Method for treating ammonia-nitrogen wastewater

Abstract

The present application relates to wastewater treatment technical field, specifically to a kind of ammonia nitrogen wastewater treatment method, the composite modified zeolite material in the present application has excellent physical adsorption capacity to ammonia nitrogen by virtue of its unique pore structure and surface properties, ammonia nitrogen molecules in wastewater can be quickly captured, then through the synergistic effect of composite photocatalyst under light and ultrasonic, strong oxidizing free radicals are generated, ammonia nitrogen molecules not completely adsorbed by zeolite material are deeply degraded, through the synergistic effect of adsorption and photocatalysis, the removal efficiency of ammonia nitrogen is significantly improved;After adsorption and photocatalytic treatment, the ammonia nitrogen concentration in wastewater has been greatly reduced, and resin adsorption treatment is used as a subsequent step, which can selectively adsorb residual trace amounts of ammonia nitrogen and other impurities, thereby realizing deep purification of wastewater and ensuring that the effluent quality meets or exceeds relevant discharge standards.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of wastewater treatment, in particular to an ammonia-nitrogen wastewater treatment method. BACKGROUND

[0002] With the acceleration of global industrialization and the continuous growth of population, various industrial production activities and human life continuously produce a large amount of ammonia-nitrogen-containing wastewater, and ammonia-nitrogen wastewater pollution has become one of the key environmental challenges restricting the sustainable development of ecological environment and threatening human health and safety. In the chemical production process, many chemical reactions use ammonia-containing raw materials or intermediates, and the wastewater after reaction often contains high concentration of ammonia-nitrogen; in the pharmaceutical industry, due to the use of nitrogen-containing organic compounds in drug synthesis and extraction, the ammonia-nitrogen content of the generated wastewater is also high; in the food processing industry, such as meat processing and bean product processing, a large amount of ammonia-nitrogen produced by protein decomposition is brought in during raw material cleaning and wastewater discharge; and in the leather tanning industry, the use of ammonia-containing tanning agents also makes the ammonia-nitrogen concentration in wastewater high.

[0003] At present, the commonly used ammonia-nitrogen wastewater treatment methods include physical method, chemical method and biological method, etc., however, these methods have problems of low treatment efficiency, high cost, easy secondary pollution, etc., therefore, it has become a technical problem to be solved in the field to study a combined treatment method combining multiple treatment technologies to improve the treatment efficiency and purification effect of ammonia-nitrogen wastewater. SUMMARY

[0004] Technical problems to be solved

[0005] In view of the above-mentioned shortcomings of the prior art, the present application provides an ammonia-nitrogen wastewater treatment method, which can effectively solve the technical defects of low treatment efficiency, high cost and easy secondary pollution of the ammonia-nitrogen wastewater treatment method in the prior art.

[0006] Technical scheme

[0007] In order to achieve the above-mentioned purposes, the present application is realized by the following technical scheme:

[0008] An ammonia-nitrogen wastewater treatment method, the treatment method is:

[0009] S1, after the composite modified zeolite material is put into the ammonia-nitrogen wastewater, oscillation treatment is carried out, and after standing for 1-2h, the supernatant is filtered, and the obtained is recorded as an adsorption treatment component;

[0010] S2, after adjusting the pH value of the adsorption treatment component to 10-11, the composite photocatalyst is put in, and the photocatalytic treatment is carried out under the condition of ultrasonic vibration, and the obtained is recorded as a degradation component;

[0011] S3, adjust the pH value of the degradation component to 7 with a hydrochloric acid solution with a concentration of 1 mol / L, and then complete the ammonia-nitrogen wastewater treatment after resin adsorption treatment.

[0012] Further, the input amount in S1 is 2-12 g / L, and the method of oscillation treatment in S1 is oscillation at a power of 100 W for 10 min.

[0013] Further, the preparation steps of the composite modified zeolite material in S1 are:

[0014] Step A, after the natural zeolite is crushed and passed through a 200-mesh sieve, it is then put into a sodium chloride solution with a concentration of 1 mol / L according to a solid-liquid ratio of 1:10, stirred at a speed of 300 r / min at a temperature of 25°C for 12 h, and then centrifuged at a speed of 7000 r / min for 10 min after standing for 12 h. The obtained centrifugal precipitate is washed with deionized water until neutral, and then the obtained product is denoted as the salt-treated component;

[0015] Step B, the salt-treated component is dried to constant weight in a drying oven at 105°C, and then calcined in a muffle furnace at 450°C for 1 h. The obtained product after being taken out and cooled to room temperature is the composite modified zeolite material.

[0016] Further, the method of filtration treatment in S1 is cyclic filtration for 2-3 h with a polyether sulfone hollow fiber ultrafiltration membrane.

[0017] Further, the pH value of the adsorption-treated component is adjusted with a sodium hydroxide solution with a concentration of 1 mol / L in S2, and the input amount of the composite photocatalyst in S2 is 0.5-1 g / L.

[0018] Further, the preparation steps of the composite photocatalyst in S2 are:

[0019] Step 1, 10 g of melamine is heated to 600°C in a muffle furnace, kept at this temperature for 2 h, and then cooled to room temperature. After grinding, it is again placed in a muffle furnace and annealed at a temperature of 550°C for 3 h. After cooling to room temperature, the obtained product is denoted as the pretreated component;

[0020] Step 2, the pretreated component is immersed in a saturated boric acid solution, and after stirring treatment, it is freeze-dried. Then it is heated to 550°C in a tube furnace under a nitrogen atmosphere for 2 h. After cooling to room temperature, it is washed with distilled water for 3-5 times, and then dried to obtain the nanometer net component;

[0021] Step 3, 5-6 g of zinc sulfate heptahydrate is dispersed in 600 mL of a sodium hydroxide solution, and after stirring and dispersing, 3-4 g of the nanometer net component is added. After adding 90 mL of ammonia water, continue to stir for 30 min. Then, in a high-pressure reaction kettle at 90°C, react for 6 h. The obtained product is denoted as the reaction component.

[0022] Step 4, centrifugal separation of the reaction components at a speed of 6000 r / min for 10 min, rinsing the centrifugal precipitate with deionized water and anhydrous ethanol for three times in sequence, and then drying treatment, and the obtained is the composite photocatalyst.

[0023] Further, the heating rate in step 1 is 2℃ / min, the annealing rate in step 1 is 2℃ / min, the stirring method in step 2 is stirring at a speed of 500 r / min for 30 min, the heating rate in step 2 is 2.3℃ / min, and the drying method in step 2 is drying at a temperature of 80℃ until constant weight.

[0024] Further, the concentration of sodium hydroxide solution in step 3 is 0.5 mol / L, the stirring method in step 3 is stirring at a speed of 500 r / min for 30 min, and the drying method in step 4 is drying at a temperature of 80-85℃ until constant weight.

[0025] Further, the ultrasonic power in the ultrasonic vibration condition in S2 is 50W, the ultrasonic frequency is 40kHz, the light source for photocatalytic treatment in S2 is a 300W xenon lamp, the fixed position of the light source is 15cm above the liquid level, and the catalytic treatment time is 2-3h.

[0026] Further, the resin adsorption treatment method in S3 is:

[0027] The adsorption resin is added to the degradation component with a pH value of 7 at an input amount of 20-40g / L, stirred at a speed of 150 r / min for 2-3h at a temperature of 25℃, and then adsorbed after standing for 3-5h, and the resin adsorption treatment is completed after removing the adsorption resin.

[0028] Beneficial effects

[0029] The application provides a method for treating ammonia-nitrogen wastewater, and has the following beneficial effects compared with the prior art:

[0030] 1. The composite modified zeolite material in the application has excellent physical adsorption capacity for ammonia-nitrogen due to its unique pore structure and surface properties, can quickly capture ammonia-nitrogen molecules in wastewater, and then, under the synergistic action of light and ultrasonic waves, the composite photocatalyst generates strong oxidizing free radicals to deeply degrade ammonia-nitrogen molecules that are not completely adsorbed by the zeolite material, thereby significantly improving the removal efficiency of ammonia-nitrogen; after adsorption and photocatalytic treatment, the ammonia-nitrogen concentration in the wastewater is greatly reduced, and then resin adsorption treatment is used as a subsequent step to selectively adsorb residual trace amounts of ammonia-nitrogen and other impurities, thereby realizing deep purification of the wastewater and ensuring that the effluent water quality meets or is better than the relevant discharge standards.

[0031] 2、The composite modified zeolite material and the composite photocatalyst used in the application are both non-toxic and harmless environment-friendly materials, and no toxic and harmful substances are generated in the preparation and use process, which is friendly to the environment, in line with the concept of sustainable development, and the waste generated in the treatment process, such as saturated zeolite material and resin, can be treated by simple regeneration or safe disposal method, which can avoid the generation of secondary pollution. Secondly, the preparation raw materials of the composite modified zeolite material and the composite photocatalyst are widely available, and the cost is low. After multiple uses, it still maintains good performance and can be reused through regeneration treatment, thereby further reducing the treatment cost. DETAILED DESCRIPTION

[0032] To make the purpose, technical scheme and advantages of the embodiments of the application clearer, the technical scheme in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0033] The application will be further described below in combination with the embodiments.

[0034] Some components in the embodiments and the comparative examples are as follows:

[0035] Natural zeolite, produced in Wenshan, Yunnan;

[0036] Sodium chloride, Zhengzhou Chunqiu Chemical Co., Ltd.;

[0037] Polyether sulfone hollow fiber ultrafiltration membrane, average relative molecular mass 60000, pore size 0.1-0.3 μm, relative molecular mass cut-off 3000-20000, Hangzhou Ausko Filtration Technology Co., Ltd.;

[0038] Melamine, National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0039] Boric acid, National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0040] Zinc sulfate heptahydrate, National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0041] Sodium hydroxide, National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0042] Anhydrous ethanol, National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0043] Hydrochloric acid, National Pharmaceutical Group Chemical Reagent Co., Ltd.;

[0044] Adsorption resin, strong polarity AH-0 resin.

[0045] Embodiment 1

[0046] The ammonia-nitrogen wastewater treatment method of the embodiment is as follows:

[0047] S1, a composite modified zeolite material is added to the ammonia-nitrogen wastewater at an input amount of 2 g / L, and oscillated at a power of 100 W for 10 min, and after standing for 1 h, the supernatant is filtered for 2 h by a polyether sulfone hollow fiber ultrafiltration membrane, and the obtained is recorded as an adsorption treatment component;

[0048] The preparation steps of the composite modified zeolite material are as follows:

[0049] Step A, the natural zeolite is crushed and passed through a 200-mesh sieve, then a sodium chloride solution with a concentration of 1 mol / L is added at a solid-liquid ratio of 1:10, stirred at a speed of 300 r / min at a temperature of 25°C for 12 h, and after standing for 12 h, centrifuged at a speed of 7000 r / min for 10 min, and the centrifuged precipitate is washed with deionized water until neutral, and the obtained is recorded as a salt treatment component;

[0050] Step B, the salt treatment component is dried to constant weight in a drying oven at 105°C, then calcined in a muffle furnace at 450°C for 1 h, and after cooling to room temperature, the obtained is the composite modified zeolite material.

[0051] S2, the pH value of the adsorption treatment component is adjusted to 10 with a sodium hydroxide solution with a concentration of 1 mol / L, and a composite photocatalyst is added at an input amount of 0.5 g / L, and photocatalytic treatment is carried out under ultrasonic vibration, and the obtained is recorded as a degradation component;

[0052] The preparation steps of the composite photocatalyst are as follows:

[0053] Step 1, 10 g of melamine is heated in a muffle furnace at a heating rate of 2°C / min to 600°C, and after holding for 2 h, it is cooled to room temperature, ground, and then placed in a muffle furnace and annealed at a temperature of 550°C at an annealing rate of 2°C / min for 3 h, and after cooling to room temperature, the obtained is recorded as a pretreatment component;

[0054] Step 2, the pretreatment component is soaked in a saturated boric acid solution, stirred at a speed of 500 r / min for 30 min, and then freeze-dried, then placed in a tube furnace under a nitrogen atmosphere and heated to 550°C at a heating rate of 2.3°C / min for 2 h, cooled to room temperature, washed with distilled water for 3 times, and dried to constant weight at a temperature of 80°C, and recorded as a nanomesh component;

[0055] Step 3, 5g of zinc sulfate heptahydrate is dispersed in 600mL of 0.5mol / L sodium hydroxide solution, stirred at 500r / min for 30min, then 3g of nanometer network component is added, 90mL of ammonia water is added, and stirred for another 30min, then reacted in a high-pressure reactor at 90℃ for 6h, and the obtained product is denoted as reaction component;

[0056] Step 4, centrifuge the reaction component at 6000r / min for 10min, rinse the centrifugal precipitate with deionized water and anhydrous ethanol for 3 times respectively, and then dry at 80℃ until the weight is constant. The obtained product is the composite photocatalyst.

[0057] In S2, the ultrasonic power of the ultrasonic vibration condition is 50W, the ultrasonic frequency is 40kHz, the light source for photocatalytic treatment is a 300W xenon lamp, the fixed position of the light source is 15cm above the liquid level, and the catalytic treatment time is 2h.

[0058] S3, adjust the pH value of the degradation component to 7 with 1mol / L hydrochloric acid solution, and then perform resin adsorption treatment to complete the ammonia-nitrogen wastewater treatment.

[0059] The method of resin adsorption treatment is as follows:

[0060] The adsorption resin is added to the degradation component with a pH value of 7 at a dosage of 20g / L, stirred at 150r / min for 2h at 25℃, and then adsorbed for 3h. After removing the adsorption resin, the resin adsorption treatment is completed.

[0061] Example 2

[0062] The ammonia-nitrogen wastewater treatment method of this embodiment is as follows:

[0063] S1, add the composite modified zeolite material to the ammonia-nitrogen wastewater at a dosage of 12g / L, and then oscillate at a power of 100W for 10min. After standing for 2h, the supernatant is filtered by circulating polyether sulfone hollow fiber ultrafiltration membrane for 3h, and the obtained product is denoted as adsorption treatment component;

[0064] The preparation steps of the composite modified zeolite material are as follows:

[0065] Step A, crush the natural zeolite and pass it through a 200-mesh sieve, then add 1mol / L sodium chloride solution at a solid-liquid ratio of 1:10, stir at 300r / min for 12h at 25℃, centrifuge at 7000r / min for 10min after standing for 12h, and rinse the centrifugal precipitate with deionized water until it is neutral. The obtained product is denoted as salt treatment component;

[0066] Step B, the salt treatment component is dried in a drying oven at 105℃ until constant weight, then baked in a muffle furnace at 450℃ for 1h, and the resulting product after cooling to room temperature is the composite modified zeolite material.

[0067] S2, after adjusting the pH value of the adsorption treatment component to 11 with a 1mol / L sodium hydroxide solution, the composite photocatalyst is added at an input amount of 1g / L, and photocatalytic treatment is carried out under ultrasonic vibration conditions, and the resulting product is denoted as the degradation component;

[0068] The preparation steps of the composite photocatalyst are as follows:

[0069] Step 1, 10g of melamine is heated in a muffle furnace at a heating rate of 2℃ / min to 600℃, and after holding for 2h, it is cooled to room temperature, then ground and placed in a muffle furnace and annealed at a temperature of 550℃ at an annealing rate of 2℃ / min for 3h, and after cooling to room temperature, the resulting product is denoted as the pretreatment component;

[0070] Step 2, the pretreatment component is soaked in a saturated boric acid solution, stirred at a speed of 500r / min for 30min, and then freeze-dried, then heated in a tube furnace under a nitrogen atmosphere at a heating rate of 2.3℃ / min to 550℃ for 2h, and after cooling to room temperature, washed with distilled water 5 times, and dried at a temperature of 80℃ until constant weight, denoted as the nanonet component;

[0071] Step 3, 6g of zinc sulfate heptahydrate is dispersed in 600mL of a 0.5mol / L sodium hydroxide solution, stirred at a speed of 500r / min for 30min, then 4g of the nanonet component is added, followed by the addition of 90mL of ammonia water, and the stirring is continued for 30min, then the reaction is carried out in a high-pressure reaction kettle at 90℃ for 6h, and the resulting product is denoted as the reaction component;

[0072] Step 4, the reaction component is centrifuged at a speed of 6000r / min for 10min, and the centrifuged precipitate is rinsed with deionized water and anhydrous ethanol 3 times in sequence, and then dried at a temperature of 85℃ until constant weight, and the resulting product is the composite photocatalyst.

[0073] In S2, the ultrasonic power of the ultrasonic vibration condition is 50W, the ultrasonic frequency is 40kHz, the light source for photocatalytic treatment is a 300W xenon lamp, the fixed position of the light source is 15cm above the liquid level, and the catalytic treatment time is 3h.

[0074] S3, the pH value of the degradation component is adjusted to 7 with a 1mol / L hydrochloric acid solution, and then resin adsorption treatment is carried out to complete the ammonia-nitrogen wastewater treatment.

[0075] The method of resin adsorption treatment is as follows:

[0076] The adsorption resin is added into the degradation component with pH value of 7 at an input amount of 40 g / L, and after stirring at a speed of 150 r / min for 3 h at a temperature of 25 ℃ and standing for 5 h, the resin adsorption treatment is completed after removing the adsorption resin.

[0077] Example 3

[0078] The ammonia-nitrogen wastewater treatment method of the embodiment is as follows:

[0079] S1, the composite modified zeolite material is added into the ammonia-nitrogen wastewater at an input amount of 7 g / L, and oscillated at a power of 100 W for 10 min, and after standing for 2 h, the supernatant is filtered for 3 h by using a polyether sulfone hollow fiber ultrafiltration membrane, and the obtained is recorded as an adsorption treatment component;

[0080] The preparation steps of the composite modified zeolite material are as follows:

[0081] Step A, the natural zeolite is crushed and passed through a 200-mesh sieve, then a sodium chloride solution with a concentration of 1 mol / L is added at a solid-liquid ratio of 1:10, and stirred at a speed of 300 r / min for 12 h at a temperature of 25 ℃, and after standing for 12 h, centrifuged at a speed of 7000 r / min for 10 min, and the centrifuged precipitate is washed with deionized water until neutral, and the obtained is recorded as a salt treatment component;

[0082] Step B, the salt treatment component is dried to constant weight in a drying oven at 105 ℃, then calcined in a muffle furnace at 450 ℃ for 1 h, and after cooling to room temperature, the obtained is the composite modified zeolite material.

[0083] S2, the pH value of the adsorption treatment component is adjusted to 11 by using a sodium hydroxide solution with a concentration of 1 mol / L, and then the composite photocatalyst is added at an input amount of 0.8 g / L, and the photocatalytic treatment is carried out under ultrasonic vibration, and the obtained is recorded as a degradation component;

[0084] The preparation steps of the composite photocatalyst are as follows:

[0085] Step 1, 10 g of melamine is heated in a muffle furnace at a heating rate of 2 ℃ / min to 600 ℃, and after holding for 2 h, cooled to room temperature, ground, and then placed in a muffle furnace and annealed at a temperature of 550 ℃ at an annealing rate of 2 ℃ / min for 3 h, and after cooling to room temperature, the obtained is recorded as a pretreatment component;

[0086] Step 2, the pretreatment component is soaked in a saturated boric acid solution, stirred at a speed of 500 r / min for 30 min, and then freeze-dried, and then placed in a tube furnace under a nitrogen atmosphere and heated to 550 ℃ at a heating rate of 2.3 ℃ / min for 2 h, and after cooling to room temperature, washed with distilled water for 4 times, and dried at a temperature of 80 ℃ to constant weight, and recorded as a nanomesh component.

[0087] Step 3, 6g of zinc sulfate heptahydrate was weighed and dispersed in 600mL of sodium hydroxide solution with a concentration of 0.5mol / L, stirred at a speed of 500r / min for 30min, then 4g of nanometer network component was added, 90mL of ammonia water was added, and stirring was continued for 30min, then the reaction was carried out in a high-pressure reaction kettle at 90℃ for 6h, and the obtained product was denoted as reaction component;

[0088] Step 4, the reaction component was centrifuged at a speed of 6000r / min for 10min, and the centrifugal precipitate was washed with deionized water and anhydrous ethanol for 3 times respectively, and then dried at a temperature of 82℃ until the weight was constant. The obtained product is a composite photocatalyst.

[0089] In S2, the ultrasonic power of the ultrasonic vibration condition is 50W, the ultrasonic frequency is 40kHz, the light source for photocatalytic treatment is a 300W xenon lamp, the fixed position of the light source is 15cm above the liquid level, and the catalytic treatment time is 3h.

[0090] S3, adjust the pH value of the degradation component to 7 with a hydrochloric acid solution with a concentration of 1mol / L, then perform resin adsorption treatment to complete the ammonia-nitrogen wastewater treatment.

[0091] The method of resin adsorption treatment is as follows:

[0092] The adsorption resin is added to the degradation component with a pH value of 7 at an input amount of 30g / L, stirred at a speed of 150r / min for 3h at a temperature of 25℃, and then adsorbed for 4h after standing. After removing the adsorption resin, the resin adsorption treatment is completed.

[0093] Comparative Example 1

[0094] The ammonia-nitrogen wastewater treatment method provided by the present comparative example is basically the same as that of Example 1, the main difference being that the composite modified zeolite material in Example 1 is replaced by natural zeolite crushed and sieved through a 200-mesh sieve.

[0095] Comparative Example 2

[0096] The ammonia-nitrogen wastewater treatment method provided by the present comparative example is basically the same as that of Example 1, the main difference being that the composite photocatalyst in Example 1 is replaced by nanometer zinc oxide.

[0097] Comparative Example 3

[0098] The ammonia-nitrogen wastewater treatment method provided by the present comparative example is basically the same as that of Example 1, the main difference being that the resin adsorption treatment in Example 1 is not performed.

[0099] Performance test

[0100] The treatment results of the ammonia-nitrogen wastewater treatment methods in Examples 1-3 and Comparative Examples 1-3 were detected, and the ammonia-nitrogen degradation rates of the wastewater treated by the ammonia-nitrogen wastewater treatment methods in Examples 1-3 and Comparative Examples 1-3 were determined by using the Nash reagent spectrophotometry, and the obtained data were recorded in the following table.

[0101]

[0102] As shown by the data in the above table, the ammonia-nitrogen degradation rates of the wastewater treated by the ammonia-nitrogen wastewater treatment methods in Examples 1-3 were obviously higher than those in Comparative Examples 1-3, which indicated that the ammonia-nitrogen in the ammonia-nitrogen wastewater could be better degraded by the treatment of adsorption and photocatalysis and then resin adsorption in the present application, and the wastewater could be better purified.

[0103] It should be noted that the relational terms herein such as first and second and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any such actual relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element preceded by "comprises... a" does not, without more constraints, foreclose the existence of additional identical elements in the process, method, article, or apparatus that comprises the recited element.

[0104] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements will not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for treating ammonia nitrogen wastewater, characterized in that: The processing method is: S1. Adding the composite modified zeolite material to the ammonia nitrogen wastewater and performing an oscillation treatment. After standing for 1-2 hours, the supernatant is filtered and the obtained solution is recorded as the adsorption treatment component; S2, adjusting the pH value of the adsorption treatment component to 10-11, adding the composite photocatalyst, and performing photocatalytic treatment under ultrasonic vibration conditions, and the obtained result is recorded as the degradation component; S3. The pH value of the degradation component is adjusted to 7 with a hydrochloric acid solution having a concentration of 1 mol / L, and then the ammonia nitrogen wastewater treatment is completed after resin adsorption treatment; The preparation steps of the composite modified zeolite material in S1 are: Step A: The natural zeolite is crushed and passed through a 200-mesh sieve, and then added to a 1 mol / L sodium chloride solution at a material-liquid ratio of 1:10, stirred at 300 r / min for 12 hours at 25°C, allowed to stand for 12 hours, and then centrifuged at 7000 r / min for 10 minutes. The centrifugal precipitate is rinsed with deionized water until neutral, and the resulting solution is recorded as the salt-treated component; Step B, drying the salt-treated component in a drying oven at 105° C. to constant weight, then calcining it in a muffle furnace at 450° C. for 1 hour, and cooling it to room temperature to obtain a composite modified zeolite material; The preparation steps of the composite photocatalyst in S2 are: Step 1: 10 g of melamine was placed in a muffle furnace and heated to 600° C., kept at this temperature for 2 hours, and then cooled to room temperature. After grinding, the mixture was placed in a muffle furnace and annealed at 550° C. for 3 hours. The mixture was cooled to room temperature and recorded as a pretreatment component. Step 2: Immerse the pretreated component in a saturated boric acid solution, stir and freeze-dry, then heat to 550°C in a tube furnace under a nitrogen atmosphere for 2 hours, cool to room temperature, wash with distilled water 3-5 times, and dry to record as the nanonet component; Step 3: Weigh 5-6 g of zinc sulfate heptahydrate and disperse it in 600 mL of sodium hydroxide solution. After stirring and dispersing, add 3-4 g of the nanomesh component, then add 90 mL of ammonia water and continue stirring for 30 minutes. Then, react in an autoclave at 90°C for 6 hours. The result is recorded as the reaction component; Step 4: centrifuge the reaction components at a speed of 6000 r / min for 10 minutes, rinse the centrifugal precipitate with deionized water and anhydrous ethanol three times in sequence, and then dry it to obtain a composite photocatalyst.

2. The method for treating ammonia nitrogen wastewater according to claim 1, wherein: The input amount of the composite modified zeolite material in S1 is 2-12 g / L, and the oscillation treatment method in S1 is oscillation at a power of 100 W for 10 minutes.

3. The method for treating ammonia nitrogen wastewater according to claim 1, wherein: The filtration treatment method in S1 is to use a polyethersulfone hollow fiber ultrafiltration membrane for circulating filtration for 2-3 hours.

4. The method for treating ammonia nitrogen wastewater according to claim 1, wherein: In S2, a sodium hydroxide solution with a concentration of 1 mol / L is used to adjust the pH value of the adsorption treatment component, and the input amount of the composite photocatalyst in S2 is 0.5-1 g / L.

5. The method for treating ammonia nitrogen wastewater according to claim 1, wherein: In the preparation steps of the composite photocatalyst, the heating rate of heating in step 1 is 2°C / min, the annealing rate of annealing in step 1 is 2°C / min, the stirring method in step 2 is stirring at a speed of 500r / min for 30min, the heating rate of heating in step 2 is 2.3°C / min, and the drying method in step 2 is drying at a temperature of 80°C to constant weight.

6. The method for treating ammonia nitrogen wastewater according to claim 1, wherein: In the preparation steps of the composite photocatalyst, the concentration of the sodium hydroxide solution in step 3 is 0.5 mol / L, the stirring and dispersing method in step 3 is stirring at a speed of 500 r / min for 30 minutes, and the drying method in step 4 is drying at a temperature of 80-85°C to constant weight.

7. The method for treating ammonia nitrogen wastewater according to claim 1, wherein: The ultrasonic power of the ultrasonic vibration condition in S2 is 50W, the ultrasonic frequency is 40kHz, the light source for the photocatalytic treatment in S2 is a 300W xenon lamp, the fixed position of the light source is 15cm above the liquid level, and the catalytic treatment time is 2-3h.

8. The method for treating ammonia nitrogen wastewater according to claim 1, wherein: The method of resin adsorption treatment in S3 is: The adsorption resin is added to the degradation component with a pH value of 7 at an input amount of 20-40 g / L, stirred at a speed of 150 r / min at a temperature of 25°C for 2-3 hours, and then allowed to stand for 3-5 hours for adsorption. After the adsorption resin is removed, the resin adsorption treatment is completed.

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