CN114873837A - Method and device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae - Google Patents

Method and device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae Download PDF

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CN114873837A
CN114873837A CN202210385684.6A CN202210385684A CN114873837A CN 114873837 A CN114873837 A CN 114873837A CN 202210385684 A CN202210385684 A CN 202210385684A CN 114873837 A CN114873837 A CN 114873837A
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algae
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nitrogen
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CN114873837B (en
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张莉
董亭君
孙再成
杨嘉春
豆全浩
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Beijing University of Technology
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    • C—CHEMISTRY; METALLURGY
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    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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Abstract

The invention provides a method and a device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae, wherein the method comprises the step of sending sewage into a short-cut denitrification-anaerobic ammonia oxidation reaction zone for treatment; algae are enriched in the short-range denitrification-anaerobic ammonia oxidation reaction zone and a photocatalytic material is added; adding acetic acid into the sewage as a carbon source; in the treatment process, visible light is used for illuminating the reaction area, the quantity of algae is controlled by adjusting illumination parameters, the dissolved oxygen concentration of the reaction area is kept at 0.9-1.5mg/L, and ammonia oxidizing bacteria are generated in situ. According to the invention, by adding the photocatalytic material into the PD/A reaction zone, the in-situ enrichment of algae in the bioreactor is promoted, and meanwhile, the means of adjusting the illumination condition is adopted, so that a micro-aerobic environment is created and maintained, the in-situ growth of AOB flora is promoted, a PD/A-PN/A system with symbiotic bacteria and algae is formed, the nitrogen and phosphorus removal of the system is enhanced, and the synchronous and efficient removal of nitrogen and phosphorus is realized.

Description

Method and device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method and a device for realizing deep nitrogen and phosphorus removal by PD/A (photo-oxidative) in-situ coupling algae.
Background
Along with the discharge of a large amount of nitrogen and phosphorus elements in the urban sewageTherefore, the dephosphorization and denitrification of sewage become important subjects in sewage treatment. Anammox refers to the utilization of NO under anoxic conditions 2 - -N as electron acceptor, NH 4 + Direct conversion of-N to N 2 . The ANAMMOX process (ANAMMOX) can realize effective treatment of high ammonia nitrogen wastewater without additional carbon source and aeration. But the actual waste water often contains NH 4 + High content of-N and NO 2 - The source of-N is unstable, thereby subjecting ANAMMOX to NO 2 - The limitation of insufficient N substrate, resulting in a decrease in denitrification efficiency. In recent years, short-cut denitrification (PD) has been used as a relatively stable means of NO capture 2 - The new approach of the-N is often coupled with ANAMMOX to form a short-cut denitrification-anaerobic ammonia oxidation (PD/A) system so as to enhance the denitrification efficiency, and in addition, compared with the traditional nitrification and denitrification process, the new approach saves about 40% of carbon source requirements, and has the effects of saving aeration energy consumption and reducing sludge yield. But the single PD/A process cannot effectively and synchronously remove phosphorus when treating sewage.
The traditional biological phosphorus removal device achieves the purpose of biological phosphorus removal of sewage by utilizing excessive phosphorus absorption of phosphorus accumulating bacteria through an anaerobic/aerobic process. By the end of the 20 th century, people find that denitrifying phosphorus accumulating bacteria can enrich phosphorus and nitrogen in an anaerobic/anoxic alternate operation environment, and create conditions for synchronous removal of nitrogen and phosphorus. On the basis, people further screen denitrifying phosphorus removal bacteria taking nitrite as an electron acceptor, thereby realizing short-range denitrifying phosphorus removal. The prior art generally has the dual purposes of an SBR reactor and an anaerobic ammonium oxidation reactor, wherein the SBR reactor firstly removes excess nitrite in the upper period through anoxic denitrification, then releases phosphorus anaerobically, absorbs phosphorus aerobically and generates partial shortcut nitrification, effluent and sludge fermentation liquor enter the anaerobic ammonium oxidation reactor together, and ammonia nitrogen and nitrite are removed through autotrophic denitrification of anaerobic ammonium oxidation bacteria, so that the nitrogen and phosphorus removal of domestic sewage is realized.
In the prior art, nitrogen and phosphorus removal is realized by utilizing the effects of shortcut nitrification, ANAMMOX and denitrifying bacteria, but the whole process is difficult to be coupled in a reactor due to the difference of survival conditions of strains, so that the process is difficult to popularize and apply; however, no method for realizing integration of deep nitrogen and phosphorus removal and coupling the nitrogen and phosphorus removal processes has been proposed in the prior art. In addition, in the above process, the denitrification process needs to consume an organic carbon source; nitrite generated by short-cut nitrification needs to provide electron donors for denitrifying phosphorus removal bacteria and ANAMMOX bacteria simultaneously, which easily causes the deficiency of the electron donors, and the nitrite donors can also cause the inhibition of the nitrogen and phosphorus removal effect of the process.
Disclosure of Invention
The invention solves the technical problem that the prior art lacks an integrated deep nitrogen and phosphorus removal method, and further provides a method and a device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae, which can realize synchronous and efficient removal of nitrogen and phosphorus, save organic carbon source consumption, and further realize carbon dioxide recycling of a bioreactor and removal of part of organic nitrogen.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae comprises the steps of sending sewage into a short-cut denitrification-anaerobic ammonia oxidation reaction zone for treatment; algae are enriched in the short-range denitrification-anaerobic ammonia oxidation reaction zone and a photocatalytic material is added; adding acetic acid into the sewage as a carbon source;
in the treatment process, visible light is used for illuminating the short-cut denitrification-anaerobic ammonia oxidation reaction zone, the quantity of algae is controlled by adjusting illumination parameters, the dissolved oxygen concentration of the short-cut denitrification-anaerobic ammonia oxidation reaction zone is kept at 0.9-1.5mg/L, and ammonia oxidizing bacteria are generated in situ.
The photocatalytic material is C 3 N 4 A material.
The photocatalytic material is C modified by 2, 4-dihydroxypyrimidine molecules 3 N 4 A material.
The algae are generated in the short-range denitrification-anaerobic ammonia oxidation reaction zone in an in-situ enrichment manner, and the relative content ratio of the algae to the sludge is Chl-a: MLVSS is 0.25-0.5 mg/g.
The adding amount of acetic acid in the sewage is 10mg TOC/L; the temperature in the reactor is 34.5-35.5 ℃, and the pH value of the inlet water is 7.0-7.5.
The starting process of the short-cut denitrification-anaerobic ammonia oxidation reaction zone is as follows: inoculating the short-range denitrification-anaerobic ammonia oxidation activated sludge which runs well, taking sewage or simulated sewage containing nitrate, ammonia nitrogen, inorganic salt and trace elements as inlet water, adding acetic acid as a carbon source, keeping the temperature of a reaction zone at 34.5-35.5 ℃, keeping the pH of the inlet water at 7.0-7.5, and running under the stirring condition until the removal rates of nitrite and ammonia nitrogen reach more than 85%; adding 150-200mg/L C into the reaction zone 3 N 4 Controlling illumination parameters, and operating the reaction until the in-situ enrichment of algae is completed and the denitrification rate reaches over 90 percent.
In the starting process, the molar ratio of ammonia nitrogen to nitrate nitrogen in the sewage containing nitrate, ammonia nitrogen, inorganic salt and trace elements or simulated sewage serving as inlet water is about 1: 1.
A device for realizing deep nitrogen and phosphorus removal by coupling PD/A (photo-oxidative) in situ with algae comprises: the device comprises a reactor, a water inlet, a water outlet, a short-cut denitrification-anaerobic ammonia oxidation reaction zone, a stirring device and a water inlet and outlet, wherein the reactor is internally provided with the short-cut denitrification-anaerobic ammonia oxidation reaction zone; the carbon source adding device is used for adding a carbon source into the reactor; the visible light irradiation device is used for irradiating the short-range denitrification-anaerobic ammonia oxidation reaction zone; the quantity of algae is controlled by adjusting the illumination parameters, so that the dissolved oxygen concentration of the short-range denitrification-anaerobic ammonia oxidation reaction zone is 0.9-1.5mg/L, and ammonia oxidizing bacteria are generated in situ.
The visible light irradiation device includes: the dissolved oxygen probe is positioned in the short-range denitrification-anaerobic ammonia oxidation reaction zone; and the pulse type light source assembly is connected with the dissolved oxygen probe through a controller, and controls the illumination frequency and the illumination time by taking the detection value of the dissolved oxygen probe as an index.
A plurality of grooves are formed in the inner wall of the middle lower part of the reactor, each groove extends along the vertical direction, the inner wall surfaces of the grooves are uniformly distributed, and the pulse type light source assembly is fixed in each groove; the illumination intensity of the pulse type light source assembly is 3000-.
The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae combines microalgae and bacteria to form a PD/A-PN/A (short-cut nitrification-anaerobic ammonia oxidation) system for symbiosis of bacteria and algae. The technical bottleneck existing in the construction of the bacteria-algae symbiotic system in the invention is that the settlement performance of sludge flocs is poor due to the small individual ratio of algae cells to gravity, and particularly, biomass is reduced due to the fact that algae flows out along with effluent, so that the solidification of the algae is completed by means of a filler carrier and the like along with the problem that the algae is not easy to fix. And the algae has low light energy utilization rate, is difficult to perform photosynthesis for growth and propagation due to insufficient light capture capacity, and cannot be enriched in situ in a bioreactor to form natural coupling with flora. In order to solve the problem, a photocatalytic material is added into a symbiotic system, and the photocatalytic material can efficiently capture light energy and generate photo-generated electrons to reduce CO under the illumination condition due to the photocatalytic property 2 。
Therefore, the photocatalytic material can be used as a light capturing agent to assist the algae in photosynthesis when being put into water, so as to make up for the defect that the algae is difficult to capture light energy. At the same time to CO 2 Immobilization also has a certain degree of contribution; and the algae spores are activated by the photocatalysis function of the photocatalysis material to be rapidly divided in water, so that the algae are enriched in situ and attached to the outer surfaces of the flora and the wall of the reactor to naturally form algae immobilization, the traditional algae immobilization procedures such as the symbiotic filling of the bacteria and the algae with a filler carrier and the like are omitted, and the economic cost is saved. Therefore, the invention utilizes the light capture characteristic of the photocatalytic material to induce the algae to be enriched in situ and naturally immobilized in the bioreactor, and solves the technical bottlenecks of difficult coupling of a bacteria-algae symbiotic system, long startup time of the reactor, poor bacteria-algae immobilization effect and difficult optical energy capture of the algae. The algae spores are activated by the photocatalysis function to be rapidly separated, and the analysis on the mechanism is that photo-generated electrons generated by the photocatalysis material can penetrate through holes on cell membranes to enter the cells and participate in the fine separationThe transfer of cellular electrons stimulates the metabolic activity of the cell.
Preferred use according to the invention is C 3 N 4 It is more preferable to use C of nanometer order as the photocatalytic material or the light-capturing agent 3 N 4 。C 3 N 4 As a semiconductor photocatalytic material with a proper electronic band structure, the material has good thermal stability and chemical stability, low price, low preparation cost and good biocompatibility, and does not produce toxic action on the growth of microorganisms. And compared with other photocatalytic materials, C 3 N 4 The system performance of the nano-particles is better, and a more efficient and more stable bacteria-algae symbiotic PD/A-PN/A system can be quickly constructed. Further, the present invention prefers C modified with 2, 4-dihydroxypyrimidine molecules 3 N 4 The material is used as a photocatalytic material, and the efficiency of constructing a stable phycobiont PD/A-PN/A system can be further improved.
The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae is a synchronous deep nitrogen and phosphorus removal process technology suitable for various water qualities:
(1) the method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling of the algae increases the phosphorus removal efficiency for the reaction system, and can achieve the high-efficiency removal of phosphorus in sewage by excessive phosphorus absorption through physiological metabolism of the algae. Phosphorus is an indispensable element for algae growth, and the method excessively takes up phosphorus in a reaction system by introducing algae, so that the phosphorus removal rate of an original PDA system which is nearly zero is improved to about 90 percent, the deep nitrogen and phosphorus removal is synchronously performed in a single reactor, a phosphorus removal unit does not need to be additionally arranged in the actual engineering, and the economic cost is greatly saved.
(2) The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae can enhance the nitrogen removal effect of a PD/A system. In the constructed bacteria-algae symbiotic system, oxygen released by algae is utilized to enable AOB flora (ammonia oxidizing bacteria) to grow in situ in a micro-aerobic state, and a PD/A-PN/A coupling process is gradually formed, wherein the AOB bacteria in the PN process can react with NH 4 + Oxidation of-N to NO 2 - N, a new factor for anammoxThe nitrite source approach optimizes the nitrite accumulation effect of the original system, strengthens the denitrification performance of the system, and enables the system to be simultaneously suitable for treating wastewater with various water qualities, such as high ammonia nitrogen wastewater, high nitrate nitrogen wastewater and the like. Compared with the method for denitrifying by using algae and a single microbial flora, the PD/A-PN/A system based on the symbiosis of the bacteria and the algae constructed by the invention strengthens the ammonia nitrogen conversion effect and provides sufficient nitrite sources for the ANAMMOX process, finally realizes the ammonia nitrogen removal rate and the nitrate removal rate close to 100 percent, and greatly improves the total nitrogen removal effect.
In addition, the invention can realize the removal of a certain amount of organic nitrogen while strengthening the removal effect of inorganic nitrogen by constructing a bacteria-algae symbiotic system. In the present invention, the algae in the symbiotic system of bacteria and algae not only take in the inorganic nitrogen in water as a nutrient but also consume and utilize organic nitrogen such as urea by assimilation, so that the present invention utilizes C 3 N 4 The light capture effect of the light capture system in the PD/A reactor is that the PD/A-PN/A system constructed by enriching algae in situ can remove organic nitrogen in the water body and strengthen the water quality purification effect.
(3) The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae can save the consumption of organic carbon sources. On one hand, the AOB bacteria in the PN process in the PD/A-PN/A system constructed by the invention play a role to supplement a new way of nitrite accumulation, and the pressure of the PD section in the original PD/A system is reduced; on the other hand, the algae is digested anaerobically in a dark reaction to generate a large amount of small molecular organic matters to provide a carbon source for PD, so that the amount of the external carbon source is reduced.
(4) The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling of algae can realize the carbon dioxide recycling of a bioreactor. The invention utilizes C 3 N 4 Capturing light energy efficiently, stimulating algae to enrich in situ in the reactor, and enabling CO to be generated through photosynthesis of algae 2 Fixing into various organic matters; in addition, the photoproduction electrons generated by the photocatalytic material can also activate the WLP (Wood Ljungdahl pathway) carbon fixation process in anammox, and the anammox carbon fixation and the algae carbon fixation form a multiple carbon fixation way in the system, so that the carbon dioxide is effectively strengthenedAnd further promotes carbon emission reduction.
In order to make the technical scheme of the method and the device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupled algae of the invention more clear, the invention is further described in detail with reference to the accompanying drawings and specific examples.
Drawings
FIG. 1 is a schematic structural diagram of a device for realizing deep denitrification and dephosphorization by PD/A in-situ coupling algae according to the present invention;
wherein the reference numerals are:
1-carbon source water inlet barrel; 2, sewage enters a water bucket; 3-liquid inlet water pump; 4-a stirring device; 5-time control switch; 6-reactor constant temperature water jacket; 7-water outlet; 8-a controller; 9-dissolved oxygen probe.
Detailed Description
The embodiment provides a device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling of algae, which comprises a batch reactor (PD/A-SBR reactor) as shown in figure 1, wherein the effective volume of the reactor is 6L, the reactor is provided with a water inlet and a water outlet, and the wall of the reactor is provided with a reactor constant-temperature water jacket 6; a carbon source adding device is arranged at the upstream of the reactor and comprises a carbon source water inlet barrel 1, and an acetic acid carbon source is added into water in the carbon source water inlet barrel 1. The upper reaches of reactor still are provided with sewage water intaking bucket 2, sewage water intaking bucket 2 and carbon source water intaking bucket 1 communicate to a total inlet channel through the lateral conduit respectively be provided with feed liquor water pump 3 on the lateral conduit, with feed liquor water pump 3 installs time switch 5 for the break-make of automatic control water pump. And the water outlet of the main water inlet pipeline is communicated with the water inlet of the reactor. The water enters the reactor to form a reaction zone, and a stirring device 4 is arranged in the reaction zone of the reactor. A water outlet barrel 7 is arranged at the downstream of the reactor, and the water at the water outlet enters the water outlet barrel 7.
The device is provided with a visible light irradiation device, the visible light irradiation device comprises a pulse type light source assembly, the pulse type light source assembly is installed on the inner wall of the reactor, a plurality of grooves are formed in the inner wall of the middle lower portion of the reactor, each groove extends in the vertical direction, the inner wall of each groove is uniformly distributed around the inner wall, and the pulse type light source assembly is fixed in each groove. The visible light illumination intensity range of the pulse type light source component is 3000-. The reactor is internally provided with a dissolved oxygen probe 9, the dissolved oxygen probe 9 extends to the lower part of the reactor, the pulse type light source assembly is connected with the dissolved oxygen probe 9 through a controller 8, and the controller 8 controls the illumination frequency and the illumination duration by taking the detection value of the dissolved oxygen probe 9 as an index.
Example 1
The embodiment provides a nitrogen and phosphorus removal method based on the device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae in FIG. 1. The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae in the embodiment takes simulated wastewater as a treatment object and comprises two stages of starting and treating.
The starting process of the device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae is as follows:
inoculating PD/A activated sludge into the reactor, controlling the suspended solid concentration of the sludge mixed liquor to be 4.5-5.5g/L, and controlling the operating parameters of the reactor as follows: the temperature is 34.5-35.5 ℃, the pH of inlet water is 7.0-7.5, the artificial synthetic sewage is used as inlet water, the hydraulic retention time is 12h, and the rotating speed of the stirring device is 700 +/-5 rpm. The operation time sequence of the PD/A-SBR reactor is that water is fed for 10min, stirring is carried out for 660min, sedimentation is carried out for 20min, water is drained for 10min, and the water drainage ratio is 50%.
When the artificially synthesized sewage is prepared, water is used as a solvent, inorganic substances and 1ml of trace element solution are added into the water, and the amount of the inorganic substances added into each liter of water is as follows: 1000mg KHCO 3 (ii) a 60mg of MgSO 4 ·5H 2 O; 60mg of CaCl 2 ·2H 2 O。
The concentrations of the respective trace elements in the trace element solution were as follows: EDTA, 15000 mg. L -1 ；CoCl 2 ·6H 2 O，240mg·L -1 ；ZnSO 4 ·7H 2 O，430mg·L -1 ；MnCl 4 ·H 2 O，990mg·L -1 ；NaMoO 4 ·2H 2 O，220mg·L -1 ；CuSO 4 ·5H 2 O，250mg·L -1 ；NaSeO 4 ·10H 2 O,210mg·L -1 ；NiCl·6H 2 O，190mg·L -1 ；H 3 BO 4 ，14mg·L -1 。
Operating the reactor according to the above operating parameters, keeping the content ratio of the ammonia nitrogen and the nitrate of the inlet water to be 1:1, and keeping the concentration of the acetic acid carbon source of the inlet water to be 45mg TOC.L -1 About, namely adding an acetic acid carbon source equivalent to 45mg of TOC into each liter of inlet water. Operating for a period every day, keeping the operating condition for a long time till 15 days, monitoring that the conversion rate of nitrite and the removal rate of ammonia nitrogen in the reactor reach more than 85 percent, the effluent nitrate is lower than about 5mg/L, and adding C into the reactor according to the adding amount of 180mg/L 3 N 4 Materials, i.e. adding 180mg of nano-C into each liter of inlet water 3 N 4 And simultaneously, introducing illumination by utilizing a visible light irradiation device in the reactor, and entering an in-situ algae enrichment stage. C added in this example 3 N 4 The material is nano-grade pure g-C prepared by a laboratory thermal polymerization method 3 N 4 Material in powder form, said nanoscale pure g-C prior to use 3 N 4 The material is first dried in a drying oven. As an alternative embodiment, commercially available nanoscale pure g-C may also be used 3 N 4 A material. The nanoscale pure g-C 3 N 4 After the material is characterized by technologies such as an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), X-ray photoelectron spectroscopy (XPS) and the like, the result shows that the prepared material has good photocatalytic performance.
Completion of g-C 3 N 4 After the materials are added, the operation parameters of the reactor are kept unchanged, the pulsed light source assembly uniformly distributed at the middle lower part of the reactor is used for illumination, the light source irradiates upwards from the middle lower part of the reactor to achieve uniform and all-directional irradiation on the sludge of the reactor, and the controller is used for quantitatively adjusting the illumination frequency and the illumination time of the pulsed irradiation. In this embodiment, the interval of the pulse irradiation time is set to 1 hour, and the total light is setDark time ratio was set to 12 h: and 12h, adjusting the light intensity of the light source component to be 6000 lux. Keeping the two reactors running synchronously in this mode, it was observed that the reactors reached a considerable amount of algae enrichment on day 25, the algae relative content Chl-a: MLVSS rises and is maintained to be about 0.35, the denitrification rate of the system reaches more than 90%, in addition, the total phosphorus removal rate reaches 70%, and based on the condition that the biomass concentration of the bacteria and algae reaches stability and the overall efficiency of the system is obviously improved, the phase of adjusting the pulse type illumination mode to optimize the comprehensive efficiency of the bacteria and algae is started.
In the stage, the pulse type illumination frequency is adjusted by a controller along with the change of DO content in the reactor, and the dissolved oxygen concentration of the reactor is kept to be 0.9-1.5 mg/L. In this embodiment, the total light-dark time ratio at this stage is 6 h: and (3) adjusting the illumination intensity to 4000lux downwards, controlling the photosynthesis intensity in this way to further maintain the balance of the biomass of the algae and the flora in the reactor, keeping the reactor in a micro-aerobic state all the time, carrying out in-situ enrichment growth of the AOB flora in the micro-aerobic state, successfully enriching the algae in situ and forming a stably running symbiotic PD/A-PN/A system of the bacteria and the algae, and finishing the starting process.
After the reactor finishes the starting process, the method for realizing deep nitrogen and phosphorus removal based on the PD/A in-situ coupling algae of the device comprises the following steps:
feeding the sewage into a reactor for treatment, and adding acetic acid as a carbon source, wherein the adding amount of the acetic acid is reduced to 10mg TOC/L, and the nitrate removal rate reaches 100% under the concentration of the carbon source, which indicates that the current amount of the carbon source can meet the high metabolic activity of denitrifying bacteria of the system; the temperature in the reactor is still maintained at 34.5-35.5 ℃, the pH of inlet water is 7.0-7.5, the hydraulic retention time is 12h, and the rotating speed of a stirring device is 700 +/-5 rpm. The operation time sequence of the PD/A-SBR reactor is that water is fed for 10min, stirring is carried out for 660min, sedimentation is carried out for 20min, water is drained for 10min, and the water drainage ratio is operated under the condition of 50%. The pulse type illumination frequency is adjusted by a controller, and the dissolved oxygen concentration of the reactor is kept to be 0.9-1.5 mg/L.
The sewage treated in the embodiment is simulated sewage, and the simulated sewage is prepared by adding inorganic substances and 1ml of trace element solution into water by taking water as a solvent during preparation. To each liter of waterThe amount of inorganic substance added was: KNO 3 ，43mg；NH 4 Cl，43mg；KH 2 PO 4 ，30mg；KHCO 3 ，1000mg；MgSO 4 ·5H 2 O，60mg；CaCl 2 ·2H 2 O，60mg。
The concentrations of the respective trace elements in the trace element solution were as follows: EDTA, 15000 mg. L -1 ；CoCl 2 ·6H 2 O，240mg·L -1 ；ZnSO 4 ·7H 2 O，430mg·L -1 ；MnCl 4 ·H 2 O，990mg·L -1 ；NaMoO 4 ·2H 2 O，220mg·L -1 ；CuSO 4 ·5H 2 O，250mg·L -1 ；NaSeO 4 ·10H 2 O，210mg·L -1 ；NiCl·6H 2 O，190mg·L -1 And H 3 BO 4 ，14mg·L -1 。
Within 40 days of the operation of the sewage treatment process, the effluent quality is detected every day, and the result shows that a bacterial-algae symbiotic PD/A-PN/A system formed by the induction of a photocatalytic material realizes a high-efficiency sewage nitrogen and phosphorus removal effect, the ammonia nitrogen removal rate is continuously increased during the operation period, the complete removal of ammonia nitrogen is finally realized, the total nitrogen removal rate is kept above 95% in 30-40 days, and meanwhile, the total phosphorus removal rate is as high as 90%. According to the method for deeply removing nitrogen and phosphorus from sewage, the ammonia nitrogen conversion rate and the phosphorus removal efficiency of the system are obviously improved, and compared with a PD/A system, the consumption of an external carbon source is greatly reduced and is reduced to 10mg of TOC/L from 45mg of TOC/L. In addition, the sedimentation performance of the activated sludge in the reactor is remarkably improved, and SVI 5 The obvious reduction is 60.2 +/-1.2 mL-g -1 The SS is reduced to 31.1 +/-1.3 mL-g -1 And (7) SS. The experimental results show that synchronous deep nitrogen and phosphorus removal can be realized by performing in-situ enrichment on algae through the addition of a photocatalyst material and pulse type illumination to establish a PD/A-PN/A system, and the activated sludge has excellent characteristics and enhanced activity.
Example 2
In this example, the same PD/A in situ coupled algae device for deep denitrification and dephosphorization as in example 1 was used as described in FIG. 1. In the embodiment, the method for realizing deep nitrogen and phosphorus removal based on PD/A in-situ coupling algae of the device also takes simulated wastewater as a treatment object, and comprises two stages of starting and treating.
The starting process of the device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling of algae in the embodiment comprises the following steps:
inoculating PD/A activated sludge into the batch reactor, controlling the concentration of suspended solids in the sludge mixed liquor to be 4.5-5.5g/L, and controlling the operation parameters of the reactor as follows: the temperature is 34.5-35.5 ℃, the pH of inlet water is 7.0-7.5, the artificially synthesized wastewater is used as inlet water, the hydraulic retention time is 12 hours, and the rotating speed of a stirring device is 700 +/-5 rpm. The operation time sequence of the batch reactor comprises the steps of water feeding for 10min, stirring for 660min, precipitating for 20min, and draining for 10min, wherein the drainage ratio is 50%.
When the artificial synthesis wastewater is prepared, water is used as a solvent, inorganic substances and 1ml of trace element solution are added into the water, and the amount of the inorganic substances added into each liter of water is as follows: 1000mg KHCO 3 (ii) a 60mg of MgSO 4 ·5H 2 O; 60mg of CaCl 2 ·2H 2 O。
The concentrations of the respective trace element compositions in the trace element solutions were as follows: EDTA, 15000 mg. L -1 ；CoCl 2 ·6H 2 O，240mg·L -1 ；ZnSO 4 ·7H 2 O，430mg·L -1 ；MnCl 4 ·H 2 O，990mg·L -1 ；NaMoO 4 ·2H 2 O，220mg·L -1 ；CuSO 4 ·5H 2 O，250mg·L -1 ；NaSeO 4 ·10H 2 O,210mg·L -1 ；NiCl·6H 2 O，190mg·L -1 ；H 3 BO 4 ，14mg·L -1 。
According to the operation mode, the ratio of the ammonia nitrogen content to the nitrate content of the inlet water is kept to be 1:1, and the concentration of the carbon source of the inlet water acetic acid is kept to be 45mg TOC.L -1 About, operating a period every day, keeping the operating condition for a long time till 15 days, wherein the nitrite conversion rate and the ammonia nitrogen removal rate of the reactor reach more than 85 percent, the effluent nitrate is lower than about 5mg/L, CdS nano-particles are added into the reactor according to the adding amount of 180mg/L, and meanwhile CdS nano-particles are added into the reactorAnd introducing illumination by using a visible light irradiation device of the PD/A-SBR reactor, and entering an in-situ algae enrichment stage. The CdS nanoparticles in the embodiment are prepared in a laboratory by a solvothermal method, and are dried in a drying oven before use. After the CdS nano-particles are characterized by technologies such as an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), an X-ray photoelectron spectroscopy (XPS) and the like, the results show that the prepared CdS nano-particles have good photocatalytic performance.
Keep reactor operating parameter unchangeable, utilize evenly distributed to shine in the reactor in the pulsed light source subassembly of lower part, the light source upwards shines from reactor middle and lower part, reaches and evenly just all-round shine reactor mud to illumination frequency, the illumination time that shines the pulsed through the controller carries out the ration and adjusts, the interval of pulse irradiation time sets up to 1h among this embodiment, total light dark time ratio sets up to 12 h: and 12h, adjusting the light intensity of the light source component to be 6000 lux. The mode is kept, the two reactors are synchronously operated, and the reactors are observed to enter a comprehensive efficiency stage of optimizing bacteria and algae at the 30 th day, wherein the relative content of algae Chl-a: MLVSS reached and stabilized around 0.3, total nitrogen removal increased to 88%, total phosphorus removal broke through from zero to 55%.
In the stage, the pulse type illumination frequency is adjusted by a controller along with the change of DO content in the reactor, and the dissolved oxygen concentration of the reactor is kept between 0.9 and 1.5 mg/L. In this embodiment, the total light-dark time ratio at this stage is 6 h: and (3) adjusting the illumination intensity to 4000lux downwards, controlling the photosynthesis intensity in this way to further maintain the balance of the biomass of the algae and the flora in the reactor, keeping the reactor in a micro-aerobic state all the time, carrying out in-situ enrichment growth of the AOB flora in the micro-aerobic state, successfully enriching the algae in situ and forming a stably running symbiotic PD/A-PN/A system of the bacteria and the algae, and finishing the starting process.
The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae based on the device in the embodiment comprises the following steps:
when the reactor finishes the starting process, the sewage is sent into the reactor for treatment, and acetic acid is also added as a carbon source, in the embodiment, in order to enable the nitrate removal rate to be close to 100%, the adding amount of the acetic acid needs 15mg TOC/L, and when the adding amount is lower than the adding amount, the nitrate removal rate is reduced. The temperature in the reactor is still maintained at 34.5-35.5 ℃, the pH of inlet water is 7.0-7.5, the hydraulic retention time is 12h, and the rotating speed of a stirring device is 700 +/-5 rpm. The operation time sequence of the PD/A-SBR reactor is that water is fed for 10min, stirring is carried out for 660min, sedimentation is carried out for 20min, water is drained for 10min, and the water drainage ratio is operated under the condition of 50%. The pulse type illumination frequency is adjusted by a controller, and the dissolved oxygen concentration of the reactor is kept to be 0.9-1.5 mg/L.
The wastewater used in this example was simulated wastewater prepared by adding an inorganic substance and 1ml of a trace element solution to water using water as a solvent. The amount of inorganic substance added per liter of water was: KNO 3 ，43mg；NH 4 Cl，43mg；KH 2 PO 4 ，30mg；KHCO 3 ，1000mg；MgSO 4 ·5H 2 O，60mg；CaCl 2 ·2H 2 O，60mg。
The concentrations of the respective trace element compositions in the trace element solutions were as follows: EDTA, 15000 mg. L -1 ；CoCl 2 ·6H 2 O，240mg·L -1 ；ZnSO 4 ·7H 2 O，430mg·L -1 ；MnCl 4 ·H 2 O，990mg·L -1 ；NaMoO 4 ·2H 2 O，220mg·L -1 ；CuSO 4 ·5H 2 O，250mg·L -1 ；NaSeO 4 ·10H 2 O，210mg·L -1 ；NiCl·6H 2 O，190mg·L -1 And H 3 BO 4 ，14mg·L -1 。
Within 40 days of the operation of the sewage treatment process, the effluent quality is detected every day, and the result shows that the bacterial-algae symbiotic PD/A-PN/A system formed by the induction of the photocatalytic material realizes the high-efficiency sewage nitrogen and phosphorus removal effect, the nitrogen removal efficiency of the system is continuously optimized during the operation of the reactor, the ammonia and nitrogen removal rate is finally kept above 95%, the total nitrogen removal rate is increased and maintained above 90%, and the total phosphorus removal rate reaches 90%. The consumption of the added carbon source is greatly reduced from 45mg of TOC/L to 15mg of TOC/L. SVI 5 The obvious reduction is 59.5 +/-0.9 mL-g -1 The SS decreased to 33.4. + -. 1.4 mL-g -1 SS。
Visible light photocatalyst g-C in example 1 compared to CdS nanoparticles in example 2 3 N 4 The system performance of the nano-particles is better, and a more efficient and more stable bacteria-algae symbiotic PD/A-PN/A system can be quickly constructed.
Example 3
In this example, the same PD/A in situ coupled algae device for deep denitrification and dephosphorization as in examples 1 and 2 was used as described in FIG. 1. In the embodiment, the method for realizing deep nitrogen and phosphorus removal based on PD/A in-situ coupling algae of the device also takes simulated wastewater as a treatment object, and comprises two stages of starting and treating.
The starting process of the device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling of algae in the embodiment comprises the following steps:
inoculating PD/A activated sludge into the batch reactor, controlling the concentration of suspended solids in the sludge mixed liquor to be 4.5-5.5g/L, and controlling the operation parameters of the reactor as follows: the temperature is 34.5-35.5 ℃, the pH of inlet water is 7.0-7.5, the artificially synthesized wastewater is used as inlet water, the hydraulic retention time is 12 hours, and the rotating speed of a stirring device is 700 +/-5 rpm. The operation time sequence of the batch reactor comprises the steps of water feeding for 10min, stirring for 660min, precipitating for 20min, and draining for 10min, wherein the drainage ratio is 50%.
When the artificial synthetic wastewater is prepared, water is used as a solvent, and inorganic substances and 1ml of trace element solution are added into the water to prepare the artificial synthetic wastewater. The amount of inorganic substance added per liter of water was: 1000mg KHCO 3 (ii) a 60mg of MgSO 4 ·5H 2 O; 60mg of CaCl 2 ·2H 2 O。
The concentrations of the respective trace element compositions in the trace element solutions were as follows: EDTA, 15000 mg. L -1 ；CoCl 2 ·6H 2 O，240mg·L -1 ；ZnSO 4 ·7H 2 O，430mg·L -1 ；MnCl 4 ·H 2 O，990mg·L -1 ；NaMoO 4 ·2H 2 O，220mg·L -1 ；CuSO 4 ·5H 2 O，250mg·L -1 ；NaSeO 4 ·10H 2 O,210mg·L -1 ；NiCl·6H 2 O，190mg·L -1 ；H 3 BO 4 ，14mg·L -1 。
The reactor operates according to the parameters, the content ratio of the ammonia nitrogen and the nitrate of the inlet water is kept to be 1:1, and the concentration of the acetic acid carbon source of the inlet water is 45mg TOC.L -1 About, operating for a period every day, keeping the operating condition for a long time till 15 days, wherein the nitrite conversion rate and the ammonia nitrogen removal rate of the reactor reach more than 85 percent, the effluent nitrate is lower than about 5mg/L, and at the moment, adding modified g-C into the reactor according to the adding amount of 180mg/L 3 N 4 And particles are simultaneously introduced with light by utilizing a light source device on the reactor to enter an in-situ algae enrichment stage. Modified g-C added in this example 3 N 4 C modified by 2, 4-dihydroxypyrimidine molecules prepared by laboratory pyrolysis 3 N 4 The material is prepared by the following specific preparation method: adding 50mg of 2, 4-dihydroxypyridine into 20g of urea, mechanically stirring uniformly, transferring the mixture into an alumina crucible with a cover, putting the crucible containing the sample into a muffle furnace, heating the crucible to 550 ℃ from room temperature at a heating rate of 5 ℃/min, and preserving the temperature for 2 hours. After the procedure is finished, naturally cooling to room temperature, taking out the obtained light yellow block-shaped solid sample, and grinding by a mortar to obtain the final light yellow powder C modified by the 2, 4-dihydroxypyrimidine molecule 3 N 4 The material, which is on the micron scale, is dried in a drying oven prior to use.
Complete modification of g-C 3 N 4 After the particles are added, the operation parameters of the reactor are kept unchanged, the visible light source components uniformly distributed on the middle lower part and the lower part of the transparent constant-temperature water jacket of the reactor are used for illumination, the light source upwards irradiates from the middle lower part of the reactor, the sludge of the reactor is uniformly and comprehensively irradiated, the pulse irradiation frequency and the pulse irradiation time are quantitatively adjusted through the controller, the pulse irradiation time interval is set to 12 hours, namely, the sunlight is continuously irradiated for 12 hours every day, and the sunlight-dark ratio is 12 hours: 12h, and adjusting the light intensity of the light source component to 6000 lux; maintaining this mode of operation until day 16, algae were observed on the reactor flora surface anda considerable enrichment on the reactor wall is achieved, the relative algae content Chl-a: MLVSS is 0.35, and the denitrification rate of the system is greatly improved to more than 90% compared with the previous stage, and in addition, the total phosphorus removal rate of the system is broken through from zero to 70%, and the stage of adjusting the pulse type illumination mode to optimize the comprehensive efficiency of bacteria and algae is started.
In the stage, the pulse type illumination frequency is adjusted by a controller along with the change of DO content in the reactor, and the dissolved oxygen concentration of the reactor is kept between 0.9 and 1.5 mg/L. In this embodiment, the total light-dark time ratio at this stage is 6 h: and (3) adjusting the illumination intensity to 4000lux downwards, controlling the photosynthesis intensity in this way to further maintain the balance of the biomass of the algae and the flora in the reactor, keeping the reactor in a micro-aerobic state all the time, carrying out in-situ enrichment growth of the AOB flora in the micro-aerobic state, successfully enriching the algae in situ and forming a stably running symbiotic PD/A-PN/A system of the bacteria and the algae, and finishing the starting process.
The method for realizing deep nitrogen and phosphorus removal by coupling PD/A (potential of Hydrogen/anaerobic) in-situ algae based on the device in the embodiment comprises the following steps:
when the reactor finishes the starting process, sending the sewage into the reactor for treatment, and adding acetic acid as a carbon source, wherein the adding amount of the acetic acid is 8mg TOC/L, and under the concentration of the carbon source, the nitrate removal rate reaches 100%; the temperature in the reactor is still maintained at 34.5-35.5 ℃, the pH of inlet water is 7.0-7.5, the hydraulic retention time is 12h, and the rotating speed of a stirring device is 700 +/-5 rpm. The operation time sequence of the PD/A-SBR reactor is that water is fed for 10min, stirring is carried out for 660min, sedimentation is carried out for 20min, water is drained for 10min, and the water drainage ratio is operated under the condition of 50%. The pulse type illumination frequency is adjusted by a controller, and the dissolved oxygen concentration of the reactor is kept to be 0.9-1.5 mg/L.
When the simulated wastewater is prepared, water is used as a solvent, and inorganic substances and 1ml of trace element solution are added into the water to prepare the simulated wastewater. The amount of inorganic substance added per liter of water was: KNO 3 ，43mg；NH 4 Cl，43mg；KH 2 PO 4 ，30mg；KHCO 3 ，1000mg；MgSO 4 ·5H 2 O，60mg；CaCl 2 ·2H 2 O，60mg。
Concentration of each trace element composition in the trace element solutionThe following were used: EDTA, 15000 mg. L -1 ；CoCl 2 ·6H 2 O，240mg·L -1 ；ZnSO 4 ·7H 2 O，430mg·L -1 ；MnCl 4 ·H 2 O，990mg·L -1 ；NaMoO 4 ·2H 2 O，220mg·L -1 ；CuSO 4 ·5H 2 O，250mg·L -1 ；NaSeO 4 ·10H 2 O，210mg·L -1 ；NiCl·6H 2 O，190mg·L -1 And H 3 BO 4 ，14mg·L -1 。
Within 40 days of the operation of the sewage treatment process, the effluent quality is detected every day, and the result shows that a bacterial-algae symbiotic PD/A-PN/A system formed by the induction of a photocatalytic material realizes a high-efficiency sewage nitrogen and phosphorus removal effect, the nitrogen removal efficiency of the system is continuously optimized during the operation of the reactor, the ammonia and nitrogen removal rate is continuously increased during the operation and finally the complete removal of ammonia and nitrogen is realized, the total nitrogen removal rate is increased and maintained to be more than 95 percent, and the total phosphorus removal rate reaches 90 percent. The consumption of the added carbon source is greatly reduced from 45mg TOC/L to 8mg TOC/L. SVI 5 The obvious reduction is 61.3 +/-1.1 mL-g -1 The SS is reduced to 29.1 +/-1.2 mL-g -1 SS。
Example 4
In this example, the same PD/A in situ coupled algae device as described in FIG. 1 for deep denitrification and dephosphorization is used, as in examples 1-3. In this embodiment, the method for realizing deep nitrogen and phosphorus removal by coupling PD/a in situ with algae based on the device uses actual industrial wastewater as a treatment object, and includes two stages of starting and treating.
The starting process of the device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae comprises the following steps:
PD/A activated sludge is inoculated into a reactor, the suspension fixed concentration of the sludge mixed liquor is 4.5-5.5g/L, coal gasification industrial wastewater is taken as inlet water, acetic acid is taken as an external carbon source, the temperature in the reactor is 34.5-35.5 ℃, the hydraulic retention time is 12h, and the rotating speed of a stirring device is 700 +/-5 rpm. The operation time sequence of the PD/A-SBR reactor is that water is fed for 10min, stirring is carried out for 660min, sedimentation is carried out for 20min, water is drained for 10min, and the water drainage ratio is operated under the condition of 50%.
The industrial wastewater is derived from sewage discharged by a coal gasification plant, and the water quality condition and the pollutant composition and content mainly comprise: TN, 190-225 mg/L; NH (NH) 4 + -N，181-224mg/L；NO 3 - -N, 130-155 mg/L; COD, 485-; TP, 30-45 mg/L; pH of 8.2-8.5; suspended Solids (SS), 56-101 mg/L. The industrial wastewater is subjected to filtration pretreatment before water inlet, and most suspended matters are removed by filtration.
According to the operation parameters, the reactor is operated for one period every day, the ammonia nitrogen removal rate of the reactor is stable and rises to more than 80 percent by 10 days, the total nitrogen removal rate is stable at about 70 percent, and the consumption of the acetic acid carbon source per period is 20mg TOC/L. Keeping the operating parameters of the reactor unchanged, and adding 180mg/L of modified g-C into the reactor 3 N 4 Modified g-C added in this example 3 N 4 2, 4-dihydroxypyrimidine molecule-modified C prepared by laboratory pyrolysis 3 N 4 The material, which was in the micron scale, was a pale yellow powder that was dried in a dry box prior to use. Utilize evenly distributed to shine in the transparent constant temperature water jacket middle and lower part of reactor visible light source subassembly, the light source upwards shines from reactor middle and lower part, reaches even and all-round shining reactor mud to illumination frequency, the illumination time that shines the pulsed through the controller carry out the ration and adjust, the interval of pulse irradiation time sets up to 12h in this embodiment, simulate sunlight 12 hours and shine in succession promptly every day, the sunlight-to-darkness is 12 h: 12h, and adjusting the light intensity of the light source component to 6000 lux; maintaining this mode of operation until day 20, a considerable enrichment of algae on the reactor flora surface and on the reactor walls was observed, the algae relative content Chl-a: MLVSS is 0.3, and the denitrification rate of the system is greatly improved to more than 85% compared with the previous stage, and in addition, the total phosphorus removal rate of the system is broken through from zero to 55%, and the stage of adjusting the pulse type illumination mode to optimize the comprehensive efficiency of bacteria and algae is started.
In the stage, the Dissolved Oxygen (DO) in the reactor is kept between 0.9 and 1.5mg/L by adjusting the frequency of pulse type illumination through a controller along with the change of the DO content in the reactor. In this embodiment, the total light-dark time ratio is 6 h: and (3) adjusting the illumination intensity to 4000lux downwards, controlling the photosynthesis intensity in this way to further maintain the balance of the biomass of the algae and the flora in the reactor, keeping the reactor in a micro-aerobic state all the time, carrying out in-situ enrichment growth of the AOB flora in the micro-aerobic state, successfully enriching the algae in situ and forming a stably running symbiotic PD/A-PN/A system of the bacteria and the algae, and finishing the starting process.
The method for realizing deep nitrogen and phosphorus removal by coupling PD/A (potential of Hydrogen/anaerobic) in-situ algae based on the device in the embodiment comprises the following steps:
after the reactor finishes the starting process, sending the sewage into the reactor for treatment, and adding acetic acid as a carbon source, wherein the adding amount of the acetic acid is 10mg TOC/L; the temperature in the reactor is still maintained at 34.5-35.5 ℃, the hydraulic retention time is 12h, and the rotating speed of the stirring device is 700 +/-5 rpm. The operation time sequence of the PD/A-SBR reactor is that water is fed for 10min, stirring is carried out for 660min, sedimentation is carried out for 20min, water is drained for 10min, and the water drainage ratio is operated under the condition of 50%. The pulse type illumination frequency is adjusted by a controller, and the Dissolved Oxygen (DO) of the reactor is kept between 0.9 and 1.5 mg/L.
In this embodiment, the industrial wastewater is still used as the sewage, and the water quality and the pollutant composition and content mainly include: TN, 190-225 mg/L; NH (NH) 4 + -N，181-224mg/L；NO 3 - -N, 130-155 mg/L; COD, 485-; TP, 30-45 mg/L; pH of 8.2-8.5; suspended Solids (SS), 56-101 mg/L.
Within 40 days of the operation of the sewage treatment process, the quality of the effluent is detected, and the result shows that the ammonia nitrogen removal rate is kept above 95%, the highest ammonia nitrogen removal rate can reach 100%, the total nitrogen removal rate is kept above 90%, the total phosphorus removal rate is as high as 90%, and the COD removal effect of the system is finally stabilized at 98%. The sedimentation performance of the activated sludge in the reactor is obviously improved, and the SVI 5 From 60.2. + -. 1.2 mL. g -1 The SS is reduced to 38.9 +/-2.3 mL-g -1 And (7) SS. The experiment results show that g-C is modified by the semiconductor photocatalytic material 3 N 4 And pulsed illumination ofThe system can enrich algae in situ, change the microenvironment of the system through photosynthetic oxygen release of the algae, realize the construction of a PD/A-PN/A system, and synchronously and deeply remove nitrogen and phosphorus from industrial wastewater with high pollutant concentration, and meanwhile, the system has good microbial activity and high stability.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the claims.

Claims (10)

1. A method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae is characterized by comprising the step of sending sewage into a short-cut denitrification-anaerobic ammonia oxidation reaction zone for treatment; algae are enriched in the short-range denitrification-anaerobic ammonia oxidation reaction zone and a photocatalytic material is added; adding acetic acid into the sewage as a carbon source;
in the treatment process, visible light is used for illuminating the short-cut denitrification-anaerobic ammonia oxidation reaction zone, the quantity of algae is controlled by adjusting illumination parameters, the dissolved oxygen concentration of the short-cut denitrification-anaerobic ammonia oxidation reaction zone is kept at 0.9-1.5mg/L, and ammonia oxidizing bacteria are generated in situ.
2. The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupled algae of claim 1, wherein the photocatalytic material is C 3 N 4 A material.
3. The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupled algae of claim 2, characterized in that the photocatalytic material is C modified by 2, 4-dihydroxypyrimidine molecule 3 N 4 A material.
4. The method for realizing deep nitrogen and phosphorus removal by coupling PD/A in situ algae according to any one of claims 1 to 3, characterized in that the algae is generated in situ in the short-cut denitrification-anaerobic ammonia oxidation reaction zone in an enrichment manner, and the relative content ratio of the algae to the sludge is Chl-a: MLVSS is 0.25-0.5 mg/g.
5. The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupled algae according to claim 4, wherein the dosage of acetic acid in the sewage is 10mg TOC/L; the temperature in the reactor is 34.5-35.5 ℃, and the pH value of the inlet water is 7.0-7.5.
6. The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupled algae according to any one of claims 1 to 5, characterized in that the start-up process of the short-cut denitrification-anaerobic ammonia oxidation reaction zone is as follows: inoculating well-operated short-cut denitrification-anaerobic ammonia oxidation activated sludge, taking sewage containing nitrate, ammonia nitrogen, inorganic salt and trace elements or simulated sewage as inlet water, adding acetic acid as a carbon source, keeping the temperature of a reaction zone at 34.5-35.5 ℃, controlling the pH of the inlet water at 7.0-7.5, and operating under a stirring condition until the removal rates of the nitrite and the ammonia nitrogen reach more than 85%; adding 150-200mg/L C into the reaction zone 3 N 4 Controlling illumination parameters, and operating the reaction until the in-situ enrichment of algae is completed and the denitrification rate reaches over 90 percent.
7. The method for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae according to claim 6, characterized in that in the starting process, the molar ratio of the contained ammonia nitrogen to the nitrate nitrogen in the sewage containing nitrate, ammonia nitrogen, inorganic salt and trace elements or the simulated sewage as the inlet water is about 1: 1.
8. A device for realizing deep nitrogen and phosphorus removal by coupling PD/A (photo-oxidative) in situ with algae is characterized by comprising:
the device comprises a reactor, a water inlet, a water outlet, a short-cut denitrification-anaerobic ammonia oxidation reaction zone, a stirring device and a water inlet and outlet, wherein the reactor is internally provided with the short-cut denitrification-anaerobic ammonia oxidation reaction zone;
the carbon source adding device is used for adding a carbon source into the reactor;
the visible light irradiation device is used for irradiating the short-range denitrification-anaerobic ammonia oxidation reaction zone; the quantity of algae is controlled by adjusting the illumination parameters, so that the dissolved oxygen concentration of the short-range denitrification-anaerobic ammonia oxidation reaction zone is 0.9-1.5mg/L, and ammonia oxidizing bacteria are generated in situ.
9. The device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae according to claim 8, characterized in that the visible light illuminating device comprises:
the dissolved oxygen probe is positioned in the short-range denitrification-anaerobic ammonia oxidation reaction zone;
and the pulse type light source assembly is connected with the dissolved oxygen probe through a controller, and controls the illumination frequency and the illumination time by taking the detection value of the dissolved oxygen probe as an index.
10. The device for realizing deep nitrogen and phosphorus removal by PD/A in-situ coupling algae according to claim 9, characterized in that a plurality of grooves are provided on the inner wall of the middle lower part of the reactor, each groove extends along the vertical direction, the plurality of grooves are uniformly distributed around the inner wall surface, and the pulse type light source assembly is fixed in the groove; the illumination intensity of the pulse type light source assembly is 3000-.
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