A deep treatment method for industrial park wastewater

Abstract

The invention discloses a method for deep treatment of industrial park wastewater. The method adopts a combined process of ozone flotation (DOF) + autotrophic-heterotrophic combined denitrification (AHCD), deeply removes COD and improves the B / C ratio of wastewater through DOF, and converts all ammonia nitrogen into nitrate nitrogen at the same time, and then removes nitrate nitrogen through AHCD. Under the condition of no introduction of exogenous agents (using the carbon source of wastewater to avoid secondary pollution), the self-sustaining carbon and nitrogen substances of wastewater are used to complete the deep co-removal of carbon and nitrogen in wastewater. The effluent of the industrial park sewage treatment plant deeply treated by the DOF+AHCD combined process meets the water quality standard of Class III surface water.

Description

Technical Field

[0001] The invention relates to a method for deep treatment of industrial park wastewater. Background Art

[0002] Industrial park wastewater is a special type of municipal wastewater, and its treatment process mostly adopts the traditional "pretreatment (chemical coagulation) + biological treatment". Although the traditional treatment process is mature and stable, it can only meet the existing emission standards (such as Class A) and is difficult to meet more stringent emission standards (surface Class III and IV water). At present, most electronic industrial park sewage treatment plants are facing the pressure of gradually increasing emission standards, just like municipal sewage treatment plants.

[0003] The key and difficulty of deep treatment of industrial park wastewater lies in the deep removal of carbon and nitrogen pollutants. The water quality of industrial park wastewater is complex and contains a wide variety of organic pollutants. After biological treatment at the industrial park sewage plant, although the COD of the wastewater can be reduced to 50-200 mg / L, the COD is almost entirely provided by difficult-to-degrade organic matter, and the B / C ratio of the wastewater is close to 0, so the biodegradability is extremely poor. At the same time, because the effluent TN of traditional biological processes represented by the AAO process is difficult to reduce to below 10 mg / L, and the effluent TN is mostly NO3 - -N, so the deep treatment system needs to be equipped with a denitrification unit, such as a denitrification filter. A simple heterotrophic denitrification filter has problems such as large carbon source consumption, high sludge yield, and easy organic matter penetration. A simple autotrophic denitrification filter has problems such as slow biofilm formation rate, low denitrification load, easy sulfate accumulation, and pH drop.

[0004] Patent 201110430856.9 discloses a wastewater treatment process for a PCB industrial park. Different wastewaters are collected and classified for pretreatment and then collected. They are sequentially passed through an anaerobic tank, an aerobic tank, an MBR tank, a clean water tank, and ultraviolet disinfection. The effluent COD is less than 40 mg / L. This process still uses the traditional pretreatment + biological treatment mode, and does not deeply treat the residual refractory organic matter in the wastewater. The effluent COD cannot meet the requirement of COD less than 30 mg / L for Class IV surface water. In addition, this process does not have a deep denitrification unit, and only relies on secondary biological treatment to remove nitrogen-containing pollutants. The effluent TN cannot meet the water quality standards for Class III and Class IV surface water.

[0005] Patent 201611169403.4 discloses a leather industrial park wastewater deep treatment system, which uses a combination of a primary aerated biological filter + sand filter + homogeneous catalytic oxidation + denitrification filter + secondary aerated biological filter to deeply treat industrial park wastewater. However, the effluent of this system can only reach the Class A standard, and the operating cost is high, the amount of reagents used is large, and there is a risk of organic matter penetration, and the deep treatment of industrial park wastewater has not been completely achieved.

[0006] From the above content, it can be seen that the existing deep treatment process of industrial park wastewater mainly adopts a combination of flotation / sedimentation + advanced oxidation + denitrification process, that is, after removing a small amount of suspended matter in the wastewater, oxidizing and removing dissolved organic matter, and finally converting nitrate nitrogen into nitrogen gas through denitrification reaction to achieve deep denitrification. Most of the traditional deep treatment processes for industrial park wastewater have problems such as incomplete removal of organic matter, introduction of a large amount of reagents, high operating costs, and difficulty in meeting the requirements of more stringent emission standards for effluent. Summary of the invention

[0007] Purpose of the invention: The purpose of the present invention is to provide a method for deep treatment of industrial park wastewater, which method does not require the addition of external agents (no introduction of organic carbon sources), does not produce secondary pollution, and can deeply remove carbon and nitrogen in the wastewater with low energy consumption, so that the effluent water quality meets the surface water quality standards of Class III.

[0008] Technical solution: The deep treatment method of industrial park wastewater described in the present invention comprises the following steps:

[0009] (1) Wastewater treated by secondary biological treatment at the sewage treatment plant in the electronic industrial park enters the ozone flotation device; the ozone flotation device includes an ozone generator, a secondary reaction flotation tank and a primary reaction tank. The ozone generated by the ozone generator is sent to the primary reaction tank. The outlet of the primary reaction tank is connected to the inlet of the secondary reaction flotation tank. The effluent of the primary reaction tank is mixed with the wastewater in the ejector and enters the secondary reaction flotation tank. The secondary reaction flotation tank uses the bubbles generated by the oxygen (containing a small amount of ozone) carried in the effluent of the primary reaction tank for flotation treatment. The exhaust port of the secondary reaction flotation tank is connected to the ozone generator. After flotation, the oxygen is sent to the ozone generator. The oxygen returns to the front end of the ozone generator and continues to be used as a gas to generate ozone. Raw materials (thereby reducing the amount of liquid oxygen raw materials added and reducing the equipment operation cost), a part of the effluent from the secondary reaction flotation tank is refluxed to the primary reaction tank, the reflux ratio is 100% to 150%, the primary reaction tank is filled with ozone catalytic oxidation filler, the filling amount of ozone catalytic oxidation filler is 60% to 80% of the effective volume of the primary reaction tank, the wastewater undergoes ozone catalytic oxidation reaction in the primary reaction tank, the hydraulic retention time in the primary reaction tank is 20 to 30 minutes, the gas flow rate from the ozone generator to the primary reaction tank is 1.5 to 3L / min, and the ozone concentration in the gas is 35 to 42mg / L; in the primary reaction tank, the mass ratio of ozone to COD in the wastewater is 0.9 to 1.5;

[0010] (2) Another part of the effluent from the secondary reaction flotation tank enters the autotrophic-heterotrophic combined denitrification filter tank, which is filled with denitrification fillers. The wastewater undergoes autotrophic-heterotrophic combined denitrification reaction in the filter tank to achieve deep denitrification.

[0011] After being treated by the ozone flotation device, the B / C ratio of the wastewater can be increased to above 0.5. Therefore, when the wastewater enters the autotrophic-heterotrophic combined denitrification filter, the organic matter can be used by microorganisms as an electron donor for heterotrophic denitrification, so there is no need to add additional carbon sources to avoid secondary pollution. At the same time, S and Fe in the denitrification filler serve as electron donors for autotrophic denitrification. The primary reaction tank is a closed tank, which effectively prevents ozone leakage. The ozone entering the secondary reaction flotation tank is very small, and it will also be decomposed in the secondary reaction flotation tank. Therefore, there will be no ozone leakage during the operation of the entire equipment.

[0012] Wherein, in step (1), the ozone catalytic oxidation filler is a composite filler in which SHC-α filler and SHC-β filler are mixed in a volume ratio of 4:1.

[0013] The preparation method of SHC-α filler specifically comprises the following steps:

[0014] (1) Grinding siderite, pyrite and smithsonite in a mass ratio of 2:1:1 is mixed, and added to a 10wt% sulfuric acid solution at 50°C in a solid-liquid mass ratio of 1:8, stirred until the ore is dissolved, and filtered; sodium citrate in an amount of 50% by mass of the ore is added, stirred for reaction at 60°C for 3-4h, and dried at 90°C for more than 14h; the dried solid is calcined at 550-700°C for 6h, cooled to room temperature, and prepared into a spherical carrier with a diameter of 5-8mm; the use of an iron-based filler as a carrier can increase the loading amount of the layered metal hydroxide (Fe(OH)3), that is, it is more conducive to the loading of the layered metal hydroxide (Fe(OH)3) on the carrier;

[0015] (2) Prepare a 5 wt% FeCl3 solution, mix the filler carrier with the FeCl3 solution at a solid-liquid ratio of 1:1 (g / mL), and stir rapidly; at the same time, slowly add 2 wt% NaOH solution and 10 wt% Na2CO3 solution (the total amount of NaOH solution and Na2CO3 solution added is 10% of the volume of the FeCl3 solution, and the added volume ratio of NaOH solution and Na2CO3 solution is 1:1), then add anhydrous ethanol at 10 mL / L, and stir rapidly for 2 h; take out the filler carrier that adsorbs Fe(OH)3, place it in a 200°C environment and dry it for more than 12 h to complete the layered metal hydroxide loading; construct a space so that copper ions can replace the position of iron hydroxide in the subsequent metal intercalation reaction;

[0016] (3) Active metal ion intercalation reaction: Under nitrogen protection, the filler loaded with layered metal hydroxide is placed in a 6 wt% amino acid complex copper solution at a pH of 7 to 9 for 4 to 5 hours to complete the metal intercalation reaction through ion exchange; then the filler is taken out, rinsed with deionized water, and dried.

[0017] Through the intercalation method, the copper in the amino acid complex copper solution is replaced into ionic copper in the filler, making the copper active. In the process of catalytic ozone oxidation, copper, as the main active center, has good catalytic activity for ozone, which can make ozone produce a large number of hydroxyl radicals (copper promotes the generation of a large number of hydroxyl radicals by losing electrons, improving the ability to oxidize and degrade organic matter), thereby achieving efficient removal of difficult-to-degrade small molecular organic matter such as protein-like, fulvic acid-like, and humic acid-like in the effluent of sewage treatment plants. In addition, the copper ions entering the filler through the metal intercalation reaction can effectively inhibit the dissolution of copper ions, so that the catalyst has high catalytic activity and prolongs the service life of the catalyst.

[0018] The preparation method of SHC-β filler specifically comprises the following steps:

[0019] (1) The biological sludge cake after filtration by the filter press is taken, ground and dried in an environment of 80°C for more than 12 hours, then calcined in an environment of 500°C for 2 hours, and after cooling to room temperature, a spherical carrier with a diameter of 5 to 8 mm is prepared; the carrier is prepared by using biological sludge to realize waste utilization;

[0020] (2) Sulfuric acid-nitric acid-hydrogen peroxide modified carbon nanotube loading: 50wt% sulfuric acid, 50wt% nitric acid and 10wt% hydrogen peroxide solution were mixed in a volume ratio of 1:1:1 (the carbon nanotubes were modified by the strong corrosiveness of the mixture of strong acid and hydrogen peroxide) to obtain a mixed solution, and then the carbon nanotubes and the mixed solution were mixed in a mass ratio of 1:4, and then the prepared filler carrier was added and ultrasonically dispersed for 2h. After the reaction, the filler was placed in an environment of 200°C and dried for more than 12h. After cooling to room temperature, it was rinsed with a large amount of deionized water and dried.

[0021] SHC-β filler adsorbs small molecules of difficult-to-degrade organic matter and catalyzes ozone at the solid-liquid contact interface to rapidly oxidize and degrade organic matter. The carbon nanotubes are modified by controlling the reaction time in a highly corrosive environment. After modification (the adsorption performance of carbon nanotubes before modification is poor), the dispersion of carbon nanotubes increases, and the number of active sites with adsorption function increases. Under the action of π-π electron interaction and Lewis acid-base pairs, the adsorption capacity of difficult-to-degrade small molecules of organic matter is improved, thereby further promoting the reduction of COD content in water bodies. At the same time, carbon nanotubes themselves also have a certain catalytic effect on ozone, thereby cooperating with SHC-α fillers to improve the degradation capacity of ozone on difficult-to-degrade small molecules of organic matter.

[0022] Under the joint action of the two catalytic oxidation fillers, the efficiency of ozone oxidation of organic matter is greatly improved, so that the B / C ratio of the wastewater after treatment by the ozone flotation device can be increased to above 0.5, ammonia nitrogen is completely converted into nitrogen and nitrate nitrogen, and SS is reduced to below 10 mg / L. The ozone flotation device can specifically destroy residual organic matter in the water, such as protein-like, fulvic acid-like, humic acid-like, etc. (the existing deep treatment methods have poor removal effects on difficult-to-degrade small molecular organic matter in the effluent of industrial park sewage treatment plants, such as protein-like, fulvic acid-like, and humic acid-like, so the B / C ratio is low), achieve deep removal of COD and convert all ammonia nitrogen into nitrate nitrogen.

[0023] Wherein, in step (2), the filter tank includes a reaction zone, the filling amount of the denitrification filler is 100% of the volume of the reaction zone, and the denitrification filler is composed of elemental sulfur particles, siderite particles, and limestone particles in a mass ratio of 6:3:1.

[0024] Wherein, in step (2), the hydraulic retention time in the filter tank is 30 to 60 min, the filtration rate is 3 to 8 m / h, and the volume load is 0.8 to 1.1 kg TN / (m 3 ·d).

[0025] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: the present invention adopts ozone flotation (DOF) + autotrophic-heterotrophic combined denitrification (AHCD) combined process, deeply removes COD and improves the B / C ratio of wastewater through DOF, and converts all ammonia nitrogen into nitrate nitrogen, and then removes nitrate nitrogen through AHCD, without the introduction of exogenous agents (using the wastewater's own carbon source to avoid secondary pollution), and utilizes the wastewater's self-sustaining carbon and nitrogen substances to complete the deep co-removal of wastewater carbon and nitrogen. The effluent of the industrial park sewage treatment plant deeply treated by the DOF+AHCD combined process meets the surface water quality standards for Class III. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is a system principle diagram of the processing system of the present invention;

[0027] Figure 2 It is a structural schematic diagram of an ozone flotation device;

[0028] Figure 3 This is a schematic diagram of the structure of autotrophic-heterotrophic combined denitrification;

[0029] Figure 4 is the COD removal rate during the operation of the DOF+AHCD combined process;

[0030] Figure 5 is the removal rate of TN during the operation of the DOF+AHCD combined process. DETAILED DESCRIPTION

[0031] like Figures 1 to 3 As shown, the deep treatment method of industrial park wastewater of the present invention is realized based on an ozone flotation device and an autotrophic-heterotrophic combined denitrification filter tank connected in series in sequence. The effluent of the ozone flotation device enters the autotrophic-heterotrophic combined denitrification filter tank through a lift pump. The ozone flotation device includes an ozone generator, a diaphragm compressor, a primary reaction tank and a secondary reaction flotation tank. The gas output by the ozone generator is sent to the primary reaction tank through the diaphragm compressor. The air inlet of the primary reaction tank is located below the tank body. The gas passes through an air distributor and enters a reaction zone filled with ozone catalytic oxidation filler; the primary reaction tank The water outlet is connected with the water inlet of the secondary reaction flotation tank, and an ejector is also provided on the connecting pipe between the two. The effluent of the primary reaction tank and the wastewater are mixed at the ejector and then enter the secondary reaction flotation tank. The secondary reaction flotation tank includes two water outlets, one of which is connected with the water inlet of the primary reaction tank, and the other is connected with the water inlet of the autotrophic-heterotrophic combined denitrification filter. The secondary reaction flotation tank also includes an exhaust port located at the top, and the exhaust port of the secondary reaction flotation tank is connected with the ozone generator through a pipe; the water inlet of the primary reaction tank is also located below the tank body.

[0032] The ozone flotation device has both ozone oxidation and dissolved air flotation functions, which can simultaneously realize the oxidation of residual refractory organic matter and the removal of suspended solids, greatly improving the biodegradability of organic pollutants without secondary pollution (ozone leakage); at the same time, the oxygen generated after ozone oxidation is recycled, thereby greatly reducing the external oxygen source and the cost of generating ozone, thereby effectively reducing the operating cost of the entire equipment for ozone catalytic oxidation; the secondary reaction flotation tank uses the bubbles generated by the ozone and oxygen carried by the effluent of the primary reaction tank to flotate and remove suspended matter, and the residual ozone can continue to undergo oxidation reaction in the flotation tank; the top of the secondary reaction flotation tank is conical, and the angle between the side wall and the horizontal plane is 50-65°. The top of the cone is provided with a sludge discharge port to discharge sludge regularly. Oxygen is collected at the top of the cone and can be returned to the front end of the ozone generator to continue to be used as a raw material for generating ozone.

[0033] Example 1

[0034] The water volume of a sewage treatment plant in an industrial park is 36000m 3 / d, and the effluent quality is shown in Table 1:

[0035] Table 1 shows the effluent quality of a sewage treatment plant in an industrial park

[0036] pH COD(mg / L) <![CDATA[BOD5(mg / L)]]> TN(mg / L) <![CDATA[NH3-N(mg / L)]]> 7～7.5 60～100 ＜10 20～25 ＜5

[0037] The method of the present invention is used to deeply treat the above-mentioned sewage, which specifically comprises the following steps:

[0038] (1) Ozone flotation: Wastewater treated by AAO at a sewage treatment plant in an industrial park first enters the ozone flotation device. The wastewater enters the secondary reaction flotation tank through the ejector, and the bubbles generated by the ozone and oxygen carried by the effluent of the primary reaction tank are used for flotation treatment. The residual ozone can continue to undergo oxidation reaction in the flotation tank. Part of the effluent from the secondary reaction flotation tank flows back to the primary reaction tank, with a reflux ratio of 100% to 110%. The primary reaction tank is equipped with two types of ozone catalytic oxidation fillers (SHC-α and SHC-β, with a volume ratio of SHC-α to SHC-β of 4:1), and the filler filling amount is 75% of the effective volume of the primary reaction tank. The wastewater undergoes ozone catalytic oxidation reaction in the primary reaction tank. In the primary reaction tank, the hydraulic retention time (HRT) is 25 minutes, the amount of gas introduced from the ozone generator into the primary reaction tank is 1.5L / min, and the ozone concentration in the gas is 35mg / L. The effluent from the primary reaction tank is mixed with the raw water in the ejector and then enters the secondary reaction flotation tank for flotation treatment. The B / C ratio in the effluent is 0.5 to 0.6. Ammonia nitrogen is not detected.

[0039] (2) Autotrophic-heterotrophic combined denitrification: DOF effluent enters the autotrophic-heterotrophic combined denitrification filter (AHCD) through a lift pump. The wastewater passes through the water distribution area and flows through the reaction zone from top to bottom. The reaction zone is filled with elemental sulfur particles, siderite particles and limestone particles mixed in a mass ratio of 6:3:1. The filling amount is 100% of the volume of the reaction zone. The wastewater undergoes autotrophic-heterotrophic combined denitrification reaction in the reaction zone to achieve deep denitrification. In the autotrophic-heterotrophic combined denitrification filter, the HRT is 45min, the filtration rate is 3-6m / h, and the volume load is 0.8-0.95kgTN / (m 3 ·d).

[0040] After treatment with the DOF+AHCD combined process, no NH3-N and SS were detected in the effluent, the effluent COD was stably less than 20 mg / L, the effluent TN was stably less than 1 mg / L, and the effluent water quality met the surface water quality standards for Class III.

[0041] Comparative Example 1

[0042] The sewage in Table 1 is collected and filtered through screen filtration, coagulation and sedimentation, hydrolysis and acidification, catalytic wet oxidation, MBR pool filtration and reverse osmosis filtration. The produced water meets the reuse requirements, and the effluent COD is controlled below 25 mg / L and the BOD5 is controlled below 10 mg / L.

[0043] The front end of this process uses pretreatment (grid filtration + coagulation and sedimentation) + biological treatment (hydrolysis and acidification) to treat the industrial park wastewater, and then uses wet catalytic oxidation + MBR + RO for deep treatment. First, this process does not have a nitrate nitrogen removal unit and cannot meet the requirements of deep denitrification. Secondly, the use of MBR + RO for deep decarbonization treatment has a poor removal effect on difficult-to-degrade small molecular organic matter (protein-like, fulvic acid-like, humic acid-like, etc.), and cannot treat the effluent of industrial park sewage treatment plants with complex water quality. Finally, the RO concentrated water is returned to the wet catalytic oxidation for further treatment, and there is no concentrated water discharge system, which gradually increases the system TDS concentration, directly leading to a decrease in the RO recovery rate and eventually the system collapses. Compared with this process, the process of the present invention can use the self-sustaining carbon and nitrogen substances in the wastewater to complete the efficient, stable and deep removal of pollutants without the introduction of exogenous agents, and the effluent meets the surface water quality standards of Class III.

[0044] Comparative Example 2

[0045] The DOF+AHCD combined system of the present invention remains unchanged, the only difference is that the built-in filler of the primary reaction tank is the existing ozone catalytic oxidation filler, and the same operation mode as Example 1 is adopted to treat the sewage in Table 1. The DOF effluent B / C ratio is 0.3-0.35, and ammonia nitrogen is not detected. The effluent results of the entire system are: effluent NH3-N and SS are not detected, the effluent COD is stable at about 40 mg / L, and the effluent TN is stable at less than 3-4 mg / L.

[0046] Comparative Example 3

[0047] The DOF+AHCD combined system of the present invention remains unchanged, the only difference is that the built-in filler of the primary reaction tank is only SHC-α, and the sewage in Table 1 is treated in the same operating mode as Example 1. The DOF effluent B / C ratio is 0.4-0.45, and ammonia nitrogen is not detected; the effluent results of the entire system are: effluent NH3-N and SS are not detected, effluent COD is stable at 30-35 mg / L, and effluent TN is stable at less than 3-4 mg / L.

[0048] Comparative Example 4

[0049] The DOF+AHCD combined system of the present invention remains unchanged, the only difference is that the built-in filler of the primary reaction tank is only SHC-β, and the sewage in Table 1 is treated in the same operating mode as Example 1. The DOF effluent B / C ratio is 0.3-0.4, and ammonia nitrogen is not detected. The effluent results of the entire system are: effluent NH3-N and SS are not detected, effluent COD is stable at 32-38 mg / L, and effluent TN is stable at less than 3-4 mg / L.

[0050] Comparative Example 5

[0051] The DOF+AHCD combined system of the present invention remains unchanged, the only difference is that the SHC-α filler and the SHC-β filler in the ozone catalytic oxidation filler built into the primary reaction tank are mixed at a volume ratio of 2:1, and the sewage in Table 1 is treated in the same operating mode as Example 1. The DOF effluent B / C ratio is 0.3-0.4, effluent NH3-N and SS are not detected, the effluent COD is stably 24-28 mg / L, and the effluent TN is stably less than 3-4 mg / L.

Claims

1. A method for deep treatment of industrial park wastewater, characterized in that: The steps include: (1) The wastewater after the secondary biological treatment is mixed with the effluent from the primary reaction tank and then sent to the secondary reaction flotation tank. The gas carried in the effluent from the primary reaction tank is used to form bubbles for flotation treatment. After the flotation treatment, the gas in the secondary reaction flotation tank enters the ozone generator, and part of the effluent from the secondary reaction flotation tank is returned to the primary reaction tank, and the other part of the effluent from the secondary reaction flotation tank enters the autotrophic-heterotrophic combined denitrification filter. (2) The ozone generator sends the ozone-containing gas into the primary reaction tank, which is filled with ozone catalytic oxidation filler. The wastewater undergoes ozone catalytic oxidation reaction in the primary reaction tank. The hydraulic retention time in the primary reaction tank is 20-30 minutes. The gas flow rate from the ozone generator to the primary reaction tank is 1.5-3L / min, and the ozone concentration in the gas is 35-42mg / L. In the primary reaction tank, the mass ratio of ozone to COD in the wastewater is 0.9-1.5; (3) The autotrophic-heterotrophic combined denitrification filter is filled with denitrifying fillers. The wastewater undergoes autotrophic-heterotrophic combined denitrification reaction in the filter, and the effluent meets the standards for discharge after the reaction.

2. The method for deep treatment of industrial park wastewater according to claim 1, characterized in that: In step (1), a portion of the effluent from the secondary reaction flotation tank is refluxed to the primary reaction tank, wherein the reflux ratio is 100% to 150%.

3. The method for deep treatment of industrial park wastewater according to claim 1, characterized in that: In step (1), the ozone catalytic oxidation filler is a combination filler of SHC-α filler and SHC-β filler mixed in a volume ratio of 4:1; the filling amount of the ozone catalytic oxidation filler is 60% to 80% of the effective volume of the primary reaction tank; The preparation method of the SHC-α filler specifically comprises the following steps: (1) Grinding siderite, pyrite and smithsonite is mixed, added into a sulfuric acid solution at high temperature, stirred until the ore is dissolved, and filtered; sodium citrate is added thereto, stirred at high temperature for reaction, and after the reaction, dried and calcined to obtain a spherical carrier; (2) Mix the filler carrier with the FeCl3 solution and stir rapidly; at the same time, slowly add the NaOH solution and the Na2CO3 solution, then add anhydrous ethanol and stir rapidly to react; take out the filler carrier that adsorbs Fe(OH)3, and complete the layered metal hydroxide loading after drying; (3) Active metal ion intercalation reaction: Under nitrogen protection, the filler loaded with layered metal hydroxide is placed in an amino acid complex copper solution with a pH of 7 to 9 to react, and the metal intercalation reaction is completed by ion exchange; then the filler is removed, rinsed with deionized water, and dried; The preparation method of the SHC-β filler specifically comprises the following steps: (1) The biological sludge cake after filtration by the filter press is ground and dried at high temperature, calcined after drying, and cooled to room temperature to obtain a spherical carrier; (2) Sulfuric acid-nitric acid-hydrogen peroxide modified carbon nanotube loading: Sulfuric acid, nitric acid and hydrogen peroxide solution are mixed to obtain a mixed solution, the carbon nanotubes are mixed with the mixed solution, and then the prepared filler carrier is added and ultrasonically dispersed. After the reaction, the filler is heat treated at high temperature, cooled to room temperature and rinsed with a large amount of deionized water.

4. The method for deep treatment of industrial park wastewater according to claim 3, characterized in that: In step (1) of the SHC-α filler preparation method, after adding sodium citrate, the mixture is dried at a temperature not lower than 90° C. for more than 14 hours; the dried solid is calcined at a temperature of 550-700° C. for 6-7 hours, and after cooling to room temperature, a spherical carrier with a diameter of 5-8 mm is prepared.

5. The method for deep treatment of industrial park wastewater according to claim 3, characterized in that: In step (3) of the SHC-α filler preparation method, the mass concentration of the amino acid complex copper solution is 6-8%, and the intercalation reaction time is 4-5 hours.

6. The method for deep treatment of industrial park wastewater according to claim 3, characterized in that: In step (2) of the SHC-β filler preparation method, 50-55wt% sulfuric acid, 50-55wt% nitric acid and 10-15wt% hydrogen peroxide solution are mixed in a volume ratio of 1:1:1, and then the carbon nanotubes and the mixed solution are mixed in a mass ratio of 1:4, and then the prepared filler carrier is added, and ultrasonic dispersion reaction is performed for 2-3 hours. After the reaction is completed, the filler is placed in an environment of 200-250°C and dried for more than 12 hours.

7. The method for deep treatment of industrial park wastewater according to claim 1, characterized in that: In step (2), the filter tank includes a reaction zone, the denitrification filler is filled with 100% of the volume of the reaction zone, and the denitrification filler is composed of elemental sulfur particles, siderite particles, and limestone particles in a mass ratio of 6:3:1-2.

8. The method for deep treatment of industrial park wastewater according to claim 1, characterized in that: In step (2), the hydraulic retention time in the filter tank is 30-60 min, the filtration rate is 3-8 m / h, and the volumetric load is 0.8-1.1 kg TN / (m 3 ·d).

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