CN114797801A - Advanced treatment magnetic resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus for sewage landscape recycling and preparation method thereof - Google Patents
Advanced treatment magnetic resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus for sewage landscape recycling and preparation method thereof Download PDFInfo
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- CN114797801A CN114797801A CN202210633641.5A CN202210633641A CN114797801A CN 114797801 A CN114797801 A CN 114797801A CN 202210633641 A CN202210633641 A CN 202210633641A CN 114797801 A CN114797801 A CN 114797801A
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- 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
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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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
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention discloses a sewage landscape recycling advanced treatment magnetic resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus and a preparation method thereof, wherein the magnetic resin is composed of a strong base anion exchange resin skeleton containing two types of quaternary ammonium salt active sites and magnetic particles wrapped in the strong base anion exchange resin skeleton, a monomer containing ester groups and epoxy groups is mixed with a cross-linking agent, a pore-forming agent, an initiator and modified magnetic particles to form an oil phase, the oil phase is uniformly mixed and then subjected to primary suspension polymerization in a water phase, secondary polymerization is carried out after primary polymerization to obtain secondary copolymerized magnetic microspheres, the ester groups on the secondary copolymerized magnetic microspheres are sequentially subjected to amination and alkylation reactions to form a type of quaternary ammonium salt, the epoxy groups and amine salt are further reacted to obtain another type of quaternary ammonium salt, and finally, a double bond on the other side of a benzene ring on the cross-linking agent is subjected to post-crosslinking reaction to obtain the magnetic anion resin containing two types of strong base quaternary ammonium sites, can be used for removing nitrogen and phosphorus substances in actual secondary effluent to meet the nitrogen and phosphorus standard in the urban sewage landscape utilization standard.
Description
Technical Field
The invention belongs to the field of resin materials, relates to a magnetic resin and a preparation method thereof, and particularly relates to a magnetic strongly-alkaline anion exchange resin which is internally wrapped with modified magnetic particles and used for adsorbing and removing nitrogen-containing and phosphorus-containing substances in sewage advanced treatment and contains two types of quaternary ammonium active sites, and a preparation method thereof.
Background
With the progress of the developing society of economy, water resource shortage has become a serious problem affecting human activities on a global scale. However, China is one of a plurality of water shortage areas, and the current situation of water shortage of China is mainly characterized by uneven water resource distribution and serious water pollution problem. The development of reclaimed water reuse by utilizing secondary effluent of urban sewage plants is a good medicine for solving the problem of water shortage. Nitrogen and phosphorus substances in the reclaimed water are main elements for causing the eutrophication of landscape water bodies, and generally, when the content of total nitrogen in the sewage is more than 0.2mg/L or the content of total phosphorus is more than 0.02mg/L, the reclaimed water can cause the obvious eutrophication of the water bodies after landscape recycling or water body discharge, thereby causing the mass propagation of algae in the water bodies, reducing the dissolved oxygen in the water bodies and causing damage to water environments and aquatic organisms.
The aim of advanced sewage treatment is to reduce effluent organic matters as far as possible so as to reach the recycling standard, nitrogen and phosphorus nutrient elements are closely related to effluent organic matters in secondary effluent, but the content of part of organic nitrogen and organic phosphorus compounds contained in the secondary effluent is low, nitrate nitrogen and orthophosphate are important components of total nitrogen and total phosphorus, so that the nitrogen and phosphorus target of advanced sewage treatment meeting the landscape recycling standard takes the removal of nitrate nitrogen and orthophosphate as the optimal selection. Both nitrate nitrogen and orthophosphate are anions, so the goal of advanced nitrogen and phosphorus removal treatment is to remove the nitrate nitrogen and orthophosphate in the anion state.
The anion resin can absorb substances which can preferentially remove anions in water, so the resin absorption technology is an advantageous process for removing nitrate nitrogen and orthophosphate by deep nitrogen and phosphorus removal. However, the conventional polystyrene anion exchange resin generally has disadvantages such as low exchange capacity and poor hydrophilicity. The magnetic ion exchange resin is a novel resin, and the resin with the magnetic particle core can be conveniently separated from the mixture and recycled in a continuous process, so that the occupied area of the resin reactor is reduced. However, due to the use of continuous mechanical stirring, the magnetic core inside the resin is easily released due to the damage of the resin, so the resin needs to have certain mechanical strength, and the common magnetic polyacrylic resin has poor mechanical strength, which easily causes the loss of the resin and the secondary pollution of water. In addition, the magnetic ion exchange resin for synchronously removing nitrogen and phosphorus substances in secondary effluent is reported rarely at present, and the research and development of novel advanced treatment magnetic ion exchange resin for synchronously removing nitrogen and phosphorus for sewage landscape recycling is of great significance. Meanwhile, the problems of low exchange capacity, low selectivity of nitrogen and phosphorus substances, poor hydrophilicity, easy breakage and release of a magnetic core and low mechanical strength of the existing magnetic resin need to be solved urgently.
Disclosure of Invention
Aiming at the problems that the prior magnetic anion exchange resin has poor capability of synchronously removing nitrogen and phosphorus and low mechanical strength, the invention provides a sewage landscape recycling advanced treatment magnetic resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus and a preparation method thereof. The resin has two types of quaternary ammonium active sites, the resin is magnetically wrapped in the resin by secondary polymerization and also has hydrophilic-OH groups, so that the adsorption removal range, removal capacity and removal efficiency of nitrogen and phosphorus substances in advanced sewage treatment are greatly improved, the mechanical strength is further improved by post-crosslinking, and the resin can be used for removing the nitrogen and phosphorus substances in actual secondary effluent to meet the nitrogen and phosphorus standards in the urban sewage landscape utilization standard.
The purpose of the invention is realized by the following technical scheme:
the sewage landscape recycling advanced treatment magnetic resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus comprises a strong base anion exchange resin skeleton containing two types of quaternary ammonium salt active sites and magnetic particles wrapped in the strong base anion exchange resin skeleton, wherein the basic structure of the strong base anion exchange resin skeleton containing the two types of quaternary ammonium salt active sites is as follows:
wherein R is 1 is-H, -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above; r 3 is-CH 2 、-CHCH 3 、-C(CH 3 ) 2 One or more of the above; r 4 is-CH 2 、-CHCH 3 、-C(CH 3 ) 2 One or more of the above; r 5 is-H, -CH 3 、-CH 2 CH 3 、 -CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above; r 6 is-CH 2 、-CH 2 CH 2 、 -CH 2 CH 2 CH 2 、-C(CH 3 ) 2 One or more of the above; r 7 is-CH or-CH 2 -CH、 -CH 2 -CH 2 -CH、-CH(CH 3 ) -one or more of-CH; r 8 is-CH 3 、-CH 2 CH 3 、 -CH 2 CH 2 CH 3 One or more of the above; r 9 is-CH 2 、-CH 2 CH 2 、-CH 2 CH 2 CH 2 、-C(CH 3 ) 2 One or more of the above; r is 10 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 One or more of them.
A preparation method of the advanced treatment magnetic resin for recycling the sewage landscape containing the two types of quaternary ammonium sites and synchronously removing nitrogen and phosphorus comprises the following steps:
step (1) oleic acid modified magnetic particles:
dissolving magnetic particles in water, adding ammonia water, oleic acid and acetone, carrying out high-temperature water bath reaction under the condition of mechanical stirring, sequentially cleaning with ethanol and water after the reaction is finished, and carrying out high-temperature vacuum drying to obtain oleic acid modified magnetic particles, wherein:
the magnetic particles are: water: ammonia water: oleic acid: 1.0-5.0 g of acetone: 100-400 mL: 5-50 mL: 0.5-5.0 mL: 0-25.0 mL;
preparing primary polymerized magnetic microspheres in the step (2):
adding oleic acid modified magnetic particles into a sealed reactor capable of being mechanically stirred, pouring an oil phase and a water phase into the reactor to be mixed with the oleic acid modified magnetic particles, then placing the reactor into a water bath kettle for mechanical stirring, heating by using programmed temperature rise, and after the reaction is finished, alternately washing the product with cold water and hot water for multiple times to obtain the once-polymerized magnetic microspheres, wherein:
the oil phase consists of a monomer 1, a cross-linking agent, a monomer 2, a monomer 3, an initiator and a pore-foaming agent;
the structures of the monomer 1, the monomer 2, the monomer 3 and the cross-linking agent are as follows in sequence:
the water phase consists of a dispersant and inorganic salt;
the monomer 1: a crosslinking agent: monomer 2: monomer 3: initiator: pore-forming agent: dispersing agent: 5-15 g of inorganic salt: 1.5-2.5 g: 1.5-2.5 g: 0.1-1.0 g: 0.12-0.36 g: 7-21 mL: 1.8-5.4 g: 4-12 g;
preparing the secondary polymerized magnetic microspheres in the step (3):
adding primary polymerized magnetic microspheres into a sealed reactor capable of being mechanically stirred, pouring a water phase into the reactor to be mixed with the primary polymerized magnetic microspheres, dropwise adding an oil phase, simultaneously placing the reactor into a water bath kettle for mechanical stirring, heating by using programmed temperature rise, after the reaction is finished, alternately washing the product with cold water and hot water for multiple times, drying the product in a vacuum oven, extracting the product with acetone, and naturally drying the product to obtain secondary polymerized magnetic microspheres, wherein:
the addition amount of the water phase is the same as that of the step (2), and the addition amount of the oil phase is 1/4-1/2 of the step (2);
and (4) aminolysis of the secondary polymerized magnetic microspheres:
adding secondary polymerization magnetic microspheres and an amination reagent into a high-temperature and high-pressure resistant reactor, standing at a high temperature for reaction, not stirring in the reaction process, washing with water after the reaction is finished, and drying in a vacuum oven to obtain the aminated magnetic microspheres, wherein:
the secondary polymerization magnetic microspheres: amination agent ═ 1 g: 5-50 mL;
the structure of the amination agent is as follows:
the high-temperature standing reaction is carried out at the temperature of 150-200 ℃ for 6-24 hours.
Step (5), amination magnetic microsphere alkylation:
adding aminated magnetic microspheres, an alkaline agent and an alkylating agent into a high-temperature and high-pressure resistant reactor, standing at high temperature for reaction, not stirring in the reaction process, washing with water after the reaction is finished, and drying in a vacuum oven to obtain the primary quaternized magnetic microspheres, wherein:
the aminated magnetic microspheres: alkylating agents: 1g of basic agent: 5-70 mL: 5-70 mL;
the alkylating agent is R 8 -Br or R 8 -Cl;
The high-temperature standing reaction is carried out at the temperature of 60-150 ℃ for 6-24 hours.
Step (6) quaternization of the epoxy functional groups:
adding a primary quaternized magnetic microsphere, a quaternized medicament and water into a high-temperature and high-pressure resistant reactor, standing at a high temperature for reaction, repeatedly rinsing the obtained resin with water until the effluent is neutral, and drying a resin sample in a vacuum oven to obtain secondary quaternized resin, wherein:
the primary quaternization magnetic microspheres: quaternizing agent: 2g of water: 1-4 g: 12 mL;
the quaternizing agent is N (R) 10 ) 3 And HCl in a molar ratio of 1: 1;
the temperature of the high-temperature standing reaction is 60-100 ℃, and the time is 6-24 hours;
step (7) post-crosslinking:
fully expanding the secondary quaternary ammonium resin in an organic solvent, adding a catalyst, carrying out vinyl suspension post-crosslinking reaction under the high-temperature standing condition, cleaning the obtained resin by using the organic solvent, cleaning by using pure water, carrying out transformation on the transformation solution, and drying in a vacuum oven to obtain the magnetic strong-basicity anion exchange resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus, wherein:
the secondary quaternization resin: catalyst: organic solvent ═ 1 g: 0.1-0.2 g: 5-15 mL;
the secondary quaternization resin: transformation solution ═ 1: 50-100 mL;
the high-temperature standing reaction is carried out at the temperature of 60-100 ℃ for 6-24 hours.
Compared with the prior art, the invention has the following advantages:
(1) the magnetic strong-basicity anion exchange resin combines the characteristics of polystyrene resin and polyacrylic resin, has high adsorption capacity, high mechanical strength, easy separation of magnetic content and good recycling effect, and can be synchronously used for removing nitrogen and phosphorus in advanced treatment.
(2) The magnetic resin containing the quaternary ammonium salt sites has the advantages that the removal range of nitrogen and phosphorus substances is enlarged, the removal capacity of the nitrogen and phosphorus substances is improved, the mechanical strength of the resin is improved through the post-crosslinking reaction of the side chains, the magnetic resin containing the quaternary ammonium salt sites is more suitable for mechanical stirring of the magnetic resin in a continuous flow reactor, and the breakage is reduced.
(3) The amination agent and the quaternization agent can act on two monomers, so that the agents are fully utilized. Three types of organic monomers are adopted for polymerization, and two types of quaternary ammonium sites are finally formed through functionalization.
(4) The quaternization of the epoxy group has-OH group, which improves the hydrophilicity of the magnetic resin and is more beneficial to the adsorption and removal of pollutants in secondary effluent.
(5) R in the magnetic resin structure 1 ~R 10 Is C, H-containing short chain with less than or equal to 3C, and has the advantages of easily obtained medicament, stable structure and simple preparation method.
(6) The secondary polymerization enables the magnetic core to be wrapped in the resin framework, and leakage of magnetic substances caused by damage of resin is avoided.
Drawings
FIG. 1 is a synthetic step of a sewage landscape recycling advanced treatment magnetic resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus;
FIG. 2 is an infrared spectrum and an X-ray photoelectron spectrum of the resin prepared in example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
The sewage landscape recycling advanced treatment magnetic resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus comprises a strong base anion exchange resin skeleton containing two types of quaternary ammonium salt active sites and magnetic particles wrapped in the strong base anion exchange resin skeleton, wherein the basic structure of the strong base anion exchange resin skeleton containing the two types of quaternary ammonium salt active sites is as follows:
wherein R is 1 、R 3 ~R 10 Is a short chain containing C, H, R is less than or equal to 3C 1 is-H, -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above; r 3 is-CH 2 、-CHCH 3 、-C(CH 3 ) 2 One or more of the above; r 4 is-CH 2 、-CHCH 3 、 -C(CH 3 ) 2 One or more of the above; r 5 is-H, -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above; r is 6 is-CH 2 、-CH 2 CH 2 、-CH 2 CH 2 CH 2 、 -C(CH 3 ) 2 One or more of the above; r 7 is-CH, -CH 2 -CH、-CH 2 -CH 2 -CH、 -CH(CH 3 ) -one or more of-CH; r 8 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 One or more of the above; r is 9 is-CH 2 、-CH 2 CH 2 、-CH 2 CH 2 CH 2 、-C(CH 3 ) 2 One or more of the above; r 10 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 One or more of them.
A preparation method of the advanced treatment magnetic resin for recycling the sewage landscape containing the two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus comprises the steps of mixing a monomer containing ester groups and epoxy groups with a cross-linking agent, a pore-forming agent, an initiator and modified magnetic particles to form an oil phase, uniformly mixing the oil phase and the oil phase, carrying out primary suspension polymerization in a water phase, further carrying out secondary polymerization on a magnetic white ball subjected to the primary polymerization to obtain secondary copolymerized magnetic microspheres, carrying out amination and alkylation reactions on the ester groups on the secondary copolymerized magnetic microspheres in sequence to form a type of quaternary ammonium salt, further reacting the epoxy groups with an amine salt to obtain another type of quaternary ammonium salt, and finally carrying out post-crosslinking reaction on a double bond on the other side of a benzene ring on the cross-linking agent to obtain the advanced treatment magnetic strong basic anion resin for recycling the sewage landscape containing the two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus. As shown in fig. 1, the method comprises the following steps:
step (1) oleic acid modified magnetic particles:
dissolving magnetic particles in water, adding ammonia water, oleic acid and acetone, carrying out high-temperature water bath reaction under the condition of mechanical stirring, sequentially cleaning with ethanol and water after the reaction is finished, and drying in vacuum at high temperature to obtain oleic acid modified magnetic particles, wherein:
the magnetic particles are: water: ammonia water: oleic acid: 1.0-5.0 g of acetone: 100-400 mL: 5-50 mL: 0.5-5.0 mL: 0-25.0 mL;
the magnetic particles are one or a mixture of more of substances such as nano iron sesquioxide, nano ferroferric oxide, nano iron cobalt, nano iron nickel, nano iron cobalt nickel and the like and alloys thereof;
the water is one or a mixture of two of deionized water and ultrapure water;
the concentration of the ammonia water is 25-28 wt%;
the water bath temperature is 70-90 ℃, and the reaction time is 10-60 min;
the number of times of sequentially cleaning the ethanol and the water is 1-5 times;
the high-temperature vacuum drying temperature is 50-90 ℃, and the drying time is 6-24 h.
Preparing the primary polymerized magnetic microspheres in the step (2):
adding oleic acid modified magnetic particles into a sealed reactor capable of being mechanically stirred, pouring an oil phase and a water phase into the reactor to be mixed with the oleic acid modified magnetic particles, then placing the reactor into a water bath kettle for mechanical stirring, heating by using a programmed temperature rise, raising the temperature from room temperature to high temperature, reacting for a certain time, and washing the product with cold water and hot water alternately for multiple times to obtain the primary polymerized magnetic microspheres, wherein:
the oil phase consists of a monomer 1, a cross-linking agent, a monomer 2, a monomer 3, an initiator and a pore-foaming agent;
the monomer 1 has a structure shown in figure 1, and the structure isContaining an ester group, R 1 is-H, -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above; r 2 is-CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above;
the structure of the cross-linking agent is shown in figure 1 and isWith a benzene ring and a C ═ C double bond, R 3 is-CH 2 、-CHCH 3 、-C(CH 3 ) 2 One or more of the above; r 4 is-CH 2 、 -CHCH 3 、-C(CH 3 ) 2 One or more of the above;
the monomer 2 has a structure as shown in figure 1Containing ester groups and epoxy groups, R 5 is-H, -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above; r 6 is-CH 2 、-CH 2 CH 2 、-CH 2 CH 2 CH 2 、-C(CH 3 ) 2 One or more of the above;
the monomer 3 has a structure as shown in figure 1Containing double bonds and epoxy groups, R 7 is-CH, -CH 2 -CH、-CH 2 -CH 2 -CH、-CH(CH 3 ) -one or more of-CH;
the initiator is one or a mixture of more of dibenzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile and azobisisobutyric acid dimethyl ester;
the pore-foaming agent is one or a mixture of toluene, n-heptane and solvent oil;
the water phase consists of a dispersant and inorganic salt;
the inorganic salt is one or a mixture of more of sodium chloride, potassium chloride, sodium carbonate and sodium sulfate;
the dispersing agent is one or a mixture of polyvinyl alcohol, gelatin, polyethylene glycol, polyvinylpyrrolidone, sodium polyacrylate and magnesium carbonate;
the monomer 1: a crosslinking agent: monomer 2: monomer 3: initiator: pore-foaming agent: dispersing agent: 5-15 g of inorganic salt: 1.5-2.5 g: 1.5-2.5 g: 0.1-1.0 g: 0.12-0.36 g: 7-21 mL: 1.8-5.4 g: 4-12 g;
and (3) heating by temperature programming, namely heating from room temperature to 60-70 ℃, wherein the heating rate is 1-3 ℃/min, heating to 80-90 ℃ at the same heating rate after reacting for 200-300 min, reacting for 200-500 min, and maintaining the rotating speed in the whole process at 400-800 r/min.
In the cold water and hot water alternate washing for multiple times, the temperature of the cold water is 4 ℃, the temperature of the hot water is 80 ℃, and the alternate washing times are 3.
Preparing the secondary polymerized magnetic microspheres in the step (3):
adding primary polymerized magnetic microspheres into a sealed reactor capable of being mechanically stirred, pouring a water phase into the reactor to be mixed with the primary polymerized magnetic microspheres, dropwise adding an oil phase, simultaneously placing the reactor into a water bath kettle for mechanical stirring, heating by using a programmed temperature rise, raising the temperature from room temperature to high temperature, after reacting for a certain time, alternately washing the product with cold water and hot water for multiple times, drying by a vacuum oven, extracting with acetone, and naturally air-drying to obtain secondary polymerized magnetic microspheres, wherein:
the addition amount of the water phase is the same as that of the step (2), and the addition amount of the oil phase is 1/4-1/2 of the step (2);
the temperature is raised to 60-70 ℃ from room temperature at the temperature raising rate of 1-3 ℃/min, the temperature is raised to 80-90 ℃ at the same temperature raising rate after reaction for 200-300 min, the reaction time is 200-500 min, and the rotating speed in the whole process is maintained at 400-800 r/min;
the temperature of the cold water and the hot water in the cold water and hot water alternate washing times is 4 ℃, the temperature of the hot water is 80 ℃, and the alternate washing times are 3;
the drying temperature of the vacuum oven is 40-60 ℃, the drying time is 16h, the acetone extraction time is 6-8 h, and the natural air drying time is 10-12 h.
And (4) aminolysis of the secondary polymerized magnetic microspheres:
adding secondary polymerization magnetic microspheres and an amination reagent into a high-temperature and high-pressure resistant reactor, standing at a high temperature for reaction, not stirring in the reaction process, washing with water after the reaction is finished, and drying in a vacuum oven to obtain the aminated magnetic microspheres, wherein:
the secondary polymerization magnetic microspheres: amination agent ═ 1 g: 5-50 mL;
the amination agent has the structure shown as figure 1R 8 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 One or more of the above; r 9 is-CH 2 、-CH 2 CH 2 、 -CH 2 CH 2 CH 2 、-C(CH 3 ) 2 One or more of the above;
the water is one or a mixture of two of deionized water and ultrapure water;
the number of washing with water is 3-5;
the high-temperature standing reaction is carried out at the temperature of 150-200 ℃ for 6-24 hours.
Step (5), amination magnetic microsphere alkylation:
adding aminated magnetic microspheres, an alkaline agent and an alkylating agent into a high-temperature and high-pressure resistant reactor, standing at high temperature for reaction, not stirring in the reaction process, washing with water after the reaction is finished, and drying in a vacuum oven to obtain the primary quaternized magnetic microspheres, wherein:
the aminated magnetic microspheres: alkylating agents: 1g of basic agent: 5-70 mL: 5-70 mL;
the alkaline agent is one or a mixture of more of sodium hydroxide, potassium hydroxide and ammonia water, and the mass concentration of the alkaline agent is 5-30%;
the alkylating agent is R 8 -Br or R 8 -Cl, as shown in FIG. 1, R 8 is-CH 3 、 -CH 2 CH 3 、-CH 2 CH 2 CH 3 One or more of, R of alkylating agent 8 Radicals and R of aminating agents 8 The groups remain consistent;
the water is one or a mixture of two of deionized water and ultrapure water;
the number of washing with water is 3-5;
the high-temperature standing reaction is carried out at the temperature of 60-150 ℃ for 6-24 hours.
Step (6) quaternization of the epoxy functional groups:
adding a primary quaternized magnetic microsphere, a quaternized medicament and water into a high-temperature and high-pressure resistant reactor, standing at a high temperature for reaction, repeatedly rinsing the obtained resin with water until the effluent is neutral, and drying a resin sample in a vacuum oven to obtain secondary quaternized resin, wherein:
the primary quaternized magnetic microspheres: quaternizing agent: 2g of water: 1-4 g: 12 mL;
the quaternizing agent is N (R) 10 ) 3 And HCl in a molar ratio of 1: 1, as shown in FIG. 1, R 10 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 One or more of the above;
the water is one or a mixture of two of deionized water and ultrapure water;
the number of washing with water is 3-5;
the temperature of the high-temperature standing reaction is 60-100 ℃, and the time is 6-24 hours;
the drying temperature of the vacuum oven is 60-80 ℃, and the drying time is 6-24 hours.
Step (7) post-crosslinking:
fully expanding the secondary quaternary ammonium resin in an organic solvent, adding a catalyst, carrying out vinyl suspension post-crosslinking reaction under the high-temperature standing condition, cleaning the obtained resin by using the organic solvent, cleaning by using pure water, carrying out transformation on the transformation solution, and drying in a vacuum oven to obtain the magnetic strong-basicity anion exchange resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus, wherein:
the secondary quaternization resin: catalyst: organic solvent ═ 1 g: 0.1-0.2 g: 5-15 mL;
the organic solvent is one or a mixture of more of dichloroethane, methanol, acetone, ethanol and toluene;
the catalyst is one or a mixture of more of ferric trichloride, aluminum trichloride, carbon tetrachloride and p-toluenesulfonic acid;
the times of cleaning by the organic solvent and the times of cleaning by pure water are 3-5 times;
the transformation solution is one or a mixture of two of sodium chloride and potassium chloride, the mass concentration is 5-30%, and the secondary quaternization resin: transformation solution ═ 1: 50-100 mL;
the temperature of the high-temperature standing reaction is 60-100 ℃, and the time is 6-24 hours;
the drying temperature of the vacuum oven is 60-80 ℃, and the drying time is 6-24 hours.
The above-mentioned steps are not an absolute order of preparation of the magnetic strongly basic anion exchange resin containing two types of quaternary ammonium sites for simultaneous removal of nitrogen and phosphorus, but can be prepared by the order of (1) - (2) - (3) - (6) - (7) - (4) - (5) or (1) - (2) - (3) - (7) - (6) - (4) - (5). As shown in FIG. 1, the two types of quaternary ammonium sites contained in the prepared fragments are not in absolute order from monomer 3, from monomer 1, from monomer 2, from left to right.
Example 1:
dissolving 3.0g of gamma-ferric oxide in 200mL of deionized water in a 250mL conical flask, adding 25mL of ammonia water (25-28 wt%), 2.5mL of oleic acid and 13mL of acetone, mechanically stirring in a water bath at 80 ℃ for 30min, washing with ethanol for 3 times, washing with ultrapure water for 3 times, and drying at 60 ℃ to obtain the oleic acid modified magnetic powder. To the above dried 250mL Erlenmeyer flask was added an oil phase comprising 10.0g of methyl methacrylate, 2.0g of divinylbenzene, 2.0g of glycidyl methacrylate, 0.3g of 3, 4-epoxy-1-butene, 0.24g of dibenzoyl peroxide, 8mL of toluene and 6mL of n-heptane. Adding 1.8g of polyvinyl alcohol, 1.8g of polyvinylpyrrolidone and 8g of NaCl into 200mL of deionized water as a water phase, transferring the water phase into an oil phase, transferring a 250mL conical flask with a plug into a water bath kettle, heating from room temperature to 70 ℃ by using a program, wherein the heating rate is 1 ℃/min, after reacting for 150min, heating to 80 ℃ at the same heating rate, reacting for 360min, and maintaining the rotating speed of the whole process at 600 r/min. The product is washed alternately with cold water (4 ℃) and hot water (80 ℃) for 3 times to obtain the primary magnetic microspheres. Then, the second polymerization was carried out under the same conditions as the first polymerization: the difference from the primary polymerization is that the oil phase does not contain magnetic powder, the oil phase is dropwise added into the water phase, the mass and volume of the oil phase are 1/4 of the primary polymerization, the product is alternately washed by cold (4 ℃) and hot water (80 ℃) for 3 times, dried in a 50 ℃ oven for 16 hours, extracted by acetone for 6 hours, and naturally dried to obtain the secondary magnetic microspheres. Then carrying out aminolysis reaction of the secondary magnetic microspheres: 2g of resin and 16mL of 3-diethylaminopropylamine were mixed in a 250mL polytetrafluoroethylene bottle, and then reacted at 175 ℃ for 7 hours without stirring, and after the reaction was completed, the mixture was washed with ultrapure water 3 times to obtain aminated magnetic microspheres. Then carrying out alkylation reaction: 20mL of 20% sodium hydroxide and 20mL of ethyl bromide were added to the above 250mL polytetrafluoroethylene bottle, and the mixture was reacted at 70 ℃ for 24 hours without stirring to obtain primary-quaternized magnetic microspheres. Followed by quaternization of the epoxy functional groups: quaternization of 2g of the once-quaternized magnetic microspheres with 3.75g of trimethylamine hydrochloride and 12mL of ultrapure water at 80 ℃ for 12 hours. The resin was repeatedly rinsed with deionized water until the effluent was neutral. The resin samples were dried at 50 ℃ for 8 hours to give a secondary aminated resin. Finally, 5g of the diquaternized resin was fully expanded in 50mL of dichloroethane, 0.5g of ferric chloride was added, and vinyl drape post-crosslinking reaction was carried out under high temperature conditions. After discharging, washing with methanol, washing with pure water, and transforming with sodium chloride solution (1g resin/50 mL 15% sodium chloride solution) to obtain the advanced treatment magnetic resin for recycling the sewage landscape containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus, wherein the resin structure is as follows:
the infrared spectrum and the X-ray photoelectron spectrum of the material characterization are shown in figure 1, and compared with the commercialized advanced treatment magnetic resin for recycling sewage landscape containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorusAnd D201X 7 resin has better effect (including total nitrogen, total phosphorus, nitrate radical and phosphate radical indexes) on treating nitrogen and phosphorus substances in secondary effluent because the secondary effluent has more sulfate radicals andand the D201X 7 resin more readily removed sulfate resulting in poor nitrogen phosphorus removal. When the resin is adopted to treat raw water meeting the primary B standard of GB 18918 + 2002 pollutant discharge Standard of urban Sewage treatment plants, the effluent quality can meet the nitrogen and phosphorus standard in the GB/T18921-2019 Standard of Water quality for urban Sewage regeneration and landscape environment.
Example 2:
dissolving 2.5g of gamma-ferric oxide in 200mL of deionized water in a 250mL conical flask, adding 25mL of ammonia water (25-28 wt%), 2.5mL of oleic acid and 13mL of acetone, mechanically stirring in a water bath at 80 ℃ for 30min, washing with ethanol for 3 times, washing with ultrapure water for 3 times, and drying at 60 ℃. To the above dried 250mL Erlenmeyer flask was added an oil phase comprising 10.0g of ethyl 2-ethacrylate, 2.0g of divinylbenzene, 2.0g of glycidyl methacrylate, 0.5g of 3, 4-epoxy-1-butene, 0.24g of dibenzoyl peroxide, 8mL of toluene and 6m L n-heptane. Adding 1.8g of polyvinyl alcohol, 1.8g of polyvinylpyrrolidone and 8g of KCl into 200mL of deionized water as a water phase, transferring the water phase into an oil phase, then transferring a 250mL conical flask with a plug into a water bath kettle, heating from room temperature to 70 ℃ by utilizing a programmed heating process, wherein the heating rate is 1 ℃/min, after reacting for 150min, heating to 80 ℃ at the same heating rate, reacting for 360min, and maintaining the rotating speed of the whole process at 600 r/min. The product is washed alternately with cold water (4 ℃) and hot water (80 ℃) for 3 times to obtain the primary magnetic microspheres. Then, the second polymerization was carried out under the same conditions as the first polymerization: the difference from the one-time polymerization is that the oil phase does not contain magnetic powder, the oil phase is dropwise added into the water phase, and the mass and the volume of the oil phase are 1/4 of the one-time polymerization. The product is washed alternately by cold (4 ℃) and hot water (80 ℃) for 3 times, dried in a 50 ℃ oven for 16 hours, extracted by acetone for 6 hours, and naturally dried to obtain the secondary magnetic microspheres. Then carrying out aminolysis reaction of the secondary magnetic microspheres: 2g of resin and 16mL of 3-dimethylaminopropylamine are mixed in a 250mL polytetrafluoroethylene bottle, then the mixture is reacted for 7 hours at the temperature of 170 ℃, the reaction is not stirred, and the mixture is washed for 3 times by ultrapure water after the reaction is finished, so that the aminated magnetic microspheres are obtained. Then carrying out alkylation reaction: 20mL of 20% sodium hydroxide and 20mL of methyl bromide were added to the above 250mL Teflon bottle, and reacted at 70 ℃ for 24 hours without stirring to obtain the primary quaternized magnetic microspheres. Followed by quaternization of the epoxy functional groups: quaternization of 2g of the once-quaternized magnetic microspheres with 3.75g of trimethylamine hydrochloride and 12mL of ultrapure water at 80 ℃ for 12 hours. The resin was repeatedly rinsed with deionized water until the effluent was neutral. The resin samples were dried at 50 ℃ for 8 hours to give a secondary aminated resin. Finally, 5g of the diquaternized resin was fully expanded in 50mL of dichloroethane, 0.5g of ferric chloride was added, and vinyl drape post-crosslinking reaction was carried out under high temperature conditions. After discharging, washing with methanol, washing with pure water, and transforming with sodium chloride solution (1g resin/50 mL 15% sodium chloride solution) to obtain the advanced treatment magnetic resin for recycling the sewage landscape containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus, wherein the resin structure is as follows:
when the resin is adopted to treat raw water meeting the primary A standard of GB 18918 + 2002 pollutant discharge standard of urban sewage treatment plants, the effluent quality can meet the nitrogen and phosphorus standard in the GB/T18921-2019 standard of water quality for urban sewage recycling landscape environment.
Example 3:
dissolving 3.0g of nano ferroferric oxide powder in 200mL of deionized water in a 250mL conical flask, adding 25mL of ammonia water (25-28 wt%), 2.5mL of oleic acid and 13mL of acetone, mechanically stirring in a water bath at 80 ℃ for 30min, washing with ethanol for 3 times, washing with ultrapure water for 3 times, and drying at 60 ℃. To the above dried 250mL Erlenmeyer flask was added an oil phase comprising 11.0g ethyl methacrylate, 2.5g divinylbenzene, 2.0g 2, 3-epoxypropyl acrylate, 0.3g 3, 4-epoxy-1-butene, 0.30g dibenzoyl peroxide, 8mL toluene and 8m L n-heptane. Adding 2.0g of polyvinyl alcohol, 2.0g of polyvinylpyrrolidone and 8g of NaCl into 200mL of deionized water as a water phase, transferring the water phase into an oil phase, transferring a 250mL conical flask with a plug into a water bath kettle, heating from room temperature to 75 ℃ by utilizing a programmed heating process at a heating rate of 1 ℃/min, after reacting for 150min, heating to 85 ℃ at the same heating rate, reacting for 360min, and maintaining the rotating speed of the whole process at 700 r/min. The product is washed alternately with cold water (4 ℃) and hot water (80 ℃) for 3 times to obtain the primary magnetic microspheres. Then, the second polymerization was carried out under the same conditions as the first polymerization: the difference from the one-time polymerization is that the oil phase does not contain magnetic powder, the oil phase is dropwise added into the water phase, and the mass and the volume of the oil phase are 1/4 of the one-time polymerization. The product is washed alternately by cold (4 ℃) and hot water (80 ℃) for 3 times, dried in a 50 ℃ oven for 16 hours, extracted by acetone for 6 hours, and naturally dried to obtain the secondary magnetic microspheres. Then carrying out aminolysis reaction of the secondary magnetic microspheres: 2g of resin and 25mL of N, N-diethylethylenediamine are mixed in a 250mL polytetrafluoroethylene bottle, then the mixture is reacted for 7 hours at the temperature of 175 ℃, the mixture is not stirred, and after the reaction is finished, the mixture is washed by ultrapure water for 3 times to obtain the aminated magnetic microsphere. Then carrying out alkylation reaction: 20mL of 20% sodium hydroxide and 30mL of ethyl bromide were added to the above 250mL polytetrafluoroethylene bottle, and the mixture was reacted at 80 ℃ for 24 hours without stirring to obtain primary-quaternized magnetic microspheres. Followed by quaternization of the epoxy functional groups: quaternization of 2g of the once-quaternized magnetic microspheres with 3.75g of triethylamine hydrochloride and 12mL of ultrapure water at 80 ℃ for 12 hours. The resin was repeatedly rinsed with deionized water until the effluent was neutral. The resin samples were dried at 50 ℃ for 8 hours to give a secondary aminated resin. Finally, 5g of the diquaternized resin was fully expanded in 50mL of dichloroethane, 0.5g of aluminum chloride was added, and vinyl drape post-crosslinking reaction was carried out under high temperature conditions. After discharging, cleaning with methanol, cleaning with pure water, and transforming with a sodium chloride solution (1g of resin/50 mL of 15% sodium chloride solution) to obtain the advanced treatment magnetic resin for recycling the sewage landscape containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus, wherein the resin structure is as follows:
when the resin is adopted to treat raw water meeting the primary A standard of GB 18918 + 2002 pollutant discharge standard of urban sewage treatment plants, the effluent quality can meet the nitrogen and phosphorus standard in the GB/T18921-2019 standard of water quality for urban sewage recycling landscape environment.
Claims (9)
1. The advanced treatment magnetic resin for recycling the sewage landscape containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus is characterized in that the magnetic resin consists of a strong base anion exchange resin skeleton containing two types of quaternary ammonium salt active sites and magnetic particles wrapped in the strong base anion exchange resin skeleton, and the basic structure of the strong base anion exchange resin skeleton containing two types of quaternary ammonium salt active sites is as follows:
wherein R is 1 is-H, -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above; r 3 is-CH 2 、-CHCH 3 、-C(CH 3 ) 2 One or more of the above; r 4 is-CH 2 、-CHCH 3 、-C(CH 3 ) 2 One or more of the above; r 5 is-H, -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above; r is 6 is-CH 2 、-CH 2 CH 2 、-CH 2 CH 2 CH 2 、-C(CH 3 ) 2 One or more of the above; r 7 is-CH, -CH 2 -CH、-CH 2 -CH 2 -CH、-CH(CH 3 ) -one or more of-CH; r 8 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 One or more of the above; r 9 is-CH 2 、-CH 2 CH 2 、-CH 2 CH 2 CH 2 、-C(CH 3 ) 2 One or more of the above; r 10 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 One or more of them.
2. The preparation method of the advanced treatment magnetic resin for recycling the sewage landscape containing the two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus according to claim 1, which is characterized by comprising the following steps:
step (1) oleic acid modified magnetic particles:
dissolving magnetic particles in water, adding ammonia water, oleic acid and acetone, carrying out high-temperature water bath reaction under the condition of mechanical stirring, sequentially cleaning with ethanol and water after the reaction is finished, and carrying out high-temperature vacuum drying to obtain oleic acid modified magnetic particles, wherein:
the magnetic particles are: water: ammonia water: oleic acid: 1.0-5.0 g of acetone: 100-400 mL: 5-50 mL: 0.5-5.0 mL: 0-25.0 mL;
preparing the primary polymerized magnetic microspheres in the step (2):
adding oleic acid modified magnetic particles into a sealed reactor capable of being mechanically stirred, pouring an oil phase and a water phase into the reactor to be mixed with the oleic acid modified magnetic particles, then placing the reactor into a water bath kettle for mechanical stirring, heating by using programmed temperature rise, and after the reaction is finished, alternately washing the product with cold water and hot water for multiple times to obtain the once-polymerized magnetic microspheres, wherein:
the oil phase consists of a monomer 1, a cross-linking agent, a monomer 2, a monomer 3, an initiator and a pore-foaming agent;
the structures of the monomer 1, the monomer 2, the monomer 3 and the cross-linking agent are as follows in sequence:
the R is 2 is-CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 and-CH 2 CH 2 CH 3 One or more of the above;
the water phase consists of a dispersant and inorganic salt;
the monomer 1: a crosslinking agent: monomer 2: monomer 3: initiator: pore-forming agent: dispersing agent: 5-15 g of inorganic salt: 1.5-2.5 g: 1.5-2.5 g: 0.1-1.0 g: 0.12-0.36 g: 7-21 mL: 1.8-5.4 g: 4-12 g;
preparing the secondary polymerized magnetic microspheres in the step (3):
adding primary polymerized magnetic microspheres into a sealed reactor capable of being mechanically stirred, pouring a water phase into the reactor to be mixed with the primary polymerized magnetic microspheres, dropwise adding an oil phase, simultaneously placing the reactor into a water bath kettle for mechanical stirring, heating by using programmed temperature rise, after the reaction is finished, alternately washing the product with cold water and hot water for multiple times, drying the product in a vacuum oven, extracting the product with acetone, and naturally drying the product to obtain secondary polymerized magnetic microspheres, wherein:
the addition amount of the water phase is the same as that of the step (2), and the addition amount of the oil phase is 1/4-1/2 of the step (2);
and (4) aminolysis of the secondary polymerized magnetic microspheres:
adding the secondary polymerized magnetic microspheres and an amination medicament into a high-temperature and high-pressure resistant reactor, standing at a high temperature for reaction, not stirring in the reaction process, washing with water after the reaction is finished, and drying in a vacuum oven to obtain the aminated magnetic microspheres, wherein:
the secondary polymerization magnetic microspheres: amination agent ═ 1 g: 5-50 mL;
the structure of the amination agent is as follows:
the high-temperature standing reaction is carried out at the temperature of 150-200 ℃ for 6-24 hours.
Step (5), amination magnetic microsphere alkylation:
adding aminated magnetic microspheres, an alkaline agent and an alkylating agent into a high-temperature and high-pressure resistant reactor, standing at high temperature for reaction, not stirring in the reaction process, washing with water after the reaction is finished, and drying in a vacuum oven to obtain the primary quaternized magnetic microspheres, wherein:
the aminated magnetic microspheres: alkylating agents: 1g of basic agent: 5-70 mL: 5-70 mL;
the alkylating agent is R 8 -Br or R 8 -Cl;
The high-temperature standing reaction is carried out at the temperature of 60-150 ℃ for 6-24 hours.
Step (6) quaternization of the epoxy functional groups:
adding a primary quaternized magnetic microsphere, a quaternized medicament and water into a high-temperature and high-pressure resistant reactor, standing at a high temperature for reaction, repeatedly rinsing the obtained resin with water until the effluent is neutral, and drying a resin sample in a vacuum oven to obtain secondary quaternized resin, wherein:
the primary quaternization magnetic microspheres: quaternizing agent: 2g of water: 1-4 g: 12 mL;
the quaternizing agent is N (R) 10 ) 3 And HCl in a molar ratio of 1: 1;
the temperature of the high-temperature standing reaction is 60-100 ℃, and the time is 6-24 hours;
step (7) post-crosslinking:
fully expanding the secondary quaternary ammonium resin in an organic solvent, adding a catalyst, carrying out vinyl suspension post-crosslinking reaction under the high-temperature standing condition, cleaning the obtained resin by using the organic solvent, cleaning by using pure water, carrying out transformation on the transformation solution, and drying in a vacuum oven to obtain the magnetic strong-basicity anion exchange resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus, wherein:
the secondary quaternization resin: catalyst: organic solvent ═ 1 g: 0.1-0.2 g: 5-15 mL;
the secondary quaternization resin: transformation solution ═ 1: 50-100 mL;
the high-temperature standing reaction is carried out at the temperature of 60-100 ℃ for 6-24 hours.
3. The preparation method of the magnetic resin for the advanced treatment of the recycling of the sewage landscape containing the two types of quaternary ammonium sites for synchronously removing the nitrogen and the phosphorus according to claim 1, wherein in the step (1), the magnetic particles are one or a mixture of several of nano iron sesquioxide, nano ferroferric oxide, nano iron cobalt, nano iron nickel, nano iron cobalt nickel and alloys thereof; the water is one or a mixture of two of deionized water and ultrapure water; the concentration of the ammonia water is 25-28 wt%; the water bath temperature is 70-90 ℃, and the reaction time is 10-60 min; the number of times of sequentially cleaning the ethanol and the water is 1-5 times; the high-temperature vacuum drying temperature is 50-90 ℃, and the drying time is 6-24 h.
4. The method for preparing the magnetic resin for the advanced treatment of the recycled sewage landscape containing the two types of quaternary ammonium sites for synchronously removing the nitrogen and the phosphorus, which is disclosed by the claim 1, is characterized in that in the step (2), the initiator is one or a mixture of more of dibenzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate; the pore-foaming agent is one or a mixture of toluene, n-heptane and solvent oil; the inorganic salt is one or a mixture of sodium chloride, potassium chloride, sodium carbonate and sodium sulfate; the dispersant is one or more of polyvinyl alcohol, gelatin, polyethylene glycol, polyvinylpyrrolidone, sodium polyacrylate and magnesium carbonate; and (3) heating by temperature programming, wherein the temperature is raised from room temperature to 60-70 ℃, the heating rate is 1-3 ℃/min, the temperature is raised to 80-90 ℃ at the same heating rate after reaction for 200-300 min, the reaction time is 200-500 min, the rotating speed in the whole process is maintained at 400-800 r/min, cold water and hot water are alternately washed for multiple times, the temperature of the cold water is 4 ℃, the temperature of the hot water is 80 ℃, and the number of the alternate washing times is 3.
5. The preparation method of the advanced treatment magnetic resin for recycling the sewage landscape containing the two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus according to claim 1, characterized in that in the step (3), the temperature is raised from room temperature to 60-70 ℃ by temperature programming and heating, the temperature raising rate is 1-3 ℃/min, after the reaction is carried out for 200-300 min, the temperature is raised to 80-90 ℃ at the same temperature raising rate, the reaction is carried out for 200-500 min, and the rotating speed in the whole process is maintained at 400-800 r/min; the temperature of cold water and hot water in the cold water washing process is 4 ℃, the temperature of hot water is 80 ℃ and the washing times are 3 times; the drying temperature of the vacuum oven is 40-60 ℃, the drying time is 16h, the acetone extraction time is 6-8 h, and the natural air drying time is 10-12 h.
6. The method for preparing the magnetic resin for the advanced treatment of the landscape architecture recycling of sewage containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus according to claim 1, wherein in the step (4), the water is one or a mixture of two of deionized water and ultrapure water; the number of washing with water is 3-5.
7. The preparation method of the magnetic resin for advanced treatment of recycling of sewage landscape containing two types of quaternary ammonium sites for synchronous removal of nitrogen and phosphorus according to claim 1, wherein in the step (5), the alkaline agent is one or a mixture of sodium hydroxide, potassium hydroxide and ammonia water, and the mass concentration is 5-30%; the water is one or a mixture of two of deionized water and ultrapure water; the number of washing with water is 3-5.
8. The method for preparing the magnetic resin for the advanced treatment of the landscape architecture recycling of sewage containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus according to claim 1, wherein in the step (6), the water is one or a mixture of two of deionized water and ultrapure water; washing with water for 3-5 times; the drying temperature of the vacuum oven is 60-80 ℃, and the drying time is 6-24 h.
9. The preparation method of the magnetic resin for advanced treatment of recycling the sewage landscape containing the two types of quaternary ammonium sites for synchronously removing the nitrogen and the phosphorus according to the claim 1, wherein in the step (7), the organic solvent is one or a mixture of more of dichloroethane, methanol, acetone, ethanol and toluene; the catalyst is one or a mixture of more of ferric trichloride, aluminum trichloride, carbon tetrachloride and p-toluenesulfonic acid; the times of cleaning with the organic solvent and the times of cleaning with pure water are 3-5 times; the transformation solution is one or a mixture of two of sodium chloride and potassium chloride, and the mass concentration of the transformation solution is 5-30%; the drying temperature of the vacuum oven is 60-80 ℃, and the drying time is 6-24 hours.
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