CN107983319B - Preparation of nano lanthanum hydroxide composite material and method for removing trace phosphorus in wastewater - Google Patents

Preparation of nano lanthanum hydroxide composite material and method for removing trace phosphorus in wastewater Download PDF

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CN107983319B
CN107983319B CN201711146003.6A CN201711146003A CN107983319B CN 107983319 B CN107983319 B CN 107983319B CN 201711146003 A CN201711146003 A CN 201711146003A CN 107983319 B CN107983319 B CN 107983319B
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composite material
lanthanum hydroxide
hydroxide composite
phosphate
nano lanthanum
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CN107983319A (en
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张庆瑞
李奕璇
孙奇娜
杨庆刚
陈贺
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Yanshan University
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    • 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
    • B01J20/22—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
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • B01J20/02—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
    • 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
    • B01J20/22—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
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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

Abstract

A preparation method of a nanometer lanthanum hydroxide composite material mainly comprises the steps of putting macroporous ion exchange resin into Tris-HCl buffer solution, obtaining a macroporous polystyrene matrix material with the surface coated with polydopamine after reaction, filtering, putting the macroporous polystyrene matrix material into La (III) salt solution, diffusing lanthanum salt to the outer surface of a sphere, and preparing the nanometer lanthanum hydroxide composite material through ammonia water in-situ precipitation, wherein the loading capacity of the nanometer lanthanum hydroxide composite material is 5.9% -35.2%; the method for removing the trace phosphorus in the wastewater by using the composite material is to fill the composite resin in an adsorption column, then enable trace phosphate polluted water to flow through a filter column filled with an adsorbent from top to bottom, and when the concentration of phosphate in effluent is higher than 0.5mg/L, use mixed liquor of NaOH and NaCl for desorption and efficient regeneration. The invention has high treatment efficiency, large treatment capacity and obvious environmental protection benefit, and the content of phosphate in the effluent of the phosphate-polluted wastewater can be reduced to below 50 ppb.

Description

Preparation of nano lanthanum hydroxide composite material and method for removing trace phosphorus in wastewater
Technical Field
The invention relates to a method for purifying waste water.
Background
Phosphorus is one of the main elements causing eutrophication in water bodies, and the discharge of a large amount of phosphorus-containing wastewater into the water bodies can cause serious eutrophication, and the generated algal toxins can cause lethal effect on drinking water. The investigation shows that the acceptable maximum phosphorus concentration in the lake is 0.03mg/L, so that the technology for efficiently purifying and treating trace phosphorus in the water body has important practical application value. The latest phosphorus discharge standard requires that the total P is less than 0.5ppm, and the wastewater treatment difficulty is increased along with the increasing environmental protection requirement. Common phosphorus removal methods include chemical precipitation, biological methods, ion exchange methods, adsorption methods, and membrane separation methods. The chemical precipitation method is characterized in that a chemical precipitator is added to generate insoluble precipitate with phosphate in wastewater, phosphorus can be separated out, and meanwhile, a formed flocculating constituent has an adsorption removal effect on the phosphorus. Common coagulating and precipitating agents include lime, alum, ferric chloride, mixtures of lime and ferric chloride, and the like. However, long-term operation results show that the addition of the chemical precipitator can cause the pH value of the wastewater to rise, hard scale sheets are formed in the pool and the water pipe, and a certain amount of sludge can be generated. The biological method is that microorganisms take in phosphorus in an aerobic state and release phosphorus in an anaerobic state in which organic matter exists. The biological phosphorus removal method has good treatment effect, does not have the defect that the sludge is difficult to treat by a chemical precipitation method, does not need to add a precipitator, but has strict requirement management and higher cost. The ion exchange method is a method for replacing phosphate anions on an exchanger to remove the phosphate anions by utilizing strong-base anion exchange resin to perform exchange reaction with the phosphate anions in the wastewater, and has simple process and better phosphate treatment depth. However, the adsorption force of the ion exchange on the phosphate treatment is only electrostatic action, the selectivity is not high, the ion exchange is influenced by competitive adsorption of conventional coexisting anions such as sulfate radical, chloride ion and carbonate in water, and the problems of low working adsorption capacity, frequent regeneration and the like exist. In conclusion, the adsorption method has attracted attention because of small occupied area, simple process, convenient operation and no secondary pollution, and is particularly suitable for the treatment of low-concentration wastewater. In the research of the adsorption method, the search for a new adsorbent is the key point for developing a new dephosphorization process.
The nanometer lanthanum hydroxide is proved to be a new generation nanometer functional material for phosphate adsorption application, and can still form stable LaPO under the environment of trace phosphate4The complex compound shows excellent adsorption force and activity. Furthermore, competing anions such as SO coexist in the water body4 2-、Cl-、NO3 -Can further promote the crystallization of LaPO 4. Although the nano lanthanum hydroxide has a large specific surface area and can provide rich active sites for chelating phosphate, the direct application of the nano lanthanum hydroxide in column adsorption or other fluid systems often generates high pressure drop due to the small particle size (generally micron-sized or nano-sized), so that the nano lanthanum hydroxide is difficult to be practically applied and solid-liquid separation is difficult. In order to solve the problem, researchers load lanthanum hydroxide on porous carrier pore channels such as activated carbon, silica gel, ion exchange resin and the like to prepare the composite adsorption material. Our earlier research work (a method for deep phosphorus removal by using embedded lanthanum oxide composite resin, CN201410349969.X) lanthanum oxide is supported inside the channels of the macroporous ion exchange resin and used for the removal of phosphate. However, the technology has obvious technical defects: (1) loading the nano particles into the porous material often causes channel blockage, thereby causing low mass transfer rate of phosphate and low utilization rate of the high-activity nano lanthanum hydroxide; (2) the loaded nano lanthanum hydroxide is easy to agglomerate, so that the special high-activity characteristic of the nano particles is lost, and the key problem to be solved is how to realize the efficient utilization of the composite nano particles.
Considering the large-particle spherical porous structure of the polystyrene resin, if the high-dispersion nano lanthanum oxide can be supported on the outer surface of the resin, the problems of the utilization rate of the nano particles and the mass transfer of phosphate are possibly solved. However, due to the influence of organic-inorganic wettability and compatibility, the highly dispersed nano lanthanum hydroxide cannot realize surface coating, and the assumption has obvious technical difficulties in preparation technology.
Disclosure of Invention
The invention aims to provide a method for preparing nano lanthanum hydroxide composite resin and removing trace phosphorus in wastewater, which can keep higher adsorption efficiency on phosphate in water when high-concentration sulfate radicals, chloride ions, nitrate radicals and other conventional anions exist in the water and can meet the control requirement of the phosphate in the new standard electroplating pollutant discharge standard (GB 21900-2008).
The invention mainly takes strong-basicity ion exchange resin as a carrier, coats polydopamine on the outer surface of the carrier, and then fixes high-activity nano lanthanum hydroxide on the surface of a polydopamine coating in a compatible polymerization and chemical bonding mode to prepare a resin-based polydopamine nano lanthanum hydroxide composite material which is used for adsorbing trace phosphorus in water for deep purification.
The preparation method of the nano lanthanum hydroxide composite material comprises the following steps:
macroporous anion exchange resin is used as an initial reaction substance, and is placed in Tris-HCl buffer solution with the mass fraction of 1-3g/L dopamine hydrochloride and the pH value of 7.5-8.5In the liquid, controlling the temperature at 20-30 deg.C, aerating for 12-24 hr, filtering to obtain mother material coated with polydopamine macroporous polystyrene, whose basic skeleton structure is styrene-divinylbenzene and surface carries quaternary ammonium group (N)+(CH3)3Cl); on the basis, according to the proportion that 100-500mL of macroporous polystyrene parent material is put into each liter of La (III) saline, the macroporous polystyrene parent material is put into La (III) saline solution with the concentration mass fraction of 1-10%, and the liquid-solid volume ratio is controlled to be 2-10: 1, controlling the temperature to be 50-60 ℃, and controlling the reaction time to be 6-8h, so that La (III) and the amido and hydroxyl on the surface of the polydopamine fully react. (ii) a Filtering, placing the PS-PDA composite material grafted with La (III) in an ammonia water solution with the solution concentration and mass fraction of 1% -4% for in-situ precipitation reaction, and controlling the liquid-solid ratio to be 2-5: 1, controlling the temperature at 50-60 ℃ for 12-24h to form nano lanthanum hydroxide on the surface of PS-PDA, and finally, placing the material in a vacuum oven at 60-80 ℃ for fixing for 4-8h to obtain the target resin-based poly-dopamine nano lanthanum hydroxide composite material, wherein the supported amount is 5.9-35.2% by mass.
The macroporous anion exchange resin can be 201x7, D201, D301 (produced by Hangzhou Congress industries, Ltd.) and the like.
The method for removing trace phosphorus in wastewater by using the nano lanthanum hydroxide composite material comprises the following steps:
the nano lanthanum hydroxide composite material is filled in an adsorption column, wastewater containing trace phosphate with the pollution concentration of 1-10mg/L flows through the adsorption column filled with the hybrid functional adsorbent from top to bottom, the temperature is controlled to be 10-60 ℃, the pH value is 3-10, the flow rate is controlled to be 0.5-50 bed layer volume (BV)/h, and the PO in the trace phosphate wastewater can be added4 3-1-10mg/L of sulfate radical, chloride ion, nitrate radical and the like with the anion concentration within 500 times of the phosphate radical ion concentration are coexisted for deep purification (calculated by P), and the phosphate content in the effluent meets the emission limit of 0.5mg/L of phosphate in a special protection area specified in the discharge Standard of electroplating pollutants.
The regeneration method of the nanometer lanthanum hydroxide composite material comprises the following steps:
when mussel is used for inspiring that the nano lanthanum hydroxide composite resin is absorbed, obvious leakage (PO) appears4 3-(in P)>0.1mg/L), stopping adsorption, and regenerating the adsorbent; the adsorbed hybrid functional adsorbent can be regenerated by adopting a mixed solution of NaOH and NaCl, wherein the concentration of NaOH is 3-10%, the concentration of NaCl is 5-8%, the regeneration flow rate is controlled to be 0.5-2BV/h, and the adsorbent can be completely regenerated through 2-5BV desorption reaction. The regeneration process may be carried out in an adsorption column. And cleaning the regenerated hybrid functional adsorbent with clear water or dilute acid solution to be neutral, and then continuously using the adsorbent. The clear water can adopt deionized water, distilled water or dilute hydrochloric acid with the dilute acid of 0.1 to 0.5 percent.
Compared with the prior art, the invention has the following advantages:
1. the high-activity nano lanthanum hydroxide can be stably bonded on the outer surface of the polystyrene resin by fully utilizing the characteristics of the polydopamine biogel, and the technical bottlenecks of low adsorption mass transfer rate and low utilization rate in the process of removing phosphate by using a conventional composite material are solved.
2. The special quaternary amine group of the carrier has strong positive electric field characteristics, and can test the high enrichment of target phosphate, thereby improving the utilization efficiency of the surface high-activity nano lanthanum hydroxide.
3. The high charge characteristic of the quaternary ammonium group and the chemical complexation of polydopamine can greatly promote the dispersion and activity of lanthanum hydroxide, and a high-dispersion small-particle nano lanthanum hydroxide coating is formed on the surface of the carrier.
4. The prepared nano lanthanum hydroxide composite material still has excellent adsorption selectivity on trace phosphate, has obvious advantages compared with similar technologies, high treatment efficiency, large treatment capacity and obvious environmental protection benefit, and the content of P (vanadium) in effluent water of phosphate-polluted wastewater is reduced from 1-10mg/L to below 50ppb after the composite material is treated.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of a resin carrier according to example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the surface of the dopamine coated composite resin prepared in example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of the surface of the resin-based dopamine coated nano lanthanum hydroxide composite resin prepared in example 1 of the present invention.
FIG. 4 is a transmission electron microscope image of the nano lanthanum hydroxide composite resin prepared in example 1 of the present invention.
Fig. 5 is an energy spectrometer analysis diagram of lanthanum element in the nano lanthanum hydroxide composite resin prepared in example 1 of the present invention.
FIG. 6 is the X-ray diffraction analysis spectrum of the nano lanthanum hydroxide composite resin prepared in example 1 of the present invention.
Detailed Description
Example 1
Measuring 50mL of D201 resin (produced by Hangzhou dispute industries, Ltd., the same below) as an initial reaction substance, firstly placing the initial reaction substance into a Tris-HCl buffer solution with the mass fraction of 1g/L dopamine hydrochloride and the pH value of 7.5, controlling the temperature to be 20 ℃, carrying out an aeration reaction for 12 hours, filtering to obtain a mother plate material of a macroporous polymeric sphere coated with polydopamine, taking 20mL of the polymeric sphere as a carrier, placing the polymeric sphere into 40mL of aqueous solution containing 1% of La (III) (calculated by the mass fraction of lanthanum, lanthanum nitrate is taken as a precursor) for a reaction at 50 ℃ for 6 hours to fully diffuse lanthanum salt to the inner surface of a pore channel of the polymeric sphere, filtering, then placing the polymeric sphere into 40mL of ammonia water with the mass fraction of 1%, fully stirring and reacting at 50 ℃ for 12 hours, filtering, placing the material in a vacuum oven for fixing at 60 ℃ for 4 hours to obtain the target resin-based polydopamine nano lanthanum hydroxide, the lanthanum hydroxide loading was 5.9%.
As shown in fig. 1, it is apparent that the resin surface has a smooth curved surface of a moon-like shape when nothing is carried on the resin surface.
As shown in fig. 2, it can be seen that after dopamine is coated on the surface of the resin, the resin surface has flaky substances and is not smooth, which indicates that dopamine is successfully loaded on the surface of the resin ball.
As shown in fig. 3, it can be seen that the resin-based dopamine coated particulate matter on the surface of the nano lanthanum hydroxide composite resin indicates that the nano lanthanum hydroxide is successfully loaded on the surface of the resin-based dopamine.
As shown in fig. 4, it can be seen that the black small rod-like substance is the nano lanthanum hydroxide.
As shown in FIG. 5, it can be seen that a large amount of lanthanum is distributed on the surface of the resin-based dopamine, and further, the nano lanthanum hydroxide is successfully loaded on the surface of the resin-based dopamine.
As shown in FIG. 6, it can be seen that none of the three materials has a distinct diffraction peak position, indicating that D201-PDA-La (OH)3The material is an amorphous polymer.
Placing 10mL of the above nanocomposite in a glass adsorption column (phi 18X 220mm), controlling the temperature at 10 deg.C and the flow rate at 0.5BV/h, and subjecting to biochemical treatment to obtain Phosphate (PO)4 3-(in terms of P)) -2 mg/L and SO4 2-＝300mg/L,Cl-＝420mg/L,NO3 -The wastewater with the pH value of 3.0 flows from top to bottom through an adsorption column filled with a hybrid functional adsorbent, and is treated by the adsorbent to obtain Phosphate (PO)4 3-The concentration (measured by P) is below 100 mu g/L, and the treatment capacity is up to 500 BV. When adsorption shows obvious leakage (PO)4 3-(in P)>0.5mg/L), the adsorption was stopped. Desorption regeneration is carried out by using 100mL of mixed solution of 3 percent NaOH and 5 percent NaCl at 25 ℃ and 0.5BV/h downstream, and the desorption rate reaches 90 percent after 2 BV. And washing the regenerated hybrid functional adsorbent with deionized water to be neutral, and then continuously using the adsorbent.
Example 2
Measuring 50mL of D201 resin (produced by Hangzhou dispute industries, Ltd., the same below) as an initial reaction substance, firstly placing the initial reaction substance into a Tris-HCl buffer solution with the mass fraction of 2.2g/L dopamine hydrochloride and the pH value of 8.5, controlling the temperature to be 30 ℃, carrying out an aeration reaction for 24 hours, then filtering to obtain a macroporous polymeric sphere mother plate material coated with polydopamine, taking 30mL of the polymeric sphere as a carrier, placing the polymeric sphere into 300mL of aqueous solution containing 10% of La (III) (calculated by the mass fraction of lanthanum, lanthanum chloride is taken as a precursor) to react for 8 hours at 60 ℃ so as to fully diffuse lanthanum salt to the inner surface of a pore channel of the polymeric sphere, filtering, then dropwise adding 150mL of ammonia water with the mass fraction of 4%, fully stirring and reacting for 24 hours at 60 ℃, filtering, placing the material in a vacuum oven for fixing for 8 hours at 80 ℃ to obtain the target resin-based polydopamine nano lanthanum hydroxide composite material, the loading of lanthanum hydroxide was 35.2%.
Placing 10mL of the above nanocomposite on glass for adsorptionControlling the temperature in the column (phi 18 x 220mm) at 60 deg.C and flow rate at 50BV/h, and biochemically treating to obtain Phosphate (PO)4 3-(in terms of P)) -10mg/L and SO4 2-＝300mg/L,Cl-＝100mg/L,NO3 -The waste water with the pH value of 10 flows from top to bottom through an adsorption column filled with a hybrid functional adsorbent, and the waste water is treated by the adsorbent to obtain the Phosphate (PO)4 3-The concentration (measured by P) is below 200 mug/L, and the processing amount is up to 700 BV. When adsorption shows obvious leakage (PO)4 3-(in P)>0.5mg/L), the adsorption was stopped. Desorption regeneration is carried out by 100mL of 10 percent NaOH and 8 percent NaCl mixed solution at 25 ℃ and 2BV/h downstream, and the desorption rate reaches 95 percent after 5 BV. The regenerated hybrid functional adsorbent can be continuously used after being washed to be neutral by using distilled water.
Example 3
Measuring 30mL of 201x7 resin (produced by Hangzhou dispute industries, Ltd.) as an initial reaction substance, firstly placing the initial reaction substance into a Tris-HCl buffer solution with the mass fraction of 1.8g/L dopamine hydrochloride and the pH value of 8.2, controlling the temperature to be 25 ℃, carrying out an aeration reaction for 16h, then filtering to obtain a macroporous polymeric sphere mother plate material coated with polydopamine, taking 20mL of the polymeric sphere as a carrier, placing the polymeric sphere into 100mL of aqueous solution containing 3% of La (III) (calculated by the mass fraction of lanthanum, lanthanum nitrate is taken as a precursor) for a reaction at 50 ℃ for 7h to fully diffuse lanthanum salt to the inner surface of a pore channel of the polymeric sphere, filtering, then dropwise adding 85mL of ammonia water with the mass fraction of 2%, fully stirring and reacting for 18h at 55 ℃, filtering, placing the material in a vacuum oven for fixing for 6h at 70 ℃ to obtain the target resin-based polydopamine nano lanthanum hydroxide composite material, the loading of lanthanum hydroxide is 10.2%.
Placing 10mL of the above nanocomposite in a glass adsorption column (phi 18X 220mm), controlling the temperature at 25 deg.C and the flow rate at 10BV/h, and subjecting the nanocomposite to biochemical treatment to obtain Phosphate (PO)4 3-(in terms of P)) -1 mg/L and SO4 2-＝300mg/L,Cl-＝120mg/L,NO3 -Passing 240mg/L wastewater with pH 5.0 from top to bottom through an adsorption column filled with a hybrid functional adsorbent, treating with the adsorbent to obtain Phosphate (PO)4 3-(in terms of P) at a concentration ofLess than 100 mug/L and the processing amount is up to 800 BV. When adsorption shows obvious leakage (PO)4 3-(in P)>0.5mg/L), the adsorption was stopped. Desorption regeneration is carried out by 100mL of mixed solution of 5 percent NaOH and 6 percent NaCl at 25 ℃ and 1BV/h downstream, and the desorption rate reaches 95 percent after 3 BV. And (3) cleaning the regenerated adsorbent by using hydrochloric acid with the mass fraction of 0.1% to be neutral, and then continuously using the adsorbent.
Example 4
Measuring 80mL of D301 resin (produced by Hangzhou dispute industries, Ltd.) as an initial reaction substance, firstly placing the initial reaction substance into a Tris-HCl buffer solution with the mass fraction of 2.2g/L dopamine hydrochloride and the pH value of 7.8, controlling the temperature to be 28 ℃, carrying out an aeration reaction for 20h, then filtering to obtain a macroporous polymeric sphere mother plate material coated with polydopamine, taking 50mL of the polymeric sphere as a carrier, placing the polymeric sphere into 300mL of aqueous solution containing 5.2% of La (III) (calculated by the mass fraction of lanthanum, lanthanum nitrate is taken as a precursor) to react for 8h at 60 ℃ so as to fully diffuse lanthanum salt to the inner surface of a pore channel of the polymeric sphere, filtering, then dropwise adding 200mL of ammonia water with the mass fraction of 3.2%, fully stirring and reacting for 22h at 60 ℃, filtering, placing the material in a vacuum oven for fixing for 7h at 80 ℃ to obtain the target resin-based polydopamine nano lanthanum hydroxide composite material, the lanthanum hydroxide loading was 17.5%.
Placing 30mL of the above nanocomposite in a glass adsorption column (phi 25 × 320mm), controlling the temperature at 38 deg.C and the flow rate at 25BV/h, and subjecting the nanocomposite to biochemical treatment to obtain Phosphate (PO)4 3-(in terms of P)) -4 mg/L and SO4 2-＝200mg/L,Cl-＝150mg/L,NO3 -The wastewater with the pH value of 7.0 which is 440mg/L flows through an adsorption column filled with a hybrid functional adsorbent from top to bottom, and the effluent Phosphate (PO) is treated by the adsorbent4 3-The concentration (measured by P) is below 100 mug/L, and the treatment capacity is up to 650 BV. When adsorption shows obvious leakage (PO)4 3-(in P)>0.5mg/L), the adsorption was stopped. Desorption regeneration is carried out by 100mL of mixed solution of 7 percent NaOH and 7 percent NaCl at 25 ℃ and 2BV/h downstream, and the desorption rate reaches 95 percent after 4 BV. And (3) cleaning the regenerated adsorbent by using hydrochloric acid with the mass fraction of 0.5% to be neutral, and then continuously using the adsorbent.
Example 5
Measuring 150mL of D201 resin (produced by Hangzhou dispute practical industries, Ltd.) as an initial reaction substance, firstly placing the initial reaction substance in a Tris-HCl buffer solution with the mass fraction of 1.8g/L dopamine hydrochloride and the pH value of 8.3, controlling the temperature to be 24 ℃, carrying out an aeration reaction for 13h, then filtering to obtain a macroporous polymeric sphere mother plate material coated with polydopamine, taking 50mL of the polymeric sphere as a carrier, placing the polymeric sphere in 400mL of aqueous solution containing 10% of La (III) (calculated by the mass fraction of lanthanum, lanthanum nitrate is taken as a precursor) for a reaction at 55 ℃ for 7h to fully diffuse lanthanum salt to the inner surface of a pore channel of the polymeric sphere, filtering, then dropwise adding 300mL of ammonia water with the mass fraction of 4%, fully stirring and reacting at 55 ℃ for 14h, filtering, placing the material in a vacuum oven at 80 ℃ for fixing for 7h to obtain the target resin-based polydopamine nano lanthanum hydroxide composite material, the loading of lanthanum hydroxide was 34.5%.
50mL of the nano composite material is placed in a glass adsorption column (phi 25 x 320mm), the temperature is controlled at 40 ℃, the flow rate is controlled at 45BV/h, and Phosphate (PO) is contained after biochemical treatment4 3-(in terms of P)) -8 mg/L and SO4 2-＝250mg/L,Cl-＝350mg/L,NO3 -Passing the waste water with pH value of 6.0 from top to bottom through an adsorption column filled with a hybrid functional adsorbent, treating with the adsorbent to obtain Phosphate (PO)4 3-The concentration (measured by P) is below 450 mug/L, and the processing amount is up to 420 BV. When adsorption shows obvious leakage (PO)4 3-(in P)>0.5mg/L), the adsorption was stopped. Desorption regeneration is carried out by using 100mL of mixed solution of 6 percent NaOH and 6 percent NaCl at 25 ℃ and 2BV/h downstream, and the desorption rate reaches 95 percent after 4 BV. And cleaning the regenerated adsorbent by deionized water in percentage by mass until the adsorbent is neutral, and then continuously using the adsorbent.
Example 6
160mL of D001 resin (produced by Hangzhou dispute industries, Ltd.) is measured to be used as an initial reaction substance, firstly the initial reaction substance is placed in a Tris-HCl buffer solution with the mass fraction of 2.5g/L dopamine hydrochloride and the pH value of 7.8, the temperature is controlled to be 24 ℃, the aeration reaction is carried out for 20h, then the initial reaction substance is filtered to obtain a macroporous polymeric sphere mother plate material coated with polydopamine, 70mL of the polymeric sphere is used as a carrier, the polymeric sphere is placed in 250mL of aqueous solution containing 8% of La (III) (calculated by the mass fraction of lanthanum, lanthanum nitrate is used as a precursor) for reaction at the temperature of 58 ℃ for 8h to ensure that lanthanum salt is fully diffused to the inner surface of a pore channel of the polymeric sphere, the filtering is carried out, then 350mL of ammonia water with the mass fraction of 3% is dripped, the mixture is fully stirred and reacted for 20h at the temperature of 60 ℃, the filtering, the loading of lanthanum hydroxide is 30.2%.
Placing 30mL of the above nanocomposite in a glass adsorption column (phi 25 × 320mm), controlling the temperature at 50 deg.C and the flow rate at 35BV/h, and subjecting the nanocomposite to biochemical treatment to obtain Phosphate (PO)4 3-(in terms of P)) -4 mg/L and SO4 2-＝230mg/L,Cl-＝310mg/L,NO3 -Passing 480mg/L wastewater with pH 7.0 from top to bottom through an adsorption column filled with a hybrid functional adsorbent, treating with the adsorbent to obtain Phosphate (PO)4 3-The concentration (measured by P) is below 250 mug/L, and the treatment amount is up to 950 BV. When adsorption shows obvious leakage (PO)4 3-(in P)>0.5mg/L), the adsorption was stopped. 100mL of 5 percent NaOH and 5 percent NaCl mixed solution is used for desorption regeneration at 25 ℃ and 1BV/h downstream, and the desorption rate reaches 96 percent after 5 BV. And cleaning the regenerated adsorbent by deionized water in percentage by mass until the adsorbent is neutral, and then continuously using the adsorbent.
Example 7
Measuring 210mL of D201 resin (produced by Hangzhou dispute industries, Ltd.) as an initial reaction substance, firstly placing the initial reaction substance into a Tris-HCl buffer solution with the mass fraction of 3g/L dopamine hydrochloride and the pH value of 7.5, controlling the temperature to be 25 ℃, carrying out an aeration reaction for 23h, then filtering to obtain a macroporous polymeric sphere mother plate material coated with polydopamine, taking 60mL of the polymeric sphere as a carrier, placing the polymeric sphere into 500mL of aqueous solution containing 6.9% of La (III) (calculated by the mass fraction of lanthanum, lanthanum nitrate is taken as a precursor) for a reaction at 60 ℃ for 8h to fully diffuse lanthanum salt to the inner surface of a pore channel of the polymeric sphere, filtering, then dropwise adding 350mL of ammonia water with the mass fraction of 4%, fully stirring and reacting for 24h at 60 ℃, filtering, placing the material in a vacuum oven for fixing for 8h at 70 ℃ to obtain the target resin-based polydopamine nano lanthanum hydroxide composite material, the loading of lanthanum hydroxide is 28%.
Placing 40mL of the above nanocomposite in a glass adsorption column (phi 25 × 320mm), controlling the temperature at 50 deg.C and the flow rate at 40BV/h, and subjecting the nanocomposite to biochemical treatment to obtain Phosphate (PO)4 3-(in terms of P)) -9 mg/L and SO4 2-＝230mg/L,Cl-＝300mg/L,NO3 -The wastewater with the pH value of 7.0 flows from top to bottom through an adsorption column filled with a hybrid functional adsorbent, and is treated by the adsorbent to obtain Phosphate (PO)4 3-The concentration (measured by P) is below 320 mu g/L, and the processing amount is up to 350 BV. When adsorption shows obvious leakage (PO)4 3-(in P)>0.5mg/L), the adsorption was stopped. Desorption regeneration is carried out by using 100mL of mixed solution of 6 percent NaOH and 6 percent NaCl at 25 ℃ and 2BV/h downstream, and the desorption rate reaches 95 percent after 4 BV. And cleaning the regenerated adsorbent by deionized water in percentage by mass until the adsorbent is neutral, and then continuously using the adsorbent.

Claims (5)

1. A preparation method of a nanometer lanthanum hydroxide composite material is characterized by comprising the following steps: taking macroporous anion exchange resin as an initial reaction substance, placing the initial reaction substance into a Tris-HCl buffer solution with the mass fraction of 1-3g/L dopamine hydrochloride and the pH value of 7.5-8.5, controlling the temperature to be 20-30 ℃, carrying out aeration reaction for 12-24h, and filtering to obtain a polydopamine-coated macroporous polystyrene matrix material, wherein the basic framework structure of the polydopamine-coated polystyrene matrix material is styrene-divinylbenzene and the surface of the polydopamine-coated macroporous polystyrene matrix material carries a quaternary ammonium group; on the basis, according to the proportion that 100-500mL of macroporous polystyrene parent material is put into each liter of La (III) saline, the macroporous polystyrene parent material is put into La (III) saline solution with the concentration mass fraction of 1-10%, and the liquid-solid volume ratio is controlled to be 2-10: 1, controlling the temperature to be 50-60 ℃ and the reaction time to be 6-8h to ensure that La (III) and the amido and hydroxyl on the surface of the polydopamine fully react; filtering, placing the PS-PDA composite material grafted with La (III) in an ammonia water solution with the solution concentration and mass fraction of 1% -4% for in-situ precipitation reaction, and controlling the liquid-solid ratio to be 2-5: 1, controlling the temperature at 50-60 ℃ for 12-24h to form nano lanthanum hydroxide on the surface of PS-PDA, and finally, placing the material in a vacuum oven at 60-80 ℃ for fixing for 4-8h to obtain the target resin-based poly-dopamine nano lanthanum hydroxide composite material, wherein the supported amount is 5.9-35.2% by mass.
2. The method for removing trace phosphorus in wastewater by using the nano lanthanum hydroxide composite material prepared by the preparation method according to claim 1 is characterized by comprising the following steps: the nano lanthanum hydroxide composite material is filled in an adsorption column, wastewater with trace phosphate pollution concentration of 1-10mg/L flows through the adsorption column filled with the hybrid functional adsorbent from top to bottom, the temperature is controlled to be 10-60 ℃, the pH value is 3-10, and the flow rate is controlled to be 0.5-50 bed layer volume (BV)/h.
3. The method for regenerating the nano lanthanum hydroxide composite material prepared by the preparation method of claim 1, which is characterized in that: when the nano lanthanum hydroxide composite material is used for adsorption and obvious leakage occurs, stopping adsorption, and regenerating the adsorbent; the hybrid functional adsorbent after adsorption can be regenerated by adopting a mixed solution of NaOH and NaCl, wherein the concentration of NaOH is 3-10%, the concentration of NaCl is 5-8%, the regeneration flow rate is controlled to be 0.5-2BV/h, complete regeneration can be realized through 2-5BV desorption reaction, the regeneration process can be carried out in an adsorption column, and the hybrid functional adsorbent after regeneration can be continuously used after being washed to be neutral by using clear water or dilute acid solution.
4. The method for removing trace phosphorus in water by using the nano lanthanum hydroxide composite material prepared by the preparation method according to claim 1 is characterized by comprising the following steps of: the macroporous anion exchange resin is D201, 001x7 or D301.
5. The method for regenerating a nano lanthanum hydroxide composite material according to claim 3, wherein: the clear water or the dilute acid solution is deionized water, distilled water or dilute hydrochloric acid with the concentration of 0.1-0.5%.
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