A method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure

Abstract

The present invention provides a method for denitrification treatment of sulfide anaerobic ammonium oxidation granular sludge with a core-shell structure. It includes a bioreactor inoculated with sulfide anaerobic ammonium oxidation granular sludge with a core-shell structure, in which wastewater continuously flows into the bioreactor inoculated with sulfide anaerobic ammonium oxidation granular sludge with a core-shell structure. The reactor couples sulfur autotrophic denitrification with anaerobic ammonium oxidation without adding an external carbon source, and ammonia nitrogen and nitrate in the water are continuously, efficiently and stably reduced to nitrogen gas. The bioreactor in the present invention is an upflow anaerobic bioreactor, and the temperature is maintained at 35°C. The present invention proposes a denitrification treatment technology for sulfide anaerobic ammonium oxidation granular sludge with a core-shell structure. The sulfide anaerobic ammonium oxidation sludge takes anaerobic ammonium oxidation granular sludge as the core, and under the catalysis of zero-valent iron, the S produced by the disproportionation reaction of sodium thiosulfate 32 For shells, nitrate is obtained through S 32 It is short-range reduced to nitrite and can be utilized by the core anaerobic ammonium oxidation granular sludge in the nano range to achieve the simultaneous degradation of ammonia nitrogen and nitrate.

Description

Technical Field

[0001] The invention relates to a sulfide anaerobic ammonia oxidation granular sludge denitrification treatment technology with a core-shell structure, belongs to the field of sewage denitrification treatment, and is suitable for achieving deep denitrification of wastewater with a low C / N ratio. Background Art

[0002] The most traditional denitrification technology is the activated sludge method, which removes nitrogen through nitrification and denitrification. In traditional nitrification and denitrification biological denitrification technology, the nitrification reaction rate is slow, and the overload of ammonia nitrogen and organic matter reduces the nitrification activity; the heterotrophic denitrification stage usually requires the sewage treatment plant to add additional organic carbon sources (such as methanol, acetic acid, glucose, etc.) as electron donors for reducing nitrates, which not only increases operating costs, but also the chemical oxygen demand of the effluent may exceed the standard; on the other hand, the large amount of chemical agents added generates a large amount of residual sludge. The effluent COD and ammonia nitrogen values ​​cannot meet the emission limits specified in the emission standards, and deep treatment is required to meet the emission standards.

[0003] In recent years, sulfur autotrophic denitrification technology has gradually attracted widespread attention in the field of water treatment at home and abroad due to its advantages such as no need for external organic carbon source, low sludge production and low cost. This technology mainly uses inorganic sulfur sources such as sulfur, pyrite and thiosulfate as electron donors to reduce nitrates to complete denitrification under the action of sulfur autotrophic denitrifying bacteria. Anaerobic ammonia oxidation technology has been gradually applied in actual sewage treatment due to its high efficiency, economy and energy saving, and its unique advantages in treating nitrogen-rich wastewater. This technology uses nitrite as an electron acceptor and ammonia nitrogen as an electron donor to generate nitrogen gas and some nitrates through electron transfer.

[0004] With the continuous development of sewage treatment technology, the autotrophic denitrification and anaerobic ammonium oxidation coupling system driven by reduced sulfur compounds has been proven to remove ammonia and nitrates at the same time. In the existing technology, thiosulfate, a common electron donor for sulfur autotrophic denitrification, is easily released into the water phase and needs to be added continuously or intermittently. Excessive consumption is uneconomical and will increase the concentration of discharged sulfate. In contrast, the low water solubility of elemental sulfur greatly reduces its dosage and greatly reduces excessive consumption.

[0005] Studying the structure and function of activated sludge can maximize sulfur autotrophic denitrification and anaerobic ammonium oxidation, but few researchers have reported on this. Therefore, exploring new sulfur autotrophic denitrification technology coupled with nitrogen conversion pathways in anaerobic ammonium oxidation technology for deep denitrification has become an urgent problem to be solved in this field. Summary of the invention

[0006] In view of the above-mentioned shortcomings and deficiencies of the prior art, and the fact that the effluent of the existing sewage treatment technology is still difficult to meet the pollutant emission standards, the present invention provides a sulfur-based anaerobic ammonium oxidation granular sludge denitrification treatment technology with a core-shell structure, comprising: the wastewater to be treated continuously flows into a bioreactor inoculated with sulfur-based anaerobic ammonium oxidation granular sludge with a core-shell structure, and sulfur autotrophic denitrification is coupled with anaerobic ammonium oxidation, so that ammonia nitrogen and nitrate in the water are continuously, efficiently and stably reduced to nitrogen gas.

[0007] In addition, the present invention provides a core-shell structure (S 32 @Anaerobic ammonium oxidation granular sludge denitrification treatment technology, in which the sulfidation anaerobic ammonium oxidation sludge is based on anaerobic ammonium oxidation granular sludge, and the S produced by the disproportionation reaction of sodium thiosulfate is catalyzed by zero-valent iron. 32 For shells, nitrate is obtained through S 32 It is reduced to nitrite in a short distance and can be used by the core anaerobic ammonium oxidation granular sludge in the nanometer range to achieve the simultaneous degradation of ammonia nitrogen and nitrate. The sulfur shell significantly improves the mechanical properties of the granular sludge and its resistance to high loading rate, and protects the anaerobic ammonium oxidation bacteria in the core from the invasion of high free ammonia, free nitrite and dissolved oxygen, which is of great significance for the treatment of high ammonia nitrogen wastewater under anaerobic conditions, and provides a scientific technical reference for the practical promotion of the treatment of wastewater with a low carbon-nitrogen ratio.

[0008] The present invention makes up for the shortcomings of the traditional biological denitrification process by promoting the practice of sulfur autotrophic denitrification and anaerobic ammonia oxidation theory, and provides scientific guidance and reliable reference for the deep denitrification of wastewater.

[0009] The purpose of the present invention is achieved through the following technical solutions:

[0010] 1) Inoculation of activated sludge:

[0011] 250-300 mL of activated sludge obtained from a local urban sewage treatment plant (Guangzhou) was inoculated into a 1-liter bioreactor and acclimated for 20-22 days to enrich and culture sulfur autotrophic denitrifying bacteria SOB; then anaerobic ammonium oxidation sludge was added to the bioreactor;

[0012] 2) Forming granular sludge and starting the bioreactor:

[0013] Contains 1.94g / L~3.5g / LNa2S2O3·5H2O, 300~350mg / L NO3 - -N, 200~300mg / L NH 4+-N simulated wastewater enters the reactor, and 5mg / L~8mg / L zero-valent iron and 10mg / L~25mg / L xanthogenic acid are added at the same time, and then the initial pH value is adjusted to 7.5; sodium thiosulfate undergoes a disproportionation reaction under the catalysis of zero-valent iron to form sulfur precipitate S 32 The sulfur precipitates produced inside the cells and attached to the cell surface will wrap the anaerobic ammonium-oxidizing bacteria, so that the sulfide anaerobic ammonium-oxidizing sludge with a core-shell structure is gradually formed in the reactor; the hydraulic retention time HRT is gradually shortened: 6 to 8 hours, so that the sludge concentration is MLVSS = 2.654 to 3.185 g / L;

[0014] When treating simulated wastewater for 20-22 days, NO3 - -N removal rate is greater than 80%, NO2 - -N accumulation and pH decrease indicate that sulfur autotrophic denitrification has started successfully; when treating simulated wastewater for 23-45 days, NH4 + -N concentration reduction and NO2 - -N and NO3 - -N concentration decreased synchronously, NH4 + -N removal rate is greater than 90%, NO3 - -N removal rate is greater than 90% and pH value rises, which indicates that the reactor of sulfur autotrophic denitrification coupled with sulfur anaerobic ammonium oxidation with core-shell structure particles has been successfully started;

[0015] 3) Run the bioreactor:

[0016] The wastewater to be treated flows through the sulfur autotrophic denitrification coupled anaerobic ammonia oxidation bioreactor with core-shell granular sludge, and the SO4 in the treated wastewater effluent is regularly detected. 2- -S concentration, NO2 - -N concentration, NO3 - -N concentration, NH4 + -N concentration, S 0 / S 2- concentration.

[0017] Furthermore, in step 1), the bioreactor is an upflow bioreactor, which is mainly composed of three parts: a water reservoir, a peristaltic pump, and a reactor; the water reservoir, the peristaltic pump, and the reactor are sequentially connected through pipelines.

[0018] Furthermore, in step 1), the volume of the bioreactor is 1 to 1.2 L, the effective water volume is 0.8 to 0.9 L, and a biological fluidized bed and a three-phase separator are provided on the upper part of the reactor; the bioreactor is placed in a water bath, the water temperature is adjusted to 35° C. to 36° C., the water inlet bucket is anaerobically treated with an anaerobic sealing membrane, and the anaerobic environment of the inlet water is maintained as a whole; the bioreactor uses a submersible pump to supply water and controls the HRT to be 6 to 8 hours; and the pH is maintained at a slightly alkaline condition of 7 to 8.5.

[0019] Furthermore, when adjusting the initial pH value, 1 mol / L sodium hydroxide and 1 mol / L hydrochloric acid are used for adjustment respectively.

[0020] Further, in step 2), the simulated wastewater composition is: 1.94g / L~3.5g / LNa2S2O3·5H2O, 2.1~2.5g / L potassium nitrate, 0.75~1.13g / L ammonium chloride, 0.01g / L monopotassium phosphate, 1g / L sodium bicarbonate, 0.25g / L magnesium sulfate and trace elements I and trace elements II; wherein, trace element I includes 5g / L EDTA and 5g / L FeSO4·7H2O; trace element II includes: 15g / L EDTA, 0.43g / L ZnSO4·7H2O, 0.99g / L MnCl4·H2O, 0.014g / L H3BO4, 0.22g / L NaMO4·2H2O, 0.25g / L CuSO4·5H2O, 0.19g / L NiCl2·6H2O, 0.21g / LNaSeO4·10H2O and 0.24g / L COCl5·6H2O.

[0021] Furthermore, in step 2), the morphological structure of the sulfur sludge in the sulfur autotrophic denitrification coupled anaerobic ammonium oxidation system is: the outer layer is light yellow precipitation, the inner layer is red anaerobic ammonium oxidizing bacteria, and the sulfur granular sludge has a typical core-shell structure; wherein the sulfur autotrophic denitrifying bacteria are attached to the spherical S 32 @ Surface of anaerobic ammonium-oxidizing particles, anaerobic ammonium-oxidizing bacteria on spherical S 32 @The core of anaerobic ammonium oxidation granular sludge.

[0022] Furthermore, in step 2), the light yellow precipitate S 32 Mainly composed of 16.54% S 0 , 12.97% S 2- and 29.1% polysulfide (Sn 2- ),of which polysulfide (Sn 2- ) is formed by the reaction of SO with sulfide on the surface of anaerobic ammonium oxidation sludge.

[0023] Further, in step 2), the bacteria in the sulfur-containing anaerobic ammonium-oxidizing granular sludge in the bioreactor are clustered by spherical and short rod-shaped bacteria, mainly composed of anaerobic ammonium-oxidizing bacteria and sulfur-autotrophic denitrifying bacteria (the percentage in brackets below indicates the abundance of the microbial community, that is, the proportion of the total microbial community), among which Candidatus_Kuenenia (anaerobic ammonium-oxidizing bacteria, 18.75%), uncultured_bacterium_f_PHOS-HE36 (18.52%), Denitratisoma (15.60%), and Chloroflexi (partial denitrifying bacteria, 5.50%) account for the main abundance.

[0024] Furthermore, in step 3), Na2S2O3·5H2O is not added when treating the wastewater.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] 1. Advantages of sulfur autotrophic denitrification coupled with anaerobic denitrification technology: Compared with traditional heterotrophic denitrification, sulfur autotrophic denitrification does not require an external organic carbon source. Under low dissolved oxygen conditions, it reaches the ultimate denitrification level and greatly reduces the amount of residual sludge. The amount of sludge produced is only one-tenth of that of heterotrophic denitrification. 0 / Sn 2- The generated nitrite can be rapidly utilized in situ by anaerobic ammonium-oxidizing bacteria, thereby reducing the accumulation of nitrite and reducing the pollution to the environment and the harm to human health. In summary, the technology of the present invention has excellent environmental and economic benefits.

[0027] 2. The polysulfide (Sn 2- ) will greatly increase S 0 The water solubility of sulfide can be increased, the toxicity of sulfide to anaerobic ammonium oxidation can be reduced, and the thermodynamic rate of sulfur autotrophic denitrification coupled with anaerobic ammonium oxidation technology can be improved.

[0028] 3. S2O3 on the surface of sulfided anaerobic ammonium oxidation sludge in the present invention 2- / S 0 / Sn 2- / SO4 2- All of them can be used as sulfur sources to drive the coupling reaction of sulfur autotrophic denitrification and anaerobic ammonia oxidation in multiple ways.

[0029] 4. In the present invention, there are some nitrifying bacteria on the surface of the sulfided anaerobic ammonium oxidation sludge. Under micro-aerobic conditions, the nitrite produced by the partial nitrification reaction of the nitrifying bacteria reacts with ammonia nitrogen to generate nitrogen gas to achieve denitrification, while protecting the internal anaerobic ammonium oxidation bacteria from being poisoned by oxygen, thereby ensuring the normal denitrification.

[0030] 5. The surface of the sulfidation anaerobic ammonium oxidation sludge particles (sulfur shell) of the present invention is rough and has irregular cracks. The gaps or pores on the surface are conducive to the transfer of electrons and mass. At the same time, many filamentous bacteria or extracellular substances (such as EPS) on the surface are conducive to cell aggregation, resisting adverse environments and protecting internal bacteria. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of an upflow bioreactor implemented in the present invention.

[0032] Figure 2 The concentration change diagram of each substance in the industrial wastewater treated in Example 1 of the present invention, wherein (a) NH4 + -N, NO2 - -N、NO3 - -N, TN concentration changes; (b) SO4 2- -S、、S 0 / S 2- Concentration changes.

[0033] Figure 3 The concentration change diagram of each substance in the treated industrial wastewater of Example 2 of the present invention, wherein (a) NH4 + -N, NO2 - -N、NO3 - -N, TN concentration changes; (b) SO4 2- -S、、S 0 / S 2- Concentration changes.

[0034] Figure 4 The concentration variation diagram of each substance in the industrial wastewater treated in Example 3 of the present invention, wherein (a) NH4 + -N, NO2 - -N、NO3 - -N, TN concentration changes; (b) SO4 2- -S、、S 0 / S 2- Concentration changes. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical scheme and advantages of the present invention more clearly understood, the following is a detailed description of a sulfide anaerobic ammonium oxidation granular sludge denitrification treatment technology with a core-shell structure provided by the present invention in combination with an embodiment. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0036] Example 1: Treatment of fermentation antibiotic pharmaceutical wastewater discharged from a pharmaceutical company

[0037] 1) Inoculation of activated sludge:

[0038] 300 mL of activated sludge obtained from the aerobic tank section of Guangzhou Lijiao Wastewater Treatment Plant was inoculated into a 1-liter bioreactor and acclimated for 22 days to enrich and culture sulfur autotrophic denitrifying bacteria SOB; then anaerobic ammonia oxidation sludge was added to the bioreactor.

[0039] 2) Forming granular sludge and starting the bioreactor:

[0040] Contains 3g / LNa2S2O3·5H2O, 350mg / L NO3 - -N, 300mg / L NH4 + -N simulated wastewater enters the reactor, and 7mg / L zero-valent iron and 22mg / L xanthogenic acid are added at the same time. The initial pH is 7.5, and the initial pH is adjusted with 1mol / L sodium hydroxide and 1mol / L hydrochloric acid respectively. Sodium thiosulfate undergoes a disproportionation reaction under the catalysis of zero-valent iron to form sulfur precipitate S 32 The sulfur precipitates produced inside the cells and attached to the cell surface will wrap the anaerobic ammonium-oxidizing bacteria, so that the sulfide anaerobic ammonium-oxidizing sludge with a core-shell structure is gradually formed in the reactor. The hydraulic retention time HRT is gradually shortened to 8h, so that the sludge concentration is MLVSS = 3.185g / L.

[0041] When treating simulated wastewater for 20-22 days, NO3 - -N removal rate is greater than 80%, NO2 - -N accumulation and pH decrease indicate that sulfur autotrophic denitrification has started successfully; when treating simulated wastewater for 23-45 days, NH4 + -N concentration reduction and NO2 - -N and NO3 - -N concentration decreased synchronously, NH4 + -N removal rate is greater than 90%, NO3 - If the -N removal rate is greater than 90% and the pH value rises, it means that the sulfur autotrophic denitrification coupled with the sulfurized anaerobic ammonium oxidation reactor with core-shell structure particles is successfully started.

[0042] 3) Run the bioreactor:

[0043] The fermented antibiotic pharmaceutical wastewater flows through the sulfur autotrophic denitrification coupled anaerobic ammonia oxidation bioreactor with core-shell granular sludge, and the SO4 in the wastewater effluent is regularly tested. 2- -S concentration, NO2 - -N concentration, NO3 - -N concentration, NH4 + -N concentration, S 0 / S 2- Concentration. The wastewater quality of the fermentation antibiotic pharmaceutical wastewater treated is: NH4+ -N 286.8mg / L, NO3 - -N355mg / L, SO4 2- -S 80.82mg / L. Figure 2 It can be seen that the ammonia nitrogen removal rate is 91%, the nitrate nitrogen removal rate is 94%, and the total nitrogen removal rate is 93%.

[0044] Example 2: Treatment of fermentation antibiotic pharmaceutical wastewater discharged from a pharmaceutical company

[0045] 1) Inoculation of activated sludge:

[0046] 280 mL of activated sludge obtained from the aerobic tank section of Guangzhou Lijiao Wastewater Treatment Plant was inoculated into a 1-liter bioreactor and acclimated for 21 days to enrich and culture sulfur autotrophic denitrifying bacteria SOB; then anaerobic ammonia oxidation sludge was added to the bioreactor.

[0047] 2) Forming granular sludge and starting the bioreactor:

[0048] Contains 2.7g / LNa2S2O3·5H2O, 310mg / L NO3 - -N, 280mg / L NH4 + -N simulated wastewater enters the reactor, and 6 mg / L zero-valent iron and 18 mg / L xanthogenic acid are added at the same time. The initial pH is 7.5, and the initial pH is adjusted with 1 mol / L sodium hydroxide and 1 mol / L hydrochloric acid respectively. Sodium thiosulfate undergoes a disproportionation reaction under the catalysis of zero-valent iron to form sulfur precipitate S 32 The sulfur precipitates produced inside the cells and attached to the cell surface will wrap the anaerobic ammonium-oxidizing bacteria, so that the sulfide anaerobic ammonium-oxidizing sludge with a core-shell structure is gradually formed in the reactor. The hydraulic retention time HRT is gradually shortened to 7h, so that the sludge concentration is MLVSS = 2.972g / L.

[0049] When treating simulated wastewater for 20-22 days, NO3 - -N removal rate is greater than 80%, NO2 - -N accumulation and pH decrease indicate that sulfur autotrophic denitrification has started successfully; when treating simulated wastewater for 23-45 days, NH4 + -N concentration reduction and NO2 - -N and NO3 - -N concentration decreased synchronously, NH4 + -N removal rate is greater than 90%, NO3 - If the -N removal rate is greater than 90% and the pH value rises, it means that the sulfur autotrophic denitrification coupled with the sulfurized anaerobic ammonium oxidation reactor with core-shell structure particles is successfully started.

[0050] 3) Run the bioreactor:

[0051] The fermented antibiotic pharmaceutical wastewater flows through the sulfur autotrophic denitrification coupled anaerobic ammonia oxidation bioreactor with core-shell granular sludge, and the SO4 in the wastewater effluent is regularly tested. 2- -S concentration, NO2 - -N concentration, NO3 - -N concentration, NH4 + -N concentration, S 0 / S 2- Concentration. The wastewater quality of the fermentation antibiotic pharmaceutical wastewater treated is: NH4 + -N 250mg / L, NO3 - -N320mg / L, SO4 2- -S 70.98mg / L. Figure 3 It can be seen that the ammonia nitrogen removal rate is 91%, the nitrate nitrogen removal rate is 93%, and the total nitrogen removal rate is 92%.

[0052] Example 3: Treatment of nickel-containing electroplating wastewater discharged from an electroplating plant

[0053] 1) Inoculation of activated sludge:

[0054] 250 mL of activated sludge obtained from the aerobic tank section of Guangzhou Lijiao Wastewater Treatment Plant was inoculated into a 1-liter bioreactor and acclimated for 20 days to enrich and culture sulfur autotrophic denitrifying bacteria SOB; then anaerobic ammonia oxidation sludge was added to the bioreactor.

[0055] 2) Forming granular sludge and starting the bioreactor:

[0056] Contains 2.7g / LNa2S2O3·5H2O, 320mg / L NO3 - -N, 250mg / L NH4 + -N simulated wastewater enters the reactor, and 5 mg / L zero-valent iron and 13 mg / L xanthogenic acid are added at the same time. The initial pH is 7.5, and the initial pH is adjusted with 1 mol / L sodium hydroxide and 1 mol / L hydrochloric acid. Sodium thiosulfate undergoes a disproportionation reaction under the catalysis of zero-valent iron to form sulfur precipitate S 32 The sulfur precipitates produced inside the cells and attached to the cell surface will wrap the anaerobic ammonium-oxidizing bacteria, so that the sulfide anaerobic ammonium-oxidizing sludge with a core-shell structure is gradually formed in the reactor. The hydraulic retention time HRT is gradually shortened to 6h, so that the sludge concentration is MLVSS = 2.654g / L.

[0057] When treating simulated wastewater for 20-22 days, NO3 - -N removal rate is greater than 80%, NO2 --N accumulation and pH decrease indicate that sulfur autotrophic denitrification has started successfully; when treating simulated wastewater for 23-45 days, NH4 + -N concentration reduction and NO2 - -N and NO3 - -N concentration decreased synchronously, NH4 + -N removal rate is greater than 90%, NO3 - If the -N removal rate is greater than 90% and the pH value rises, it means that the sulfur autotrophic denitrification coupled with the sulfurized anaerobic ammonium oxidation reactor with core-shell structure particles is successfully started.

[0058] 3) Run the bioreactor:

[0059] The nickel-containing electroplating wastewater flows through the sulfur autotrophic denitrification coupled anaerobic ammonia oxidation bioreactor with core-shell granular sludge, and the SO4 in the treated wastewater effluent is regularly detected. 2- -S concentration, NO2 - -N concentration, NO3 - -N concentration, NH4 + -N concentration, S 0 / S 2- Concentration. The water quality of the treated nickel-containing electroplating wastewater is: NH4 + -N 250mg / L, NO3 - -N 320mg / L, SO4 2- -S70.98mg / L. Figure 4 It can be seen that the ammonia nitrogen removal rate is 91%, the nitrate nitrogen removal rate is 92%, and the total nitrogen removal rate is 91%.

Claims

1. A method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure, characterized in that The following steps are involved: 1) Inoculation of activated sludge: 250-300 mL of activated sludge was inoculated into the bioreactor and acclimatized for 20-22 days to enrich and culture sulfur autotrophic denitrifying bacteria SOB; then anaerobic ammonium oxidation sludge was added into the bioreactor; 2) Formation of sulfided granular sludge and start-up of bioreactor: Contains 1.94g / L~3.5g / LNa2S2O3·5H2O, 300~350mg / L NO3 − -N, 200~300mg / L NH 4+ -N simulated wastewater enters the reactor, and 5mg / L~8mg / L zero-valent iron and 10mg / L~25mg / L xanthogenic acid are added at the same time, and then the initial pH value is adjusted to 7.5; sodium thiosulfate undergoes a disproportionation reaction under the catalysis of zero-valent iron to form sulfur precipitate S 32 The sulfur precipitates produced inside the cells and attached to the cell surface will wrap the anaerobic ammonium-oxidizing bacteria, so that the sulfide anaerobic ammonium-oxidizing sludge with a core-shell structure is gradually formed in the reactor; the hydraulic retention time HRT is gradually shortened: 6~8h, so that the sludge concentration is MLVSS=2.654~3.185g / L; When treating simulated wastewater for 20-22 days, NO3 − -N removal rate is greater than 80%, NO2 − -N accumulation and pH decrease indicate that sulfur autotrophic denitrification has started successfully; When treating simulated wastewater for 23-45 days, NH4 + -N concentration reduction and NO2 − -N and NO3 − -N concentration decreased synchronously, NH4 + -N removal rate is greater than 90%, NO3 − -N removal rate was greater than 90% and the pH value increased, indicating that the reactor for sulfur autotrophic denitrification coupled with sulfur anaerobic ammonium oxidation with core-shell structure particles was successfully started; The wastewater to be treated flows through a bioreactor with sulfur autotrophic denitrification coupled with anaerobic ammonia oxidation of core-shell granular sludge, and the SO4 in the effluent of the treated wastewater is regularly tested. 2- -S concentration, NO2 − -N concentration, NO3 − -N concentration, NH4 + -N concentration, S 0 / S 2− concentration.

2. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 1, characterized in that: In step 1), the bioreactor is an upflow bioreactor, which is mainly composed of three parts: a water reservoir, a peristaltic pump, and a reactor; the water reservoir, the peristaltic pump, and the reactor are sequentially connected through pipelines.

3. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 1, characterized in that: In step 1), the volume of the bioreactor is 1-1.2 L, the effective water volume is 0.8-0.9 L, and a biological fluidized bed and a three-phase separator are arranged on the upper part of the reactor; the bioreactor is placed in a water bath, the water temperature is adjusted to 35°C-36°C, the water inlet bucket is anaerobically treated with an anaerobic sealing film, and the anaerobic environment of the inlet water is generally maintained; the bioreactor uses a submersible pump to supply water and controls the HRT to be 6-8h; and the pH is maintained at a slightly alkaline level of 7-8.

5.

4. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 1, characterized in that: When adjusting the initial pH value, 1 mol / L sodium hydroxide and 1 mol / L hydrochloric acid are used for adjustment respectively.

5. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 1, characterized in that: In step 2), the simulated wastewater composition is: 1.94g / L~3.5g / LNa2S2O3·5H2O, 2.1~2.5g / L potassium nitrate, 0.75~1.13g / L ammonium chloride, 0.01g / L monopotassium phosphate, 1g / L sodium bicarbonate, 0.25g / L magnesium sulfate and trace elements I and trace elements .

6. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 5, characterized in that: Trace elements I include 5g / L EDTA and 5g / L FeSO4·7H2O; trace elements II include: 15g / L EDTA, 0.43g / L ZnSO4·7H2O, 0.99g / L MnCl4·H2O, 0.014g / L H3BO4, 0.22g / L NaMO4·2H2O, 0.25g / L CuSO4·5H2O, 0.19g / L NiCl2·6H2O, 0.21g / L NaSeO4·10H2O and 0.24g / L COCl5·6H2O.

7. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 1, characterized in that: In step 2), the morphological structure of the sulfur sludge in the sulfur autotrophic denitrification coupled anaerobic ammonium oxidation system is: the outer layer is light yellow precipitation, the inner layer is red anaerobic ammonium oxidizing bacteria, and the sulfur granular sludge has a typical core-shell structure; the sulfur autotrophic denitrifying bacteria are attached to the spherical S 32 @ Surface of anaerobic ammonium-oxidizing particles, anaerobic ammonium-oxidizing bacteria on spherical S 32 @The core of anaerobic ammonium oxidation granular sludge.

8. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 1, characterized in that: In step 2), the yellowish precipitate S 32 By 16.54% S 0 , 12.97% S 2− and 29.1% polysulfide Sn 2− Composition, in which polysulfide Sn 2− It is formed by the reaction of SO with sulfide on the surface of anaerobic ammonium oxidation sludge.

9. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 1, characterized in that: In step 2), the bacteria in the sulfide anaerobic ammonium-oxidizing granular sludge in the bioreactor are aggregated into clusters of spherical and short rod-shaped bacteria.

10. The method for denitrification of anaerobic ammonium oxidation granular sludge with a core-shell structure according to claim 1, characterized in that: In step 3), Na2S2O3·5H2O is not added when treating the wastewater.

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