CN111422941A - Method for deeply purifying phosphate radicals in water body by using imino resin - Google Patents

Method for deeply purifying phosphate radicals in water body by using imino resin Download PDF

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CN111422941A
CN111422941A CN202010206756.7A CN202010206756A CN111422941A CN 111422941 A CN111422941 A CN 111422941A CN 202010206756 A CN202010206756 A CN 202010206756A CN 111422941 A CN111422941 A CN 111422941A
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resin
imino
adsorption
water body
water
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CN111422941B (en
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潘丙军
廖雪
陈都
王楼
李佳锋
周丽佳
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Zhejiang University of Technology ZJUT
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    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a method for deeply purifying phosphate radicals in a water body by using imino resin, which comprises the following steps: adjusting the pH value of the phosphorus-containing water body; enabling the filtrate to pass through an adsorption tower filled with imino resin to obtain a deeply purified water body; the skeleton of the imino resin is polystyrene-divinylbenzene, and an imino group is grafted on the skeleton; when the adsorption leakage point is reached, desorption is carried out by using a desorption agent, and then regeneration treatment is carried out. The method adopts the resin which takes polystyrene-divinylbenzene as a framework and is grafted with imine groups as an adsorbing material to carry out deep purification treatment on phosphate radicals in the water body, and the discovery that when the water body value is 3.0-10.0, high-concentration Cl coexists‑、NO3 ‑、HCO3 ‑、SO4 2‑And SiO3 2‑Under the condition of (2), the phosphate content (measured by P) of the effluent can still be reduced from 0.05-50 mg/L to below 0.01 mg/L.

Description

Method for deeply purifying phosphate radicals in water body by using imino resin
Technical Field
The invention relates to the technical field of sewage treatment and resource recycling, in particular to a method for deeply purifying phosphate radicals in a water body by using imino resin, and specifically relates to a method for deeply purifying phosphate radicals in a water body by using imino resin materials with high adsorption capacity and selectivity on phosphate radicals.
Background
Phosphorus is one of the essential nutrients of all living beings and also one of the indispensable elements for human life activities and modern agriculture. The discharge of excessive phosphorus elements into the water body can cause serious water eutrophication and destroy the ecological environment, so that the realization of deep purification of the phosphorus elements in the water body has important significance for water quality safety guarantee. The conventional phosphorus removal process cannot meet the increasingly strict discharge standard of phosphorus, and the advanced treatment of phosphorus in water becomes an urgent need in the field of water pollution treatment.
The conventional phosphorus treatment process usually achieves the removal of phosphorus in a water body by a physicochemical or biochemical method, but has high operation cost and is easy to generate sludge to cause secondary pollution. A great deal of research shows that fixed bed adsorption is a high-efficiency pollutant purification technology. However, the water body often coexists with competitive ions such as chloride ions, nitrate ions, bicarbonate ions, sulfate ions, silicate ions and the like, and therefore the adsorption material is required to have good adsorption selectivity for phosphate ions. The traditional adsorbing materials comprise mesoporous silicate, zeolite, diatomite, activated carbon, anion exchange resin and the like, and the adsorbing selectivity of the mesoporous silicate, the zeolite, the diatomite, the activated carbon, the anion exchange resin and the like to phosphate radicals is not satisfactory.
The molecular imprinting polymer based on the molecular recognition effect is not widely applied to removal of phosphorus in water for the moment because of the problems of difficulty in functional monomer selection, template removal and the like, and the metal hydrated oxide nano composite material (Fe, Zr, Mn, L a and the like) developed in recent years shows certain adsorption selectivity on phosphate ions based on the inner layer complexation, but has some problems, such as the Fe dissolution condition of the Fe-based composite material under the condition that the pH is less than 3, secondary pollution caused by the Fe dissolution condition, unstable hydrated iron oxide under the environment and easy conversion into hematite with low adsorption capacity, and the L a-based adsorbent is not easy to recycle.
Under the general condition, phosphorus in the water body exists in a hydrogen phosphate radical/dihydrogen phosphate radical anion form and can be used as a hydrogen bond donor and a hydrogen bond acceptor group to form a hydrogen bond effect with an adsorption material, so that the development of a functional material only having the hydrogen bond acceptor function can realize the selective adsorption of phosphate radicals in the water body. Literature search shows that no method for deeply purifying phosphate radical by using imino resin is disclosed.
Disclosure of Invention
Aiming at the problems of low treatment depth, instability, difficult regeneration and reutilization and the like of the traditional phosphate radical purification technology in the water body, the invention provides a method for deeply purifying phosphate radicals in the water body by using imino resin, and the method can compete for anion Cl in the coexistence of the water body-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of the phosphate radical is far higher than that of the target phosphate radical ions, and the deep purification of the phosphorus in the water body is realized under a wider pH value range.
The specific technical scheme is as follows:
a method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following steps:
(1) adjusting the pH value of the phosphorus-containing water body, and filtering to obtain a filtrate;
(2) enabling the filtrate obtained in the step (1) to pass through an adsorption tower filled with imino resin to enable phosphate in the water body to be adsorbed on the imino resin, and obtaining the deeply purified water body;
the skeleton of the imino resin is polystyrene-divinylbenzene, and imino groups are grafted on the skeleton;
(3) stopping adsorption when the adsorption reaches an adsorption leakage point, and desorbing by using a mixed aqueous solution containing NaOH and NaCl to desorb phosphate radicals from the adsorption-saturated imino resin; and then washing the imino resin with water until the imino resin is neutral, and performing regeneration treatment on the imino resin.
The imine group resin adopted by the invention is an imine group (R '═ N-R') grafted on the skeleton of the polystyrene porous resin, can generate hydrogen bond action with phosphate radical of water body, but not generate hydrogen bond action with other common anions in water, and is an adsorption material with high efficiency and selectivity on the phosphate radical of water body.
Further, in the step (1), the pH value is 3.0-10.0, the mass concentration of phosphate radicals in the water body is 0.05-50 mg/L calculated by the mass of phosphorus elements, and the mass concentration of other coexisting anions in the water body is less than 500 times of the mass concentration of the phosphate radicals.
Further, the preparation method of the imino resin comprises the following steps:
i) swelling chlorine balls by using a dichloromethane swelling agent, filtering out the swelling agent, adding a mixed solution containing ethylenediamine and ethanol, carrying out ethylenediamine grafting reaction under the condition of water bath, filtering out the mixed solution, carrying out Soxhlet extraction, and drying; the chlorine ball is styrene-divinylbenzene resin after chloromethylation;
ii) placing the resin dried in the step i) into a dichloromethane swelling agent for secondary swelling, adding anhydrous zinc chloride as a catalyst for Friedel-crafts reaction, and performing Soxhlet extraction after the reaction is finished;
iii) washing the resin obtained in the step ii) to be neutral by using ultrapure water, and drying to obtain the imino resin.
Further, in the step i), the volume ratio of the ethylenediamine to the ethanol in the mixed solution is 1: 1; the mass volume ratio of the chlorine balls to the mixed solution is 1: 10-20.
Further, in the step i), the temperature of the ethylene diamine grafting reaction is 45-55 ℃ and the time is 12-24 hours.
Further, in the step ii), the mass ratio of the anhydrous zinc chloride to the chlorine balls is 1: 5-8; after adding the catalyst, the mixture is reacted for 2 hours at 90 ℃ and then heated to 110 ℃ for 10 hours.
Furthermore, in the step (3), the adsorption leakage point is that the mass concentration of phosphate radicals in the effluent is more than 0.01 mg/L according to the mass of phosphorus elements.
Further, in the step (3), in the mixed aqueous solution, the mass percentage concentration of NaOH is 2-10%, and the mass percentage concentration of NaCl is 2-10%; the mixed aqueous solution is regenerated at a flow rate of 1 to 5 bed volumes of the resin layer per hour at 15 to 60 ℃ while passing through the imino resin.
Further, the steps (2) and (3) adopt a single-tower adsorption-desorption or multi-tower series adsorption-single-tower desorption operation mode.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts the resin which takes polystyrene-divinylbenzene as a framework and is grafted with imine groups as an adsorbing material to carry out deep purification treatment on phosphate radicals in the water body, and the discovery that when the water body value is 3.0-10.0, high-concentration Cl coexists-、NO3 -、HCO3 -、SO4 2-And SiO3 2-Under the condition of (2), the phosphate content (measured by P) of the effluent can still be reduced from 0.05-50 mg/L to below 0.01 mg/L.
(2) The method has large treatment capacity and stable adsorption material, and can be used for a long time.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are only illustrative of the present invention, but the scope of the present invention is not limited thereto.
The imino resin involved in the following examples is an adsorption material of resin containing imino group on polystyrene-divinylbenzene structure, and the specific preparation method is as follows:
i) swelling a certain amount of chlorine balls (i.e. chloromethylated styrene-divinylbenzene white balls) with pure dichloromethane reagent overnight, filtering out swelling agent, and adding V(B)Diamine): v(ethanol/DMF)1:1 (the mass volume ratio of the chlorine ball to the mixed solution is 1: 20), performing ethylenediamine grafting in a water bath at 50 ℃, filtering the mixed solution after 12 hours of reaction, performing Soxhlet extraction, and drying;
ii) placing the resin dried in the step i) into a dichloromethane reagent for secondary swelling overnight, adding anhydrous zinc chloride with the mass ratio of 1:8 to chlorine spheres as a catalyst, reacting at 90 ℃ for 2 hours, heating to 110 ℃ for reaction for 10 hours, and performing Soxhlet extraction; finally, the obtained resin is washed to be neutral by ultrapure water and dried to obtain the target imino resin.
Example 1
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 1ppm, Cl-、NO3 -、HCO3 -、，SO4 2-、SiO3 2-The concentration of (1) is 100ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 6500BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, and then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 2
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (1), the adsorption temperature is controlled to be 5 +/-2 ℃, and the adsorption effect and the treatment capacity are basically unchanged.
Example 3
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (1), the adsorption temperature is controlled to be 40 +/-5 ℃, and the adsorption effect and the treatment capacity are basically unchanged.
Example 4
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (1), the flow rate of the filtrate passing through the adsorption column of the imino-containing resin bed layer is changed to 5BV/h, and the adsorption effect and the treatment capacity are basically unchanged.
Example 5
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (1), the flow rate of the filtrate passing through the adsorption column of the imino-containing resin bed layer is changed to 25BV/h, and the adsorption effect and the treatment capacity are basically unchanged.
Example 6
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 0.2ppm, Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of each is 20ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 25000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 2%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, and then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 7
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 0.05ppm and Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of each 10ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 20m L (about 10 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 90000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 2%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, and then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 8
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 20ppm, Cl-、NO3 -、HCO3 -、SiO3 2-、SO4 2-The concentration of all the components is 2000ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 200m L (about 100 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and at the flow rate of 5BV/h, the treatment capacity is about 300BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, 1000m of L mixed solution of NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 98%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 9
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 50ppm, Cl-、NO3 -、HCO3 -、SiO3 2-、SO4 2-The concentration of (1) is 5000ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 200m L (about 100 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and at the flow rate of 5BV/h, the treatment capacity is about 150BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, 1000m of L mixed solution of NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 98%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 10
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, 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 adsorption effect and the treatment capacity are basically unchanged.
Example 11
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (1), the pH value of the phosphorus-containing water body is adjusted to 5.0, and the adsorption effect and the treatment capacity are basically unchanged.
Example 12
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (1), the pH value of the phosphorus-containing water body is adjusted to 9.0, and the adsorption effect and the treatment capacity are basically unchanged.
Example 13
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, 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 adsorption effect and the treatment capacity are basically unchanged.
Example 14
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 1ppm, Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of each is 20ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 11000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 30 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 15
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 1ppm, Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of all the components is 50ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 9000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 16
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (1), Cl in the phosphorus-containing water body (P (V) mixed solution)-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of (A) is changed into 200ppm, and the adsorption effect and the treatment capacity are basically unchanged.
Example 17
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (1), Cl in the phosphorus-containing water body (P (V) mixed solution)-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of the catalyst is changed to 500ppm, and the adsorption effect and the treatment capacity are basically unchanged.
Example 18
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 1ppm, Cl-、NO3 -、HCO3 -The concentration of (1) is 100ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 12000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 19
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) regulating the concentration of phosphorus-containing water body (P (V)) to 1ppm and SO4 2-、SiO3 2-The concentration of (1) is 100ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 9000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 20
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) regulating the concentration of phosphorus-containing water body (P (V)) to 1ppm, HCO3 -、SO4 2-The concentration of (1) is 100ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 11000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 21
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 1ppm, Cl-、SiO3 2-The concentration of (1) is 100ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) passes through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and at the flow rate of 15BV/h, the treatment capacity is more than 11000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 22
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 1ppm, Cl-、NO3 -、SO4 2-The concentration of (1) is 100ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) passes through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and at the flow rate of 15BV/h, the treatment capacity is more than 11000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 23
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 1ppm, Cl-、NO3 -、HCO3 -Concentration 50ppm, SO4 2-、SiO3 2-The concentration of (1) is 100ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 7000BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 24
A method for deeply purifying phosphate radicals in a water body by using imino resin comprises the following specific steps:
(1) adjusting the concentration of phosphorus-containing water body (P (V)) to 1ppm, Cl-、NO3 -、HCO3 -In a concentration of 100ppm, SO4 2-、SiO3 2-The concentration of (1) is 50ppm) is adjusted to 7.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of imino resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in the step (1) is passed through the adsorption column containing imino resin bed layer at 25 +/-5 ℃ and the flow rate of 15BV/h, the treatment capacity is about 8200BV, and the concentration of effluent P (V) is reduced by less than 10 ppb;
(3) when the adsorption reaches a leakage point (the concentration of P (V) of the adsorbed effluent is more than 10ppb), the adsorption is stopped, a mixed solution of 300m L NaOH and NaCl (the weight percentage concentration of the NaOH and the NaCl is 5%) is used for desorption by passing through a resin bed layer at the temperature of 25 +/-5 ℃ and the flow rate of 1BV/h, the desorption rate is more than 99%, then the adsorption material is washed to be neutral by water for regeneration, and the total regeneration rate of the adsorption material is more than 80%.
Example 25
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (3), the weight percentage concentration of NaOH and NaCl in the mixed solution of NaOH and NaCl is 10%, and the desorption effect and the treatment capacity are basically unchanged.
Example 26
The deep purification of phosphate in the water body is carried out by adopting the same method as the example 1, and the difference is that: in the step (3), the weight percentage concentration of NaOH and NaCl in the mixed solution of NaOH and NaCl is 2%, and the desorption effect and the treatment capacity are basically unchanged.

Claims (9)

1. A method for deeply purifying phosphate radicals in a water body by using imino resin is characterized by comprising the following steps:
(1) adjusting the pH value of the phosphorus-containing water body, and filtering to obtain a filtrate;
(2) enabling the filtrate obtained in the step (1) to pass through an adsorption tower filled with imino resin to enable phosphate in the water body to be adsorbed on the imino resin, and obtaining the deeply purified water body;
the skeleton of the imino resin is polystyrene-divinylbenzene, and imino groups are grafted on the skeleton;
(3) stopping adsorption when the adsorption reaches an adsorption leakage point, and desorbing by using a mixed aqueous solution containing NaOH and NaCl to desorb phosphate radicals from the adsorption-saturated imino resin; and then washing the imino resin with water until the imino resin is neutral, and performing regeneration treatment on the imino resin.
2. The method for deeply purifying phosphate in water by using imino resin as claimed in claim 1, wherein in step (1), the pH value is 3.0-10.0, the mass concentration of phosphate in water is 0.05-50 mg/L based on the mass of phosphorus element, and the mass concentration of other coexisting anions in water is less than 500 times of the mass concentration of phosphate.
3. The method for deeply purifying phosphate in water by using imino resin as claimed in claim 1, wherein the method for preparing imino resin comprises:
i) swelling chlorine balls by using a dichloromethane swelling agent, filtering out the swelling agent, adding a mixed solution containing ethylenediamine and ethanol, carrying out ethylenediamine grafting reaction under the condition of water bath, filtering out the mixed solution, carrying out Soxhlet extraction, and drying; the chlorine ball is polystyrene-divinylbenzene resin after chloromethylation;
ii) placing the resin dried in the step i) into a dichloromethane swelling agent for secondary swelling, adding anhydrous zinc chloride as a catalyst for Friedel-crafts reaction, and performing Soxhlet extraction after the reaction is finished;
iii) washing the resin obtained in the step ii) to be neutral by using pure water, and drying to obtain the imino resin.
4. The method for deeply purifying phosphate in water by using imino resin as claimed in claim 3, wherein in step i), the volume ratio of ethylenediamine to ethanol in the mixed solution is 1: 1; the mass volume ratio of the chlorine balls to the mixed solution is 1: 10-20.
5. The method for deeply purifying phosphate in water by using imino resin as claimed in claim 3, wherein in step i), the temperature of the ethylene diamine grafting reaction is 45-55 ℃ and the time is 12-24 hours.
6. The method for deeply purifying phosphate in water by using imino resin as claimed in claim 3, wherein in step ii), the mass ratio of the anhydrous zinc chloride to the chlorine spheres is 1: 5-8; after adding the catalyst, the mixture is reacted for 2 hours at 90 ℃ and then heated to 110 ℃ for 10 hours.
7. The method for deeply purifying phosphate in water by using imino resin as claimed in claim 1, wherein in step (3), the mass concentration of phosphate in effluent is greater than 0.01 mg/L as the adsorption leakage point based on the mass of phosphorus.
8. The method for deeply purifying phosphate in water by using imino resin as claimed in claim 1, wherein in step (3), in the mixed aqueous solution, the mass percent concentration of NaOH is 2-10%, and the mass percent concentration of NaCl is 2-10%; the mixed aqueous solution is regenerated at a flow rate of 1 to 5 bed volumes of the resin layer per hour at 15 to 60 ℃ while passing through the imino resin.
9. The method for deeply purifying phosphate in water by using imino resin as claimed in claim 1, wherein the steps (2) and (3) are performed by single-tower adsorption-desorption or multi-tower series adsorption-single-tower desorption.
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CN113083259A (en) * 2021-04-23 2021-07-09 浙江工业大学 Method for deeply purifying fluorine ions in water by utilizing strong-base resin-based neodymium-loaded nano composite material
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