阅读说明：本技术 一种去除低浓度氨氮的改性树脂 (Modified resin for removing low-concentration ammonia nitrogen ) 是由 王姝 成小英 江桥 陈涛 于 2021-09-09 设计创作，主要内容包括：本发明公开了一种去除低浓度氨氮的改性树脂,所述改性树脂的制备方法包括如下步骤：(1)树脂原料预处理后水洗至中性,超声改性后烘干；(2)将步骤(1)烘干的树脂置于硫酸铜溶液中改性后,烘干得到硫酸铜改性的树脂；(3)将步骤(2)硫酸铜改性的树脂置于NaOH溶液中振荡、水洗至中性后烘干,得到去除低浓度氨氮的改性树脂。本发明所制备的改性树脂可以很好的去除低浓度氨氮废水中的氨氮。(The invention discloses a modified resin for removing low-concentration ammonia nitrogen, and a preparation method of the modified resin comprises the following steps: (1) pretreating a resin raw material, washing the pretreated resin raw material with water to be neutral, performing ultrasonic modification, and drying the resin raw material; (2) placing the resin dried in the step (1) in a copper sulfate solution for modification, and drying to obtain copper sulfate modified resin; (3) and (3) placing the copper sulfate modified resin obtained in the step (2) in NaOH solution, oscillating, washing with water to neutrality, and drying to obtain the modified resin for removing low-concentration ammonia nitrogen. The modified resin prepared by the invention can well remove ammonia nitrogen in low-concentration ammonia nitrogen wastewater.)

1. The modified resin for removing low-concentration ammonia nitrogen is characterized in that the preparation method of the modified resin comprises the following steps:

(1) pretreating a resin raw material, washing the pretreated resin raw material with water to be neutral, performing ultrasonic modification, and drying the resin raw material;

(2) modifying the resin dried in the step (1) in a copper sulfate solution, and drying to obtain ultrasonic-copper sulfate modified resin;

(3) and (3) placing the resin modified by the ultrasonic-copper sulfate in the step (2) in NaOH solution, oscillating, washing with water to be neutral, and drying to obtain the modified resin for removing the low-concentration ammonia nitrogen.

2. The modified resin according to claim 1, wherein in the step (1), the resin is a strongly acidic cation resin.

3. The modified resin as claimed in claim 1, wherein in the step (1), the resin is T-42 resin and has a particle size of 0.53 to 0.63 mm.

4. The modified resin as claimed in claim 1, wherein in the step (1), the pretreatment is carried out by the following specific method: and (3) after the resin is cleaned, adding HCl solution, stirring, washing to be neutral, adding NaOH solution, stirring, washing to be neutral, and drying to be constant weight.

5. The modified resin of claim 4, wherein the volume ratio of the resin to the HCl solution is 1:8, the molar concentration of the HCl solution is 1 mol/L; the stirring speed is 150-300 r/min, and the time is 20-30 min; the volume ratio of the resin to the NaOH solution is 1:8, and the molar concentration of the NaOH solution is 1 mol/L; the drying temperature is 50-60 ℃.

6. The modified resin as claimed in claim 1, wherein in the step (1), the power of the ultrasound is 50-120W, the temperature is 30-50 ℃, and the time is 15-240 min; the drying temperature is 50-60 ℃, and the drying time is 3-24 h.

7. The modified resin as claimed in claim 1, wherein in the step (2), the molar concentration of the copper sulfate solution is 0.01-0.03 mol/L; the volume ratio of the dried resin to the copper sulfate solution is 1: 20-1: 200; the modification is carried out for 12 to 48 hours by oscillating at 200 to 400 r/min; the drying temperature range is 50-60 ℃, and the drying time is 3-24 h.

8. The modified resin of claim 1, wherein in the step (3), the volume ratio of the resin modified by ultrasonic-copper sulfate to the NaOH solution is 1: 20-1: 200; the molar concentration of NaOH in the NaOH solution is 1 mol/L.

9. The modified resin as claimed in claim 1, wherein in the step (3), the oscillating speed is 200 to 400r/min and the oscillating time is 12 to 48 hours; the drying temperature is 50-60 ℃, and the drying time is 3-24 h.

10. The application of the modified resin as claimed in any one of claims 1 to 9, wherein the modified resin is used for 5 to 50mg/L ammonia nitrogen wastewater.

Technical Field

The invention relates to the technical field of resin modification, in particular to modified resin for removing low-concentration ammonia nitrogen.

Background

In recent years, as the industrialization process of China is accelerated, the discharge amount of sewage is increased, and the concentration of ammonia nitrogen in certain riverways of China exceeds the standard, the ammonia nitrogen mainly comes from industrial waste water, municipal sewage and agricultural wastes, or is decomposed from organic nitrogen compounds in the waste water and the wastes. At present, the treatment method for ammonia nitrogen wastewater comprises an air stripping method, a breakpoint chlorination method, a chemical precipitation method, an ion exchange method and various biological methods including a nitrification and denitrification method. The ion exchange method has stable and easily controlled reaction process, better application prospect, capability of removing various ions and lower operation cost, thereby being a method for treating the ammonia nitrogen wastewater with better development prospect at the present stage. At present, zeolite is mostly used for removing ammonia nitrogen in water, ion exchange resin is also applied, and the ion exchange resin has the characteristics of low price, recoverability and the like, but the ion exchange resin has various models nationwide, and reports are few compared with zeolite, so further research is needed.

At present, although many scholars research on removal of ammonia nitrogen in wastewater, most scholars aim at removal of high-concentration ammonia nitrogen wastewater, and few studies on removal of low-concentration ammonia nitrogen in a river channel are performed. It is critical to develop a new resin that is economically feasible and has good removal capability.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a modified resin for removing low-concentration ammonia nitrogen. The modified resin is prepared by combining ultrasonic modification, copper sulfate modification and alkali modification, and the prepared modified resin can well remove ammonia nitrogen in low-concentration ammonia nitrogen wastewater.

The technical scheme of the invention is as follows:

a modified resin for removing low-concentration ammonia nitrogen is prepared by the following steps:

(1) pretreating a resin raw material, washing the pretreated resin raw material with water to be neutral, performing ultrasonic modification, and drying the resin raw material;

(2) modifying the resin dried in the step (1) in a copper sulfate solution, and drying to obtain ultrasonic-copper sulfate modified resin;

(3) and (3) placing the resin modified by the ultrasonic-copper sulfate in the step (2) in NaOH solution, oscillating, washing with water to be neutral, and drying to obtain the modified resin for removing the low-concentration ammonia nitrogen.

Further, in the step (1), the resin is a strongly acidic cation resin.

Further, in the step (1), the resin is T-42 resin, and the particle size is 0.53-0.63 mm.

Further, in the step (1), the specific method of the pretreatment is as follows: and (3) after the resin is cleaned, adding HCl solution, stirring, washing to be neutral, adding NaOH solution, stirring, washing to be neutral, and drying to be constant weight.

Further, the volume ratio of the resin to the HCl solution is 1:8, the molar concentration of the HCl solution is 1 mol/L; the stirring speed is 200-400 r/min, and the time is 20-30 min; the volume ratio of the resin to the NaOH solution is 1:8, and the molar concentration of the NaOH solution is 1 mol/L; the drying temperature is 50-60 ℃.

Further, in the step (1), the power of the ultrasound is 50-120W, the temperature is 30-50 ℃, and the time is 15-240 min; the drying temperature is 50-60 ℃, and the drying time is 3-24 h.

Further, in the step (2), the molar concentration of the copper sulfate solution is 0.01-0.03 mol/L; the volume ratio of the dried resin to the copper sulfate solution is 1: 20-1: 200; the modification is carried out for 12 to 48 hours by oscillating at 200 to 400 r/min; the drying temperature is 50-60 ℃, and the drying time is 3-24 h.

Further, in the step (3), the volume ratio of the ultrasonic-copper sulfate modified resin to the NaOH solution is 1: 20-1: 200; the molar concentration of NaOH in the NaOH solution is 1 mol/L.

Further, in the step (3), the oscillating speed is 200-400 r/min, and the time is 12-48 h; the drying temperature is 50-60 ℃, and the drying time is 3-24 h.

The application of the modified resin is used for removing ammonia nitrogen in 5-50 mg/L ammonia nitrogen wastewater.

The beneficial technical effects of the invention are as follows:

(1) compared with unmodified resin, the modified resin prepared by the invention has the advantages that the effect of removing low-concentration ammonia nitrogen concentration is obviously improved, the removal rate is improved by 22.6% under the condition that the ammonia nitrogen concentration is 50mg/L, and the removal of ammonia nitrogen in wastewater with the ammonia nitrogen concentration of 5mg/L can be realized at the lowest.

(2) The resin is modified by ultrasound, so that impurities on the surface and in the resin are reduced, more binding sites are exposed, and resin pore channels are enlarged; and the ultrasonic modification is Cu of the next step²⁺More adsorption on the resin provides conditions; then modifying the resin with copper sulfate, using Cu²⁺Replacing H on the original resin⁺，Cu²⁺Can react with NH₃·H₂The O generates a complex reaction to further improve the removal efficiency of ammonia nitrogen, but the Cu²⁺Easy to fall off, so that NaOH is used to modify the resin into causticized resin, and the causticized copper-based resin can avoid OH in the solution^-The stability is enhanced.

(3) The modified resin prepared by the invention overcomes the defect that NH is generated when the traditional ultrasonic modified resin is actually used through the synergistic effect of the three resins₄ ⁺Will be exposed to OH^-The modified resin prepared by the invention adopts a physicochemical combination method, combines ultrasonic physical modification with chemical modification of copper sulfate and sodium hydroxide, and improves the removal effect of the ion exchange resin on ammonia nitrogen in the actual water body through synergistic effect.

Drawings

FIG. 1 is a diagram showing the effect of different addition amounts of three modified resins prepared in example 1 and comparative examples 2 and 3 of the present invention on ammonia nitrogen removal.

Detailed Description

The present invention will be described in detail with reference to the accompanying drawings and examples.

Example 1:

a modified resin for removing low-concentration ammonia nitrogen is prepared by the following steps:

after washing a T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Cisco technologies, Ltd.) with deionized water, the resin was mixed in a volume ratio of 1:8 (because the particle size of the resin is smaller, the generated gap is negligible), adding the solution into 1mol/L HCl solution, stirring the solution for 20min at the speed of 200r/min, washing the solution to be neutral by deionized water, adding 1mol/LNaOH solution, wherein the volume ratio of the NaOH solution to the resin is 8:1 (because the particle size of the resin is smaller, the generated gap is negligible), continuing stirring the solution for 20min at the speed of 200r/min, washing the solution to be neutral by deionized water, drying the solution to constant weight at 50 ℃, and finishing the pretreatment of the resin raw material.

And putting 50g of the pretreated T-42 cation exchange resin into pure water, carrying out ultrasonic modification for 15min at the ultrasonic power of 120W and the temperature of 30 ℃, and drying for 3h in a constant-temperature drying oven at the temperature of 50 ℃ after finishing the ultrasonic modification to obtain the ultrasonic modified resin. .

And then the volume ratio of the resin to the copper sulfate is 1:20 (because the particle size of the resin is smaller, the generated gap is negligible), adding the resin modified by ultrasonic into a copper sulfate solution of 0.01mol/L, oscillating and modifying for 12h at 200r/min, washing the resin to be neutral by pure water after finishing, and finally drying the resin for 3h at 50 ℃ in a constant-temperature drying oven to obtain the resin modified by ultrasonic-copper sulfate.

And (3) modifying the resin modified in the two ways in a volume ratio of 1:20, placing the resin in 1mol/L NaOH solution, oscillating for 12h at 200r/min, finally washing the resin to be neutral by pure water, placing the resin in a constant-temperature drying box, and drying for 3h at 50 ℃ to obtain the modified resin with low-concentration ammonia nitrogen removed.

Example 2:

a modified resin for removing low-concentration ammonia nitrogen is prepared by the following steps:

after washing a T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Cisco technologies, Ltd.) with deionized water, the resin was mixed in a volume ratio of 1: and 8, adding the solution into 1mol/L HCl solution, stirring the solution at the speed of 300r/min for 25min, washing the solution with deionized water until the solution is neutral, adding 1mol/L NaOH solution, keeping the volume ratio of NaOH solution to resin at 8:1, stirring the solution at the speed of 300r/min for 25min, washing the solution with deionized water until the solution is neutral, and drying the solution at 55 ℃ until the weight is constant, thereby finishing the pretreatment of the resin raw material.

And putting 50g of the pretreated T-42 cation exchange resin into pure water, carrying out ultrasonic modification for 15min at the ultrasonic power of 120W and the temperature of 30 ℃, and drying for 13.5h in a constant-temperature drying oven at the temperature of 55 ℃ to obtain the ultrasonic modified resin.

And then the volume ratio of the resin to the copper sulfate is 1: and 20, adding the ultrasonic modified resin into 0.02mol/L copper sulfate solution, carrying out oscillation modification at 300r/min for 24h, washing the resin to be neutral by using pure water after finishing oscillation modification, and finally drying the resin for 13.5h at the temperature of 55 ℃ in a constant-temperature drying oven to obtain the ultrasonic-copper sulfate modified resin.

And (3) modifying the resin modified in the two ways in a volume ratio of 1:20, placing the resin in 1mol/L NaOH solution, oscillating for 24h at 300r/min, finally washing the resin to be neutral by pure water, placing the resin in a constant-temperature drying box, and drying for 13.5h at 55 ℃ to obtain the modified resin for removing low-concentration ammonia nitrogen.

Example 3:

a modified resin for removing low-concentration ammonia nitrogen is prepared by the following steps:

after washing a T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Cisco technologies, Ltd.) with deionized water, the resin was mixed in a volume ratio of 1: and 8, adding the solution into 1mol/L HCl solution, stirring the solution at the speed of 400r/min for 30min, washing the solution with deionized water to be neutral, adding 1mol/L NaOH solution, keeping the volume ratio of NaOH solution to resin at 8:1, stirring the solution at the speed of 400r/min for 30min, washing the solution with deionized water to be neutral, drying the solution at the temperature of 60 ℃ to constant weight, and finishing the pretreatment of the resin raw material.

50g of the pretreated T-42 cation exchange resin is put into pure water, and is subjected to ultrasonic modification for 15min at the ultrasonic power of 120W and the temperature of 30 ℃, and then is dried for 3h at the temperature of 60 ℃ in a constant-temperature drying oven after the ultrasonic modification is finished, so that the ultrasonic modified resin is obtained.

And then the volume ratio of the resin to the copper sulfate is 1:20, adding the ultrasonic modified resin into 0.03mol/L copper sulfate solution, oscillating and modifying for 48h at 400r/min, washing with pure water to be neutral after finishing, and finally drying for 3h at 60 ℃ in a constant-temperature drying oven to obtain the ultrasonic-copper sulfate modified resin.

And (3) modifying the resin modified in the two ways in a volume ratio of 1:20, placing the resin in 1mol/L NaOH solution, oscillating for 48h at 400r/min, finally washing the resin to be neutral by pure water, placing the resin in a constant-temperature drying box, and drying for 24h at 60 ℃ to obtain the modified resin with low-concentration ammonia nitrogen removed.

Example 4:

a modified resin for removing low-concentration ammonia nitrogen is prepared by the following steps:

after washing a T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Cisco technologies, Ltd.) with deionized water, the resin was mixed in a volume ratio of 1: and 8, adding the solution into 1mol/L HCl solution, stirring the solution at the speed of 400r/min for 30min, washing the solution with deionized water to be neutral, adding 1mol/L NaOH solution, keeping the volume ratio of NaOH solution to resin at 8:1, stirring the solution at the speed of 400r/min for 30min, washing the solution with deionized water to be neutral, drying the solution at the temperature of 60 ℃ to constant weight, and finishing the pretreatment of the resin raw material.

And putting 50g of the pretreated T-42 cation exchange resin into pure water, carrying out ultrasonic modification for 30min at the ultrasonic power of 50W and the temperature of 50 ℃, and then drying for 24h at the temperature of 60 ℃ in a constant-temperature drying oven after the ultrasonic modification is finished to obtain the ultrasonic modified resin.

And then the volume ratio of the resin to the copper sulfate is 1: 50, adding the ultrasonic modified resin into 0.03mol/L copper sulfate solution, oscillating and modifying for 48h at 400r/min, washing with pure water to be neutral after finishing, and finally drying for 3h at 60 ℃ in a constant-temperature drying oven to obtain the ultrasonic-copper sulfate modified resin.

And (3) modifying the resin modified in the two ways in a volume ratio of 1: and (3) placing the resin 50 in a 1mol/L NaOH solution, oscillating for 48h at 400r/min, finally washing the resin to be neutral by using pure water, placing the resin in a constant-temperature drying box, and drying for 24h at the temperature of 60 ℃ to obtain the modified resin with low-concentration ammonia nitrogen removed.

Example 5:

a modified resin for removing low-concentration ammonia nitrogen is prepared by the following steps:

after washing a T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Cisco technologies, Ltd.) with deionized water, the resin was mixed in a volume ratio of 1: and 8, adding 1mol/L HCl solution, stirring at the speed of 400r/min for 30min, washing with deionized water to be neutral, adding 1mol/L NaOH solution, wherein the volume ratio of NaOH solution to resin is 8:1, continuously stirring at the speed of 400r/min for 30min, washing with deionized water to be neutral, and drying at the temperature of 60 ℃ to be constant in weight to finish the pretreatment of the resin raw material.

50g of the pretreated T-42 cation exchange resin is put into pure water, ultrasonic modification is carried out for 240min at the ultrasonic power of 100W and the temperature of 40 ℃, and after the ultrasonic modification is finished, drying is carried out in a constant-temperature drying oven for 3h at the temperature of 60 ℃ to obtain the ultrasonic modified resin.

And then the volume ratio of the resin to the copper sulfate is 1:200, adding the ultrasonic modified resin into 0.03mol/L copper sulfate solution, oscillating and modifying for 48h at 400r/min, washing with pure water to be neutral after finishing, and finally drying for 24h at 60 ℃ in a constant-temperature drying oven to obtain the ultrasonic-copper sulfate modified resin.

And (3) modifying the resin modified in the two ways in a volume ratio of 1:200 is placed in 1mol/L NaOH solution, oscillated at 400r/min for 48h, finally washed to be neutral by pure water, and placed in a constant temperature drying box to be dried for 24h at 60 ℃ to obtain the modified resin with low-concentration ammonia nitrogen removed.

Comparative example 1:

after washing a T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Cisco technologies, Ltd.) with deionized water, the resin was mixed in a volume ratio of 1: and 8, adding 1mol/L HCl solution, stirring at the speed of 200r/min for 20min, washing with deionized water to be neutral, adding 1mol/L NaOH solution, wherein the volume ratio of NaOH solution to resin is 8:1, continuously stirring at the speed of 200r/min for 20min, washing with deionized water to be neutral, and drying at the temperature of 50 ℃ to be constant in weight to finish the pretreatment of the resin raw material.

50g of pretreated T-42 cation exchange resin is put into pure water, and the volume ratio of the resin to the copper sulfate solution is 1:20, putting the resin into 0.01mol/L copper sulfate solution, modifying for 12h under the oscillation of 200r/min, washing the resin to be neutral by pure water after finishing the modification, and finally drying the resin for 3h at 50 ℃ in a constant-temperature drying oven to obtain the resin modified by the copper sulfate alone.

Comparative example 2:

after washing a T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Cisco technologies, Ltd.) with deionized water, the resin was mixed in a volume ratio of 1: and 8, adding the solution into 1mol/L HCl solution, stirring the solution at the speed of 200r/min for 20min, washing the solution with deionized water until the solution is neutral, adding 1mol/L NaOH solution, keeping the volume ratio of NaOH solution to resin at 8:1, stirring the solution at the speed of 200r/min for 20min, washing the solution with deionized water until the solution is neutral, and drying the solution at the temperature of 50 ℃ until the weight is constant, thereby finishing the pretreatment of the resin raw material.

50g of the pretreated T-42 cation exchange resin is put into pure water, ultrasonic treatment is carried out for 15min at the ultrasonic power of 120W and the temperature of 30 ℃, and after the ultrasonic treatment is finished, the resin is dried in a constant-temperature drying oven for 3h at the temperature of 50 ℃ to obtain the resin which is independently modified by ultrasonic treatment.

Comparative example 3:

after washing a T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Cisco technologies, Ltd.) with deionized water, the resin was mixed in a volume ratio of 1: and 8, adding the solution into 1mol/L HCl solution, stirring the solution at the speed of 200r/min for 20min, washing the solution with deionized water until the solution is neutral, adding 1mol/L NaOH solution, keeping the volume ratio of NaOH solution to resin at 8:1, stirring the solution at the speed of 200r/min for 20min, washing the solution with deionized water until the solution is neutral, and drying the solution at the temperature of 50 ℃ until the weight is constant, thereby finishing the pretreatment of the resin raw material.

And putting 50g of the pretreated T-42 cation exchange resin into pure water, carrying out ultrasonic modification for 15min at the ultrasonic power of 120W and the temperature of 30 ℃, and drying for 3h in a constant-temperature drying oven at the temperature of 50 ℃ after finishing the ultrasonic modification to obtain the ultrasonic modified resin.

And then the volume ratio of the resin to the copper sulfate is 1: and 20, adding the ultrasonic modified resin into 0.01mol/L copper sulfate solution, carrying out oscillation modification at 200r/min for 24h, washing the resin to be neutral by using pure water after finishing oscillation modification, and finally drying the resin for 3h at 50 ℃ in a constant-temperature drying oven to obtain the ultrasonic-copper sulfate modified resin.

Comparative example 4:

the T-42 cation exchange resin was directly pretreated according to the method of example 1, that is, the T-42 cation exchange resin (the resin having a particle size of 0.58. + -. 0.05mm as supplied from Kohai Cisco) was washed with deionized water and then mixed in a volume ratio of 1: and 8, adding the solution into 1mol/L HCl solution, stirring the solution at the speed of 200r/min for 20min, washing the solution with deionized water until the solution is neutral, adding 1mol/L NaOH solution, keeping the volume ratio of NaOH solution to resin at 8:1, stirring the solution at the speed of 200r/min for 20min, washing the solution with deionized water until the solution is neutral, and drying the solution at the temperature of 50 ℃ until the weight is constant, thereby finishing the pretreatment of the resin raw material. Adsorbing with the pretreated resin.

Test example:

the adsorption amount was measured by the following method using the resins prepared in example 1 and comparative examples 1 to 4.

Respectively taking 1g of the resins prepared in the embodiment 1 and the comparative examples 1-4, putting the resins into a conical flask, adding 250mL of simulated wastewater with the ammonia nitrogen concentration of 50mg/L into the conical flask, adjusting the pH to 7, oscillating the wastewater for 3h in a constant-temperature oscillation box with the rotation speed of 200r/min, sampling and measuring the ammonia nitrogen concentration for 3h, sequentially removing the ammonia nitrogen by the resins, and measuring and calculating the adsorption capacity of the resins. The ammonia nitrogen concentration is obtained by measuring with a Nashi reagent spectrophotometry (HJ 535-2009). Ammonia nitrogen adsorption capacity (Q)_t) The calculation formula is as follows:

Q_t＝(C₀-C)·V/m

wherein: c₀: initial ammonia nitrogen concentration, mg/L; c: the ammonia nitrogen concentration in the water after the reaction is mg/L;

v: the volume of the ammonia nitrogen solution, L; m: resin mass, g.

The adsorption amounts of the examples and comparative examples are shown in table 1.

TABLE 1

Categories	Example 1	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
						Ammonia nitrogen adsorption capacity (mg/g)	8.15	7.54	7.23	7.81	6.0

As can be seen from Table 1, the adsorption capacity of the original resin is improved to a certain extent by different modification modes, and the adsorption capacities of the resin modified by copper sulfate, ultrasonic modification, ultrasonic-copper sulfate modification and ultrasonic-copper sulfate-NaOH are respectively improved by 25.67%, 20.50%, 30.17% and 35.83% compared with the original resin, so that the modification mode of the embodiment 1 is better than that of the comparative examples 1-3, and the adsorption capacity of the modified resin is greatly improved by synergistic effect.

FIG. 1 is a graph showing the influence of the addition amount of three modified resins prepared in example 1 and comparative examples 2 and 3 on the removal efficiency of ammonia nitrogen wastewater, and it can be seen from FIG. 1 that the ammonia nitrogen removal rate of all three modified resins prepared in example 1 and comparative examples 2 and 3 increases with the addition amount, wherein the ultrasonic-copper sulfate-NaOH modified resin prepared in example 1 has the best effect and the ammonia nitrogen removal rate can reach 98.4% at most compared with comparative examples 2 and 3, because the roughness of the resin surface is changed and the impurities on the resin surface and in the resin are reduced by the ultrasonic modified resin; cu used in copper sulfate modified resin²⁺Instead of H on the original resin⁺，Cu²⁺Then with NH₄ ⁺The complex reaction is generated, and the removal rate is improved; however, this treatment is not stable, Cu²⁺Easy to fall off, and then NaOH is used to modify the resin into causticized resin, and the causticized copper-based resinThe influence of OH-in the solution can be avoided, and the stability is enhanced, so that the modified resin combining the three modification modes has the best removal rate of ammonia nitrogen.

The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the above embodiments. It is to be understood that other modifications and variations directly derivable or suggested by those skilled in the art without departing from the spirit and concept of the present invention are to be considered as included within the scope of the present invention.