TECHNICAL FIELD

The present invention belongs to the fields of functional polymers and wastewater treatment. In particular, the present application relates to a resin for removing phosphorus from waste water solution.

BACKGROUND

Phosphorus-containing wastewater is one of the typical industrial wastewaters with extremely serious pollution. Phosphorus-containing wastewater contains a large amount of phosphates, which mainly come from various industrial raw materials, agricultural raw materials and detergents. Once discharged into rivers without proper treatments, it will seriously pollute the natural environment. Phosphorus-containing wastewater will lead to eutrophication of waste water solution, and then lead to the phenomenon of red tide, which will result in abnormal waste water solution, discoloration, water quality deterioration and foul smell and thus worsen the waste water solution conditions, giving a dangerous signal that the water ecology is damaged. In recent years, the deterioration of water quality in rivers, lakes, oceans and other waters has become increasingly serious. Generally speaking, a waste water solution is considered to be in eutrophication when the mass concentration of total phosphorus in the waste water solution exceeds 20 mg/L. Therefore, effective treatment of phosphorus-containing wastewater is of great practical significance. The effective treatment of phosphorus-containing wastewater using targeting processes to enable it to reach a discharging standard is an important topic in environmental protection.

Typical treatment methods of phosphorus-containing wastewater comprise coagulation sedimentation method, crystallization method, ion exchange adsorption method, electrodialysis method, reverse osmosis method, etc. At present, phosphorus is removed from wastewater by mainly using aluminum salts, lime and other materials that can generate insoluble phosphate precipitates with phosphate. However, the method is inefficient when concentrations of phosphorus-containing wastewater are relatively low and thus serious pollutions would be caused. The ion exchange adsorption method can solve this problem very well. However, the existing ion exchange resin for removing phosphate has the problems of low selectivity, slow adsorption rate and low adsorption capacity. The present patent is mainly aimed at optimizing and innovating the ion exchange adsorption method by using lanthanum-oxygen bond to selectively adsorb phosphate ions, so as to improve the adsorption rate and adsorption capacity of the resin. At the same time lanthanum-oxygen bond has high selectivity for phosphate ions. With the rapid development of industry in China, the discharge standards in China are increasingly stringent, so the resin for removing phosphorus has broad application prospects.

SUMMARY OF THE INVENTION

It is found that lanthanum oxide has a high selectivity for phosphorus adsorption through coordination with phosphate ions, and the raw materials of lanthanum are cheap. However, lanthanum oxide is inconvenient to use in practical applications, so it is necessary to find suitable carriers to facilitate the applications. Typical carriers comprise silica gel, molecular sieve, activated carbon, etc. Meanwhile, macroporous ion exchange resin is also a good carrier.

In order to overcome the shortcomings of the prior art, the present invention provides an ion exchange resin for removing phosphorus from waste water solution, which is easy to carry out desorption by using an alkali liquor. Compared with the prior technology for removing phosphorus, the ion exchange resin of the present invention is convenient to use and low in cost, without causing secondary pollutions.

The present invention provides a resin loaded with lanthanum for removing phosphorus, wherein the resin has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 8-25 m²/g and a pore size distribution of 3-15 nm, a wet apparent density of 0.68-0.74 g/cm³; a wet true density of 1.12-1.18 g/cm³; a water content of 43-57% (w/w); and is loaded with a functional group having a lanthanum-oxygen bond to enable selectively adsorbing of phosphate ions from waste water solution by the resin. It is easy to undergo ion exchange with phosphate ions in the system. The resin for removing phosphorus from waste water solution is prepared by a method comprising the following steps of:

step (1): preparing an oil phase using a monofunctional monomer, a cross-linking agent, a pore-forming agent and an initiator, preparing an aqueous phase using a dispersant and water, preparing a resin via suspension polymerization reaction, and removing the pore-forming agent from the resin after polymerization reaction is completed, obtaining a resin-based sphere;

step (2): carrying out a chlorination reaction and an amination reaction of the resin-based sphere, and carrying out a hydrolysis reaction by adding an alkali to the resin after the amination reaction, obtaining an amine sphere;

step (3): reacting the amine sphere with an organic weak acid, obtaining a weak acid cation resin; and

step (4): loading a lanthanum compound onto the surface of the weak acid cation resin, obtaining a resin for removing phosphorus.

Further, the monofunctional monomer in the step (1) is selected from the group consisting of styrene series, acrylic series, acrylonitrile series and any combination thereof.

The cross-linking agent in the step (1) is selected from the group consisting of divinylbenzene, diisocyanate ester, N,N-methylenebisacrylamide, and any combination thereof. The cross-linking agent is present in an amount of 2-30% (W/W) with respect to the monomer, which means a crosslinking degree of 2-30% (W/W). Preferably, the cross-linking agent is present in an amount of 4-15% (W/W), more preferably 5-10% (W/W), with respect to the monomer.

The pore-forming agent in the step (1) is selected from the group consisting of toluene, isooctane, gasoline, aviation gasoline, n-heptane, cyclohexane, liquid paraffin, white oil and any combination thereof.

The initiator in the step (1) is selected from the group consisting of lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, tert butyl hydroperoxide, ditert butyl peroxide, diisopropylbenzene peroxide, potassium persulfate, sodium persulfate, ammonium persulfate 2,2′-azobis(2-methylpropionitrile), 2,2′-azobis(2,4-dimethyl)valeronitrile, and any combination thereof.

The dispersant in the step (1) is selected from the group consisting of polyvinyl alcohol, gelatin, fatty acids, aliphatic amides, paraffins, celluloses and any combination thereof.

A ratio of the aqueous phase to the oil phase in the step (1) is 10:1-1:1 V/V.

The suspension polymerization reaction in the step (1) is carried out at a temperature of 40-100° C. using a gradient heating method which comprises heating to 40-60° C. at a first stage, 60-80° C. at a second stage and 80-100° C. at a third stage.

The chlorination reaction in the step (2) is carried out using chloromethyl ether. The chlorination reaction in the step (2) is carried out in the presence of a catalyst selected from the group consisting of zinc chloride, aluminum chloride, ferric chloride, boron trifluoride, niobium pentachloride, trifluoromethanesulfonate and any combination thereof and a solvent selected from the group consisting of methanol, ethanol, acetone, toluene, isopropanol, ether, dimethoxymethane and any combination thereof. The chlorination reaction in the step (2) is carried out at a temperature of 25-50° C. for a period of 1-15 h.

The amination reaction in the step (2) is carried out at a temperature of 50-120° C. The amination reaction is carried outing using an agent selected from the group consisting of phthalimide, ethylenediamine, hexamethylene imine, dimethylamine, trimethylamine, hexaethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and any combination thereof.

The hydrolysis reaction in the step (2) is carried out in the presence of a catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bisulfite, sulfuric acid, nitric acid, hydrochloric acid and any combination thereof. The hydrolysis reaction in the step (2) is carried out at a temperature of 85-130° C.

The organic weak acid used in the step (3) for reacting with the amine sphere is selected from the group consisting of chloroacetic acid, chloropropionic acid, dichloroacetic acid, phosphoric acid+formaldehyde, pyrophosphoric acid+formaldehyde, and any combination thereof. Said reacting the amine sphere with an organic weak acid in the step (3) is carried out at a temperature of 40-90° C. Said reacting the amine sphere with an organic weak acid in the step (3) is carried out in the presence of a catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bisulfite and any combination thereof.

The lanthanum compound used in the step (4) is selected from the group consisting of lanthanum chloride, lanthanum nitrate, lanthanum sulfate, lanthanum phosphate, the hydrates thereof and any mixture thereof. Said loading a lanthanum compound onto the surface of the weak acid cation resin in the step (4) is achieved by reacting at a temperature of 35-90° C. Said loading a lanthanum compound onto the surface of the weak acid cation resin is achieved by reacting in the presence of a solvent selected from the group consisting of water, methanol, ethanol, formic acid, ethylene glycol, propylene glycol, glycerol, acetic acid, propionic acid, isopropanol, any mixture thereof, and any mixture of water with the above reagents in any ratio. In the step (4), said loading a lanthanum compound onto the surface of the weak acid cation resin is achieved by reacting in the presence of a catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bisulfite, ammonia and any combination thereof. Said loading a lanthanum compound onto the surface of the weak acid cation resin in the step (4) is achieved by reacting for 1-30 h.

The macroporous ion exchange resin prepared by present invention can selectively adsorb phosphate ions, hydrogen phosphate ions and dihydrogen phosphate ions from waste water solution but hardly adsorb other anions. The resin is renewable, and thus is more economical and efficient than the traditional disposable phosphorus adsorbents and produces less secondary pollutions.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present application will be further illustrated with reference to following embodiments. However, these embodiments are only for illustrating, rather than limitations to the present invention detailed in the claims.

EXAMPLE 1

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 19.4 m²/g and a median pore diameter of 8.6 nm; a wet apparent density of 0.718 g/cm³; a wet true density of 1.15 g/cm³; and a water content of 47.9% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 7 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 85%.

EXAMPLE 2

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 10 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 18.7 m²/g and a median pore diameter of 7.6 nm; a wet apparent density of 0.723 g/cm³; a wet true density of 1.14 g/cm³; and a water content of 45.8% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 14 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 82%.

EXAMPLE 3

An oil phase is prepared using 20 g 55% (w/w) of divinylbenzene, 80 g of styrene, 50 g of toluene and 1.2 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 60° C. for 2 h, heating up to 80° C. and holding for 2 h, heating up to 95° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 17.9 m²/g and a median pore diameter of 8.2 nm; a wet apparent density of 0.721 g/cm³; a wet true density of 1.19 g/cm³; and a water content of 46.3% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 21 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 84%.

EXAMPLE 4

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of carboxymethyl cellulose into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere is mixed with 12 g of chloromethyl ether, 100 g of acetone and 1 g ferric chloride as a catalyst, stirred at 38° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 17.9 m²/g and a median pore diameter of 7.2 nm; a wet apparent density of 0.731 g/cm³; a wet true density of 1.21 g/cm³; and a water content of 48.5% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 17 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 81%.

EXAMPLE 5

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 8 h at 90° C., and then 15 g of 8% (w/w) potassium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 15 g of chloroacetic acid and then added slowly into 40 g of 20% (w/w) sodium hydroxide solution to perform reaction at 60° C. for 10h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 17.9 m²/g and a median pore diameter of 6.9 nm; a wet apparent density of 0.722 g/cm³; a wet true density of 1.14 g/cm³; and a water content of 48.3% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 16 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 83%.

EXAMPLE 6

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g lanthanum nitrate and added into 300 ml of 25% (w/w) isopropanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 17.7 m²/g and a median pore diameter of 7.5 nm; a wet apparent density of 0.716 g/cm³; a wet true density of 1.19 g/cm³; and a water content of 44.8% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 16 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 83%.

EXAMPLE 7

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L potassium hydroxide solution is added dropwise slowly until the system reaches a pH of 11. Stir for 6 h at 50° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 15.6 m²/g and a median pore diameter of 10.5 nm; a wet apparent density of 0.724 g/cm³; a wet true density of 1.23 g/cm³; and a water content of 47.2% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 31 ppm, and the adsorption is stopped.

Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 82%.

EXAMPLE 8

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 19.1 m²/g and a median pore diameter of 8.2 nm; a wet apparent density of 0.724 g/cm³; a wet true density of 1.17 g/cm³; and a water content of 46.8% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 6 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 5 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 31 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 6% (w/w) potassium hydroxide+5% (w/w) sodium carbonate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 81%.

EXAMPLE 9

An oil phase is prepared using 20 g 55% (w/w) of divinylbenzene, 80 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 40° C. for 2 h, heating up to 60° C. and holding for 2 h, heating up to 75° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 17.5 m²/g and a median pore diameter of 9.2 nm; a wet apparent density of 0.723 g/cm³; a wet true density of 1.13 g/cm³; and a water content of 48.2% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 17 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 81%.

EXAMPLE 10

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 25 g lanthanum phosphate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 18.4 m²/g and a median pore diameter of 7.5 nm; a wet apparent density of 0.724 g/cm³; a wet true density of 1.11 g/cm³; and a water content of 47.2% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 4 with 0.5 mol/L hydrochloric acid solution, then passed through the column at a flow rate of 3 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 13 ppm, and the adsorption is stopped. Wash with 2 BV water. A solution of 8% (w/w) sodium hydroxide+5% (w/w) sodium sulfate is prepared to carry out desorption with 5 BV, and wash with 2 BV water. The desorption rate is 85%.

EXAMPLE 11

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of styrene, 70 g of toluene and 1 g of BPO. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of polyvinyl alcohol and 1 g of gelatin into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 70° C. and holding for 2 h, heating up to 85° C. and holding for 2 h. After completion of the polymerization reaction, toluene is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere are mixed with 12 g of chloromethyl ether, 100 g of dimethoxymethane and 1 g zinc chloride as a catalyst, stirred at 42° C. and kept for 12 hours, and then washed with water to obtain a chlorinated resin. 15 g of phthalimide is added to the chlorinated resin to carry out amination reaction for 10 h at 80° C., and then 15 g of 10% (w/w) sodium hydroxide is added to perform hydrolysis reaction for 2 h at 160° C. The resulted is washed with water to obtain an amine sphere. 50 g of the amine sphere is mixed with 18 g of chloroacetic acid and then added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 19.4 m²/g and a median pore diameter of 8.6 nm; a wet apparent density of 0.718 g/cm³; a wet true density of 1.15 g/cm³; and a water content of 47.9% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about of about 8 with 0.5 mol/L sulfuric acid solution, then passed through the column at a flow rate of 6 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 32 ppm, and the adsorption is stopped. Wash with 4 BV water. A solution of 8% (w/w) sodium hydroxide +5% (w/w) sodium nitrate is prepared to carry out desorption with 10 BV, and wash with 4 BV water. The desorption rate is 82%.

EXAMPLE 12

An oil phase is prepared using 30 g 55% (w/w) of divinylbenzene, 70 g of acrylonitrile, 70 g of isooctane and 1 g of isopropyl benzene hydroperoxide. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of carboxymethyl cellulose into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 65° C. and holding for 2 h, heating up to 80° C. and holding for 2 h. After completion of the polymerization reaction, isooctane is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere is mixed with 15 g of hexamethyleneimine to carry out amination reaction for 10 h at 80° C. Then 50 g of the resulted amine sphere is mixed with 18 g of chloropropionic acid and added slowly into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g of the weak acid cation resin is mixed with 15 g Lanthanum (III) chloride hexahydrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The obtained resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 17.8 m²/g and a median pore diameter of 8.2 nm; a wet apparent density of 0.727 g/cm³; a wet true density of 1.18 g/cm³; and a water content of 46.5% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 8 with 0.5 mol/L sulfuric acid solution, then passed through the column at a flow rate of 6 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 31 ppm, and the adsorption is stopped. Wash with 4 BV water. A solution of 8% (w/w) sodium hydroxide +5% (w/w) sodium nitrate is prepared to carry out desorption with 10 BV, and wash with 4 BV water. The desorption rate is 79%.

EXAMPLE 13

An oil phase is prepared using 12 g N,N-methylenebisacrylamide, 70 g of acrylonitrile, 70 g of aviation gasoline and 1 g of dicumyl peroxide. An aqueous phase is prepared by adding 500 ml of water into a 1 L reaction tank and 0.5 g of hydroxyethyl cellulose into the water, and stirring to dissolve. A suspension polymerization reaction is carried out by adding the oil phase into the reaction tank, stirring and holding at 50° C. for 2 h, heating up to 75° C. and holding for 2 h, heating up to 90° C. and holding for 2 h. After completion of the polymerization reaction, the aviation gasoline is removed by boiling with water at 95° C. for 1.5 h, and the resulted is washed to obtain a resin-based sphere.

50 g of the resin-based sphere is mixed with 15 g of triethylne tetramine to carry out amination reaction for 10 h at 95° C. 50 g of the resulted amine sphere is mixed with 18 g of dichloroacetic acid and slowly added into 50 g of 20% (w/w) sodium hydroxide solution to perform reaction at 50° C. for 10 h. The resulted is washed with water to neutral, obtaining a weak acid cation resin.

50 g weak acid cation resin is mixed with 15 g lanthanum nitrate and added into 300 ml of 25% (w/w) ethanol solution, and stirred for 2 h at room temperature. Then 200 ml of 1 mol/L sodium hydroxide solution is added dropwise slowly until the system reaches a pH of 13. Stir for 6 h at 60° C. to obtain a resin for removing phosphorus. The prepared resin for removing phosphorus has a particle size of 0.5-0.8 mm; a porous structure with a specific surface area of 16.3 m²/g and a median pore diameter of 7.7 nm; a wet apparent density of 0.734 g/cm³; a wet true density of 1.11 g/cm³; and a water content of 44.7% (w/w).

5 ml of the resin for removing phosphorus is packed in a column. A 400 ppm sodium orthophosphate solution is prepared and adjusted to a pH of about 8 with 0.5 mol/L sulfuric acid solution, then passed through the column at a flow rate of 6 BV/h. When 50 ml has been passed through the column for adsorption, the resulted barren solution has a phosphorus content of 38 ppm, and the adsorption is stopped. Wash with 4 BV water. A solution of 8% (w/w) sodium hydroxide +5% (w/w) sodium nitrate is prepared to carry out desorption with 10 BV, and wash with 4 BV water. The desorption rate is 81%.