A multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater
By coupling SNAD granular sludge with H-PN flocculent sludge in an improved UASB reactor, the problem of incomplete nitrogen removal in high ammonia nitrogen wastewater was solved, achieving efficient and low-energy removal of nitrogen and organic matter, simplifying the operation process and reducing equipment footprint and costs.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHENYANG JIANZHU UNIVERSITY
- Filing Date
- 2024-12-04
- Publication Date
- 2026-05-26
AI Technical Summary
Existing anaerobic ammonia oxidation processes cannot effectively remove all nitrogen from high ammonia nitrogen wastewater. Furthermore, the activity of anaerobic ammonia oxidizing bacteria decreases under high ammonia nitrogen conditions. Traditional SNAD equipment occupies a large area and inhibits bacterial activity, while the split-type water inlet method is not ideal.
An improved UASB reactor was adopted, and a multi-pathway integrated synchronous denitrification method was formed by controlling the coupling of SNAD granular sludge and H-PN flocculent sludge. This method includes high ammonia nitrogen wastewater influent control, granular sludge cultivation and packing reinforcement. The SNAD granular sludge system was formed by coupling SAD granular sludge and H-PN flocculent sludge to achieve synergistic denitrification of ammonia oxidation, anaerobic ammonia oxidation and denitrification.
It achieves efficient removal of nitrogen from high ammonia nitrogen wastewater, improves total nitrogen removal rate and organic matter removal rate, reduces energy consumption, simplifies operation process, and reduces land area and sludge treatment costs.
Smart Images

Figure CN119591241B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of wastewater biological treatment technology, specifically relating to a multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater. Background Technology
[0002] Currently, there is a wide variety of nitrogen-rich wastewater (e.g., anaerobic sludge digestate, landfill leachate, swine wastewater, and biogas slurry). For treating this type of wastewater, nitrification and denitrification have been shown to consume more energy (electricity, chemicals, etc.). Anaerobic ammonia oxidation (AAO) is a process where anaerobic or anoxic bacteria (AnAOB) use NH4+ to oxidize nitrogen under anaerobic or hypoxic conditions. + -N is an electron donor, NO2 - -N acts as the electron acceptor, converting into nitrogen gas. Reaction equation:
[0003]
[0004] Therefore, the Anammox process has advantages such as low carbon emissions and high nitrogen removal efficiency. This process can remove NH4 from wastewater without aeration. + -N and NO2 - -N can save a lot of electricity.
[0005] A single anaerobic ammonium oxidation process cannot remove all nitrogenous substances from the system, such as nitrate (NO3). — N; and anaerobic ammonia oxidizing bacteria degrade NH4 in water. + -N and NO2 - After adding -N, some NO3 will be produced. - -N, using a single anaerobic ammonia oxidation process to degrade total nitrogen (TN) in the system is not feasible. Furthermore, most nitrogen-rich wastewater contains a certain amount of organic matter, and anaerobic ammonia oxidizing bacteria have reportedly low tolerance to organic matter; carbon sources are likely to inhibit their activity. Therefore, combining anaerobic ammonia oxidation with denitrification is considered. However, when the wastewater contains high levels of NH4+... + -N, contains almost no NO2. - When nitrogen (-N) is present, the anaerobic ammonia oxidation activity decreases, reducing water treatment efficiency. Therefore, the SNAD process was designed to treat nitrogen-rich wastewater. Existing split-type SNAD equipment has a large footprint, and the sequencing batch influent method inhibits bacterial activity, which are significant drawbacks. Summary of the Invention
[0006] This invention provides a multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater. In wastewater containing high ammonia nitrogen, it can achieve synergistic denitrification through ammonia oxidation, anaerobic ammonia oxidation and denitrification, and the effluent operation is stable.
[0007] The technical solution of the present invention is as follows:
[0008] A multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater utilizes a modified UASB (upflow anaerobic sludge blanket) reactor. Under controlled influent conditions of high ammonia nitrogen wastewater, the method controls the formation of an SNAD (coupled SAD granular sludge and H-PN flocculent sludge) granular sludge system and enhances its operation. The specific steps are as follows: high ammonia nitrogen wastewater influent control, SAD (anaerobic ammonia oxidation coupled with denitrification) granular sludge cultivation, H-PN (partial nitrification) flocculent sludge cultivation and acclimatization, coupling SAD granular sludge and H-PN flocculent sludge to form an SNAD granular sludge system, and SNAD granular sludge system packing reinforcement.
[0009] Furthermore, the improved UASB reactor, suitable for multi-pathway integrated simultaneous denitrification of high ammonia nitrogen wastewater, includes a main reactor, an inlet device, a water bath circulation device, a dual three-phase separator, an aeration device, a reflux metering pump, and an outlet tank. The inlet device includes an inlet tank, a pH meter, a DO meter, a pH and DO combined meter, a thermometer, and an inlet metering pump. The water bath circulation device includes a submersible pump and a temperature-controlled water bath. The aeration device includes an aeration disc and an aeration pump. The main reactor has a height-to-diameter ratio of 12:1, comprising an upper reaction zone and a lower reaction zone, with a height ratio of 1:1 between the upper and lower reaction zones. The dual three-phase separator is located at the top of the main reactor. The outlet of the inlet tank is connected to a valve at 35% of the total height from the bottom of the main reactor via the inlet metering pump. A pH meter is installed in the inlet tank and the main reactor. A DO meter and a thermometer are installed in the main reactor. The pH meter and DO meter are connected to a combined pH and DO meter. A temperature-controlled water bath is connected to the inlet of the main reactor at 10% of its total height from the bottom via the submersible pump. The outlet of the main reactor at 10% of its total height from the top is connected to the temperature-controlled water bath via a return pipe. The aeration disc is located inside the main reactor at 40% of its total height from the bottom. The aeration pump is located outside the main reactor and connected to the aeration disc via a pipeline. A return outlet is located at 10% of its total height from the top of the main reactor and connected to a return metering pump via a pipeline. The return metering pump is connected to the return inlet at the bottom of the main reactor via a pipeline. The outlet tank is connected to a dual three-phase separator via a pipeline.
[0010] Furthermore, the multi-path integrated synchronous denitrification method suitable for high ammonia nitrogen wastewater includes influent control of SAD granular sludge cultivation, H-PN flocculent sludge cultivation and acclimatization, and SNAD granular sludge system influent control.
[0011] The influent for SAD granular sludge cultivation is controlled as a continuous flow, with the ammonia nitrogen concentration (NH4+) in the influent controlled. + ) and nitrite (NO2) - The concentration and ratio of ammonia nitrogen (NH4Cl) and nitrite (NO2) are specified.- The concentration of ammonia nitrogen (NH4) in the influent is provided by NaNO2. + The concentration of nitrite (NO2) in the influent should be controlled between 20 and 350 mg / L. - The concentration was controlled between 25 and 450 mg / L, and the density of NO2 was... - ) / ρ(NH4 + The carbon source for the AnAOB stage is CH3COONa, and the carbon density is approximately 1.08 to 1.32. + )+ρ(NO2 - The pH value is 0.25–0.30; the pH control range for the AnAOB stage is 7–8.5; ρ(KH2PO4) / ρ(TN) = 3.5–5.5%, and ρ(KH2PO4) ≥ 6.0 mg / L; ρ(MgSO4·7H2O) = 300–450 mg / L, ρ(CaCl2·2H2O) = 50–65 mg / L; 1–2 mL each of trace elements I and II are added to 1 L of influent.
[0012] The influent for H-PN flocculent sludge cultivation and acclimatization was controlled as a continuous flow, with control over ammonia nitrogen (NH4) in the influent. + ) and Chemical Oxygen Demand (COD) cr The concentration of ammonia nitrogen is provided by NH4Cl, and COD... cr The concentration is provided by CH3COONa, and the influent ammonia nitrogen (NH4) is... + The applicable concentration range is 200–1200 mg / L, and the influent COD cr The applicable concentration range is 200-3000 mg / L; NaOH is used as the pH adjustment solution, and the pH control range is 8.5-9.0; the dissolved oxygen (DO) is controlled at 1.5-3.5 mg / L; ρ(KH2PO4) / ρ(TN) = 1.5-3.0%, and ρ(KH2PO4) ≥ 6.0 mg / L; ρ(MgSO4·7H2O) = 100-150 mg / L, ρ(CaCl2·2H2O) = 20-30 mg / L; 0.5-1 mL each of trace elements I and II are added to 1 L of influent.
[0013] The SNAD granular sludge system uses continuous flow influent to control ammonia nitrogen (NH4) in the influent. + ), nitrite (NO2) - ) and Chemical Oxygen Demand (COD) cr The concentration and ratio of ammonia nitrogen (NH4Cl) and nitrite (NO2) are specified. - The concentration is provided by NaNO2, COD cr The concentration is provided by CH3COONa, and the applicable range for influent total nitrogen (TN) concentration is 200–1200 mg / L. Influent COD...cr (CH3COONa) is suitable for concentrations ranging from 50 to 450 mg / L; ρ(NO2) — N) / ρ(NH4 + -N) gradually decreases from 1.0 to 0, ρ(COD) cr The ratio of KH2PO4 to TN is controlled within the range of 0.15–0.45; NaHCO3 is used as the inorganic carbon source; ρ(KH2PO4) / ρ(TN) = 2.5–3.5%, and ρ(KH2PO4) ≥ 6.0 mg / L; ρ(MgSO4·7H2O) = 150–300 mg / L, ρ(CaCl2·2H2O) = 40–60 mg / L; 0.8–1.25 mL each of trace elements I and II are added to 1 L of influent.
[0014] Trace element I: ρ(EDTA) = 5000 mg / L, ρ(FeSO4) = 5000 mg / L;
[0015] Trace elements II: ρ(EDTA)=15000mg / L, ρ(ZnSO4·7H2O)=430mg / L, ρ(MnCl2·4H2O)=990mg / L, ρ(H3BO4)=14mg / L, ρ(C uSO4·5H2O)=250mg / L, ρ(NaMoO4·2H2O)=220mg / L, ρ(NaSeO4·10H2O)=210mg / L, ρ(NiCl2·6H2O)=190mg / L.
[0016] Furthermore, the multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater includes the following SAD granular sludge cultivation methods: anaerobic ammonia oxidation sludge acclimation stage, anaerobic ammonia oxidation granular sludge formation stage, denitrification sludge coupled cultivation stage, and SAD granular sludge formation stage. The SAD granular sludge cultivation runs for 200–400 days. The SAD granular sludge cultivation process is conducted in the dark at a water temperature of 32±3℃. The SAD granular sludge cultivation uses an upflow anaerobic sludge bed with a reflux system, and the reflux is achieved using a pulse metering pump. The flow rate was 0.1–1.1 ml / stroke, the frequency was 120–180 strokes / min, and the pressure was 2–10 bar. The activity of obligate anammox bacteria (SAA) in SAD granular sludge reached 2.0–2.5 gN / (g-VSS / d); the activity of obligate denitrifying bacteria (SDA) reached 0.3–0.4 gN / (g-VSS / d); the nitrogen loading (NLR) gradually increased during the anammox sludge acclimatization stage and the anammox granular sludge formation stage, from 0.1 kg-N / (m³). 3 / d) increased to 3.0 kg-N / (m 3 / d), until the TN removal rate reaches over 95%; during the denitrification sludge coupled cultivation stage and the SAD granular sludge formation stage, the NLR gradually decreases, from 3.0 kg-N / (m 3 / d) decreased to 1.0 kg-N / (m 3 / d); the carbon removal load (CRR) gradually increased, from 0.1 kg-C / (m 3 / d) rises to 0.4 kg-C / (m 3 / d), until the COD removal rate reaches more than 98% and the TN removal rate is not less than 85%.
[0017] Furthermore, the multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater includes a H-PN flocculent sludge cultivation and acclimatization process comprising a full nitrification stage, a short-cut nitrification stage, and a semi-nitrification stage. In the full nitrification stage, the hydraulic retention time (HRT) is 12 hours, with continuous aeration for 12 hours, controlling the aeration rate at 5-10 L / min and the DO at 4-5 mg / L. In the short-cut nitrification stage, the HRT is 10 hours, with continuous aeration for 10 hours, controlling the aeration rate at 2.5-6.5 L / min and the DO at 0.5-1.8 mg / L. In the semi-nitrification stage, the HRT is 12 hours, with intermittent aeration, each cycle consisting of four cycles of aeration and aeration stoppage, ending with aeration stoppage and sedimentation. The aeration rate is controlled at 1.0-2.5 L / min, and the DO at 0.25-1.3 mg / L. The H-PN flocculent sludge effluent contains nitrite (NO2). - ) and ammonia nitrogen (NH4) + The ratio is 1 to 1.3.
[0018] Furthermore, the process parameters in the formation process of the SNAD granular sludge system, which is suitable for multi-pathway integrated simultaneous denitrification of high ammonia nitrogen wastewater, include: operating control parameters and end-of-period index parameters; the operating control parameters include: ρ(NO2) — N) / ρ(NH4 + -N), control DO and aeration intensity in the upper and lower reaction zones, control reaction zone temperature, control reflux ratio and reflux method, control free ammonia (FA), free nitrite (FNA) and FA / FNA ratio, control pH, and control HRT; end-of-period indicator parameters include: controlling the activated sludge index (SVI) of granular sludge. 30 Volatile suspended solids (VSS) / suspended solids (SS) are used to measure sludge performance, morphology, and particle size characteristics, control changes in extracellular polymeric substances (EPS) content and composition, control system microbial abundance and functional characteristics, and control microbial activity.
[0019] Furthermore, the multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater includes the following SNAD granular sludge system formation process: the initial stage of SAD granular sludge addition as stage I, the SAD granular sludge adaptation period as stage II, the H-PN flocculent sludge addition stage as stage III, and the SNAD granular sludge adaptation stage as stage VI; SNAD granular sludge system packing reinforcement as stage V; each stage adjusts the system strategy with operating control parameters, and when the end-of-stage indicator parameters reach certain requirements, the system enters the next stage and adjusts the operating control parameters accordingly.
[0020] The specific process is as follows:
[0021] Stage I operating control parameters: ρ(NO2-N) / ρ(NH4) + -N) gradually decreased from 1.0 to 0.7; adjusted the relationship between system air supply and oxygen consumption, with an aeration intensity of 3-5 L / min to ensure DO = 0.8-1.0 mg / L in the upper reaction zone and DO = 0.1-0.2 mg / L in the lower reaction zone; controlled the reflux ratio at 30-40, using a reflux metering pump pulse inlet method, with a reflux metering pump pulse stroke flow rate / inlet flow rate of 0.1-1.1, a frequency of 120-180 strokes / min, and a pressure of 2-10 bar; FA = 5-10 mg / L, FNA = 2-8 μg / L, pH = 8.36-8.85, H The response time (RT) is 20-30 hours. The control parameters at the end of Stage I are: total nitrogen removal rate (TNRE) increased to over 70%, and organic matter removal rate (CRE) increased to over 65%; SVI30 in the upper reaction zone is 220-300 mL / g, VSS / SS ≥ 0.95; granular sludge with a particle size of 1-3 mm in the lower reaction zone accounts for no less than 85%, and VSS / SS ≥ 0.72; EPS content in the sludge layer of the upper reaction zone is 180-200 mg / g VSS, and the EPS structure distribution is soluble EPS (S-EPS) and loosely bound EPS (S-EPS). The ratio of bound EPS (LB-EPS) and tightly bound EPS (TB-EPS) was 35%:10%:55%; the EPS content in the sludge layer of the lower reaction zone was 500-520 mg / g VSS, and the EPS structure distribution was S-EPS, LB-EPS, and TB-EPS in the ratio of 32%:13%:55%; the protein-polysaccharide ratio (PN / PS) in the EPS of the upper reaction zone was 0.2-0.4; the PN / PS ratio in the EPS of the lower reaction zone was 1.2-1.3; the α-helix / (random coil + β-sheets) ratio of the protein secondary structure in the EPS reached 60-63%; and the obligate anaerobic ammonium oxidizing bacteria activity (SAA) reached 120-135 mg N·g VSS. -1 ·h-1 The activity of obligate denitrifying bacteria (sDNA) reached 25–35 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 9–12 mg N·g VSS. -1 ·h -1 At the phylum level, the relative abundances of the major bacterial groups Proteobacteria, Planctomycetota, Bacteroidota, and Chloroflexi reached 40-50%, 25-40%, 5-20%, and 2-10%, respectively. At the genus level, the relative abundances of the major bacterial groups Candidatus Kuenenia, Commonas, Zoogloea, Denitrosoma, and Nitrosomonas reached 25-35%, 20-25%, 0-1%, 5-10%, and 0-1%, respectively.
[0022] Phase II operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) was gradually reduced from 0.7 to 0.4, and the relationship between the system's air supply and oxygen consumption was adjusted. The aeration intensity was 3.5-6.5 L / min to ensure that the DO in the upper reaction zone was 0.9-1.6 mg / L and the DO in the lower reaction zone was 0.1-0.2 mg / L. The reflux ratio was controlled at 25-35, and the reflux method adopted was a reflux metering pump pulse water inlet method. The reflux metering pump pulse stroke flow rate was 0.1-1.1 ml / stroke, the frequency was 110-160 strokes / min, and the pressure was 2-10 bar. FA was 7-12 mg / L, FNA was 3-7 μg / L, pH was 8.0-8.25, and HRT was 20-25 h. The control parameters at the end of stage II were: the system TNRE increased to above 75%, CRE increased to 70%, and SVI30 in the upper reaction zone was 20. The concentration of EPS in the sludge layer of the upper reaction zone is 0-250 mL / g, VSS / SS ≥ 0.83, with granular sludge of 1-3 mm diameter accounting for no less than 75% and VSS / SS ≥ 0.78; the EPS content in the sludge layer of the upper reaction zone is 190-210 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 37%:12%:56%; the EPS content in the sludge layer of the lower reaction zone is 460-490 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the PN / PS ratio in the EPS of the upper reaction zone is 0.4-0.5; the PN / PS ratio in the EPS of the lower reaction zone is 1.1-1.2; the activity of obligate anaerobic ammonia oxidizing bacteria (SAA) reaches 115-125 mgN·gVSS. -1 ·h -1The activity of obligate denitrifying bacteria (sDNA) reached 30–40 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 10–15 mg N·g VSS. -1 ·h -1 ;
[0023] Stage III operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) gradually decreased from 0.4 to 0.2, adjusting the system's air supply and oxygen consumption relationship, with an aeration intensity of 4-7 L / min; ensuring DO = 1.2-2.0 mg / L in the upper reaction zone and DO = 0.1-0.2 mg / L in the lower reaction zone; controlling the reflux ratio at 25-30, using a reflux metering pump pulse inlet method, with a pulse stroke flow rate of 0.1-1.1 ml / stroke, a frequency of 130-200 strokes / min, and a pressure of 2-10 bar; FA = 8-11 mg / L, FNA = 3.5-7 μg / L, adjusting pH to 7.65-8.05; HRT of 15-20 h; end-stage control parameters for Stage III: system TNRE increased to over 80%, CRE increased to over 80%; SVI30 in the upper reaction zone was 1. The sludge content in the upper reaction zone is 80–210 mL / g, VSS / SS ≥ 0.74, with at least 70% of the granular sludge in the lower reaction zone having a particle size of 1–3 mm and a VSS / SS ≥ 0.85; the EPS content in the upper reaction zone sludge layer is 210–240 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 37%:12%:56%; the EPS content in the lower reaction zone sludge layer is 400–430 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the PN / PS ratio in the upper reaction zone EPS is 0.5–0.6; the PN / PS ratio in the lower reaction zone EPS is 0.8–0.9; and the obligate anaerobic ammonia oxidizing bacteria activity (SAA) reaches 110–125 mgN·g VSS. -1 ·h -1 The activity of obligate denitrifying bacteria (sDNA) reached 30-35 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 25–30 mg N·g VSS. -1 ·h -1 ;
[0024] Phase IV operating control parameters: ρ(NO2-N) / ρ(NH4) +-N) gradually decreased from 0.2 to 0, adjusting the relationship between system air supply and oxygen consumption, with an aeration intensity of 5-7 L / min; ensuring DO = 1.5-1.8 mg / L in the upper reaction zone and DO = 0.1-0.2 mg / L in the lower reaction zone; controlling the reflux ratio at 20-30, using a reflux metering pump pulse inlet method, with a pulse stroke flow rate of 0.1-1.1 ml / stroke, a frequency of 120-160 strokes / min, and a pressure of 2-10 bar; FA = 9-11 mg / L, FNA = 3-5 μg / L, adjusting pH to 7.65-8.05; HRT of 10-15 h; end-stage IV control parameters: system TNRE increased to 95%, CRE increased to 90%; SVI30 in the upper reaction zone is... The sludge content in the upper reaction zone is 170-180 mL / g, VSS / SS ≥ 0.67, with at least 65% of the granular sludge in the lower reaction zone having a particle size of 1-3 mm and a VSS / SS ≥ 0.9; the EPS content in the upper reaction zone sludge layer is 230-250 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the EPS content in the lower reaction zone sludge layer is 260-280 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 35%:10%:55%; the PN / PS ratio in the upper reaction zone EPS is 0.6-0.7; the PN / PS ratio in the lower reaction zone EPS is 0.4-0.6; the α-helix / (random coil + β-sheets) ratio of the protein secondary structure in the EPS reaches 77-80%; and the obligate anaerobic ammonium oxidizing bacteria activity (SAA) reaches 100-120 mg N·g VSS. -1 ·h -1 The activity of obligate denitrifying bacteria (sDNA) reached 40–55 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 60–75 mg N·g VSS. -1 ·h -1 At the phylum level, the relative abundances of the major bacterial groups Proteobacteria, Planctomycetota, Bacteroidota, and Chloroflexi reached 40-50%, 15-25%, 15-35%, and 2-15%, respectively. At the genus level, the relative abundances of the major bacterial groups Candidatus Kuenenia, Commonas, Zoogloea, Denitrosoma, and Nitrosomonas reached 10-35%, 5-10%, 2-5%, 15-35%, and 10-25%, respectively.
[0025] V-stage operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) is 0. Adjust the system's air supply and oxygen consumption to ensure that DO in the upper reaction zone is 1.5-2.5 mg / L and DO in the lower zone is 0.1-0.2 mg / L; aeration intensity is 5-6 L / min; reflux ratio is controlled at 20-30, and reflux is achieved using a reflux metering pump with pulse inlet. The reflux metering pump pulse stroke flow rate is 0.1-1.1 ml / stroke, frequency is 100-120 strokes / min, and pressure is 2-10 bar; FA is 9-10 mg / L, FNA is 4-5 μg / L, and pH is adjusted to 7.65-8.05; HRT is 10-20 h; V-stage end control parameters: maintain system TNRE at 85-95%, CRE at 80-90%; lower reaction... The sludge in the upper reaction zone shall contain no less than 60% granular sludge with a particle size of 1-3 mm, and a VSS / SS ratio ≥ 0.92; the EPS content in the sludge layer of the upper reaction zone shall be 290-320 mg / g VSS, and the EPS structure distribution shall be S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the EPS content in the sludge layer of the lower reaction zone shall be 200-230 mg / g VSS, and the EPS structure distribution shall be S-EPS, LB-EPS, and TB-EPS in a ratio of 35%:10%:55%; the PN / PS ratio in the EPS of the upper reaction zone shall be 0.7-0.8; the PN / PS ratio in the EPS of the lower reaction zone shall be 0.25-0.35; and the activity of obligate anaerobic ammonia oxidizing bacteria (SAA) shall reach 100-120 mgN·gVSS. -1 ·h -1 The activity of obligate denitrifying bacteria (sDNA) reached 40–55 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 60–75 mg N·g VSS. -1 ·h -1 .
[0026] Furthermore, in the aforementioned multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater, the upper reaction zone of the main reactor is dominated by black granular sludge and flocculent sludge, accounting for 35-55% and 15-45% respectively; the lower reaction zone is dominated by red granular sludge and black granular sludge, accounting for more than 55% and more than 35% respectively; the upper reaction zone realizes semi-nitrification (H-PN) and denitrification functions, with the main functional bacteria accounting for more than 55%; the lower reaction zone realizes anaerobic ammonia oxidation and denitrification coupling (SAD) functions, with the main functional bacteria accounting for more than 75%.
[0027] Furthermore, in the aforementioned multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater, polyurethane block packing is used in the SNAD granular sludge system packing enhancement; the polyurethane block packing has dimensions of (1-2.5)cm × (1-2.5)cm × (1-2.5)cm, a porosity of 96-99%, and an organic loading rate of 0.7-1.2Kg / m³. 3 ·d, specific surface area is 30000-35000 m² 2 / m 3 The pore size is 1mm to 1.5mm, and the density is 0.97 to 1.05g / cm³. 3 .
[0028] The beneficial effects of this invention are as follows:
[0029] 1. This invention uses ammonia nitrogen as the sole nitrogen source for the influent, with a concentration of 200–1200 mg / L, and the ρ(NO2) in the influent... - ) / ρ(NH4 + The pH range is 0 to 1.0. During its operation, temperature, pH, organic carbon source and other conditions need to be controlled simultaneously. Through the anaerobic ammonia oxidation-denitrification (SAD) granular sludge cultivation stage and short-cut nitrification coupling, ammonia oxidizing bacteria, anaerobic ammonia oxidizing bacteria and denitrifying bacteria can coexist in the system. It can simultaneously remove nitrate nitrogen produced by anaerobic ammonia oxidation itself and nitrogen sources and COD content in wastewater, which are mainly ammonia nitrogen, thus improving the total nitrogen removal efficiency of the system. During the cultivation period, there is no need to deliberately remove oxygen from the wastewater.
[0030] 2. In this invention, a portion of the high-concentration ammonia nitrogen in the influent is converted into nitrite. The converted nitrite and remaining ammonia nitrogen are then returned to the bottom SAD treatment via a reflux pump, repeating this cycle continuously. This influent mode allows ammonia-oxidizing bacteria to partially convert ammonia nitrogen into nitrite, which is then absorbed by anaerobic ammonia-oxidizing bacteria. Furthermore, the organic matter in the influent provides energy for both ammonia-oxidizing and denitrifying bacteria. It effectively controls the influent pH within a reasonable range and regulates dissolved oxygen (DO) to achieve a suitable influent concentration for the bottom SAD sludge in the upper semi-nitrified return water.
[0031] 3. The method of this invention is simple and easy to operate, overcoming the problems of decreased denitrification efficiency and high ammonia nitrogen content in low C / N dissolved oxygen wastewater. It achieves the goal of highly efficient denitrification and carbon reduction by coupling ammonia-oxidizing bacteria, anaerobic ammonia-oxidizing bacteria, and denitrifying bacteria into one system. It overcomes the technical difficulty of multi-species coexistence, achieving synergistic and efficient denitrification and carbon removal by ammonia-oxidizing bacteria, anaerobic ammonia-oxidizing bacteria, and denitrifying bacteria in an integrated continuous flow influent mode.
[0032] 4. The H-PN flocculent sludge and SAD sludge involved in this invention have a high sludge age, which reduces the sludge treatment costs caused by sludge discharge compared to the traditional activated sludge process.
[0033] 5. To achieve efficient and stable removal of TN by SNAD, this invention focuses on controlling the following aspects:
[0034] 1) Control the influent parameters and concentration: When ρ(NO2) — N) / ρ(NH4 + When the -N ratio is low, the system contains a small amount of AOB functional bacteria, which can convert excess ammonia nitrogen into nitrite to supply AnAOB, and the system has a circulating pump to buffer ρ(NO2). — N) / ρ(NH4 + -N) impact;
[0035] 2) Inlet point and method: The inlet and aeration of the upper part will be preferentially contacted with short-cut nitrification to realize the conversion of ammonia nitrogen into nitrite, and FA concentration and low DO will be used to suppress NOB;
[0036] 3) pH, FA, FNA, FA / FNA: pH is obviously a crucial factor for SNAD systems. The pH that can be adapted to varies at different stages of SNAD formation, which will directly affect FA and FNA. At the same time, FA and FNA determine the treatment effect of short-cut nitrification and anaerobic ammonia oxidation. During the formation of the SNAD system, the pH adjustment gradually decreases. Therefore, the realization of an integrated continuous flow SNAD system boils down to pH. The addition of semi-nitrifying flocculent sludge can effectively improve the system's ability to convert ammonia nitrogen into nitrite.
[0037] 4) Recirculation ratio: Due to recirculation, the lower DO is mainly controlled by the aeration rate of the upper zone. The addition of aeration rate does not reduce the denitrification performance of the system. On the one hand, part of the DO concentration in the lower zone is utilized by aerobic microorganisms in the bottom zone. On the other hand, Anammox generates nitrogen gas, which discharges DO from the system.
[0038] 5) Packing material: After the packing material is added, a biofilm forms, which alters the oxygen-containing environment, increases anaerobic bacteria, and promotes the production of NO3. - -N is converted to NO2 - -N disrupts the balance of semi-nitrifying bacteria, NO2 - -N / NH4 + The ratio of -N fluctuates significantly, and the efficiency of the semi-nitrification system in the upper region increases with time.
[0039] 6) SVI 30 SVI (Sedimentation Performance Index) is an important indicator for measuring the settling performance of aerobic sludge. It is also a key indicator for the SVI of semi-nitrifying flocculent sludge in the upper zone. 30The overall trend is downward, which may be due to the combined effect of the pulse and aeration shear force of the bottom metering pump, which causes the upper flocculent sludge to gradually become granular, thus exhibiting good settling performance. Furthermore, PN / PS gradually decreases while VSS / SS gradually increases. Attached Figure Description
[0040] Figure 1 This is a schematic diagram of an improved UASB reactor; where: 1. Main reactor, 2. Dual three-phase separator, 3. Reflux metering pump, 4. Inlet tank, 5. Inlet metering pump, 6. Temperature-controlled water bath, 7. Submersible pump, 8. Aeration disc, 9. Aeration pump, 10. Outlet tank, 11. pH and DO combined meter, 12. pH meter, 13. DO meter;
[0041] Figure 2 The images and microscopic images of SNAD granular sludge are shown below; (a) is a real-world image of stage I granular sludge, (b) is a 1k SEM image of stage I, (c) is a 5k SEM image of stage I, (d) is a real-world image of stage V granular sludge, (e) is a 1k SEM image of stage V, and (f) is a 5k SEM image of stage V.
[0042] Figure 3 The image shows the effect of SNAD process treatment; where (a) is NH4. + (a) shows the influent and effluent concentrations and removal rates of nitrogen (NO2), (b) shows the influent and effluent concentrations and removal rates of COD (COD), and (c) shows the NO2 concentrations and removal rates of nitrogen (NO2). — N and NO3 — N influent and effluent concentrations and removal rates, (d) represents TN influent and effluent concentrations and removal rates, (e) represents free ammonia (FA) influent and effluent concentrations, (f) represents free nitrite (FNA) influent and effluent concentrations; (g) represents DO at the top and bottom, and (h) represents the pH values of the influent, effluent, and bottom.
[0043] Figure 4 This is a diagram showing the distribution of microbial communities in the SNAD granular sludge system; where A represents the sludge on the lower side of the reactor, B represents the sludge on the upper side of the reactor, and C represents the sludge on the upper side of the reactor. Detailed Implementation
[0044] A multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater is proposed. This method utilizes a modified UASB reactor to control the formation of an SNAD granular sludge system under controlled influent conditions and to enhance the operation of the SNAD granular sludge system. The specific steps are as follows: high ammonia nitrogen wastewater influent control, SAD granular sludge cultivation, H-PN flocculent sludge cultivation and acclimatization, coupling of SAD granular sludge and H-PN flocculent sludge to form an SNAD granular sludge system, and reinforcement of the SNAD granular sludge system packing.
[0045] like Figure 1 As shown, the improved UASB reactor includes a main reactor 1, an inlet device, a water bath circulation device, a dual three-phase separator 2, an aeration device, a reflux metering pump 3, and an outlet tank 10. The inlet device includes an inlet tank 4, a pH meter 12, a DO meter 13, a pH and DO combined meter 11, a thermometer, and an inlet metering pump 5. The water bath circulation device includes a submersible pump 7 and a temperature-controlled water bath 6. The aeration device includes an aeration disc 8 and an aeration pump 9. The main reactor 1 has a height-to-diameter ratio of 12:1 and includes an upper reaction zone and a lower reaction zone, with a height ratio of 1:1 between the upper and lower reaction zones. The dual three-phase separator 2 is located at the top of the main reactor 1. The outlet of the inlet tank 4 is connected to a valve at 35% of the total height of the main reactor 1 from the bottom via the inlet metering pump 5. A pH meter is installed in the inlet tank 4 and the main reactor 1. 12. A DO meter 13 and a thermometer are installed in the main reactor 1. The pH meter 12 and DO meter 13 are connected to a pH and DO combined measuring instrument 11. A temperature-controlled water bath 6 is connected to the inlet of the main reactor 1 at 10% of its total height from the bottom via the submersible pump 7. The outlet of the main reactor 1 at 10% of its total height from the top is connected to the temperature-controlled water bath 6 via a return pipe. The aeration disc 8 is located inside the main reactor 1 at 40% of its total height from the bottom. The aeration pump 9 is located outside the main reactor 1 and connected to the aeration disc 8 via a pipeline. A return outlet is located at 10% of its total height from the top of the main reactor 1 and connected to the return metering pump 3 via a pipeline. The return metering pump 3 is connected to the return inlet at the bottom of the main reactor 1 via a pipeline. The outlet tank 10 is connected to the dual three-phase separator 2 via a pipeline. In use, a wastewater liquid mixture is added to the inlet tank 4.
[0046] The influent control steps for high ammonia nitrogen wastewater include influent control for SAD granular sludge cultivation, influent control for H-PN flocculent sludge cultivation and acclimatization, and influent control for SNAD granular sludge system.
[0047] The influent for SAD granular sludge cultivation is controlled as a continuous flow, with the ammonia nitrogen concentration (NH4+) in the influent controlled. + ) and nitrite (NO2) - The concentration and ratio of ammonia nitrogen (NH4Cl) and nitrite (NO2) are specified. - The concentration of ammonia nitrogen (NH4) in the influent is provided by NaNO2. + The concentration of nitrite (NO2) in the influent should be controlled between 20 and 350 mg / L. - The concentration was controlled between 25 and 450 mg / L, and the density of NO2 was... - ) / ρ(NH4 + The carbon source for the AnAOB stage is CH3COONa, and the carbon density is approximately 1.08 to 1.32. + )+ρ(NO2 -The pH value is 0.25–0.30; the pH control range for the AnAOB stage is 7–8.5; ρ(KH2PO4) / ρ(TN) = 3.5–5.5%, and ρ(KH2PO4) ≥ 6.0 mg / L; ρ(MgSO4·7H2O) = 300–450 mg / L, ρ(CaCl2·2H2O) = 50–65 mg / L; 1–2 mL each of trace elements I and II are added to 1 L of influent.
[0048] The influent for H-PN flocculent sludge cultivation and acclimatization was controlled as a continuous flow, with control over ammonia nitrogen (NH4) in the influent. + ) and Chemical Oxygen Demand (COD) cr The concentration of ammonia nitrogen is provided by NH4Cl, and COD... cr The concentration is provided by CH3COONa, and the influent ammonia nitrogen (NH4) is... + The applicable concentration range is 200–1200 mg / L, and the influent COD cr The applicable concentration range is 200-3000 mg / L; NaOH is used as the pH adjustment solution, and the pH control range is 8.5-9.0; the dissolved oxygen (DO) is controlled at 1.5-3.5 mg / L; ρ(KH2PO4) / ρ(TN) = 1.5-3.0%, and ρ(KH2PO4) ≥ 6.0 mg / L; ρ(MgSO4·7H2O) = 100-150 mg / L, ρ(CaCl2·2H2O) = 20-30 mg / L; 0.5-1 mL each of trace elements I and II are added to 1 L of influent.
[0049] The SNAD granular sludge system uses continuous flow influent to control ammonia nitrogen (NH4) in the influent. + ), nitrite (NO2) - ) and Chemical Oxygen Demand (COD) cr The concentration and ratio of ammonia nitrogen (NH4Cl) and nitrite (NO2) are specified. - The concentration is provided by NaNO2, COD cr The concentration is provided by CH3COONa, and the applicable range for influent total nitrogen (TN) concentration is 200–1200 mg / L. Influent COD... cr (CH3COONa) is suitable for concentrations ranging from 50 to 450 mg / L; ρ(NO2) — N) / ρ(NH4 + -N) gradually decreases from 1.0 to 0, ρ(COD) crThe ratio of KH2PO4 to TN is controlled within the range of 0.15–0.45; NaHCO3 is used as the inorganic carbon source; ρ(KH2PO4) / ρ(TN) = 2.5–3.5%, and ρ(KH2PO4) ≥ 6.0 mg / L; ρ(MgSO4·7H2O) = 150–300 mg / L, ρ(CaCl2·2H2O) = 40–60 mg / L; 0.8–1.25 mL each of trace elements I and II are added to 1 L of influent.
[0050] Trace element I: ρ(EDTA) = 5000 mg / L, ρ(FeSO4) = 5000 mg / L;
[0051] Trace elements II: ρ(EDTA)=15000mg / L, ρ(ZnSO4·7H2O)=430mg / L, ρ(MnCl2·4H2O)=990mg / L, ρ(H3BO4)=14mg / L, ρ(C uSO4·5H2O)=250mg / L, ρ(NaMoO4·2H2O)=220mg / L, ρ(NaSeO4·10H2O)=210mg / L, ρ(NiCl2·6H2O)=190mg / L.
[0052] The SAD granular sludge cultivation process includes, in sequence, the anaerobic ammonia oxidation sludge acclimation stage, the anaerobic ammonia oxidation granular sludge formation stage, the denitrification sludge coupled cultivation stage, and the SAD granular sludge formation stage; the SAD granular sludge cultivation run lasts 200–400 days; the SAD granular sludge cultivation process is conducted in the dark, with a water temperature of 32±3℃; the SAD granular sludge cultivation uses an upflow anaerobic sludge bed with a reflux system, and the reflux uses a pulse metering pump with a stroke flow rate of 0.1–1.1 ml / m³. The stroke frequency was 120–180 strokes / min, and the pressure was 2–10 bar. The activity of obligate anammox bacteria (SAA) in SAD granular sludge reached 2.0–2.5 gN / (g-VSS / d); the activity of obligate denitrifying bacteria (SDA) reached 0.3–0.4 gN / (g-VSS / d); the nitrogen load (NLR) gradually increased during the anammox sludge acclimatization stage and the anammox granular sludge formation stage, from 0.1 kg-N / (m³). 3 / d) increased to 3.0 kg-N / (m 3 / d), until the TN removal rate reaches over 95%; during the denitrification sludge coupled cultivation stage and the SAD granular sludge formation stage, the NLR gradually decreases, from 3.0 kg-N / (m 3 / d) decreased to 1.0 kg-N / (m 3 / d); the carbon removal load (CRR) gradually increased, from 0.1 kg-C / (m 3 / d) rises to 0.4 kg-C / (m 3 / d), until the COD removal rate reaches more than 98% and the TN removal rate is not less than 85%.
[0053] The H-PN flocculent sludge cultivation and acclimatization steps include a total nitrification stage, a short-cut nitrification stage, and a semi-nitrification stage. In the total nitrification stage, the hydraulic retention time (HRT) is 12 hours, with continuous aeration for 12 hours, controlling the aeration rate at 5-10 L / min and the dissolved oxygen (DO) at 4-5 mg / L. In the short-cut nitrification stage, the HRT is 10 hours, with continuous aeration for 10 hours, controlling the aeration rate at 2.5-6.5 L / min and the DO at 0.5-1.8 mg / L. In the semi-nitrification stage, the HRT is 12 hours, with intermittent aeration, each cycle consisting of four cycles of aeration and aeration stoppage, ending with aeration stoppage and sedimentation; the aeration rate is controlled at 1.0-2.5 L / min; and the DO is controlled at 0.25-1.3 mg / L. The H-PN flocculent sludge effluent contains nitrite (NO2). - ) and ammonia nitrogen (NH4) + The ratio is 1 to 1.3.
[0054] The process parameters for the formation of the SNAD granular sludge system include: operational control parameters and end-of-period indicator parameters; the operational control parameters include: ρ(NO2) — N) / ρ(NH4 + -N), control DO and aeration intensity in the upper and lower reaction zones, control reaction zone temperature, control reflux ratio and reflux method, control free ammonia (FA), free nitrite (FNA) and FA / FNA ratio, control pH, and control HRT; end-of-period indicator parameters include: controlling the activated sludge index (SVI) of granular sludge. 30 The SNAD granular sludge system uses volatile suspended solids (VSS) / suspended solids (SS) to measure sludge performance, morphology, and particle size characteristics, controls changes in extracellular polymeric substances (EPS) content and composition, controls system microbial abundance and functional characteristics, and controls microbial activity. The SNAD granular sludge system formation process includes: Stage I (initial SAD granular sludge addition), Stage II (SAD granular sludge adaptation period), Stage III (H-PN flocculent sludge addition), Stage VI (SNAD granular sludge adaptation period), and Stage V (SNAD granular sludge system packing enhancement). Each stage adjusts the system strategy using operational control parameters. Once the end-of-stage indicator parameters meet certain requirements, the system enters the next stage and adjusts the operational control parameters accordingly. The specific process is as follows:
[0055] Stage I operating control parameters: ρ(NO2-N) / ρ(NH4) +-N) gradually decreased from 1.0 to 0.7; adjusted the relationship between system air supply and oxygen consumption, with an aeration intensity of 3-5 L / min to ensure DO = 0.8-1.0 mg / L in the upper reaction zone and DO = 0.1-0.2 mg / L in the lower reaction zone; controlled the reflux ratio at 30-40, using a reflux metering pump pulse inlet method, with a reflux metering pump pulse stroke flow rate / inlet flow rate of 0.1-1.1, a frequency of 120-180 strokes / min, and a pressure of 2-10 bar; FA = 5-10 mg / L, FNA = 2-8 μg / L, pH = 8.36-8.85, H The response time (RT) is 20-30 hours. The control parameters at the end of Stage I are: total nitrogen removal rate (TNRE) increased to over 70%, and organic matter removal rate (CRE) increased to over 65%; SVI30 in the upper reaction zone is 220-300 mL / g, VSS / SS ≥ 0.95; granular sludge with a particle size of 1-3 mm in the lower reaction zone accounts for no less than 85%, and VSS / SS ≥ 0.72; EPS content in the sludge layer of the upper reaction zone is 180-200 mg / g VSS, and the EPS structure distribution is soluble EPS (S-EPS) and loosely bound EPS (S-EPS). The ratio of bound EPS (LB-EPS) and tightly bound EPS (TB-EPS) was 35%:10%:55%; the EPS content in the sludge layer of the lower reaction zone was 500-520 mg / g VSS, and the EPS structure distribution was S-EPS, LB-EPS, and TB-EPS in the ratio of 32%:13%:55%; the protein-polysaccharide ratio (PN / PS) in the EPS of the upper reaction zone was 0.2-0.4; the PN / PS ratio in the EPS of the lower reaction zone was 1.2-1.3; the α-helix / (random coil + β-sheets) ratio of the protein secondary structure in the EPS reached 60-63%; and the obligate anaerobic ammonium oxidizing bacteria activity (SAA) reached 120-135 mg N·g VSS. -1 ·h -1 The activity of obligate denitrifying bacteria (sDNA) reached 25–35 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 9–12 mg N·g VSS. -1 ·h -1At the phylum level, the relative abundances of the major bacterial groups Proteobacteria, Planctomycetota, Bacteroidota, and Chloroflexi reached 40-50%, 25-40%, 5-20%, and 2-10%, respectively. At the genus level, the relative abundances of the major bacterial groups Candidatus Kuenenia, Commonas, Zoogloea, Denitrosoma, and Nitrosomonas reached 25-35%, 20-25%, 0-1%, 5-10%, and 0-1%, respectively.
[0056] Phase II operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) was gradually reduced from 0.7 to 0.4, and the relationship between the system's air supply and oxygen consumption was adjusted. The aeration intensity was 3.5-6.5 L / min to ensure that the DO in the upper reaction zone was 0.9-1.6 mg / L and the DO in the lower reaction zone was 0.1-0.2 mg / L. The reflux ratio was controlled at 25-35, and the reflux method adopted was a reflux metering pump pulse water inlet method. The reflux metering pump pulse stroke flow rate was 0.1-1.1 ml / stroke, the frequency was 110-160 strokes / min, and the pressure was 2-10 bar. FA was 7-12 mg / L, FNA was 3-7 μg / L, pH was 8.0-8.25, and HRT was 20-25 h. The control parameters at the end of stage II were: the system TNRE increased to above 75%, CRE increased to 70%, and SVI30 in the upper reaction zone was 20. The concentration of EPS in the sludge layer of the upper reaction zone is 0-250 mL / g, VSS / SS ≥ 0.83, with granular sludge of 1-3 mm diameter accounting for no less than 75% and VSS / SS ≥ 0.78; the EPS content in the sludge layer of the upper reaction zone is 190-210 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 37%:12%:56%; the EPS content in the sludge layer of the lower reaction zone is 460-490 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the PN / PS ratio in the EPS of the upper reaction zone is 0.4-0.5; the PN / PS ratio in the EPS of the lower reaction zone is 1.1-1.2; the activity of obligate anaerobic ammonia oxidizing bacteria (SAA) reaches 115-125 mgN·gVSS. -1 ·h -1 The activity of obligate denitrifying bacteria (sDNA) reached 30–40 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 10–15 mg N·g VSS. -1 ·h -1 ;
[0057] Stage III operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) gradually decreased from 0.4 to 0.2, adjusting the system's air supply and oxygen consumption relationship, with an aeration intensity of 4-7 L / min; ensuring DO = 1.2-2.0 mg / L in the upper reaction zone and DO = 0.1-0.2 mg / L in the lower reaction zone; controlling the reflux ratio at 25-30, using a reflux metering pump pulse inlet method, with a pulse stroke flow rate of 0.1-1.1 ml / stroke, a frequency of 130-200 strokes / min, and a pressure of 2-10 bar; FA = 8-11 mg / L, FNA = 3.5-7 μg / L, adjusting pH to 7.65-8.05; HRT of 15-20 h; end-stage control parameters for Stage III: system TNRE increased to over 80%, CRE increased to over 80%; SVI30 in the upper reaction zone was 1. The sludge content in the upper reaction zone is 80–210 mL / g, VSS / SS ≥ 0.74, with at least 70% of the granular sludge in the lower reaction zone having a particle size of 1–3 mm and a VSS / SS ≥ 0.85; the EPS content in the upper reaction zone sludge layer is 210–240 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 37%:12%:56%; the EPS content in the lower reaction zone sludge layer is 400–430 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the PN / PS ratio in the upper reaction zone EPS is 0.5–0.6; the PN / PS ratio in the lower reaction zone EPS is 0.8–0.9; and the obligate anaerobic ammonia oxidizing bacteria activity (SAA) reaches 110–125 mgN·g VSS. -1 ·h -1 The activity of obligate denitrifying bacteria (sDNA) reached 30-35 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 25–30 mg N·g VSS. -1 ·h -1 ;
[0058] Phase IV operating control parameters: ρ(NO2-N) / ρ(NH4) +-N) gradually decreased from 0.2 to 0, adjusting the relationship between system air supply and oxygen consumption, with an aeration intensity of 5-7 L / min; ensuring DO = 1.5-1.8 mg / L in the upper reaction zone and DO = 0.1-0.2 mg / L in the lower reaction zone; controlling the reflux ratio at 20-30, using a reflux metering pump pulse inlet method, with a pulse stroke flow rate of 0.1-1.1 ml / stroke, a frequency of 120-160 strokes / min, and a pressure of 2-10 bar; FA = 9-11 mg / L, FNA = 3-5 μg / L, adjusting pH to 7.65-8.05; HRT of 10-15 h; end-stage IV control parameters: system TNRE increased to 95%, CRE increased to 90%; SVI30 in the upper reaction zone is... The sludge content in the upper reaction zone is 170-180 mL / g, VSS / SS ≥ 0.67, with at least 65% of the granular sludge in the lower reaction zone having a particle size of 1-3 mm and a VSS / SS ≥ 0.9; the EPS content in the upper reaction zone sludge layer is 230-250 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the EPS content in the lower reaction zone sludge layer is 260-280 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 35%:10%:55%; the PN / PS ratio in the upper reaction zone EPS is 0.6-0.7; the PN / PS ratio in the lower reaction zone EPS is 0.4-0.6; the α-helix / (random coil + β-sheets) ratio of the protein secondary structure in the EPS reaches 77-80%; and the obligate anaerobic ammonium oxidizing bacteria activity (SAA) reaches 100-120 mg N·g VSS. -1 ·h -1 The activity of obligate denitrifying bacteria (sDNA) reached 40–55 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 60–75 mg N·g VSS. -1 ·h -1 At the phylum level, the relative abundances of the major bacterial groups Proteobacteria, Planctomycetota, Bacteroidota, and Chloroflexi reached 40-50%, 15-25%, 15-35%, and 2-15%, respectively. At the genus level, the relative abundances of the major bacterial groups Candidatus Kuenenia, Commonas, Zoogloea, Denitrosoma, and Nitrosomonas reached 10-35%, 5-10%, 2-5%, 15-35%, and 10-25%, respectively.
[0059] V-stage operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) is 0. Adjust the system's air supply and oxygen consumption to ensure that DO in the upper reaction zone is 1.5-2.5 mg / L and DO in the lower zone is 0.1-0.2 mg / L; aeration intensity is 5-6 L / min; reflux ratio is controlled at 20-30, and reflux is achieved using a reflux metering pump with pulse inlet. The reflux metering pump pulse stroke flow rate is 0.1-1.1 ml / stroke, frequency is 100-120 strokes / min, and pressure is 2-10 bar; FA is 9-10 mg / L, FNA is 4-5 μg / L, and pH is adjusted to 7.65-8.05; HRT is 10-20 h; V-stage end control parameters: maintain system TNRE at 85-95%, CRE at 80-90%; lower reaction... The sludge in the upper reaction zone shall contain no less than 60% granular sludge with a particle size of 1-3 mm, and a VSS / SS ratio ≥ 0.92; the EPS content in the sludge layer of the upper reaction zone shall be 290-320 mg / g VSS, and the EPS structure distribution shall be S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the EPS content in the sludge layer of the lower reaction zone shall be 200-230 mg / g VSS, and the EPS structure distribution shall be S-EPS, LB-EPS, and TB-EPS in a ratio of 35%:10%:55%; the PN / PS ratio in the EPS of the upper reaction zone shall be 0.7-0.8; the PN / PS ratio in the EPS of the lower reaction zone shall be 0.25-0.35; and the activity of obligate anaerobic ammonia oxidizing bacteria (SAA) shall reach 100-120 mgN·gVSS. -1 ·h -1 The activity of obligate denitrifying bacteria (sDNA) reached 40–55 mg N·g VSS. -1 ·h -1 The specific ammonia oxidation activity (SAOA) reaches 60–75 mg N·g VSS. -1 ·h -1 .
[0060] The upper reaction zone of the main reactor is dominated by black granular sludge and flocculent sludge, accounting for 35-55% and 15-45% respectively; the lower reaction zone is dominated by red granular sludge and black granular sludge, accounting for more than 55% and more than 35% respectively. The upper reaction zone realizes the functions of semi-nitrification (H-PN) and denitrification, with the main functional bacteria accounting for more than 55%; the lower reaction zone realizes the function of anaerobic ammonia oxidation and denitrification coupling (SAD), with the main functional bacteria accounting for more than 75%.
[0061] Polyurethane block packing is used for the reinforcement of the SNAD granular sludge system; the size of the polyurethane block packing is (1-2.5)cm×(1-2.5)cm×(1-2.5)cm, the porosity is 96-99%, and the organic loading rate is 0.7-1.2Kg / m³. 3·d, specific surface area is 30000-35000 m² 2 / m 3 The pore size is 1mm to 1.5mm, and the density is 0.97 to 1.05g / cm³. 3 .
[0062] like Figure 2 As shown in the SNAD stage diagram (f), the granules dominated by Anammox clearly resemble cauliflower in shape, with more bacteria wrapped around them on the outside. Compared to the SAD stage diagram (c), diagram (f) clearly shows an increase in both long and short rod-shaped bacteria. It is speculated that the short rod-shaped bacteria on the outer layer of the granular sludge are AOB bacteria, and the long rod-shaped bacteria are DNB bacteria. This indicates the formation of a symbiotic system of anaerobic ammonia oxidizing bacteria, ammonia oxidizing bacteria, and denitrifying bacteria.
[0063] like Figure 3 As shown, aeration is an important condition for cultivating AOBs in stage I. By adjusting the aeration rate, the DO concentration in the upper zone of the system is ensured to be approximately 0.8–1 mg / L, and the DO concentration in the lower zone is approximately 0–0.2 mg / L. Because of the recirculation, the DO concentration in the lower zone is mainly controlled by the aeration in the upper zone. The figure shows that the denitrification performance of the system does not decrease due to the added aeration. On the one hand, the DO concentration in the recirculation is low, and some of it is utilized by the aerobic microorganisms at the bottom. On the other hand, Anammox produces nitrogen gas, which can displace DO from the system. At this point, NO2... - -N / NH4 + The -N ratio did not pose a threat to the SNAD system. The system contained a small amount of AOB functional bacteria that could convert excess ammonia nitrogen into nitrite, supplying it to AnAOB. Furthermore, the system had a circulation pump to buffer shocks. In stages II and III, the system's pollutant removal efficiency decreased. At this point, the ammonia nitrogen content was high, and the semi-nitrification effect was poor. Considering the significant impact of FA on semi-nitrification, the pH was lowered to reduce FNA and FA in the water. With pH ≈ 8, the system gradually returned to normal. In stage IV, FA = 10 mg / L, FNA = 4.5 μg / L, and only NH4... + Under -N conditions, the impact on DNB in the SNAD system is minimal. By adjusting the influent pH, the system's TNRE ≈ 95% after 150 days. In the V stage, square polyurethane packing material, already stable in the semi-nitrification system, was added to the upper zone to achieve long-term stable operation of the SNAD system. The operational results are shown in the figure. The system's effect on NH4+ is... + The removal effect of -N is quite remarkable.
[0064] like Figure 4As shown, high-throughput analysis was used to detect the sludge at the bottom of the reactor, the upper part of the reactor, and the upper part of the reactor, which confirmed that the SNAD system contained high abundances of anaerobic ammonia oxidizing bacteria (Candidatus_Kuenenia), ammonia oxidizing bacteria (Nitrosomonas), and denitrifying bacteria (Denitratisoma).
Claims
1. A multi-pathway integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater, characterized in that, Using an improved UASB reactor, under controlled conditions of high ammonia nitrogen wastewater influent, the formation of the SNAD granular sludge system was controlled, and the operation of the SNAD granular sludge system was enhanced. The specific steps are as follows: high ammonia nitrogen wastewater influent control, SAD granular sludge cultivation, H-PN flocculent sludge cultivation and acclimatization, coupling of SAD granular sludge and H-PN flocculent sludge to form the SNAD granular sludge system, and reinforcement of the SNAD granular sludge system packing. The SAD granular sludge cultivation method includes, in sequence, the anammox sludge acclimatization stage, the anammox granular sludge formation stage, the denitrification sludge coupled cultivation stage, and the SAD granular sludge formation stage. The H-PN flocculent sludge cultivation and acclimatization process includes the full nitrification stage, the short-cut nitrification stage, and the semi-nitrification stage in sequence. The formation process of the SNAD granular sludge system includes: the initial stage of SAD granular sludge addition as stage I, the SAD granular sludge adaptation period as stage II, the H-PN flocculent sludge addition stage as stage III, the SNAD granular sludge adaptation period as stage VI, and the SNAD granular sludge system packing enhancement as stage V. The system strategy is adjusted by adjusting the operating control parameters in each stage. When the end-of-stage indicator parameters reach certain requirements, the system enters the next stage and the operating control parameters are adjusted accordingly. The specific process is as follows: Stage I operating control parameters: ρ(NO2-N) / ρ(NH4) + -N) gradually decreased from 1.0 to 0.7; the relationship between the system's air supply and oxygen consumption was adjusted, with an aeration intensity of 3-5 L / min to ensure that the DO in the upper reaction zone of the system was 0.8~1.0 mg / L and the DO in the lower reaction zone was 0.1~0.2 mg / L; the reflux ratio was controlled at 30~40, and the reflux method adopted was a reflux metering pump pulse water inlet method, with a reflux metering pump pulse stroke flow rate / inlet flow rate of 0.1~1.1, a frequency of 120~180 strokes / min, and a pressure of 2-10 bar; FA = 5~10 mg / L, FNA = 2~8 μg / L, pH = 8.36~8.85, HRT = 20-30 h; Phase I end control parameters: Total nitrogen removal rate (TNRE) increased to over 70%, organic matter removal rate (CRE) increased to over 65%; SVI30 in the upper reaction zone was 220~300 mL / g, VSS / SS ≥ 0.95; granular sludge with a particle size of 1-3 mm in the lower reaction zone was no less than 85%, VSS / SS ≥ 0.72; EPS content in the sludge layer of the upper reaction zone was 180~200 mg / g VSS; EPS structure distribution: dissolved EPS (S-EPS), loosely bound EPS (LB-EPS), and tightly bound EPS (Tightly Bound EPS). The EPS (EPS, TB-EPS) ratio was 35%:10%:55%; the EPS content in the sludge layer of the lower reaction zone was 500~520 mg / g VSS, and the EPS structure distribution was S-EPS, LB-EPS, and TB-EPS in a ratio of 32%:13%:55%; the protein and polysaccharide ratio (PN / PS) in the EPS of the upper reaction zone was 0.2~0.4; the PN / PS ratio in the EPS of the lower reaction zone was 1.2~1.3; the α-helix / (random coil + β-sheets) ratio of the protein secondary structure in the EPS reached 60~63%; and the SAA activity of obligate anaerobic ammonia oxidizing bacteria reached 120~135 mgN•g VSS. -1 •h -1 The active SDNA of obligate denitrifying bacteria reaches 25-35 mgN•gVSS. -1 •h -1 The specific ammonia oxidation activity of SAOA reaches 9~12 mgN•gVSS. -1 •h -1 At the phylum level, the relative abundances of the major bacterial groups Proteobacteria, Planctomycetota, Bacteroidota, and Chloroflexi reached 40-50%, 25-40%, 5-20%, and 2-10%, respectively. At the genus level, the relative abundances of the major bacterial groups Candidatus Kuenenia, Commonas, Zoogloea, Denitrosoma, and Nitrosomonas reached 25-35%, 20-25%, 0-1%, 5-10%, and 0-1%, respectively. Phase II operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) was gradually reduced from 0.7 to 0.4, and the relationship between the system's air supply and oxygen consumption was adjusted. The aeration intensity was 3.5-6.5 L / min to ensure that the DO in the upper reaction zone was 0.9-1.6 mg / L and the DO in the lower reaction zone was 0.1-0.2 mg / L. The reflux ratio was controlled at 25-35, and the reflux method adopted was a reflux metering pump pulse water inlet method. The reflux metering pump pulse stroke flow rate was 0.1-1.1 ml / stroke, the frequency was 110-160 strokes / min, and the pressure was 2-10 bar. FA was 7-12 mg / L, FNA was 3-7 μg / L, pH was 8.0-8.25, and HRT was 20-25 h. The control parameters at the end of stage II were: the system TNRE increased to above 75%, CRE increased to 70%, and the SVI30 in the upper reaction zone was 2. 0.00~250mL / g, VSS / SS≥0.83, granular sludge with a particle size of 1-3mm in the lower reaction zone should not be less than 75%, VSS / SS≥0.78; EPS content in the sludge layer of the upper reaction zone should be 190~210mg / gVSS, and the EPS structure distribution should be S-EPS, LB-EPS, TB-EPS ratio of 37%:12%:56%; EPS content in the sludge layer of the lower reaction zone should be 460~490mg / gVSS, and the EPS structure distribution should be S-EPS, LB-EPS, TB-EPS ratio of 30%:20%:50%; PN / PS in EPS of the upper reaction zone should be 0.4~0.5; PN / PS in EPS of the lower reaction zone should be 1.1~1.2; the activity SAA of obligate anaerobic ammonia oxidizing bacteria should reach 115~125mgN•gVSS. -1 •h -1 The active SDNA of obligate denitrifying bacteria reaches 30-40 mgN•gVSS. -1 •h -1 The specific ammonia oxidation activity of SAOA reaches 10~15 mgN•gVSS. -1 •h -1 ; Stage III operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) gradually decreased from 0.4 to 0.2, adjusting the system's air supply and oxygen consumption relationship, with an aeration intensity of 4-7 L / min; ensuring DO = 1.2~2.0 mg / L in the upper reaction zone and DO = 0.1~0.2 mg / L in the lower reaction zone; controlling the reflux ratio at 25~30, using a reflux metering pump pulse inlet method, with a pulse stroke flow rate of 0.1~1.1 ml / stroke, a frequency of 130~200 strokes / min, and a pressure of 2-10 bar; FA = 8~11 mg / L, FNA = 3.5~7 μg / L, adjusting pH to 7.65~8.05; HRT = 15-20 h; end-stage control parameters for Stage III: system TNRE increased to over 80%, CRE increased to over 80%; SVI30 in the upper reaction zone is... The sludge content in the upper reaction zone is 180~210 mL / g, VSS / SS≥0.74, with at least 70% of the granular sludge in the lower reaction zone having a particle size of 1-3 mm and a VSS / SS≥0.85; the EPS content in the upper reaction zone sludge layer is 210~240 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 37%:12%:56%; the EPS content in the lower reaction zone sludge layer is 400~430 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; the PN / PS ratio in the upper reaction zone EPS is 0.5~0.6; the PN / PS ratio in the lower reaction zone EPS is 0.8~0.9; the SAA activity of obligate anaerobic ammonia oxidizing bacteria reaches 110~125 mgN•gVSS. -1 •h -1 The active SDNA of obligate denitrifying bacteria reaches 30-35 mgN•gVSS. -1 •h -1 The specific ammonia oxidation activity of SAOA reaches 25~30 mgN•gVSS. -1 •h -1 ; Phase IV operating control parameters: ρ(NO2-N) / ρ(NH4) + -N) gradually decrease from 0.2 to 0, adjust the relationship between system air supply and oxygen consumption, and aerate at 5-7 L / min; ensure DO = 1.5~1.8 mg / L in the upper reaction zone and DO = 0.1~0.2 mg / L in the lower reaction zone; control the reflux ratio at 20~30, using a reflux metering pump pulse inlet method, with a pulse stroke flow rate of 0.1~1.1 ml / stroke, frequency of 120~160 strokes / min, and pressure of 2-10 bar; FA = 9~11 mg / L, FNA = 3~5 μg / L, adjust pH to 7.65~8.05; HRT is 10-15 h; end-stage IV control parameters: system TNRE increased to 95%, CRE increased to 90%; SVI30 in the upper reaction zone is... 170~180 mL / g, VSS / SS≥0.67, with at least 65% of granular sludge with a particle size of 1-3 mm in the lower reaction zone and VSS / SS≥0.9; EPS content in the sludge layer of the upper reaction zone is 230~250 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; EPS content in the sludge layer of the lower reaction zone is 260~280 mg / g VSS, with an EPS structure distribution of S-EPS, LB-EPS, and TB-EPS in a ratio of 35%:10%:55%; PN / PS in EPS of the upper reaction zone is 0.6~0.7; PN / PS in EPS of the lower reaction zone is 0.4~0.6; the ratio of α-helix / (random coil + β-sheets) of protein secondary structure in EPS reaches 77~80%; the SAA activity of obligate anaerobic ammonia oxidizing bacteria reaches 100~120 mgN•gVSS. -1 •h -1 The active SDNA of obligate denitrifying bacteria reaches 40-55 mg N•g VSS. -1 •h -1 The specific ammonia oxidation activity of SAOA reaches 60~75 mgN•gVSS. -1 •h -1 At the phylum level, the relative abundances of the major bacterial groups Proteobacteria, Planctomycetota, Bacteroidota, and Chloroflexi reached 40-50%, 15-25%, 15-35%, and 2-15%, respectively. At the genus level, the relative abundances of the major bacterial groups Candidatus Kuenenia, Commonas, Zoogloea, Denitrosoma, and Nitrosomonas reached 10-35%, 5-10%, 2-5%, 15-35%, and 10-25%, respectively. V-stage operation control parameters: ρ(NO2-N) / ρ(NH4) + -N) is 0. Adjust the system's air supply and oxygen consumption to ensure that DO in the upper reaction zone is 1.5~2.5 mg / L and DO in the lower zone is 0.1~0.2 mg / L; aeration intensity is 5-6 L / min; reflux ratio is controlled at 20~30, and reflux is achieved using a reflux metering pump pulse inlet method, with a pulse stroke flow rate of 0.1~1.1 ml / stroke, a frequency of 100~120 strokes / min, and a pressure of 2-10 bar; FA=9~10 mg / L, FNA=4~5 μg / L, and pH adjusted to 7.65~8.05; HRT is 10-20 h; V-stage end-of-stage control parameters: maintain system TNRE at 85~95%, CRE at 80~90%; lower reaction... In the reaction zone, granular sludge with a particle size of 1-3 mm accounts for no less than 60%, and VSS / SS ≥ 0.92; in the upper reaction zone, the EPS content in the sludge layer is 290-320 mg / g VSS, and the EPS structure distribution is S-EPS, LB-EPS, and TB-EPS in a ratio of 30%:20%:50%; in the lower reaction zone, the EPS content in the sludge layer is 200-230 mg / g VSS, and the EPS structure distribution is S-EPS, LB-EPS, and TB-EPS in a ratio of 35%:10%:55%; the PN / PS ratio in the EPS of the upper reaction zone is 0.7-0.8; and the PN / PS ratio in the EPS of the lower reaction zone is 0.25-0.35; the SAA activity of obligate anaerobic ammonia oxidizing bacteria reaches 100-120 mgN•gVSS. -1 •h -1 The active SDNA of obligate denitrifying bacteria reaches 40-55 mg N•g VSS. -1 •h -1 The specific ammonia oxidation activity of SAOA reaches 60~75 mgN•gVSS. -1 •h -1 .
2. The multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater according to claim 1, characterized in that, The improved UASB reactor includes a main reactor, an inlet device, a water bath circulation device, a dual three-phase separator, an aeration device, a reflux metering pump, and an outlet tank. The inlet device includes an inlet tank, a pH meter, a DO meter, a pH and DO combined meter, a thermometer, and an inlet metering pump. The water bath circulation device includes a submersible pump and a temperature-controlled water bath. The aeration device includes an aeration disc and an aeration pump. The main reactor has a height-to-diameter ratio of 12:1 and includes an upper reaction zone and a lower reaction zone, with a height ratio of 1:1 between the upper and lower reaction zones. The dual three-phase separator is located at the top of the main reactor. The outlet of the inlet tank is connected to a valve at 35% of the total height of the main reactor from the bottom via the inlet metering pump. A pH meter is installed inside the inlet tank and the main reactor. A DO meter and a thermometer are installed in the main reactor. The pH meter and DO meter are connected to a combined pH and DO meter. A temperature-controlled water bath is connected to the inlet of the main reactor at 10% of its total height from the bottom via the submersible pump. The outlet of the main reactor at 10% of its total height from the top is connected to the temperature-controlled water bath via a return pipe. The aeration disc is located inside the main reactor at 40% of its total height from the bottom. The aeration pump is located outside the main reactor and connected to the aeration disc via a pipeline. A return outlet is located at 10% of the total height from the top of the main reactor and connected to a return metering pump via a pipeline. The return metering pump is connected to the return inlet at the bottom of the main reactor via a pipeline. The outlet tank is connected to a dual three-phase separator via a pipeline.
3. The multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater according to claim 2, characterized in that, High ammonia nitrogen wastewater influent control includes SAD granular sludge cultivation influent control, H-PN flocculent sludge cultivation and acclimatization influent control, and SNAD granular sludge system influent control; The influent for SAD granular sludge cultivation is controlled as a continuous flow, with the ammonia nitrogen concentration (NH4) in the influent controlled. + With nitrite NO2 - Concentration and ratio, where ammonia nitrogen is provided by NH4Cl, and nitrite NO2 - The concentration is provided by NaNO2, and the influent ammonia nitrogen NH4 is provided by NaNO2. + The concentration should be controlled between 20 and 350 mg / L, and the influent nitrite (NO2) should be controlled. - The concentration is controlled at 25~450 mg / L, ρ(NO2) - ) / ρ(NH4 + )≈1.08~1.32; The AnAOB stage uses CH3COONa as the carbon source, ρ(COD) / (ρ(NH4)≈1.08~1.32; + )+ρ(NO2) - The pH value is 0.25~0.30; the pH control range during the AnAOB stage is 7-8.5; ρ(KH2PO4) / ρ(TN) = 3.5~5.5%, and ρ(KH2PO4) ≥ 6.0 mg / L; ρ(MgSO4·7H2O) = 300~450 mg / L, ρ(CaCl2·2H2O) = 50~65 mg / L; 1-2 mL each of trace elements I and II are added to 1L of influent; The influent for H-PN flocculent sludge cultivation and acclimatization was controlled as a continuous flow, with control of ammonia nitrogen (NH4) in the influent. + Chemical Oxygen Demand (COD) cr Concentration, where ammonia nitrogen is provided by NH4Cl, COD cr The concentration is provided by CH3COONa, and the influent ammonia nitrogen NH4 is provided by CH3COONa. + The applicable concentration range is 200~1200 mg / L, and the influent COD cr The applicable concentration range is 200-3000 mg / L; NaOH is used as the pH adjustment solution, and the pH control range is 8.5-9.0; the dissolved oxygen (DO) is controlled at 1.5-3.5 mg / L; ρ(KH2PO4) / ρ(TN) = 1.5-3.0%, and ρ(KH2PO4) ≥ 6.0 mg / L; ρ(MgSO4·7H2O) = 100-150 mg / L, ρ(CaCl2·2H2O) = 20-30 mg / L; 0.5-1 mL each of trace elements I and II are added to 1 L of influent. The SNAD granular sludge system uses continuous flow influent to control ammonia nitrogen (NH4) in the influent. + Nitrite NO2 - Chemical Oxygen Demand (COD) cr Concentration and ratio, where ammonia nitrogen is provided by NH4Cl, and nitrite NO2 - Concentration provided by NaNO2, COD cr The concentration is provided by CH3COONa; the applicable range for influent total nitrogen (TN) concentration is 200~1200 mg / L; and the influent COD... cr (CH3COONa) concentration range applicable 50~450mg / L; ρ(NO2) — N) / ρ(NH4) + -N) gradually decreases from 1.0 to 0, ρ(COD) cr The ratio of KH2PO4 to total nitrogen (TN) should be controlled within the range of 0.15 to 0.45; NaHCO3 should be used as the inorganic carbon source; ρ(KH2PO4) / ρ(TN) should be 2.5 to 3.5%, and ρ(KH2PO4) should be ≥ 6.0 mg / L; ρ(MgSO4·7H2O) should be 150 to 300 mg / L, and ρ(CaCl2·2H2O) should be 40 to 60 mg / L; 0.8 to 1.25 mL of each of trace elements I and II should be added to 1 L of influent. Trace element I: ρ(EDTA) = 5000 mg / L, ρ(FeSO4) = 5000 mg / L; Trace elements II: ρ(EDTA)=15000mg / L, ρ(ZnSO4·7H2O)=430mg / L, ρ(MnCl2·4H2O)=990mg / L, ρ(H3BO4)=14mg / L, ρ(C uSO4·5H2O)=250mg / L, ρ(NaMoO4·2H2O)=220mg / L, ρ(NaSeO4·10H2O)=210mg / L, ρ(NiCl2·6H2O)=190mg / L.
4. The multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater according to claim 2, characterized in that, SAD granular sludge cultivation lasted 200-400 days. The cultivation process was conducted in the dark at a water temperature of 32±3℃. An upflow anaerobic sludge bed was used with a reflux system. The reflux was achieved using a pulse metering pump with a flow rate of 0.1-1.1 ml / stroke, a frequency of 120-180 strokes / min, and a pressure of 2-10 bar. The SAD granular sludge showed that the activity of obligate anaerobic ammonia oxidizing bacteria (SAA) reached 2.0-2.5 gN / (g-VSS / d), and the activity of obligate denitrifying bacteria (SDA) reached 0.3-0.4 gN / (g-VSS / d). The acclimatization stage of the anaerobic ammonia oxidizing sludge and the anaerobic ammonia... During the formation stage of oxidative granular sludge, the nitrogen load (NLR) gradually increases from 0.1 kg-N / (m³ / d) to 3.0 kg-N / (m³ / d), until the total nitrogen (TN) removal rate reaches over 95%. During the denitrification sludge coupling cultivation stage and the SAD granular sludge formation stage, the NLR gradually decreases from 3.0 kg-N / (m³ / d) to 1.0 kg-N / (m³ / d). The carbon removal load (CRR) gradually increases from 0.1 kg-C / (m³ / d) to 0.4 kg-C / (m³ / d), until the COD removal rate reaches over 98% and the TN removal rate is not less than 85%.
5. The multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater according to claim 2, characterized in that, The hydraulic retention time (HRT) for the full nitrification stage is 12 hours, with continuous aeration for 12 hours, controlling the aeration rate at 5-10 L / min and the dissolved oxygen (DO) at 4-5 mg / L. The HRT for the short-cut nitrification stage is 10 hours, with continuous aeration for 10 hours, controlling the aeration rate at 2.5-6.5 L / min and the DO at 0.5-1.8 mg / L. The HRT for the semi-nitrification stage is 12 hours, with intermittent aeration, each cycle consisting of four cycles of aeration and aeration stoppage, ending with aeration stoppage and sedimentation; the aeration rate is controlled at 1.0-2.5 L / min; and the DO at 0.25-1.3 mg / L. The nitrite (NO2) in the H-PN flocculent sludge effluent is... - With ammonia nitrogen NH4 + The ratio is 1 to 1.
3.
6. The multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater according to claim 2, characterized in that, The process parameters for the formation of the SNAD granular sludge system include: operational control parameters and end-of-period indicator parameters; the operational control parameters include: ρ(NO2) — N) / ρ(NH4) + -N), control DO and aeration intensity in the upper and lower reaction zones, control reaction zone temperature, control reflux ratio and reflux method, control free ammonia (FA), free nitrite (FNA) and FA / FNA ratio, control pH, and control HRT; end-of-period indicator parameters include: controlling the activated sludge index (SVI) of granular sludge. 30 Volatile suspended solids (VSS) / suspended solids (SS) are used to measure sludge performance, morphology, and particle size characteristics, control changes in extracellular polymeric substances (EPS) content and composition, control system microbial abundance and functional characteristics, and control microbial activity.
7. The multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater according to claim 2, characterized in that, The upper reaction zone of the main reactor is dominated by black granular sludge and flocculent sludge, accounting for 35-55% and 15-45% respectively; the lower reaction zone is dominated by red granular sludge and black granular sludge, accounting for more than 55% and more than 35% respectively; the upper reaction zone realizes the functions of semi-nitrification (H-PN) and denitrification, with the main functional bacteria accounting for more than 55%; the lower reaction zone realizes the coupled functions of anaerobic ammonia oxidation and denitrification (SAD), with the main functional bacteria accounting for more than 75%.
8. The multi-path integrated simultaneous denitrification method suitable for high ammonia nitrogen wastewater according to claim 1, characterized in that, Polyurethane block packing is used in the reinforcement of the SNAD granular sludge system; the size of the polyurethane block packing is (1-2.5) cm × (1-2.5) cm × (1-2.5) cm, the porosity is 96-99%, and the organic loading rate is 0.7-1.2 kg / m³. 3 ·d, specific surface area is 30000-35000 m² 2 / m 3 The pore size is 1mm to 1.5mm, and the density is 0.97 to 1.05g / cm³. 3 .