Method for treating high-concentration ammonium fluoride wastewater in electronic industry

Abstract

The invention discloses a method for treating high-concentration ammonium fluoride wastewater in the electronic industry, which specifically comprises the following steps: firstly, carrying out induced crystallization fluorine resourceful treatment to remove fluoride in the wastewater; performing enzyme catalytic decomposition of hydrogen peroxide to remove hydrogen peroxide in the wastewater; and finally, carrying out integrated anaerobic ammonia oxidation treatment to remove ammonia nitrogen in the wastewater. According to the method disclosed by the invention, a combined process of induced crystallization fluorine recycling, enzyme catalysis hydrogen peroxide decomposition and integrated anaerobic ammonia oxidation is adopted, fluoride removal and fluorine recycling are synchronously realized through an induced crystallization process, and hydrogen peroxide is efficiently removed through an enzymatic reaction; high-efficiency treatment of high-ammonia-nitrogen wastewater is realized through a short-cut nitrification-anaerobic ammonia oxidation process under a low-energy-consumption condition, and the problems of high agent consumption, high sludge yield, high operation cost and low ammonia-nitrogen removal rate of a traditional ammonium fluoride wastewater treatment process (air stripping and chemical coagulation) are solved.

Description

Technical Field

[0001] The invention relates to a method for treating high-concentration ammonium fluoride wastewater in the electronics industry. Background Art

[0002] The electronics industry produces a large amount of high-concentration ammonium fluoride wastewater during the production process. The main pollutants are fluoride, ammonia nitrogen and hydrogen peroxide. The concentrations of fluoride and ammonia nitrogen range from 1 to 10 g / L. The current treatment process for high-concentration ammonium fluoride wastewater in the electronics industry is air stripping + chemical coagulation, that is, ammonia nitrogen is first removed by air stripping, and then fluorine is removed by chemical coagulation. Due to factors such as the nature of the wastewater, this process has problems such as low ammonia nitrogen removal rate (70-85%), secondary pollution (ammonium sulfate, fluoride-containing sludge), large consumption of reagents, and high operating costs. Summary of the invention

[0003] Purpose of the invention: The purpose of the present invention is to provide a method for treating high-concentration ammonium fluoride wastewater in the electronics industry, which can simultaneously remove fluoride, ammonia nitrogen and hydrogen peroxide in the wastewater, and greatly improve the removal efficiency of ammonia nitrogen through the Bio-Manam reactor, with a removal rate of more than 95%.

[0004] Technical solution: The method for treating high-concentration ammonium fluoride wastewater in the electronics industry of the present invention is specifically as follows: the method first performs induced crystallization fluorine resource treatment to remove fluoride in the wastewater and realize fluorine resource recovery; then performs enzyme catalytic decomposition of hydrogen peroxide to remove hydrogen peroxide in the wastewater; and finally performs integrated anaerobic ammonia oxidation treatment to remove ammonia nitrogen in the wastewater;

[0005] Among them, the Bio-Manam reactor is used in the integrated anaerobic ammonium oxidation treatment process, and a Manam membrane module is arranged in the reactor. The Manam membrane filaments used in the Manam membrane module are prepared by the following method:

[0006] (1) Place a PVDF hollow fiber membrane (nominal pore size 0.1 μm) in a NaOH solution with a pH of 9.0 and soak for 2 h (to clean the surface coating or impurities of the PVDF membrane); after soaking, rinse the outside of the PVDF hollow fiber membrane with deionized water for 30 min, and then dry it at room temperature;

[0007] (2) Dissolving polydimethylsiloxane (PDMS) in n-hexane to prepare a PDMS solution with a mass fraction of 5 to 9%; immersing a PVDF hollow fiber membrane in the PDMS solution and circulating it for 6 to 10 hours; after the circulation, draining the PDMS solution and rinsing it with deionized water for 60 minutes; after rinsing, curing it in an environment of 70 to 85°C for 10 to 16 hours; PDMS is loaded on the outside of the PVDF membrane (outside the PVDF membrane wall) as an oxygen-permeable coating, and the PDMS layer transfers oxygen to water when ventilation is carried out in the PVDF membrane, and prevents water from penetrating into the PVDF membrane fibers;

[0008] (3) First prepare a trisaminomethane-hydrochloric acid buffer solution with a concentration of 10 to 20 mmol / L; dissolve dopamine hydrochloride (DOPA) and persulfate in the trisaminomethane-hydrochloric acid buffer solution to prepare a DOPA solution with a concentration of 1 to 10 mg / L, in which n(persulfate):n(DOPA)=1.0 to 1.1; persulfate is a strong oxidant that can oxidize DOPA to dopamine;

[0009] (4) The PVDF hollow fiber membrane obtained in step (2) is sequentially immersed in DOPA solutions with concentrations of 1, 2, 5, and 10 mg / L for 1 to 3 h (the purpose of sequential immersion is to obtain DOPA layers of different thicknesses and contents on the outside of the PVDF hollow fiber membrane, thereby improving its biocompatibility and enabling the DOPA layer to serve as a carbon source during the biofilm attachment process, greatly enhancing the attachment and growth ability of microorganisms on the outside of the membrane). After drying, the membrane fibers are rinsed with deionized water for 30 min to obtain Manam membrane fibers.

[0010] The present invention modifies the PVDF membrane in the above manner, which can effectively improve the biofilm rate. On the one hand, the highly biocompatible environment created by the DOPA layer is suitable for the attachment and growth of microorganisms. On the other hand, PDMS can increase the transfer concentration of oxygen outside the membrane, thereby effectively improving the enrichment rate of functional bacteria such as AOB and AnAOB. ​​Therefore, the membrane silk modified by PDMS has an asymmetric wetting structure with one side hydrophilic and one side hydrophobic, and the hydrophilicity of the outer surface is significantly enhanced, so that the biofilm can be attached to the membrane surface more quickly while improving the oxygen mass transfer efficiency of the membrane silk, and effectively extending the life of the membrane silk (avoiding water from entering the inner side of the membrane silk, reducing the possibility of water entering the inside of the membrane silk, thereby improving the life of the membrane silk). The Bio-Manam reactor using the Manam membrane assembly has the advantages of short startup cycle, good treatment effect, and strong impact resistance, thereby quickly realizing low-consumption and efficient removal of high-concentration ammonia nitrogen.

[0011] Wherein, at least one layer of Manam membrane components is arranged in the Bio-Manam reactor; each layer of Manam membrane components contains multiple groups of Manam membrane components arranged in parallel, each group of membrane components includes an air inlet, an air inlet distributor, Manam membrane filaments, a waste gas collection chamber and an air outlet, the gas enters the air inlet distributor through the air inlet, the air inlet distributor transports the gas to multiple hollow Manam membrane filaments arranged in parallel, the waste gas after the reaction enters the waste gas collection chamber, and is discharged from the membrane component from the air outlet; the Bio-Manam reactor also includes a water inlet arranged at the bottom of the reactor, a water outlet arranged at the top of the reactor, an air inlet main pipe connected to an external aeration device, and an exhaust main pipe for discharging the waste gas from the reactor; the air inlet of each group of membrane components is connected to the air inlet main pipe of the reactor, and the air outlet of each group of membrane components is connected to the exhaust main pipe of the reactor.

[0012] The density of Manam membrane modules placed in the reactor is 270-320 m 2 / m 3 ; It can be freely combined according to the size of the reactor, and multiple layers of Manam membrane components can be placed according to the height of the reactor; the wastewater inlet is set at the bottom of the reactor, and the wastewater passes through the reactor from bottom to top. The reactor is also equipped with acid and alkali agent dosing pipelines. The acid agent is sulfuric acid with a mass concentration of 10%, and the alkaline agent is NaOH, Na 2 CO 3 The mass concentration of the mixed solution is 10%. The reactor is also equipped with an online pH detection instrument to control the acid and alkali dosing to maintain the pH in the reactor at 7.0-7.7. The reactor is also equipped with an online DO detection instrument to control the aeration volume to maintain the DO in the reactor at 0.10-0.18 mg / L. The online pH and DO instruments are set at the top of the sludge area of ​​the reactor.

[0013] Due to the bubble-free aeration and heterogeneous mass transfer of the Manam membrane fibers, as well as the existence of mass transfer resistance, a gradient distribution of oxygen and pollutant concentrations is generated in the biofilm, thus forming a layered structure. In the inner layer of the biofilm, the high oxygen content is conducive to the enrichment of autotrophic nitrifying bacteria, and the ammonia nitrogen that penetrates into the membrane in the water body is converted into nitrite nitrogen; in the outermost layer of the biofilm, the dissolved oxygen concentration is the lowest, and the ammonia nitrogen is sufficient, which is suitable for the anaerobic ammonia oxidation reaction. The nitrogen formed by the reaction is transferred to the water and the nitrogen pollutants are removed. The air enters the reactor from the Manam membrane fibers, forming an aerobic biofilm on the side close to the membrane fibers and an anaerobic biofilm on the side away from the membrane fibers.

[0014] During the operation of the Bio-Manam reactor, anaerobic ammonium oxidation enhancing agent (EnAnam) was continuously added at a dosage of 1 L / m 3(One liter of agent is added to every cubic meter of wastewater); the formula of the anaerobic ammonium oxidation strengthening agent is: 0.6 mol / L fulvic acid, 0.3 mol / L boric acid, 0.05 mol / L magnesium chloride and 0.05 mol / L ferric chloride. The fulvic acid and boric acid in EnAnam can increase the EPS production of AnAOB bacteria, increase the speed of signal factor production, strengthen the "quorum sensing" effect, and improve the denitrification efficiency.

[0015] Among them, trace element reagents were continuously added to the Bio-Manam reactor inlet regulating tank at a dosage of 0.5L / m 3 ; The formula of trace element agent is: CuSO 4 200mg / L, Na 2 MO 4 100mg / L and MnSO 4 150mg / L.

[0016] Wherein, a heating pipe is arranged in the water inlet regulating tank, and a heat preservation layer is arranged outside the Bio-Manam reactor, so that the internal temperature of the Bio-Manam reactor is controlled to be 31-34° C. during operation.

[0017] The induced crystallization fluorine resource treatment is specifically: using an induced crystallization fluidized bed reactor for fluorine resource treatment; adding fluorite seeds into the reactor, the amount of seeds added is 30-40 kg / m 2 (Add 30-40 kg of seed per square meter of reactor cross section), seed particle size is 100-120 mesh; reactor water load is 3.6-4.5 kgF / m 2 ·h, the rising flow rate is 7-14m / h; the reactor is equipped with an online pH detection instrument, and compound calcium salt is added during the operation of the reactor to control the internal pH of the reactor to 5.5-6.7, the Ca / F ratio is 0.50-0.56, the seed crystal stays in the reactor for 5-8 days, and the reaction pH is adjusted to induce crystallization to generate fluorite. Compared with the induced crystallization defluorination technology of the prior art, the compound calcium salt is directly added to the reactor, and there is no need to add liquid alkali in advance to adjust the pH value. It can reduce the number of pre-reactors, simplify the process, and avoid the high concentration of ammonia volatilizing into the air after the pH is increased.

[0018] The enzymatic decomposition of hydrogen peroxide treatment is specifically as follows: inducing the effluent of the crystallization fluidized bed reactor to enter the reaction tank, adding enzyme (hydrogen peroxide catalytic decomposition enzyme) to the reaction tank, and the dosage is m(enzyme):m(H 2 O 2 )=0.2~0.3, stir and react for 45~60min.

[0019] Among them, H is removed in the reaction tank 2 O2 The wastewater then enters the activated carbon filter to 2 O 2 For deep removal, the activated carbon filter effluent H 2 O 2 The residual concentration is less than 0.1 mg / L.

[0020] Beneficial effects: Compared with the prior art, the present invention has the following significant effects: the present invention adopts the combined process of "induced crystallization fluorine resource utilization + enzyme-catalyzed hydrogen peroxide decomposition + integrated anaerobic ammonium oxidation", efficiently removes hydrogen peroxide through enzymatic reaction, simultaneously realizes fluoride removal and fluorine resource reuse through induced crystallization process, and realizes efficient treatment of high ammonia nitrogen wastewater under low energy consumption conditions through short-range nitrification-anaerobic ammonium oxidation process, solving the problems of large reagent consumption, large sludge production, high operating cost and low ammonia nitrogen removal rate in the traditional ammonium fluoride wastewater treatment process (stripping + chemical coagulation). For the same influent conditions (influent ammonia nitrogen concentration 700-1000mg NH 4+ -N / L), the biofilm thickness on the membrane filaments increased significantly by adopting the process of the present invention, the biomass per unit volume increased from 1.0-1.3g / L to 3.5-4.5g / L, and the denitrification load increased from 0.3kgN / (m 3 ·d) Increase to 1.0~1.6kgN / (m 3 ·d) The effluent ammonia nitrogen content dropped from 200-320 mg / L to below 80 mg / L. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of the structure of the Bio-Manm reactor and membrane assembly of the present invention;

[0022] Figure 2 It is a schematic diagram of the principle of anaerobic ammonia oxidation of the Bio-Manm reactor of the present invention;

[0023] Figure 3 The figure is a process flow chart of the treatment method of the present invention. DETAILED DESCRIPTION

[0024] like Figures 1-2As shown, at least one layer of Manam membrane assembly 2 is arranged in the Bio-Manam reactor 3 of the present invention; each layer of Manam membrane assembly contains a plurality of sets of Manam membrane assembly 2 arranged in parallel, each set of membrane assembly 2 includes an air inlet 2-2, an air inlet distributor 2-3, a Manam membrane filament 2-1, a waste gas collection chamber 2-5 and an air outlet 2-4, the gas enters the air inlet distributor 2-3 through the air inlet 2-2, the air inlet distributor 2-3 transports the gas to a plurality of hollow Manam membrane filaments 2-1 arranged in parallel, and after the reaction The waste gas enters the waste gas collecting chamber 2-5 and is discharged from the membrane assembly from the air outlet 2-4; the Bio-Manam reactor 3 also includes a water inlet 3-2 arranged at the bottom of the reactor, a water outlet 3-3 arranged at the upper part of the reactor, an air inlet main pipe 3-4 connected to the external aeration device, and an exhaust main pipe 3-5 for discharging the waste gas from the reactor; the air inlet 2-2 of each group of Manam membrane components 2 is connected to the air inlet main pipe 3-4 of the reactor, and the air outlet 2-4 of each group of Manam membrane components 2 is connected to the exhaust main pipe 3-5 of the reactor.

[0025] The Manam membrane modules 2 are placed in the Bio-Manam reactor 3 at a density of 270 to 320 m 2 / m 3 ; It can be freely combined according to the size of the reactor, and multiple layers of Manam membrane components can be placed according to the height of the reactor; the wastewater inlet is set at the bottom of the reactor, and the wastewater passes through the reactor from bottom to top. The reactor is also equipped with acid and alkali agent dosing pipelines. The acid agent is sulfuric acid with a mass concentration of 10%, and the alkaline agent is NaOH, Na 2 CO 3 The mass concentration of the mixed solution is 10%. The reactor is also equipped with an online pH detection instrument to control the acid and alkali dosing to maintain the pH in the reactor at 7.0-7.7. The reactor is also equipped with an online DO detection instrument to control the aeration volume to maintain the DO in the reactor at 0.10-0.18 mg / L. The online pH and DO instruments are set at the top of the sludge area of ​​the reactor.

[0026] The Manam membrane filaments used in the Manam membrane assembly of the present invention are prepared by the following method:

[0027] (1) Place a PVDF hollow fiber membrane (nominal pore size 0.1 μm) in a NaOH solution with a pH of 9.0 and soak for 2 h (to clean the surface coating or impurities of the PVDF membrane); after soaking, rinse the outside of the PVDF hollow fiber membrane with deionized water for 30 min, and then dry it at room temperature;

[0028] (2) Dissolve polydimethylsiloxane (PDMS) in n-hexane to prepare a 5% PDMS solution; immerse a PVDF hollow fiber membrane in the PDMS solution and circulate it for 8 hours; after the circulation, drain the PDMS solution and rinse it with deionized water for 60 minutes; after rinsing, place it in an 80°C environment for curing for 10 hours; PDMS is loaded on the outside of the PVDF membrane (outside the PVDF membrane wall) as an oxygen-permeable coating, and the PDMS layer transfers oxygen to water when ventilation is carried out in the PVDF membrane, and prevents water from penetrating into the PVDF membrane fibers; thus, a PVDF hollow fiber membrane with a PDMS layer loaded on the outside of the tube wall is obtained;

[0029] (3) First, prepare a 10 mmol / L tris-aminomethane-hydrochloric acid buffer solution; dissolve dopamine hydrochloride (DOPA) and persulfate in the tris-aminomethane-hydrochloric acid buffer solution to prepare DOPA solutions with concentrations of 1, 2, 5, and 10 mg / L, respectively. In each concentration of DOPA solution, n(persulfate):n(DOPA)=1.0-1.1;

[0030] (4) The PVDF hollow fiber membrane obtained in step (2) is sequentially immersed in DOPA solutions with concentrations of 1, 2, 5, and 10 mg / L for 2 h respectively (the purpose of sequential immersion is to obtain DOPA layers of different thicknesses and contents on the outside of the PVDF hollow fiber membrane, thereby improving its biocompatibility and enabling the DOPA layer to serve as a carbon source during the biofilm attachment process, greatly enhancing the attachment and growth ability of microorganisms on the outside of the membrane). After drying, the membrane fibers are rinsed with deionized water for 30 min to obtain Manam membrane fibers.

[0031] Each Manam membrane filament in the Manam membrane assembly 2 includes a support layer 1-1 with a hollow mesh structure, a PVDF membrane layer 1-2 fixed on the support layer 1-1, and a PDMS modified layer 1-3 loaded on the PVDF membrane layer 1-2 (the DOPA layer outside the PDMS modified layer 1-3 has been consumed as a carbon source when the biofilm is formed).

[0032] Example 1

[0033] High concentration ammonium fluoride wastewater from a chip factory, water volume 12m 3 / d, and its water quality is shown in the following table:

[0034] Table 1 shows the water quality of high concentration ammonium fluoride wastewater from a chip factory

[0035] pH <![CDATA[NH 3 -N(mg / L)]]> F(mg / L) <![CDATA[H 2 O 2 (mg / L)]]> TOC(mg / L) ＜0.5 2000～3000 2000～3000 1500～4000 ＜10

[0036] The above ammonium fluoride wastewater is treated by the treatment method of the present invention, such as Figure 3 As shown, the specific steps include:

[0037] (1) Water quality and quantity regulation: High-concentration ammonium fluoride wastewater first enters the wastewater regulating tank and mixes with other wastewater (low-concentration fluoride wastewater), with the flow ratio of the two being 1:2;

[0038] (2) Induced crystallization fluorine resource treatment: ammonium fluoride wastewater enters the fluidized bed water regulating tank from the wastewater regulating tank, and then enters the induced crystallization fluidized bed reactor. The induced crystallization fluidized bed reactor is used for fluorine resource treatment; fluorite seeds are added into the reactor, and the seed addition amount is 30kg / m 2 , seed particle size is 100-120 mesh; reactor water load is 4.0-4.4 kgF / m 2 ·h, the rising flow rate is 9-13m / h; the reactor is equipped with a pH online detection instrument, and liquid alkali and composite calcium salt are added during operation. The composite calcium salt is Ca(OH) 2 , CaCl 2 In the mixed solution, n(Ca(OH) 2 ): n(CaCl 2 )=1~1.14, the pH inside the reactor is controlled at 5.5~6.5, and the Ca / F ratio is 0.54; the seed crystals stay in the reactor for 7 days; the induced crystallization fluidized bed reactor is equipped with an exhaust gas collection system, and the ammonia-containing exhaust gas generated during the operation of the reactor enters the plant exhaust gas treatment system for treatment;

[0039] (3) Hydrogen peroxide catalytic decomposition treatment: Induce the effluent of the crystallization fluidized bed reactor into the reaction tank, add enzyme (hydrogen peroxide catalytic decomposition enzyme) to the reaction tank, and the dosage is m(enzyme):m(H 2 O 2 )=0.2~0.3, stir and react for 45min; after the reaction, H 2 O 2 The residual concentration is less than 2 mg / L;

[0040] (4) Activated carbon filtration: remove H in the reaction tank 2 O 2 The wastewater enters the activated carbon filter, which 2 O 2 For deep removal, the activated carbon filter effluent H 2 O 2 Not detected;

[0041] (5) Integrated anaerobic ammonium oxidation treatment: The effluent from the activated carbon filter enters the inlet regulating tank of the integrated anaerobic ammonium oxidation reactor (Bio-Manam), and then enters the Bio-Manam reactor; trace element reagents are continuously added to the inlet regulating tank of the Bio-Manam reactor (the formula of the trace element reagent is: CuSO 4 200mg / L, Na2 MO 4 100mg / L and MnSO 4 150mg / L), dosage is 0.5L / m 3 ; A heating pipe is provided in the regulating tank, and an insulation layer is provided outside the Bio-Manam reactor to control the internal temperature of the Bio-Manam reactor to be 31-34°C during operation;

[0042] Bio-Manam reactor volume load 1.22kgN / (m 3 ·d); Manam membrane modules are installed at the bottom of the Bio-Manam reactor. The height of the membrane modules is 2.4m and the placement density is 290m 2 / m 3 ; The reactor is equipped with an online pH detection instrument to control the acid and alkali dosing to maintain the pH in the reactor at 7.0-7.7; the reactor is also equipped with an online DO detection instrument to control the aeration volume to maintain the DO in the reactor at 0.10-0.18 mg / L; the online pH and DO instruments are set on the upper part of the reactor; the liquid rising velocity in the reactor is controlled by a circulating pump to maintain the liquid rising velocity at 3.0-4.5 m / h; during the operation of the Bio-Manam reactor, the anaerobic ammonium oxidation enhancement agent (EnAnam) is continuously added, and the dosage is 1 L / m 3 ; The formula of anaerobic ammonium oxidation enhancing agent is: fulvic acid 0.6moL / L, boric acid 0.3moL / L, magnesium chloride 0.05moL / L and ferric chloride 0.05moL / L.

[0043] Table 2 shows the effluent quality of each unit in the treatment process of Example 1

[0044]

Claims

1. A method for treating high-concentration ammonium fluoride wastewater in the electronics industry, characterized in that: Specifically, the method first performs induced crystallization fluorine resource treatment to remove fluoride in the wastewater; then performs enzyme catalytic decomposition of hydrogen peroxide to remove hydrogen peroxide in the wastewater; and finally performs integrated anaerobic ammonia oxidation treatment to remove ammonia nitrogen in the wastewater; Among them, the Bio-Manam reactor is used in the integrated anaerobic ammonium oxidation treatment process, and a Manam membrane module is arranged in the reactor. The Manam membrane filaments used in the Manam membrane module are prepared by the following method: (1) Soaking the PVDF hollow fiber membrane in a NaOH solution; after soaking, rinsing the PVDF hollow fiber membrane with deionized water, and then drying it at room temperature; (2) dissolving polydimethylsiloxane in n-hexane to prepare a PDMS solution with a mass fraction of 5 to 9%; immersing a PVDF hollow fiber membrane in the PDMS solution and circulating it for 6 to 10 hours; after the circulation is completed, the PDMS solution is discharged, dried and then rinsed with deionized water; after rinsing, high-temperature curing is performed to obtain a PVDF hollow fiber membrane with a PDMS layer loaded on the outer side of the tube wall; (3) First prepare a trisaminomethane-hydrochloric acid buffer solution; dissolve dopamine hydrochloride and persulfate in the trisaminomethane-hydrochloric acid buffer solution to prepare a DOPA solution with a concentration of 1 to 10 mg / L, wherein n(persulfate):n(DOPA)=1.0 to 1.1; (4) The PVDF hollow fiber membrane obtained in step (2) is sequentially immersed in DOPA solutions with concentrations of 1, 2, 5, and 10 mg / L for 1 to 3 hours respectively; after drying, deionized water is passed through the membrane fibers to rinse them, thereby obtaining Manam membrane fibers.

2. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 1, characterized in that: In step (2), after rinsing, place in an environment of 70 to 85° C. for curing for 10 to 16 hours.

3. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 1, characterized in that: At least one layer of Manam membrane components is arranged in the Bio-Manam reactor; each layer of Manam membrane components contains multiple groups of Manam membrane components arranged in parallel, and each group of membrane components includes an air inlet, an air inlet distributor, Manam membrane filaments, a waste gas collection chamber and an air outlet. The gas enters the air inlet distributor through the air inlet, and the air inlet distributor transports the gas to multiple hollow Manam membrane filaments arranged in parallel. The waste gas after the reaction enters the waste gas collection chamber and is discharged from the membrane component from the air outlet; the Bio-Manam reactor also includes a water inlet arranged at the bottom of the reactor, a water outlet arranged at the upper part of the reactor, an air inlet main pipe connected to an external aeration device, and an exhaust main pipe for discharging the waste gas from the reactor; the air inlet of each group of membrane components is connected to the air inlet main pipe of the reactor, and the air outlet of each group of membrane components is connected to the exhaust main pipe of the reactor.

4. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 3, characterized in that: The Bio-Manam reactor is also provided with acid and alkali agent dosing pipelines, an online pH detection instrument and an online DO detection instrument, so that the pH of the reactor is maintained at 7.0-7.7 and the DO is maintained at 0.10-0.20 mg / L during operation.

5. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 3, characterized in that: During the operation of the Bio-Manam reactor, the anaerobic ammonium oxidation enhancing agent was continuously added at a dosage of 1 L / m 3 ; The formula of anaerobic ammonium oxidation enhancing agent is: fulvic acid 0.6moL / L, boric acid 0.3moL / L, magnesium chloride 0.05moL / L and ferric chloride 0.05moL / L.

6. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 3, characterized in that: Continuously add trace element reagents to the Bio-Manam reactor inlet regulating tank at a dosage of 0.5L / m 3 ;The formula of trace element agent is: CuSO4 200mg / L, NaCl 100mg / L, Na2MO4 100mg / L and MnSO4 150mg / L.

7. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 6, characterized in that: A heating pipe is arranged in the water inlet regulating tank, and a heat preservation layer is arranged outside the Bio-Manam reactor, so that the internal temperature of the Bio-Manam reactor is controlled to be 31-34° C. during operation.

8. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 1, characterized in that: The induced crystallization fluorine resource treatment is specifically: using an induced crystallization fluidized bed reactor to carry out fluorine resource treatment; adding fluorite seeds into the reactor, and the amount of seed added is 30-40 kg / m 2 , seed particle size is 100-120 mesh; reactor water load is 3.6-4.5 kgF / m 2 ·h, the rising flow rate is 12-14m / h; the reactor is equipped with a pH online detection instrument, and liquid alkali and composite calcium salt are added during the operation of the reactor to control the internal pH of the reactor to be 5.5-6.7, the Ca / F ratio to be 0.50-0.56, the seed crystal residence time in the reactor to be 5-8 days, and the reaction pH is adjusted to induce crystallization to form fluorite.

9. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 1, characterized in that: The enzyme catalyzed decomposition of hydrogen peroxide treatment is specifically as follows: inducing the effluent of the crystallization fluidized bed reactor to enter the reaction tank, adding enzyme to the reaction tank, the dosage of which is m(enzyme):m(H2O2)=0.2-0.3, and stirring the reaction for 45-60 minutes.

10. The method for treating high-concentration ammonium fluoride wastewater in the electronics industry according to claim 9, characterized in that: After H2O2 is removed in the reaction tank, the wastewater enters the activated carbon filter for deep removal of H2O2.

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