (the phosphate radical concentration of the outlet water is more than 0.01 mg/L (calculated by P)), the operation is stopped, and the treatment effect and the treatment capacity are basically unchanged.
Example 4
The same method as in example 1 is adopted to carry out the deep removal of phosphate radical in water body, and the difference is that: in the step (3), the temperature of the filtrate passing through the bed layer filled with the adsorption material is controlled at 40+/-2 ℃, and the experimental result is as follows: when reaching the leakage point (the phosphate radical concentration of the outlet water is more than 0.01 mg/L (calculated by P)), the operation is stopped, and the treatment effect and the treatment capacity are basically unchanged.
Example 5
The same method as in example 1 is adopted to carry out the deep removal of phosphate radical in water body, and the difference is that: in the step (1), the pH value of the phosphorus-containing water body is adjusted to 3.0, and the experimental result is as follows: when the operation is stopped when the leakage point is reached (the phosphate concentration of the outlet water is more than 0.01 mg/L (calculated by P)), the adsorption effect is improved, and the treatment capacity of the phosphate-containing wastewater is about 9800 BV.
Example 6
The same method as in example 1 is adopted to carry out the deep removal of phosphate radical in water body, and the difference is that: in the step (1), the pH value of the phosphorus-containing water body is adjusted to 10.0, and the experimental result is that: when the operation is stopped at the leakage point (the phosphate concentration of the outlet water is more than 0.01 mg/L (calculated by P)), the adsorption effect is reduced, and the treatment capacity of the phosphate-containing wastewater is about 5600 BV.
Example 7
A method for deeply removing phosphate radical in water by utilizing resin-based neodymium-carrying nano composite material comprises the following specific steps:
(1) 30 mL (about 18 g) resin-based neodymium-loaded nanocomposite material was loaded into a jacketed glass adsorption column (Φ32×360 mm);
(2) Phosphate-containing waste water (concentration of 0.05 mg/L (calculated as P), cl-, NO) 3- 、SO 4 2- 、HCO 3 - The concentration of (2) is 10 mg/L and the HA concentration is 5 mg/L), filtering to remove suspended particles, and adjusting the pH of the filtrate to 6;
(3) Passing the filtrate obtained in the step (2) through an adsorption column filled with a resin-based neodymium-carrying nanocomposite bed layer at the temperature of 25+/-5 ℃ at the flow rate of 15 BV/h, and reducing the phosphate concentration of the effluent to below 0.01 mg/L (calculated by P);
(4) Stopping operation when reaching a leakage point (the concentration of phosphate radical of outlet water is more than 0.01 mg/L (calculated by P)), wherein the treatment capacity of the phosphate radical-containing wastewater is about 16800 BV, and carrying out desorption regeneration and transformation by using a mixed solution of 300 mL mass percent of 10 percent NaOH and 5 percent NaCl at the temperature of 25+/-5 ℃ and the flow of 1BV/h through a resin bed layer;
(5) After the composite material in the step (4) is regenerated and transformed, the composite material is cleaned until the water outlet of the adsorption tower is nearly neutral, and then the composite material is re-entered into the step (3) for recycling, wherein the total regeneration rate of the composite material is more than 90%.
Example 8
A method for deeply removing phosphate radical in water by utilizing resin-based neodymium-carrying nano composite material comprises the following specific steps:
(1) 100 mL (about 60 g) resin-based neodymium-loaded nanocomposite material was loaded into a jacketed glass adsorption column (Φ32×360 mm);
(2) Phosphate-containing wastewater (concentration of 5 mg/L (calculated as P), cl - 、NO 3 - 、SO 4 2- 、HCO 3 - The concentration of (2) is 500 mg/L and the HA concentration is 50 mg/L), filtering to remove suspended particles, and adjusting the pH of the filtrate to 6;
(3) Passing the filtrate obtained in the step (2) through an adsorption column filled with a resin-based neodymium-carrying nanocomposite bed layer at the temperature of 25+/-5 ℃ at the flow rate of 15 BV/h, and reducing the phosphate concentration of the effluent to below 0.01 mg/L (calculated by P);
(4) Stopping operation when reaching a leakage point (the concentration of phosphate radical of outlet water is more than 0.01 mg/L (calculated by P)), wherein the treatment capacity of the phosphate radical-containing wastewater is about 6200 BV, and carrying out desorption regeneration and transformation by using a mixed solution of 10% NaOH and 5% NaCl at a mass fraction of 500 mL at a temperature of 25+/-5 ℃ at a flow rate of 1BV/h through a resin bed layer;
(5) After the composite material in the step (4) is regenerated and transformed, the composite material is cleaned until the water outlet of the adsorption tower is nearly neutral, and then the composite material is re-entered into the step (3) for recycling, wherein the total regeneration rate of the composite material is more than 90%.
Example 9
A method for deeply removing phosphate radical in water by utilizing resin-based neodymium-carrying nano composite material comprises the following specific steps:
(1) 100 mL (about 60 g) resin-based neodymium-loaded nanocomposite material was loaded into a jacketed glass adsorption column (Φ32×360 mm);
(2) Phosphate-containing wastewater (concentration of 10 mg/L (calculated as P), cl - 、NO 3 - 、SO 4 2- 、HCO 3 - The concentration of (2) is 1000 mg/L and the HA concentration is 100 mg/L), filtering to remove suspended particles, and adjusting the pH of the filtrate to 6;
(3) Passing the filtrate obtained in the step (2) through an adsorption column filled with a resin-based neodymium-carrying nanocomposite bed layer at the temperature of 25+/-5 ℃ at the flow rate of 15 BV/h, and reducing the phosphate concentration of the effluent to below 0.01 mg/L (calculated by P);
(4) Stopping operation when reaching a leakage point (the concentration of phosphate radical of outlet water is more than 0.01 mg/L (calculated by P)), wherein the treatment capacity of the phosphate radical-containing wastewater is about 4500 BV, and the mixed solution of 1000 mL mass percent of 10 percent NaOH and 5 percent NaCl is subjected to desorption regeneration and transformation by downstream flow through a resin bed layer at the flow rate of 1BV/h at the temperature of 25+/-5 ℃;
(5) After the composite material in the step (4) is regenerated and transformed, the composite material is cleaned until the water outlet of the adsorption tower is nearly neutral, and then the composite material is re-entered into the step (3) for recycling, wherein the total regeneration rate of the composite material is more than 90%.
Example 10
A method for deeply removing phosphate radical in water by utilizing resin-based neodymium-carrying nano composite material comprises the following specific steps:
(1) 200 mL (about 120 g) resin-based neodymium-loaded nanocomposite material was loaded into a jacketed glass adsorption column (Φ32×360 mm);
(2) Phosphate-containing wastewater (concentration: 30 mg/L (P), cl - 、NO 3 - 、SO 4 2- 、HCO 3 - The concentration of (2) is 1500 mg/L and the HA concentration is 150 mg/L), filtering to remove suspended particles, and adjusting the pH of the filtrate to 6;
(3) Passing the filtrate obtained in the step (2) through an adsorption column filled with a resin-based neodymium-carrying nanocomposite bed layer at the temperature of 25+/-5 ℃ at the flow rate of 15 BV/h, and reducing the phosphate concentration of the effluent to below 0.01 mg/L (calculated by P);
(4) Stopping operation when reaching a leakage point (the concentration of phosphate radical of outlet water is more than 0.01 mg/L (calculated by P)), wherein the treatment capacity of the phosphate radical-containing wastewater is about 3700 BV, and carrying out desorption regeneration and transformation by using a mixed solution of 2000 mL mass fraction of 10% NaOH and 5% NaCl at a temperature of 25+/-5 ℃ and a flow of 1BV/h through a resin bed layer;
(5) After the composite material in the step (4) is regenerated and transformed, the composite material is cleaned until the water outlet of the adsorption tower is nearly neutral, and then the composite material is re-entered into the step (3) for recycling, wherein the total regeneration rate of the composite material is more than 90%.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.

Claims (10)

1. The application of the resin-based neodymium-carrying nanocomposite material for deeply removing phosphate in water is characterized by comprising the following steps of:
s1: filling the resin-based neodymium-carrying nano composite material into an adsorption tower;
s2: filtering the waste water containing phosphate radical to remove suspended particles, and regulating the pH value of the filtrate to be 2-12; the mass concentration of other coexisting anions and natural organic matters in the water body is smaller than that of phosphorus500 times of the mass concentration of acid radical ions; other coexisting anions include Cl - 、NO 3 - 、SO 4 2- 、HCO 3 - The natural organic matters in the water body are humic acid, and the mass concentration is calculated by total organic carbon TOC;
the mass concentration of phosphate radical in the water body in the phosphate radical-containing wastewater in the step S2 is 0.05-30 mg/L calculated by P;
s3: passing the phosphate radical-containing wastewater filtrate in the step S2 through the adsorption tower in the step S1; the operation temperature of the adsorption tower in the step S3 is 5-45 ℃;
s4: stopping adsorption when the concentration of phosphate radicals in the effluent of the adsorption tower reaches a penetration point in the step S3, and carrying out desorption regeneration and transformation on the composite material;
s5: after the composite material is regenerated and transformed in the step S4, the composite material is washed by water until the water discharged from the adsorption tower is neutral, and then the composite material is re-entered into the step S3 for recycling;
the substrate of the resin-based neodymium-carrying nanocomposite is a quaternary ammonium polystyrene-divinylbenzene copolymerized sphere, nano pore channels are uniformly distributed on the substrate, nano hydrated neodymium oxide particles are uniformly distributed in the pore channels, the particle size of the nano hydrated neodymium oxide particles is 15-50 nm, and the load of the nano hydrated neodymium oxide on the composite is 6.5-20.3% based on neodymium element.
2. The application of the resin-based neodymium-supported nanocomposite material for deeply removing phosphate in water, as claimed in claim 1, wherein the particle size of the quaternary ammonium-based polystyrene-divinylbenzene copolymer sphere is 0.6-0.9 mm, and the average pore diameter of the nano pore canal on the copolymer sphere is 20-80nm.
3. The application of removing phosphate radical in water based on resin-based neodymium-carried nanocomposite according to claim 1 or 2, wherein the preparation method of the resin-based neodymium-carried nanocomposite comprises the following steps:
1) Washing the quaternary ammonium group polystyrene-divinylbenzene copolymerized sphere with ethanol, soaking the sphere in a strong alkali solution and a strong acid solution in sequence, washing the sphere with ultrapure water until the pH is neutral, and drying the sphere in an incubator to obtain the pretreated quaternary ammonium group polystyrene-divinylbenzene copolymerized sphere;
2) Adding the quaternary ammonium group polystyrene-divinylbenzene copolymer spheres pretreated in the step 1) into a solution containing neodymium salt, and dipping under the condition of water bath heating;
3) After the step 2) is completed, taking out the copolymer spheres, naturally airing, and then transferring the copolymer spheres to NaOH solution for heating and stirring in a water bath;
4) Finally filtering out the copolymer spheres, washing with water to neutrality, then rinsing with saturated sodium chloride solution, then washing with ultrapure water until the pH is neutral, and drying in a constant temperature box to obtain the resin-based neodymium-carrying nanocomposite.
4. The application of the resin-based neodymium-supported nanocomposite for deeply removing phosphate in water, as claimed in claim 3, wherein in the step 1), the strong alkali solution is a NaOH solution with a pH of 13-14, the strong acid solution is a HCl solution with a pH of 1-2, the soaking time in the strong alkali solution and the soaking time in the strong acid solution are respectively 4-6 hours, and the drying temperature is 50-60 ℃.
5. The application of the resin-based neodymium-supported nanocomposite for deeply removing phosphate in water according to claim 3, wherein in the step 2), neodymium salt is neodymium chloride hexahydrate, the mass ratio of the copolymer sphere to the neodymium salt is 1 (1-1.5), the heating temperature of a water bath is 50-60 ℃, stirring is continuously carried out at a speed of 150-200 rpm at the heating temperature, and the soaking time is 20-30 hours.
6. The application of the resin-based neodymium-supported nanocomposite material for deeply removing phosphate in water according to claim 5, wherein in the step 2), the impregnation time is 24 hours.
7. The application of the resin-based neodymium-supported nanocomposite for deeply removing phosphate in water, as claimed in claim 3, wherein in the step 3), the mass concentration of NaOH solution is 10-20%, the mass ratio of the copolymer spheres to the NaOH solution is 1 (20-30), the water bath heating temperature is 50-60 ℃, and the water bath heating reaction time is 10-15 hours;
in the step 4), the saturated sodium chloride solution is used for rinsing for 6-10 hours, the drying temperature is 50-60 ℃, and the drying time is 20-30 hours.
8. The application of the resin-based neodymium-supported nanocomposite based on deep removal of phosphate in water, as claimed in claim 1, wherein the operating temperature of the adsorption tower in the step S3 is 20-30 ℃, and the water outlet flow rate of the adsorption tower is 10-20 BV/h.
9. The application of the resin-based neodymium-carried nanocomposite for deeply removing phosphate in water, as claimed in claim 1, is characterized in that in the step S4, naOH-NaCl mixed solution is adopted to desorb and regenerate the resin-based neodymium-carried nanocomposite, the mass fraction of NaOH in the NaOH-NaCl mixed solution is 7-13%, the mass fraction of NaCl is 3-8%, the flow rate is 1-5 BV/h, the volume consumption is 5-15 times of the filling volume of the resin-based neodymium-carried nanocomposite in an adsorption tower, and the mass concentration of phosphate in the effluent water in terms of P is more than 0.01 mg/L; in the step S5, the flow rate of the cleaning water is 20-30 BV/h.
10. The application of the resin-based neodymium-supported nanocomposite material for deeply removing phosphate in water according to claim 1, wherein the adsorption towers in the steps S2 and S3 adopt a single-tower adsorption-desorption or multi-tower series adsorption-single-tower desorption operation mode.
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