Active bio-manganese oxide pool (ABMP), its construction method and application

Abstract

This application discloses an activated biological manganese oxide tank (ABMP), its construction method, and its application. The construction method includes the following steps: S1, culturing anaerobic denitrification granular sludge for 20-40 days, with the influent ammonia nitrogen concentration: nitrite nitrogen concentration = 1:1-1:3, and the culture water temperature at 28-32℃; S2, adding 15-25 mg / L of Mn with the influent. 2+ Continue cultivation for 20-40 days; S3, increase the concentrations of the first ammonia nitrogen and the first nitrite nitrogen in the influent to the second ammonia nitrogen and the second nitrite nitrogen concentrations, and increase Mn 2+ The concentration was increased to 35-45 mg / L, the culture water temperature was raised to 38-42℃, and the influent C / N ratio was maintained at 2-3. Culture was continued for 20-40 days, with the ratio of the second ammonia nitrogen concentration to the second nitrite nitrogen concentration being 1:1-1:3. This application uses the concentrations of ammonia nitrogen, nitrite nitrogen, and Mn in the influent to... 2+ Phased regulation of concentration, combined with the introduction of AHLs to promote the production of bio-manganese oxides (BioMnO). x The accumulation and construction of ABMP. The anaerobic denitrification granular sludge reactor of this application can maintain manganese circulation and nitrogen conversion in the reactor for a long time, while achieving highly efficient denitrification under extremely low carbon-nitrogen ratio conditions.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of microbial wastewater denitrification technology, and more particularly to an active biomanganese oxide pool (ABMP) and a construction method and application thereof, an anaerobic denitrification granular sludge reactor and a treatment method for low carbon-nitrogen ratio wastewater. x BACKGROUND

[0002] Eutrophication of water bodies is one of the most disturbing water quality problems faced by mankind in recent decades. Eutrophication can seriously damage the supply, regulation and maintenance functions and cultural functions of water ecosystem services, which not only causes damage to the ecological environment, but also affects human water safety. In the geochemical cycle, nitrogen cycle is mainly carried out through the processes of ammonification, nitrification and denitrification. Domestic sewage and industrial wastewater contain various pollutants, including nitrogen-containing compounds, which need to be removed before discharge.

[0003] Anaerobic ammonium oxidation (Anammox) is an efficient autotrophic microbial denitrification technology, which oxidizes ammonia nitrogen (NH4 - -N) to nitrogen gas (N2) by using nitrite (NO2 + -N) as an electron acceptor under anaerobic conditions. Compared with the traditional nitrification-denitrification process, Anammox does not require external organic carbon source and aeration, thus has the advantages of low energy consumption and low sludge yield. However, the Anammox process is highly sensitive to environmental conditions such as temperature, salinity and organic pollutant content. The concentration of heavy metal ions in the environment has a significant impact on the growth of Anammox bacteria and the operation effect of Anammox process.

[0004] Manganese is the third most abundant transition metal element in the earth's crust, is a coenzyme that constitutes many microbial enzymes, and participates in microbial energy and redox metabolism. In water bodies, manganese mainly exists in the form of divalent (Mn(II)) and tetravalent (Mn(IV)), and is converted between different valence states through redox reactions. Microorganisms participate in the manganese cycle through redox reactions, and the redox cycle of manganese in water bodies has an important influence on microbial denitrification process. Studies have reported manganese-driven autotrophic denitrification (NDMO), which realizes the simultaneous removal of nitrate and organic pollutants by using (Mn(II)) as an inorganic electron donor. In addition, the bio-manganese oxide (BioMnO x ) produced by this process can also act as an electron acceptor to induce a new manganese ammonium oxidation (Mnammox) process, thereby forming a manganese-nitrogen cycle in the reactor. Because of its ability to simultaneously remove nitrogen and organic pollutants, it has become one of the frontiers of microbial denitrification research. At the same time, MnO x ​In comparison, bio-manganese oxide BioMnO x It has a larger specific surface area and higher catalytic activity, and at the same time, it has strong redox capabilities and catalytic performance.

[0005] Current research on the interaction between manganese and the Anammox system is quite one-sided. Most studies are limited to the effect of manganese on the nitrogen removal efficiency of anammox reactors, neglecting the speciation and valence state changes of manganese in Anammox reactors, as well as the bio-manganese oxide BioMnO. x Accumulation in reactors and its application value. Bio-manganese oxide (BioMnO) x Accumulation of ABMP in microbial denitrification reactors is usually very slow, which leads to its role in microbial denitrification reactors often being overlooked, and the construction methods of ABMP have not been studied in depth. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this application is to cross-integrate the redox cycle of manganese with the microbial metabolism of nitrogen, so as to provide a rapid construction method of ABMP and an efficient denitrification method for wastewater with low carbon-to-nitrogen ratio.

[0007] Bio-manganese oxide (BioMnO) x The continuously accumulated ABMP, as an important reaction center in the manganese cycle of the Mnammox-NMDO system, has the characteristics of strong redox ability and large specific surface area. On the one hand, it can act as an electron acceptor to oxidize ammonia nitrogen (3MnO2 + NH4) in nitrogen-containing wastewater. + +4H + →3Mn 2+ +NO2 - +4H2O), on the other hand, the reduced low-valent manganese can drive manganese autotrophic denitrification (5Mn). 2+ +2NO3 - +4H₂O→5MnO₂+N₂+8 ... + 3Mn 2+ +2NO2 - +2H₂O→3MnO₂+N₂+4H + (), thus being oxidized to a higher valence, thereby realizing the manganese cycle in the system.

[0008] However, bio-manganese oxide BioMnO x Accumulation of nitrogen in microbial denitrification reactors is typically a very long process. This application addresses the accumulation of Mn in the influent. 2+ The phased regulation of concentrations of nitrogen, ammonia nitrogen, and nitrite nitrogen, as well as the culture water temperature, and the further introduction of AHLs, especially quorum sensing molecules like C8-HSL, to enhance the electron transfer ability and conductive flagella synthesis of denitrifying microorganisms, thereby promoting the interaction between denitrifying microorganisms and Mn to a certain extent.2+ Electron transfer between them improves manganese oxidation efficiency and accelerates the production of bio-manganese oxides (BioMnO). x The accumulation and construction of ABMPs. ABMPs significantly influence the diversity of nitrogen metabolism pathways in the microbial community. In the anaerobic microbial denitrification process dominated by Anammox, the construction of ABMPs will serve as a "bridge" for the coupling of the Anammox system with the Mnammox-NMDO system (0.24Mn). 2+ +NH4 + +1.84NO2 - +0.24H + →0.36NO3 - (+2.48N2↑+2.12H2O+0.24MnO2), achieving efficient manganese recycling and nitrogen removal.

[0009] More specifically, in a first aspect, this application provides a method for constructing an ABMP, comprising the following steps:

[0010] S1. Culture the anaerobic denitrification granular sludge for 20-40 days, with the influent first ammonia nitrogen concentration: first nitrite nitrogen concentration = 1:1-1:3, and the culture water temperature is 28-32℃.

[0011] S2, Add 15-25 mg / L of Mn with the influent. 2+ Continue cultivation for 20-40 days;

[0012] S3. Increase the concentrations of the first ammonia nitrogen and the first nitrite nitrogen in the influent to the second ammonia nitrogen and the second nitrite nitrogen concentrations, thereby increasing Mn. 2+ The concentration was increased to 35-45 mg / L, and the influent C / N ratio was kept at 2-3. The culture water temperature was increased to 38-42℃, and the culture was continued for 20-40 days. The ratio of the second ammonia nitrogen concentration to the second nitrite nitrogen concentration was 1:1-1:3.

[0013] Preferably, steps S1-S3 further include maintaining a stirring speed of 30-60 rpm, and / or a first ammonia nitrogen concentration of 15-30 mg / L, and / or a second ammonia nitrogen concentration of 1.5-2.5 times the first ammonia nitrogen concentration.

[0014] Preferably, the anaerobic denitrification granular sludge contains anaerobic ammonia-oxidizing bacteria with a relative abundance of 30-50%.

[0015] Preferably, step S2 further includes: adding 0.05-0.075 mg / L AHLs with the influent, and / or maintaining the influent C / N ratio at 0.5-1.5.

[0016] Preferably, step S3 further includes: increasing the concentration of AHLs in the influent to 0.1-0.2 mg / L.

[0017] Secondly, this application provides an active bio-manganese oxide pool ABMP, which is prepared by the above-described method for constructing an active bio-manganese oxide pool ABMP.

[0018] Thirdly, this application provides an anaerobic denitrification granular sludge reactor, which constructs an activated biological manganese oxide tank ABMP using the above-mentioned method for constructing an activated biological manganese oxide tank ABMP, or includes the above-mentioned activated biological manganese oxide tank ABMP.

[0019] Fourthly, this application provides the application of the above-mentioned activated biological manganese oxide tank ABMP or the above-mentioned anaerobic denitrification granular sludge reactor in the treatment of wastewater with a low carbon-to-nitrogen ratio.

[0020] Preferably, the C / N ratio in the low C / N ratio wastewater is ≤3.

[0021] Fifthly, this application provides a method for treating wastewater with a low carbon-to-nitrogen ratio, comprising passing the wastewater with a low carbon-to-nitrogen ratio into an anaerobic denitrification granular sludge reactor, wherein the C / N ratio in the wastewater with a low carbon-to-nitrogen ratio is ≤3.

[0022] Preferably, the low carbon-to-nitrogen ratio wastewater is supplied continuously with a hydraulic retention time of ≥12h.

[0023] The technical solution of this application achieves the following technical effects:

[0024] 1. During the cultivation of anaerobic denitrification granular sludge, the concentrations of ammonia nitrogen, nitrite nitrogen, and Mn in the influent are monitored. 2+ Phased regulation of concentration to promote the production of biogenic manganese oxide (BioMnO), which contains multiple valence states and is dominated by tetravalent manganese. x The accumulation and construction of ABMP. Specifically, in the first stage, anaerobic denitrification granular sludge is stabilized for 20-40 days at a water temperature of 28-32℃, with the influent first ammonia nitrogen concentration: first nitrite nitrogen concentration = 1:1-1:3; in the second stage, 15-25 mg / L of Mn is added with the influent. 2+ Continue culturing for 20-40 days; in the third stage, increase the concentrations of the first ammonia nitrogen and the first nitrite nitrogen in the influent to the second ammonia nitrogen and the second nitrite nitrogen concentrations, and increase Mn. 2+ Increase the concentration to 35-45 mg / L, raise the culture water temperature to 38-42℃, and maintain the influent C / N ratio of 2-3. Continue culturing for 20-40 days, with the ratio of the second ammonia nitrogen concentration to the second nitrite nitrogen concentration being 1:1-1:3.

[0025] 2. In the process of constructing ABMP, this application introduces AHLs, a quorum sensing molecule, to enhance the electron transfer ability and conductive flagella synthesis of denitrifying microorganisms, thereby promoting the interaction between denitrifying microorganisms and Mn to a certain extent.2+ Electron transfer between them improves manganese oxidation efficiency and accelerates the production of bio-manganese oxides (BioMnO). x The accumulation of knowledge and the construction of ABMP.

[0026] 3. This application constructs an anaerobic denitrification granular sludge reactor using ABMP. When treating nitrogen-containing wastewater, especially wastewater with a low C / N ratio, ABMP will act as the reaction center for the Anammox-coupled Mnammox-NMDO system, during which NH4+... + -N oxidation produces NO3-N (Anammox) and NO2. - -N(Mnammox), the reduced low-valent manganese can then be converted into NO3 by microorganisms. - -N and NO2 - -N is reduced to N2 (NMDO), achieving efficient nitrogen removal with a total nitrogen removal rate of over 90%.

[0027] 4. The anaerobic denitrification granular sludge reactor constructed in this application can maintain manganese circulation and nitrogen conversion in the reactor for a long time. At the same time, it can achieve high-efficiency denitrification under extremely low carbon-to-nitrogen ratio conditions (C / N≤3, for example, C / N=0.5-2), and the amount of residual sludge is low. There is no generation of greenhouse gases such as N2O in the traditional nitrification-denitrification process.

[0028] The following will further explain the concept, specific structure and technical effects of this application in conjunction with the accompanying drawings, so as to fully understand the purpose, features and effects of this application. Attached Figure Description

[0029] Figure 1 These are comparative images of granular sludge morphology during the second stage of ABMP construction in Example 1 of this application. The left image shows the ABMP construction before construction, and the right image shows the ABMP construction after construction.

[0030] Figure 2 This is a SEM image of ABMP adhering to the surface of the anaerobic denitrification granular sludge in the third stage of Example 1 of this application.

[0031] Figure 3 This is another SEM image of ABMP adhering to the surface of the anaerobic denitrification granular sludge in the third stage of Example 1 of this application.

[0032] Figure 4 This is a TEM image of ABMP adhering to the surface of the anaerobic denitrification granular sludge in the third stage of Example 1 of this application. It can be seen that the bio-manganese oxide BioMnO x EPS distributed around denitrifying microorganisms.

[0033] Figure 5This refers to the change in the mass percentage of manganese on the surface of granular sludge in the reactor before and after the construction of ABMP in Example 1 of this application. The data were obtained from EDS energy dispersive spectroscopy.

[0034] Figure 6 This is a comparison of XPS spectra of granular sludge in the reactor before and after the ABMP construction in Example 1 of this application.

[0035] Figure 7 This is a comparison of XRD patterns of granular sludge in the reactor before and after the ABMP construction in Example 1 of this application.

[0036] Figure 8 It is NH4 in Example 5 + -N, TN, NO2 - -N、Mn 2+ Statistical chart of changes in influent and effluent concentrations.

[0037] Figure 9 It is NH4 in Example 6 + -N, TN, NO2 - -N、Mn 2+ Statistical chart of changes in influent and effluent concentrations.

[0038] Figure 10 It is NH4 in Example 7 + -N, TN, NO2 - -N、Mn 2+ Statistical chart of changes in influent and effluent concentrations.

[0039] Figure 11 It is NH4 in Example 8 + -N, TN, NO3 - -N、Mn 2+ Statistical chart of changes in influent and effluent concentrations. Detailed Implementation

[0040] The following specific examples illustrate the implementation of this application. Those skilled in the art can easily understand other advantages and effects of this application from the content disclosed in this specification. This application can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of this application. It should be noted that, unless otherwise specified, the following embodiments and features in the embodiments can be combined with each other.

[0041] Some exemplary embodiments of this application have been described for illustrative purposes. It should be understood that this application may be implemented in other ways not specifically shown in the accompanying drawings.

[0042] The "Active BioMnO" mentioned in this application x-Pool(x=1-2)”, abbreviated as ABMP, refers to Mn 2+ As an electron donor participating in the life activities of microorganisms with manganese oxidation capabilities, the polymer formed after oxidation contains manganese oxides in multiple valence states. Compared with manganese oxides obtained by chemical processes, bio-manganese oxide pools have a larger specific surface area, stronger biocompatibility, and stronger redox capabilities.

[0043] The method for constructing ABMP provided in this application involves controlling the concentrations of ammonia nitrogen, nitrite nitrogen, and Mn in the influent during the cultivation of anaerobic denitrification granular sludge. 2+ Phased regulation of concentration to promote the production of bio-manganese oxide BioMnO x The accumulation and construction of ABMP. Specifically, it includes the following three stages: The first stage involves the stable cultivation of anaerobic denitrification granular sludge for 20-40 days at a culture water temperature of 28-32℃, wherein the influent ammonia nitrogen concentration: nitrite nitrogen concentration = 1:1-1:3; The second stage involves the addition of 15-25 mg / L of Mn with the influent. 2+ Continue culturing for 20-40 days; in the third stage, increase the concentrations of the first ammonia nitrogen and the first nitrite nitrogen in the influent to the second ammonia nitrogen and the second nitrite nitrogen concentrations, and increase Mn. 2+ Increase the concentration to 35-45 mg / L, raise the culture water temperature to 38-42℃, and maintain the influent C / N ratio at 2-3. Continue culture for 20-40 days, with the ratio of second ammonia nitrogen to second nitrite nitrogen at 1:1-1:3. Each stage is described in detail below.

[0044] Regarding the first phase

[0045] For the cultivation of anaerobic denitrification granular sludge, an anaerobic microbial denitrification reactor is required to contain the sludge. This reactor has good sealing performance, is equipped with a reaction zone and a sedimentation zone, and has a stirring device and a microbial retention device, as well as supporting inlet and outlet water facilities. The reactor is submerged in an opaque, insulated tank with a built-in temperature-controlled heating rod to maintain the water temperature at 28℃-32℃ and the stirring speed at 30-60 rpm.

[0046] Anaerobic denitrification granular sludge was inoculated into the above-mentioned anaerobic microbial denitrification reactor, which had been tested for sealing performance, maintaining MLVSS at 7000-8000 mg / L, and the relative abundance of anaerobic ammonia-oxidizing bacteria in the anaerobic denitrification granular sludge was 30-50%.

[0047] In some embodiments, a peristaltic pump is used as the inlet device to supply water to the anaerobic microbial denitrification reactor. During continuous flow operation of the reactor, the hydraulic retention time (HRT) is maintained at a set time (e.g., 24h, 12h, etc., selected according to actual conditions) based on the effective reactor volume and inlet flow rate. During this stage, the inlet ammonia nitrogen concentration : nitrite nitrogen concentration = 1:1-1:3; for example, if the inlet ammonia nitrogen concentration is 20 mg / L, then the inlet nitrite nitrogen concentration is 20-60 mg / L. It should be understood that the specific concentration values ​​of the first ammonia nitrogen concentration and the first nitrite nitrogen concentration are not limited in this application, as long as they are sufficient to meet the growth requirements of anaerobic ammonia-oxidizing bacteria. Regarding the specific concentrations of ammonia nitrogen and nitrite nitrogen, since the sludge inoculated in this application is anaerobic sludge dominated by Anammox, these microorganisms simultaneously denitrify ammonia nitrogen and nitrite nitrogen in a certain ratio (1:1.32). However, other denitrifying bacteria are also present in the inoculated sludge. Therefore, the ammonia nitrogen concentration: nitrite nitrogen concentration is set at 1:1 to 1:3. In the stabilization stage after sludge inoculation, when the ammonia nitrogen concentration is too high, the concentration of free ammonia (NH3) increases, which is highly toxic to bacteria, inhibiting their activity and proliferation. Similarly, when the nitrite nitrogen concentration is too high, it is even more toxic to bacteria. Therefore, it is preferable that the ammonia nitrogen concentration in the first stage is not higher than 40 mg / L (e.g., 15-30 mg / L) and the nitrite nitrogen concentration is not higher than 80 mg / L. It should be understood that if the bacteria can still survive and denitrify normally at concentrations higher than this, ammonia nitrogen concentrations higher than 40 mg / L and nitrite nitrogen concentrations higher than 80 mg / L are still applicable.

[0048] During the first stage of cultivation, the dissolved oxygen concentration in the influent was controlled below 0.5 mg / L through nitrogen aeration to provide a suitable living environment for anaerobic ammonia-oxidizing bacteria. The water temperature inside the reactor was controlled at 28-32℃ to provide suitable growth conditions for the bacterial community, which is mainly engaged in anaerobic ammonia oxidation.

[0049] The cultivation period for the first stage, i.e., the period during which the anaerobic microbial denitrification reactor operates stably, can be selected according to actual conditions, as long as the MLVSS of the anaerobic denitrification granular sludge does not decrease significantly and the total nitrogen removal rate of the anaerobic denitrification granular sludge to the influent reaches more than 70%. Examples include 20 days, 30 days, 25 days, and 35 days. The number of days in the following embodiments does not constitute a limitation of this application. In some embodiments, the cultivation period for the first stage is 20-40 days.

[0050] Regarding the second phase

[0051] After the first stage is completed, the second stage of cultivation begins. In this stage, the ammonia nitrogen and nitrite nitrogen concentrations, temperature, and stirring speed remain the same as in the first stage. The difference lies in the addition of 15-25 mg / L of manganese nitrogen (Mn) with the influent.2+ As a preferred option, anhydrous manganese chloride is added with the influent because chloride ions are relatively stable in the reactor. Other manganese salts, such as manganese sulfate and manganese nitrate, may introduce other ions. Regarding Mn... 2+ The specific concentration was set with the consideration that it would not produce biotoxicity or serious negative effects on the microorganisms inoculated in this application, and could participate in the denitrification process of the microorganisms.

[0052] In some of these embodiments, after the influent aqueous solution is prepared, it is aerated with nitrogen for more than 30 minutes to remove dissolved oxygen (<0.5 mg / L) from the solution.

[0053] The inventors of this application discovered that, during the construction of ABMP, the introduction of AHLs, a quorum sensing molecule, can enhance the electron transfer ability and conductive flagella synthesis of denitrifying microorganisms, thereby promoting the interaction between denitrifying microorganisms and Mn to a certain extent. 2+ Electron transfer between them improves manganese oxidation efficiency and accelerates the production of bio-manganese oxides (BioMnO). x The accumulation of bio-manganese oxides (BMOs) and the formation of ABMP. Therefore, as a preferred option, 0.05-0.075 mg / L AHLs are added with the influent, for example, 0.05 mg / L AHLs in the form of C8-HSL. It should be understood that the addition of AHLs can accelerate the formation of bio-manganese oxides (BioMnO). x The accumulation of ABMP can be omitted in practice, but this does not affect the successful construction of ABMP.

[0054] In this stage, to drive the activity of Mnammox bacteria in the reactor, an organic carbon source can be introduced into the influent, for example, maintaining a C / N ratio of 0.5-1.5. The carbon source can be in the form of sodium acetate, but other forms are also possible, such as sodium citrate, etc., and this application is not limited to any particular form. In this stage, Mn... 2+ The introduction of Mn stimulated an increase in the abundance of manganese autotrophic denitrifying bacteria to some extent, while the addition of AHLs promoted the formation of conductive flagella in the microorganisms. Manganese autotrophic denitrifying bacteria utilize Mn... 2+ Mn acts as an inorganic electron donor for the reduction of nitrite. 2+ During this process, it is oxidized to a higher oxidation state, resulting in bio-manganese oxide BioMnO. x Start accumulating.

[0055] The cultivation time for the second stage can be selected according to the actual situation. SEM characterization revealed that active bio-manganese oxides (BioMnO) with a particle size of 20-50 nm began to appear on the surface of the anaerobic denitrification granular sludge. xAlternatively, an increase in the proportion of tetravalent manganese observed by XPS characterization indicates the completion of the second stage. Therefore, the duration may be, for example, 30 days, 25 days, or 35 days. The number of days in the following embodiments does not constitute a limitation of this application. In some embodiments, the first stage cultivation time is 20-40 days.

[0056] Regarding the third phase

[0057] After the second stage is completed, the third stage of cultivation begins. This stage increases the concentrations of ammonia nitrogen and nitrite nitrogen in the influent, and increases Mn. 2+ Increase the concentration to 35-45 mg / L, raise the culture water temperature to 38-42℃, and maintain the influent C / N ratio at 2-3, with the influent ammonia nitrogen concentration: influent nitrite nitrogen concentration at 1:1-1:3. At this stage, the addition of more carbon sources causes manganese ammonia-oxidizing bacteria to prefer utilizing organic carbon sources for manganese reduction. However, organic carbon sources and bio-manganese oxides (BioMnO)... x After binding, it will coat its surface, thereby reducing its active sites for accepting electrons and hindering the formation of bio-manganese oxides (BioMnO). x The reduction of bio-manganese oxide BioMnO x The accumulation of NMDO bacteria further leads to the formation of ABMP. Furthermore, since NMDO bacteria have a wider temperature adaptability compared to Mnammox bacteria, raising the water temperature to 38-42℃ at this stage is more conducive to the NMDO process and facilitates the formation of BioMnO2. x Further accumulation.

[0058] In the third stage, the anaerobic denitrification granular sludge in the reactor begins to change color, and the activated biological manganese oxide tank (BioMnO)... x The construction of the pool caused the color of the granular sludge to change from light red to dark brown, due to the large amount of bio-manganese oxides (BioMnO). x It adheres to the surface of granular sludge. With the active biological manganese oxide tank, BioMnO... x -Pool construction complete, containing bio-manganese oxide BioMnO with a particle size of 50-100nm. x The ABMPs are evenly distributed on the surface of the granular sludge and encapsulated by EPS. This encapsulated portion of ABMPs more readily accepts electrons from organic carbon sources and ammonia nitrogen, becoming the reaction center of the Anammox-coupled Mnammox-NMDO system. After successful ABMP construction, the proportion of tetravalent manganese on the surface of the granular sludge significantly increased. This indicates that free manganese ions entering the reactor are captured by EPS and oxidized to higher-valent manganese, thus being fixed on the surface of the anaerobic denitrification granular sludge.

[0059] In some embodiments, the ammonia nitrogen concentration in the third stage is 1.5-2.5 times that in the first stage, and more preferably, the ammonia nitrogen concentration in the third stage is twice that in the first stage.

[0060] In some of these embodiments, with the third stage Mn 2+ As the concentration increases, the number of electron donors increases accordingly. As a preferred option, the concentration of AHLs is increased, for example to 0.1-0.2 mg / L, to improve electron transfer efficiency.

[0061] In some of these embodiments, the stirring speed can be the same as in the previous stage, or it can be any value between 30 and 60 rpm.

[0062] This application also provides an ABMP, which is prepared by the above-described method for constructing ABMP, and will not be described in detail here.

[0063] This application further provides an anaerobic denitrification granular sludge reactor, which constructs ABMP using the aforementioned method, or includes the aforementioned ABMP. This anaerobic denitrification granular sludge reactor can also be understood as the reactor obtained after completing the first, second, and third stages described above. When treating nitrogen-containing wastewater, especially wastewater with a low carbon-to-nitrogen ratio (C / N ≤ 3, e.g., C / N = 0.5-2), the ABMP will become the reaction center of the Anammox-coupled Mnammox-NMDO system, during which NH4+... + -N oxidation produces NO3 - -N (Anammox) and NO2 - -N(Mnammox), the reduced low-valent manganese can then be converted into NO3 by microorganisms. - -N and NO2 - -N is reduced to N2 (NMDO), achieving highly efficient nitrogen removal with a total nitrogen removal rate exceeding 90%. Furthermore, this anaerobic denitrification granular sludge reactor can maintain manganese circulation and nitrogen conversion in the reactor for extended periods, with low residual sludge volume and no generation of greenhouse gases such as N2O as in traditional nitrification-denitrification processes.

[0064] This application further provides a method for treating wastewater with a low carbon-to-nitrogen ratio, comprising passing the wastewater with a low carbon-to-nitrogen ratio into the aforementioned anaerobic denitrification granular sludge reactor, wherein the C / N ratio of the wastewater with a low carbon-to-nitrogen ratio is ≤3 (e.g., C / N = 0.5-2), and the inorganic nitrogen in the wastewater with a low carbon-to-nitrogen ratio is a mixture of ammonia nitrogen and nitrite nitrogen, a mixture of ammonia nitrogen and nitrate nitrogen, or a mixture of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen.

[0065] In some of these embodiments, the low C / N ratio wastewater is fed continuously with a hydraulic retention time of ≥12h.

[0066] Example 1: Construction of ABMP

[0067] Phase 1

[0068] In this embodiment, the granular sludge seed liquor was taken from an anaerobic ammonia oxidation (UASB) reactor that had been operating for more than one year. 16S rRNA sequencing revealed that the dominant bacteria in the sludge were Brocadia, a typical anaerobic ammonia oxidizing bacteria genus, accounting for 40% of the relative abundance.

[0069] Granular sludge seed culture was inoculated into an anaerobic microbial denitrification reactor whose sealing performance had been tested, maintaining an MLVSS of 7000 mg / L. The entire reactor was immersed in an opaque, covered, insulated box equipped with two temperature-controlled heating rods and a stirring device, ensuring that the internal water temperature of the reactor was maintained at 28°C and the stirring speed at 60 rpm throughout the entire cultivation process.

[0070] Prepare simulated wastewater according to the following formula and continuously feed it into the reactor using a peristaltic pump, with a hydraulic retention time of 24 hours. Run the reactor stably for 30 days to allow the inoculated sludge to adapt to the new environment. At this point, the MLVSS of the denitrifying granular sludge should not decrease significantly, and the total nitrogen removal rate of the denitrifying granular sludge from the influent should reach over 70%. The simulated wastewater composition includes: NH4+. + -N 20mg / L (prepared with NH4Cl), NO2 - -N 40mg / L (prepared with NaNO2). Simultaneously, the following trace elements required for microorganisms were prepared: NaHCO3 100mg / L, KH2PO4 50mg / L, CaCl2 20mg / L, MgSO4 25mg / L. All reagents used in this example were purchased from Shanghai Titan Biotechnology Co., Ltd. and Shanghai Yuanye Biotechnology Co., Ltd.

[0071] Throughout the entire cultivation process, dissolved oxygen (DO) was strictly controlled, and in-situ testing was performed on the reactor effluent, with DO < 0.5 mg / L.

[0072] Phase Two

[0073] During this stage, the nitrogen concentration, temperature, and stirring speed in the simulated wastewater remained constant. 20 mg / L of MnCl2 was added to the influent. 2+ Simultaneously, 0.05 mg / L AHLs were added to the influent in the form of C8-HSL. To drive the activity of Mnammox bacteria in the reactor, an organic carbon source was introduced into the influent in the form of sodium acetate, maintaining a C / N ratio of 1. During this stage, Mn... 2+ The introduction of Mn stimulated an increase in the abundance of manganese autotrophic denitrifying bacteria to some extent, while the addition of C8-HSL promoted the formation of conductive flagella in the microorganisms. Manganese autotrophic denitrifying bacteria utilize Mn... 2+Mn acts as an inorganic electron donor for the reduction of nitrite. 2+ During the process, it is oxidized to a higher oxidation state, resulting in bio-manganese oxide BioMnO. x Accumulation begins. The second phase of operation will continue for 30 days based on the first phase, meaning the reactor will continue operating from day 31 to day 60.

[0074] Phase Three

[0075] Increase NH4 in the influent + The NO2 concentration in the influent is 40 mg / L. - The -N concentration was 80 mg / L, the culture water temperature was increased to 42℃, and the C / N ratio was increased to 2, while the influent Mn was increased. 2+ The concentration was 40 mg / L, and C8-HSL was 0.2 mg / L. The stirring speed remained the same as in the previous stage. In this stage, the addition of more carbon source led the manganese ammonia-oxidizing bacteria to favor the use of organic carbon sources for manganese reduction. However, organic carbon and bio-manganese oxide (BioMnO)... x After binding, it will coat its surface, thereby reducing its active sites for accepting electrons and hindering the formation of bio-manganese oxides (BioMnO). x The reduction of ABMP promotes its accumulation and construction. Furthermore, since NMDO bacteria have a wider temperature adaptability than Mnammox bacteria, raising the water temperature to 42℃ at this stage is more conducive to the NMDO process and facilitates BioMnO2 production. x Further accumulation. The second phase of operation will continue for 30 days based on the first phase, meaning the reactor will continue operating from day 61 to day 90.

[0076] At this stage, the granular sludge in the reactor begins to change color; the ABMP construction process causes the granular sludge to change from light red to dark brown (e.g., ...). Figure 1 (As shown), this is due to a large number of bio-manganese oxides, BioMnO, with a particle size of 50-100 nm. x Evenly distributed on the surface of granular sludge and coated with EPS (e.g. Figure 2 and Figure 3 As shown in the image, TEM images also confirm that EPS is filled with a large amount of biogenic manganese oxide (BioMnO). x (like Figure 4 As shown in the figure, this encapsulated ABMP readily accepts electrons from organic carbon sources and ammonia nitrogen, becoming the reaction center of the Anammox-coupled Mnammox-NMDO system. EDS-mapping results (as shown in the figure) Figure 5As shown in the figure, the mass percentage of manganese on the surface of the granular sludge was significantly increased before and after the construction of ABMP. Furthermore, XPS spectra indicate (as shown in the figure) Figure 6 As shown in the figure, after successful ABMP construction, the proportion of tetravalent manganese on the surface of granular sludge increased significantly. This indicates that free manganese ions entering the reactor are captured by EPS and oxidized to high-valent manganese, thus being fixed on the surface of the granular sludge. XRD patterns (as shown) Figure 7 The conclusions shown also confirm the presence of manganese oxides after ABMP construction. These indications suggest that ABMP was successfully constructed in the reactor through the regulation of the influent substances in the second and third stages.

[0077] Example 2: Construction of ABMP

[0078] Phase 1

[0079] In this embodiment, the granular sludge seed liquor was taken from an anaerobic ammonia oxidation (UASB) reactor that had been operating for more than one year. 16S rRNA sequencing revealed that the dominant bacteria in the sludge were Brocadia, a typical anaerobic ammonia oxidizing bacteria genus, accounting for 30% of the relative abundance.

[0080] Granular sludge seed culture was inoculated into an anaerobic microbial denitrification reactor whose sealing performance had been tested, maintaining an MLVSS of 8000 mg / L. The entire reactor was immersed in an opaque, covered, insulated box equipped with two temperature-controlled heating rods and a stirring device, ensuring that the internal water temperature of the reactor was maintained at 32°C and the stirring speed at 40 rpm throughout the entire cultivation process.

[0081] Prepare simulated wastewater according to the following formula and continuously feed it into the reactor using a peristaltic pump, with a hydraulic retention time of 24 hours. Run the reactor stably for 25 days to allow the inoculated sludge to adapt to the new environment. At this point, the MLVSS of the denitrifying granular sludge should not decrease significantly, and the total nitrogen removal rate of the denitrifying granular sludge from the influent should reach over 70%. The simulated wastewater composition includes: NH4+. + -N 15mg / L (prepared with NH4Cl), NO2 - -N 45mg / L (prepared with NaNO2). Simultaneously, the following trace elements required for microorganisms were prepared: NaHCO3 100mg / L, KH2PO4 50mg / L, CaCl2 20mg / L, MgSO4 25mg / L. All reagents used in this example were purchased from Shanghai Titan Biotechnology Co., Ltd. and Shanghai Yuanye Biotechnology Co., Ltd.

[0082] Throughout the entire cultivation process, dissolved oxygen (DO) was strictly controlled, and in-situ testing was performed on the reactor effluent, with DO < 0.5 mg / L.

[0083] Phase Two

[0084] During this stage, the nitrogen concentration, temperature, and stirring speed in the simulated wastewater remained constant. 15 mg / L of MnCl2 was added to the influent. 2+ Simultaneously, 0.075 mg / L of C8-HSL was added to the influent. To drive the activity of Mnammox bacteria in the reactor, an organic carbon source was introduced into the influent in the form of sodium acetate, maintaining a C / N ratio of 0.5. During this stage, Mn... 2+ The introduction of Mn stimulated an increase in the abundance of manganese autotrophic denitrifying bacteria to some extent, while the addition of C8-HSL promoted the formation of conductive flagella in the microorganisms. Manganese autotrophic denitrifying bacteria utilize Mn... 2+ Mn acts as an inorganic electron donor for the reduction of nitrite. 2+ During the process, it is oxidized to a higher oxidation state, resulting in bio-manganese oxide BioMnO. x Accumulation begins. The second phase of operation will continue for 20 days based on the first phase, meaning the reactor will continue operating from day 26 to day 45.

[0085] Phase Three

[0086] Increase NH4 in the influent + -N concentration is 22.5 mg / L, influent NO2 - The -N concentration was 67.5 mg / L, the culture water temperature was increased to 40℃, and the C / N ratio was increased to 2, while the influent Mn content was increased. 2+ The concentration was 35 mg / L, and C8-HSL was 0.1 mg / L. The stirring speed remained the same as in the previous stage. In this stage, the addition of more carbon sources led the manganese ammonia-oxidizing bacteria to favor the use of organic carbon sources for manganese reduction. However, organic carbon and bio-manganese oxides (BioMnO)... x After binding, it will coat its surface, thereby reducing its active sites for accepting electrons and hindering the formation of bio-manganese oxides (BioMnO). x The reduction of ABMP promotes its accumulation and construction. Furthermore, because NMDO bacteria have a wider temperature adaptability than Mnammox bacteria, raising the water temperature to 40°C at this stage is more conducive to the NMDO process and facilitates BioMnO2 production. x Further accumulation. The second phase of operation will continue for 27 days based on the first phase, meaning the reactor will continue operating from day 46 to day 72.

[0087] During this stage, the granular sludge in the reactor begins to change color. The construction process of ABMP causes the color of the granular sludge to change from light red to dark brown (see attached figure). This is due to the large amount of bio-manganese oxide (BioMnO) with a particle size of 50-100 nm. xThe EPS is evenly distributed on the surface of the granular sludge and is coated with it (attached image omitted). Furthermore, TEM images confirm that the EPS is filled with a large amount of bio-manganese oxide (BioMnO). x (Figure omitted), and this encapsulated ABMP readily accepts electrons from organic carbon sources and ammonia nitrogen, becoming the reaction center of the Anammox-coupled Mnammox-NMDO system. EDS-mapping results (Figure omitted) also show a significant increase in the mass percentage of manganese on the granular sludge surface before and after ABMP construction. Furthermore, XPS spectra (Figure omitted) indicate that the proportion of tetravalent manganese on the granular sludge surface greatly increased after successful ABMP construction, suggesting that free manganese ions entering the reactor are captured by EPS and oxidized to higher-valent manganese, thus being fixed on the granular sludge surface. XRD patterns (Figure omitted) also confirm the presence of manganese oxides after ABMP construction. These indications suggest that ABMP was successfully constructed in the reactor through the regulation of influent materials in the second and third stages.

[0088] Example 3: Construction of ABMP

[0089] Phase 1

[0090] In this embodiment, the granular sludge seed liquor was taken from an anaerobic ammonia oxidation (UASB) reactor that had been operating for more than one year. 16S rRNA sequencing revealed that the dominant bacteria in the sludge were Brocadia, a typical anaerobic ammonia oxidizing bacteria genus, accounting for 50% of the relative abundance.

[0091] Granular sludge seed culture was inoculated into an anaerobic microbial denitrification reactor whose sealing performance had been tested, maintaining an MLVSS of 7500 mg / L. The entire reactor was immersed in an opaque, covered, insulated box equipped with two temperature-controlled heating rods and a stirring device, ensuring that the internal water temperature of the reactor was maintained at 29°C and the stirring speed at 30 rpm throughout the entire cultivation process.

[0092] Prepare simulated wastewater according to the following formula and continuously feed it into the reactor using a peristaltic pump, with a hydraulic retention time of 24 hours. Run the reactor stably for 35 days to allow the inoculated sludge to adapt to the new environment. At this point, the MLVSS of the denitrifying granular sludge should not be significantly reduced, and the total nitrogen removal rate of the denitrifying granular sludge from the influent should reach over 70%. The simulated wastewater composition includes: NH4+. + -N 30mg / L (prepared with NH4Cl), NO2 --N 30mg / L (prepared with NaNO2). Simultaneously, the following trace elements required by the microorganisms were prepared: NaHCO3 100mg / L, KH2PO4 50mg / L, CaCl2 20mg / L, MgSO4 25mg / L. All reagents used in this example were purchased from Shanghai Titan Biotechnology Co., Ltd. and Shanghai Yuanye Biotechnology Co., Ltd.

[0093] Throughout the entire cultivation process, dissolved oxygen (DO) was strictly controlled, and in-situ testing was performed on the reactor effluent, with DO < 0.5 mg / L.

[0094] Phase Two

[0095] During this stage, the nitrogen concentration, temperature, and stirring speed in the simulated wastewater remained constant. 25 mg / L of MnCl2 was added to the influent. 2+ Simultaneously, 0.06 mg / L AHLs were added to the influent in the form of C8-HSL. To drive the activity of Mnammox bacteria in the reactor, an organic carbon source was introduced into the influent in the form of sodium acetate, maintaining a C / N ratio of 1.5. During this stage, Mn... 2+ The introduction of Mn stimulated an increase in the abundance of manganese autotrophic denitrifying bacteria to some extent, while the addition of C8-HSL promoted the formation of conductive flagella in the microorganisms. Manganese autotrophic denitrifying bacteria utilize Mn... 2+ Mn acts as an inorganic electron donor for the reduction of nitrite. 2+ During the process, it is oxidized to a higher oxidation state, resulting in bio-manganese oxide BioMnO. x Accumulation begins. The second phase of operation will continue for 35 days based on the first phase, meaning the reactor will continue operating from day 36 to day 70.

[0096] Phase Three

[0097] Increase NH4 in the influent + The NO2 concentration in the influent is 45 mg / L. - The -N concentration was 45 mg / L, the culture water temperature was increased to 38℃, and the C / N ratio was increased to 2.5, while the influent Mn content was increased. 2+ The concentration was 45 mg / L, and the C8-HSL concentration was 0.15 mg / L. The stirring speed remained the same as in the previous stage. In this stage, the addition of more carbon source led the manganese ammonia-oxidizing bacteria to favor the use of organic carbon sources for manganese reduction. However, organic carbon and bio-manganese oxides (BioMnO)... x After binding, it will coat its surface, thereby reducing its active sites for accepting electrons and hindering the formation of bio-manganese oxides (BioMnO). xThe reduction of ABMP promotes its accumulation and construction. Furthermore, since NMDO bacteria have a wider temperature adaptability than Mnammox bacteria, raising the water temperature to 38°C at this stage is more conducive to the NMDO process and facilitates BioMnO2 production. x Further accumulation. The second phase of operation will continue for 40 days based on the first phase, meaning the reactor will continue to run from day 71 to day 110.

[0098] During this stage, the granular sludge in the reactor begins to change color. The construction process of ABMP causes the color of the granular sludge to change from light red to dark brown (see attached figure). This is due to the large amount of bio-manganese oxide (BioMnO) with a particle size of 50-100 nm. x The EPS is evenly distributed on the surface of the granular sludge and is coated with EPS (attached image omitted). Furthermore, TEM images confirm that the EPS is also rich in bio-manganese oxide (BioMnO). x (Figure omitted), and this encapsulated ABMP readily accepts electrons from organic carbon sources and ammonia nitrogen, becoming the reaction center of the Anammox-coupled Mnammox-NMDO system. EDS-mapping results (Figure omitted) also show a significant increase in the mass percentage of manganese on the granular sludge surface before and after ABMP construction. Furthermore, XPS spectra (Figure omitted) indicate that the proportion of tetravalent manganese on the granular sludge surface greatly increased after successful ABMP construction, suggesting that free manganese ions entering the reactor are captured by EPS and oxidized to higher-valent manganese, thus being fixed on the granular sludge surface. XRD patterns (Figure omitted) also confirm the presence of manganese oxides after ABMP construction. These indications suggest that ABMP was successfully constructed in the reactor through the regulation of influent materials in the second and third stages.

[0099] Example 4: Construction of ABMP

[0100] Phase 1

[0101] In this embodiment, the granular sludge seed liquor was taken from an anaerobic ammonia oxidation (UASB) reactor that had been operating for more than one year. 16S rRNA sequencing revealed that the dominant bacteria in the sludge were Brocadia, a typical anaerobic ammonia oxidizing bacteria genus, accounting for 45% of the relative abundance.

[0102] Granular sludge seed culture was inoculated into an anaerobic microbial denitrification reactor whose sealing performance had been tested, maintaining an MLVSS of 7800 mg / L. The entire reactor was immersed in an opaque, covered, insulated box equipped with two temperature-controlled heating rods and a stirring device, ensuring that the internal water temperature of the reactor was maintained at 30°C and the stirring speed at 50 rpm throughout the entire cultivation process.

[0103] Prepare simulated wastewater according to the following formula and continuously feed it into the reactor using a peristaltic pump, with a hydraulic retention time of 24 hours. Run the reactor stably for 30 days to allow the inoculated sludge to adapt to the new environment. At this point, the MLVSS of the denitrifying granular sludge should not decrease significantly, and the total nitrogen removal rate of the denitrifying granular sludge from the influent should reach over 70%. The simulated wastewater composition includes: NH4+. + -N 20mg / L (prepared with NH4Cl), NO2 - -N 40mg / L (prepared with NaNO2). Simultaneously, the following trace elements required for microorganisms were prepared: NaHCO3 100mg / L, KH2PO4 50mg / L, CaCl2 20mg / L, MgSO4 25mg / L. All reagents used in this example were purchased from Shanghai Titan Biotechnology Co., Ltd. and Shanghai Yuanye Biotechnology Co., Ltd.

[0104] Throughout the entire cultivation process, dissolved oxygen (DO) was strictly controlled, and in-situ testing was performed on the reactor effluent, with DO < 0.5 mg / L.

[0105] Phase Two

[0106] During this stage, the nitrogen concentration, temperature, and stirring speed in the simulated wastewater remained constant. 20 mg / L of MnCl2 was added to the influent. 2+ During this stage, Mn 2+ The introduction of manganese-autotrophic denitrifying bacteria stimulated an increase in abundance to some extent. Manganese-autotrophic denitrifying bacteria utilize Mn... 2+ Mn acts as an inorganic electron donor for the reduction of nitrite. 2+ During the process, it is oxidized to a higher oxidation state, resulting in bio-manganese oxide BioMnO. x Accumulation begins. The second phase of operation will continue for 30 days based on the first phase, meaning the reactor will continue operating from day 31 to day 60.

[0107] Phase Three

[0108] Increase NH4 in the influent + The NO2 concentration in the influent is 40 mg / L. - The -N concentration was 80 mg / L, the culture water temperature was increased to 41℃, and the C / N ratio was increased to 2, while the influent Mn was increased. 2+ The concentration was 40 mg / L, and the stirring speed remained the same as in the previous stage. In this stage, the addition of more carbon source led the manganese-oxidizing bacteria to favor the use of organic carbon sources for manganese reduction. However, organic carbon and bio-manganese oxide (BioMnO)... x After binding, it will coat its surface, thereby reducing its active sites for accepting electrons and hindering the formation of bio-manganese oxides (BioMnO).x The reduction of bio-manganese oxides in the BioMnO pool promotes the activity of bio-manganese oxides. x - Pool accumulation and completion of ABMP construction. Furthermore, since NMDO bacteria have a wider temperature adaptability compared to Mnammox bacteria, raising the water temperature to 41℃ at this stage is more conducive to the NMDO process and facilitates BioMnO4 production. x Further accumulation. The second phase of operation will continue for 30 days based on the first phase, meaning the reactor will continue operating from day 61 to day 90.

[0109] At this stage, the granular sludge in the reactor begins to change color, and the activated bio-manganese oxide tank (BioMnO)... x The construction of the pool caused the granular sludge to change color from light red to dark brown (see attached image), due to the large amount of bio-manganese oxide (BioMnO) with a particle size of 50-100 nm. x The EPS is evenly distributed on the surface of the granular sludge and is coated with EPS (attached image omitted). Furthermore, TEM images confirm that the EPS is also rich in bio-manganese oxide (BioMnO). x (Figure omitted), and this encapsulated ABMP readily accepts electrons from organic carbon sources and ammonia nitrogen, becoming the reaction center of the Anammox-coupled Mnammox-NMDO system. EDS-mapping results (Figure omitted) also show a significant increase in the mass percentage of manganese on the granular sludge surface before and after ABMP construction. Furthermore, XPS spectra (Figure omitted) indicate that the proportion of tetravalent manganese on the granular sludge surface greatly increased after successful ABMP construction, suggesting that free manganese ions entering the reactor are captured by EPS and oxidized to higher-valent manganese, thus being fixed on the granular sludge surface. XRD patterns (Figure omitted) also confirm the presence of manganese oxides after ABMP construction. These indications suggest that ABMP was successfully constructed in the reactor through the regulation of influent materials in the second and third stages.

[0110] Example 5: Treatment of Simulated Wastewater with Low Carbon-to-Nitrogen Ratio

[0111] Simulated wastewater was introduced into the anaerobic microbial denitrification reactor successfully constructed by ABMP in Example 1 for denitrification treatment.

[0112] The reactor operates continuously with a hydraulic retention time of 24 hours and a water temperature maintained at 33℃±1℃. Simulated wastewater enters the reactor through an inlet pipe and a peristaltic pump, where denitrification occurs through the interaction of anaerobic denitrifying microorganisms and ABMP.

[0113] Simulated wastewater parameters: NH4 +-N 40mg / L, NO2 - -N 80mg / L, Mn 2+ The concentrations are 40 mg / L, NaHCO3 100 mg / L, KH2PO4 50 mg / L, CaCl2 20 mg / L, and MgSO4 25 mg / L. The C / N ratio is controlled at 0.5. After the influent solution is prepared, it is aerated with high-purity nitrogen for more than 30 minutes to remove dissolved oxygen (<0.3 mg / L).

[0114] During the reaction, Mn in bio-manganese oxides 4+ As an electron acceptor, it participates in the manganese ammonia oxidation process and is reduced to Mn. 3+ And Mn 3+ It has strong redox capabilities, but is also extremely unstable, being rapidly reduced to Mn during the reaction. 2 + Mn in low valence state 2+ It also drives manganese autotrophic denitrification, acting as an electron donor for NO2. - -N is used to restore.

[0115] Testing showed that, over a period of 0-30 days, this application significantly improved the removal of ammonia nitrogen and nitrite nitrogen from the simulated wastewater (see Table 1). The removal rate of ammonia nitrogen exceeded 95%, and the removal rate of nitrite nitrogen approached 100%. Furthermore, no accumulation of nitrite nitrogen in the effluent, a phenomenon observed in conventional Anammox reactors, was found.

[0116] Table 1

[0117]

[0118] As a variation of this embodiment, the inventors of this application also attempted to control the amount of NH4 entering the water daily. + -N concentration and NO2 - The -N concentration was adjusted, and the denitrification results were as follows: Figure 8 As shown.

[0119] Example 6: Treatment of Simulated Wastewater with Low Carbon-to-Nitrogen Ratio (Part 2)

[0120] This embodiment is similar to Embodiment 5, except that no exogenous Mn is added. 2+ .

[0121] Simulated wastewater was introduced into the anaerobic microbial denitrification reactor successfully constructed by ABMP in Example 1 for denitrification treatment.

[0122] The reactor operates continuously with a hydraulic retention time of 24 hours and a water temperature maintained at 33℃±1℃. Simulated wastewater enters the reactor through an inlet pipe and a peristaltic pump, where denitrification occurs through the interaction of anaerobic denitrifying microorganisms and ABMP.

[0123] Simulated wastewater parameters: NH4 + -N 40mg / L, NO2 - -N 80mg / L, NaHCO3 100mg / L, KH2PO4 50mg / L, CaCl2 20mg / L, MgSO4 25mg / L. The C / N ratio is controlled at 0.5. After the influent solution is prepared, it is aerated with high-purity nitrogen for more than 30 minutes to remove dissolved oxygen (<0.3mg / L).

[0124] During the reaction, Mn in bio-manganese oxides 4+ As an electron acceptor, it participates in the manganese ammonia oxidation process and is reduced to Mn. 2+ Mn in low valence state 2+ It also drives manganese autotrophic denitrification, acting as an electron donor for NO2. - -N is used for reduction. And during this process, no exogenous Mn is used. 2+ The addition of ABMP allows for denitrification solely through the interaction between anaerobic denitrifying microorganisms and ABMP.

[0125] Tests showed no exogenous Mn. 2+ With the addition of ABMP, nitrogen removal was achieved solely through the interaction between anaerobic denitrifying microorganisms and ABMP. Ammonia nitrogen removal rates exceeded 90%, and nitrite nitrogen removal rates exceeded 95%, with no nitrate nitrogen accumulation observed in the effluent (as shown in Table 2). Furthermore, the manganese ion concentration in the effluent decreased exponentially and stabilized at 1-2 mg / L after 10 days, indicating that ABMP was immobilized in the reactor, preventing manganese leakage during the reaction that could lead to excessively high manganese ion concentrations in the effluent and cause toxicity. Therefore, this application not only rapidly constructed an anaerobic reactor with ABMP as the reaction center but also achieved nitrogen removal without the addition of exogenous Mn. 2+ Under these conditions, relying solely on the interaction between denitrifying microorganisms and ABMP, long-term manganese cycling and nitrogen conversion were completed in the reactor, and the reactor demonstrated stable and efficient treatment of nitrogen-containing simulated wastewater.

[0126] Table 2

[0127]

[0128] As a variation of this embodiment, the inventors of this application also attempted to control the amount of NH4 entering the water daily. + -N concentration and NO2 - The -N concentration was adjusted, and the denitrification results were as follows: Figure 9 As shown, this application rapidly constructs an anaerobic reactor with ABMP as the reaction center, and exhibits a long-term and significant denitrification effect on high-load nitrogen-containing wastewater of different concentrations.

[0129] Example 7: Treatment of actual wastewater with low carbon-to-nitrogen ratio

[0130] Similar to Example 6, diluted domestic wastewater was introduced into the anaerobic microbial denitrification reactor successfully constructed using ABMP in Example 1 (as an example) for denitrification treatment. The hydraulic retention time was 24 hours, and the water temperature was maintained at 35℃±1℃. Wastewater parameters: NH4 + -N 38±2mg / L, NO2 - -N 41±1 -110±12 mg / L. Simultaneously, trace elements required by microorganisms, NaHCO3 100 mg / L, KH2PO4 50 mg / L, CaCl2 20 mg / L, and MgSO4 25 mg / L, were added to the wastewater. Sodium acetate was also added as an organic carbon source to control the C / N ratio to 0.5. After the influent solution was prepared, it was aerated with high-purity nitrogen for more than 30 minutes to remove dissolved oxygen (<0.3 mg / L).

[0131] Testing showed that, over a 30-day treatment period, this application significantly reduced nitrite and ammonia nitrogen levels in the actual wastewater. Figure 10 As shown in Table 3, there is no exogenous Mn 2+ With the addition of [specific ingredient], denitrification is achieved solely through the interaction between anaerobic denitrifying microorganisms and ABMP, resulting in a nitrite nitrogen removal efficiency exceeding 95% and an ammonia nitrogen removal rate exceeding 90%. Furthermore, the manganese ion concentration in the effluent decreases exponentially and stabilizes at 1-2 mg / L after 10 days, indicating that ABMP is immobilized in the reactor, preventing manganese leakage during the reaction that could lead to excessively high manganese ion concentrations and toxic effects in the effluent. Therefore, this application demonstrates a highly efficient denitrification effect on wastewater containing both ammonia and nitrite nitrogen, relying solely on the interaction between denitrifying microorganisms and ABMP.

[0132] Table 3

[0133]

[0134] Example 8: Treatment of actual wastewater with low carbon-to-nitrogen ratio (II)

[0135] Similar to Example 6, diluted domestic wastewater was introduced into the anaerobic microbial denitrification reactor successfully constructed using ABMP in Example 1 (as an example) for denitrification treatment. The hydraulic retention time was 24 hours, and the water temperature was maintained at 35℃±1℃. Wastewater parameters: NH4 + -N 42±2mg / L, NO3 --N 37±3-121±11 mg / L. Simultaneously, trace elements required by microorganisms were added to the wastewater: NaHCO3 100 mg / L, KH2PO4 50 mg / L, CaCl2 20 mg / L, and MgSO4 25 mg / L. Sodium acetate was also added as an organic carbon source to control the C / N ratio to 0.5. After the influent solution was prepared, it was aerated with high-purity nitrogen for more than 30 minutes to remove dissolved oxygen (<0.3 mg / L).

[0136] Testing showed that, over a 30-day treatment period, this application significantly reduced nitrate and ammonia nitrogen levels in the actual wastewater. Figure 11 As shown in Table 4, there is no exogenous Mn 2+ With the addition of [specific ingredient], denitrification is achieved solely through the interaction between anaerobic denitrifying microorganisms and ABMP, with removal rates of both nitrate and ammonia nitrogen exceeding 90%. Furthermore, the manganese ion concentration in the effluent decreases exponentially and stabilizes at 1-2 mg / L after 10 days, indicating that ABMP is immobilized in the reactor, preventing manganese leakage during the reaction that could lead to excessively high manganese ion concentrations and toxic effects in the effluent. Therefore, this application demonstrates a highly efficient denitrification effect on actual wastewater containing ammonia and nitrate nitrogen, relying solely on the interaction between denitrifying microorganisms and ABMP.

[0137] Table 4

[0138]

[0139] The above embodiments are merely illustrative of the principles and effects of this application and are not intended to limit this application. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of this application. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in this application should still be covered by the claims of this application.

Claims

1. A method of constructing an active biological manganese oxide pool (ABMP) comprising, The method comprises the following steps: S1, culturing anaerobic denitrifying granular sludge for 20-40 days, wherein the influent first ammonia nitrogen concentration: first nitrite nitrogen concentration = 1:1-1:3, the culture water temperature is 28-32℃, the first ammonia nitrogen concentration is 15-30 mg / L, and the dissolved oxygen concentration is controlled below 0.5 mg / L; S2, adding 15-25 mg / L of Mn with the influent water 2+ , 0.05-0.075 mg / L AHLs for 20-40 days, maintaining C / N = 0.5-1.5 in the influent water; S3, increasing the first ammonia nitrogen concentration and the first nitrite nitrogen concentration to the second ammonia nitrogen concentration and the second nitrite nitrogen concentration, increasing Mn 2+ concentration to 35-45 mg / L, increasing the culture water temperature to 38-42℃, increasing the influent AHLs concentration to 0.1-0.2 mg / L, and keeping the influent C / N = 2-3, continuing to culture for 20-40 days, wherein the second ammonia nitrogen concentration: the second nitrite nitrogen concentration = 1:1-1:3, the second ammonia nitrogen concentration is 1.5-2.5 times the first ammonia nitrogen concentration; The active biogenic manganese oxide pool refers to Mn 2+ As an electron donor, it participates in the life activities of manganese-oxidizing microorganisms and is oxidized to form polymers containing manganese oxides with various valence states.

2. The method of constructing an active biological manganese oxide pool (ABMP) according to claim 1, wherein, The steps S1-S3 further comprise maintaining the stirring speed at 30-60 rpm.

3. The method of constructing an active biogenic manganese oxide pool (ABMP) according to claim 1, wherein, The relative abundance of anaerobic ammonia oxidation bacteria in the anaerobic denitrifying granular sludge accounts for 30-50% of the anaerobic denitrifying granular sludge.

4. An active biological manganese oxide pool (ABMP) characterized in that, The active biological manganese oxide pool ABMP is prepared by the construction method of any one of claims 1-3.

5. An anaerobic denitrifying granular sludge reactor, characterized by, The active biological manganese oxide pool ABMP comprises the active biological manganese oxide pool ABMP of claim 4.

6. The application of the anaerobic denitrifying granular sludge reactor of claim 5 in treating low carbon-nitrogen ratio wastewater.

7. Use according to claim 6, wherein The C / N in the low carbon-nitrogen ratio wastewater is ≤3.

8. A method for treating low carbon-to-nitrogen ratio wastewater, characterized by, The method comprises the following steps: The C / N in the low carbon-nitrogen ratio wastewater is ≤3.

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