Carbon, nitrogen and phosphorus removal process of manganese oxide prepared by in-situ method cooperated with MBBR reactor

Abstract

This invention discloses an in-situ method for preparing manganese oxides in conjunction with an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal, relating to the field of wastewater treatment technology. The invention includes: preparing the required treatment system; and preparing the supernatant containing Mn through targeted acclimation of activated sludge. 2+ Manganese-oxidizing mixed bacteria at a concentration of 2–5 mg / L; MBBR reactor for biofilm formation start-up, wastewater and Mn 2+ The salt solution was mixed and then passed into the MBBR reactor, with Mn added. 2+ As wastewater flows upwards through the MBBR reactor, it passes over packing material containing growing microorganisms and manganese oxides. During this process, the wastewater and the manganese oxide-loaded packing material achieve thorough contact, resulting in carbon reduction, nitrogen removal, and phosphorus removal. This invention addresses this by adding Mn to the MBBR reactor. 2+ This allows manganese oxides to be generated in situ within the MBBR reactor. Combined with the MBBR process, this achieves full contact between manganese oxides and wastewater, improving the carbon reduction, nitrogen removal, and phosphorus removal effects.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sewage treatment, in particular to a carbon reduction, denitrification and phosphorus removal process of manganese oxide prepared by in-situ method and MBBR reactor. BACKGROUND

[0002] With the acceleration of urbanization, water resource shortage problem is increasingly prominent, at the same time, due to the poor water quality caused by "water pollution type of water shortage" further aggravates the shortage of water resources, and the treatment and reuse of sewage can alleviate the shortage of water resources to some extent, which is also an important way to supplement water conservation. In addition, due to the influence of human activities, water eutrophication and coexistence of various pollutants are more and more common. Generally, the polluted water contains eutrophication substances (such as nitrogen, phosphorus), and a large amount of refractory organic matter. These eutrophication substances and refractory organic matter migrate and transform with water flow, further penetrate into soil and even groundwater, which poses a serious threat to human health and water ecological environment. Therefore, in order to protect the water quality and ecological safety of water system, urban sewage needs to be strictly treated before being discharged into the receiving water body.

[0003] At present, among many water treatment technologies, the bioremediation technology using the metabolism of microorganisms to degrade pollutants and remove nitrogen and phosphorus is widely used. However, microorganisms are easily limited by the growth environment, and the large amount of methanol, acetic acid and other carbon sources leads to high cost and other limitations. In addition, the existing water treatment technology has high operating cost and large occupied area, which is easy to cause secondary pollution.

[0004] In order to simultaneously achieve the treatment effect of removing nitrate and refractory organic matter, manganese oxide mediated biological treatment technology has attracted more and more attention. Through manganese redox cycle coupled with denitrification, the reaction speed of biological pathway can be improved, and the demand of microorganisms for organic carbon can be significantly reduced. At the same time, manganese oxide can oxidize refractory organic matter to realize that organic pollutants ions or molecules are oxidized into small molecules or ions, which are further degraded and utilized by microorganisms, so that microorganisms can obtain energy and grow.

[0005] The existing technology related to manganese oxide mediated microbial simultaneous denitrification and removal of organic pollutants has been reported, including:

[0006] Application No. 201210031269.7 discloses a method for treating refractory micro-pollutants by natural manganese ore-microorganism cooperation, which specifically includes the following steps: sewage is input into the reactor from the bottom of the anaerobic bioreactor, and the sewage flows from bottom to top in the anaerobic bioreactor, passing through the natural manganese ore filler with a large number of microorganisms growing therein. In this process, Mn 4+The refractory micro-pollutants in the sewage are taken as electron donors and electron acceptors, and under the action of microorganisms (dissimilation-Mn reducing bacteria), the electron transfer is promoted, so that the refractory micro-pollutants are degraded, and then the effluent is discharged from the top of the anaerobic biological reactor. Although the method uses the natural manganese ore as the filling layer of the anaerobic biological reactor, the effective removal of the refractory organic pollutants in the sewage, including the persistent organic pollutants (POPs), the precursor of trihalomethane (THMFP), the endocrine disruptors (EDCs) and the pharmaceutical and personal care products (PPCPs) and the like, is realized. However, the method is to directly add the natural manganese ore and form a natural manganese ore filling layer, and then contact the sewage in the anaerobic biological reactor from bottom to top to degrade the pollutants in the sewage. The contact between the natural manganese ore filling layer and the organic matters in the sewage is limited, and the role of the manganese oxide in the natural manganese ore filling layer cannot be fully played. In addition, the content of the manganese oxide in the natural manganese ore is low, and the oxidation activity is limited, and it is difficult to reach the high activity state of the nascent manganese oxide, so that the long-term and high-efficiency removal effect of nitrate and refractory organic matters cannot be guaranteed.

[0007] Therefore, the prior art still needs to be further improved. SUMMARY

[0008] The purpose of the present application is to provide a carbon reduction, denitrification and phosphorus removal process of manganese oxide prepared by in-situ method and MBBR reactor, which can generate manganese oxide in-situ in the MBBR reactor by adding divalent manganese ions into the MBBR reactor, and realize the full contact between the manganese oxide and the sewage by combining the MBBR process, so as to improve the carbon reduction, denitrification and phosphorus removal effect.

[0009] In order to achieve the above purpose, the present application adopts the following technical solutions:

[0010] A carbon reduction, denitrification and phosphorus removal process of manganese oxide prepared by in-situ method and MBBR reactor, which comprises the following steps in sequence:

[0011] a. Prepare the required treatment system

[0012] The treatment system comprises a water inlet tank, an MBBR reactor, a sedimentation tank and a water outlet tank, the water inlet tank is used to provide sewage and a salt solution of Mn 2+ to the MBBR reactor, the MBBR reactor is fed from the side lower part and discharged from the side upper part; the sedimentation tank is used to receive the effluent of the MBBR reactor; and the filler in the MBBR reactor is a cylindrical multi-cavity polyethylene filler;

[0013] b. Prepare manganese oxidation mixed bacteria: prepare manganese oxidation mixed bacteria with a concentration of 2-5 mg / L of Mn 2+ in the supernatant by directional acclimation of activated sludge;

[0014] c. Start-up of biofilm in MBBR reactor:

[0015] Primary biofilm formation: activated sludge and manganese oxide mixed bacteria were mixed as inoculated sludge at a mass ratio of 4-10:1, the inoculated sludge was mixed with sewage at a ratio of 1:1, and the MBBR reactor was filled into the muffled exposure stage. After a certain time of muffled exposure treatment, the inoculated sludge was emptied; the step was repeated to complete the primary biofilm formation.

[0016] Sewage and Mn 2+ salt solution were mixed and entered the water inlet tank, and then entered the MBBR reactor at a flow rate of 0.2-1.0 L / h from the outlet of the water inlet tank, 10-30 mg of Mn 2+ was added per 1 L of sewage, and the water was fed for 8-12 h each time, lasting for 5-10 d.

[0017] Sewage and Mn 2+ salt solution were mixed and entered the water inlet tank, and then entered the MBBR reactor at a flow rate of 0.5-2.0 L / h from the outlet of the water inlet tank, 10-30 mg of Mn 2+ was added per 1 L of sewage, and the hydraulic retention time of the MBBR reactor was controlled at 2-6 h, and the effluent reached a stable state after 5-7 d of operation; Mn 2+ existed in the MBBR reactor in the form of manganese oxide and was firmly loaded on the filler with microorganisms;

[0018] d. Sewage and Mn 2+ salt solution were mixed and entered the MBBR reactor, 20-50 mg of Mn 2 + During the upward flow of the sewage in the MBBR reactor, the sewage and the filler loaded with manganese oxide were in full contact to remove carbon, nitrogen and phosphorus.

[0019] e. When the mass content of Mn 2+ in the effluent of the MBBR reactor exceeded 50% of the influent, the addition of Mn 2+ salt solution was stopped, and sewage was directly fed into the MBBR reactor for carbon, nitrogen and phosphorus removal.

[0020] The above-mentioned manganese oxide prepared in situ cooperated with the carbon, nitrogen and phosphorus removal process of the MBBR reactor, the MBBR reactor was a cylinder, wrapped with tin foil paper on the outside, a perforated partition plate was arranged at a distance of 5 cm from the bottom of the MBBR reactor, the diameter of the filler was 10-50 mm, the filling rate of the filler was 70%, the perforated partition plate was below the water distribution area, and the water inlet of the MBBR reactor was located on the side wall of the water distribution area.

[0021] The above-mentioned in-situ preparation of manganese oxides in conjunction with an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal has an outlet on the side wall 5 cm from the top of the MBBR reactor, which is connected to the inlet of the sedimentation tank.

[0022] The above-mentioned in-situ preparation method of manganese oxide in conjunction with an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal includes the following steps in step b: Adding glucose as a culture carrier to wastewater (10-50 mg of glucose per 1 L of wastewater); using activated sludge as inoculum; adding 10-30 mg / L of MnCl2 to the inoculum; and anaerobic shaking culture at 35°C for 2-5 days until the supernatant contains Mn... 2+ The concentration is 10–20 mg / L;

[0023] Using acclimatized activated sludge as inoculum, repeat this step 2–5 times until Mn in the supernatant is found. 2+ A manganese-oxidizing mixed bacteria was obtained at a concentration of 2–5 mg / L.

[0024] The above-mentioned in-situ preparation method of manganese oxide synergistically utilizes an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal. 2+ The salt solution is a MnCl2 solution.

[0025] The above-mentioned in-situ preparation of manganese oxides in conjunction with an MBBR reactor for carbon reduction, nitrogen removal and phosphorus removal involves a settling tank with a conical sludge hopper inside, a sludge discharge port below the sludge hopper, and a 5cm distance between the effluent outlet of the settling tank and the top.

[0026] The above-mentioned in-situ preparation of manganese oxides in conjunction with an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal involves the effluent from the settling tank entering the effluent tank through the effluent outlet.

[0027] The above-mentioned in-situ preparation of manganese oxides in conjunction with an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal, wherein the influent tank is connected to a wastewater tank and a Mn... 2+ Reservoir tank.

[0028] The above-mentioned in-situ preparation of manganese oxides in conjunction with an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal is applied to the degradation of organic matter, specifically for the degradation of organic matter in rural sewage, sewage treatment plant effluent, or black and odorous water bodies.

[0029] Compared with the prior art, the present invention brings the following beneficial technical effects:

[0030] (1) This invention proposes an in-situ method for preparing manganese oxides in conjunction with an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal. Unlike existing technologies, this invention does not directly add manganese oxides—manganese ore—to the reactor. Instead, it utilizes divalent manganese salts and microorganisms in the MBBR reactor to prepare manganese oxides in situ, thus achieving manganese redox under biochemical action. The deep removal of organic matter from wastewater simultaneously reduces carbon, nitrogen, and phosphorus without generating secondary pollution, making it a green and low-carbon technology.

[0031] (2) The present invention uses cylindrical porous polyethylene filler, which has a solid structure and a large effective specific surface area, making it easy for microorganisms and manganese oxide to adhere.

[0032] (3) The present invention uses fluidized bed process to increase the contact between functional packing and wastewater, and the in-situ newly generated manganese oxide has a stronger oxidation capacity, thereby enhancing the treatment effect.

[0033] (4) This invention has low energy consumption and low water treatment cost. It can be applied to sewage treatment plant effluent, rural sewage, black and odorous water bodies and other sewage containing recalcitrant organic matter. Its COD, TN and TP removal rates can reach 70% to 90%, realizing deep removal of organic matter from sewage while simultaneously reducing carbon, nitrogen and phosphorus. Attached Figure Description

[0034] The present invention will be further described below with reference to the accompanying drawings:

[0035] Figure 1 This is a simplified diagram of the processing system required for the carbon reduction, nitrogen removal, and phosphorus removal process of manganese oxides prepared in situ using an MBBR reactor in conjunction with the present invention.

[0036] Figure 2 This is a statistical chart showing the changes in COD influent and effluent concentrations and removal rates in Example 1;

[0037] Figure 3 This is a statistical chart showing the changes in TN influent and effluent concentrations and removal rates in Example 1;

[0038] Figure 4 NO3 in Example 1 - -N influent and effluent concentration and removal rate variation statistical chart;

[0039] Figure 5 NH4 as in Example 1 + -N influent and effluent concentration and removal rate variation statistical chart;

[0040] Figure 6 This is a statistical chart showing the changes in TP influent and effluent concentrations and removal rates in Example 1.

[0041] In the picture:

[0042] 1. Pump, 2. Perforated baffle, 3. Packing, 4. Exhaust pipe, 5. Valve, 6. Sludge discharge port, 7. Bell mouth, 8. Umbrella-shaped baffle, 9. Sewage tank, 10. Mn 2+ 11. Storage tank, 12. Inlet tank, 13. MBBR reactor, 14. Sedimentation tank, 15. Outlet tank. Detailed Implementation

[0043] This invention proposes a process for carbon reduction, nitrogen removal, and phosphorus removal using manganese oxides prepared in situ in conjunction with an MBBR reactor. To make the advantages and technical solutions of this invention clearer and more explicit, the invention will be further described below with reference to specific embodiments.

[0044] The filler mentioned in this invention is a porous polyethylene filler.

[0045] The Mn mentioned in this invention 2+ The salt solution is a MnCl2 solution.

[0046] like Figure 1 As shown, the processing system required by the present invention includes an inlet tank 11, an MBBR reactor 12, a settling tank 13, and an outlet tank 14. The inlet of the MBBR reactor 12 is located on the lower side, and the inlet tank is connected to the inlet. A pump 1 is installed on the connecting pipe. The outlet of the MBBR reactor is located on the upper side, and a valve 5 is installed on the outlet pipe. The effluent from the MBBR reactor enters the settling tank through the inlet, where solid matter settles at the bottom. The bottom of the inlet pipe of the settling tank is a funnel-shaped opening 7, and below the funnel is an umbrella-shaped baffle 8. Clean water enters the outlet tank through the outlet of the settling tank. An exhaust port is located at the top of the MBBR reactor 12, and an exhaust pipe 4 is connected to the exhaust port.

[0047] Specifically, the inlet of water tank 11 is connected to the sewage tank 9, Mn 2+ The storage tank 10 is connected to the sewage and Mn. 2+ After mixing in inlet tank 11, the wastewater is fed into the MBBR reactor through the outlet of the inlet tank. The wastewater can be effluent from sewage treatment plants, rural sewage, black and odorous water bodies, and other wastewater containing recalcitrant organic matter.

[0048] Specifically, the MBBR reactor is cylindrical and wrapped with tin foil. A porous baffle 2 is installed 5cm from the bottom of the MBBR reactor. The packing material 3 has a diameter of 10-50mm, a porosity greater than 95%, and a packing ratio of 70%. The water distribution zone is located below the porous baffle, and the inlet of the MBBR reactor is located on the side wall of the water distribution zone. The height-to-diameter ratio of the MBBR reactor ranges from 3 to 5:1; the packing material is cylindrical porous polyethylene packing material, and the packing ratio (the ratio of packing material to reactor volume) is 20%-80%. The residence time of wastewater in the MBBR reactor is 2-24 hours.

[0049] Specifically, the height-to-diameter ratio of the sedimentation tank ranges from 2 to 5:1. A conical sludge hopper with a sloping side angle of 30° to 60° is installed at the bottom of the sedimentation tank. A sludge discharge port 6 is installed below the sludge hopper. The hydraulic retention time of the sedimentation tank is 0.5 to 2 hours.

[0050] The difference between this invention and existing technologies is that it does not require the direct addition of manganese oxides to the reactor, but rather allows Mn to be added... 2+ It participates in the reaction in the MBBR reactor, and is composed of Mn 2+ Transform into Mn 4+ Mn is controlled by the water outlet. 2+ The amount added.

[0051] In addition, the present invention uses manganese-oxidizing mixed bacteria, which has a better carbon reduction, nitrogen removal and phosphorus removal effect than pure bacteria in the prior art. For example, pure bacteria in the prior art are mainly used to remove certain organic matter and nitrogen, while the manganese-oxidizing mixed bacteria of the present invention have a wider range of applications.

[0052] The preparation method of manganese-oxidizing mixed bacteria is as follows: It is obtained through targeted acclimation of activated sludge. Wastewater to be treated, with 10–50 mg / L glucose added, is used as the culture carrier. Activated sludge is used as the inoculum (20%–50%, v / v), and 10–30 mg / L MnCl2 is added. The mixture is anaerobically cultured with shaking at 35°C for 2–5 days until the Mn(II) concentration in the supernatant reaches 10–20 mg / L. The acclimated activated sludge is used as the inoculum, and the above steps are repeated 2–5 times until the Mn(II) concentration in the supernatant reaches 2–5 mg / L. Targeted acclimation is then successful, and the manganese-oxidizing mixed bacteria are obtained. The activated sludge includes, but is not limited to, denitrification sludge and secondary sedimentation tank sludge from wastewater treatment plants.

[0053] Before treating wastewater, the MBBR reactor needs to be started up with biofilm formation. The specific method is as follows:

[0054] The first stage is the aeration phase, where activated sludge and manganese-oxidizing bacteria are mixed at a mass ratio of 4–10:1 as inoculum sludge. The inoculum sludge is then mixed with wastewater at a mass ratio of 1:1 and filled into the MBBR reactor. After 24–48 hours of aeration, the sludge is drained, and the inoculum sludge is refilled. This process is repeated for 5–15 days to complete the initial biofilm formation.

[0055] sewage and Mn 2+ After mixing with the salt solution, the solution is introduced into the MBBR reactor at a low influent flow rate (0.2–1.0 L / h), with 10–30 mg of Mn added per 1 L of wastewater. 2+ Each water intake lasts 8–12 hours, for a period of 5–10 days.

[0056] sewage and Mn 2+ After mixing with the salt solution, the solution is introduced into the MBBR reactor at a high flow rate (0.5–2.0 L / h), with 10–30 mg of Mn added to each 1 L of wastewater. 2+ The hydraulic retention time of the MBBR reactor was controlled at 2–6 hours, and after 5–7 days of operation, the effluent reached a stable state; Mn 2+ When the microorganisms exist in the MBBR reactor as manganese oxides and are firmly loaded onto the packing material, the biofilm initiation process is successfully completed.

[0057] The following is a detailed description of the carbon reduction, nitrogen removal, and phosphorus removal process of manganese oxides prepared in situ using an MBBR reactor according to the present invention.

[0058] Specifically, the following steps are included:

[0059] After the MBBR reactor is started with biofilm formation, wastewater and Mn will be discharged. 2+ The salt solution was mixed and then fed into the MBBR reactor, with 20-50 mg of Mn added to each 1 L of wastewater. 2+ As wastewater flows from bottom to top in the MBBR reactor, it passes through packing material that grows microorganisms and manganese oxides. During this process, the wastewater comes into full contact with the manganese oxide-loaded packing material to reduce carbon, nitrogen, and phosphorus.

[0060] When Mn in the effluent of the MBBR reactor 2+ Stop adding Mn when its mass content exceeds 50% of the influent. 2+ The salt solution; carbon reduction, nitrogen removal and phosphorus removal are carried out by directly feeding wastewater into the MBBR reactor.

[0061] Example 1:

[0062] The following study focuses on phosphorus-containing water from the secondary effluent of a wastewater treatment plant, and utilizes the method of this invention for carbon reduction, nitrogen removal, and phosphorus removal treatment.

[0063] This embodiment provides an in-situ manganese oxide MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal using the aforementioned process. The system setup adopts the treatment system of this invention, and the water pipe connections and water flow direction are shown by arrows. The MBBR reactor in this embodiment is made of plexiglass, with an inner diameter of 8cm and a height of 40cm. A porous baffle is installed 5cm from the bottom to ensure uniform water distribution and to support the microorganisms and manganese oxide load in the porous polyethylene packing. The sampling port is 5cm from the top of the MBBR reactor.

[0064] The specific composition analysis of the water prepared for the experiment in the water inlet tank is shown in Table 1.

[0065] Table 1

[0066] Serial number Water quality index Concentration (mg / L) 1 TN 6～10 2 NH4 + -N]] 0.3～0.8 3 NO3 - -N]] 5～9 4 TP 1.2～1.5 5 COD 12～20 6 pH 6.5～7.5

[0067] The specific steps for building and starting the processing system of this invention in this embodiment are as follows:

[0068] Step 1: Manganese-oxidizing mixed bacteria were prepared by selectively acclimating activated sludge from the secondary sedimentation tank of a wastewater treatment plant. Wastewater to be treated, with 20 mg / L glucose added, was used as the culture medium. Activated sludge (1 L, 50%, v / v) was used as the inoculum, and 15 mg / L MnCl2 was added. The mixture was anaerobically cultured with shaking at 35°C for 3 days until the Mn(II) concentration in the supernatant reached 10 mg / L. The acclimated activated sludge was used as the inoculum, and the above step was repeated 5 times until the Mn(II) concentration in the supernatant reached 2–5 mg / L, yielding the manganese-oxidizing mixed bacteria. The manganese-oxidizing mixed bacteria were then mixed with activated sludge from the secondary sedimentation tank of the wastewater treatment plant at a 1:5 ratio to obtain the inoculum sludge.

[0069] Step 2: Fill the MBBR reactor with 15mm diameter porous polyethylene packing material at a filling rate of 70% into the reactor with an inner diameter of 8cm and a height of 40cm.

[0070] Step 3: Inoculate sludge into the MBBR reactor, and start the in-situ manganese oxide MBBR reactor by continuous influent at a low flow rate of 0.2 L / h and a high flow rate of 0.5 L / h, respectively, and manganese oxide-microbial fixation stage. The experimental water is phosphorus-containing wastewater prepared from the secondary effluent of a wastewater treatment plant. The preparation process is as follows: add a certain amount of pre-prepared inorganic salt solution to the secondary effluent taken from the wastewater treatment plant, stir the above liquid evenly, transfer the prepared water sample to the wastewater tank, and aerate with N2 for 2 hours to achieve anaerobic state.

[0071] Mn required to be added to the inlet water 2+ By adjusting Mn 2+ Pump flow control between the storage liquid and the inlet tank (Mn) 2+ Amount to be added;

[0072] Mn 2+Mn in the stock solution 2+ The concentration was 200 mg / L, prepared using MnCl2. The preparation process was as follows: a certain amount of pre-prepared MnCl2 solution was added to tap water, and the liquid was stirred evenly before transferring the prepared solution to MnCl2. 2+ The liquid was placed in a storage tank and aerated with N2 for 2 hours to achieve an anaerobic state.

[0073] Step 4: After the in-situ manganese oxide MBBR reactor is successfully started up, during the stable operation period, the experimental water in the inlet tank is introduced into the MBBR reactor through a peristaltic pump and continuously operated in the laboratory at 20-30℃, with a hydraulic retention time of 12h.

[0074] Step 5: After the in-situ manganese oxide MBBR reactor is running stably, monitor COD, TN, and NO3 regularly. - -N, NH4 + Changes in pollutants such as -N and TP, as well as the carbon source utilization rate, organic matter removal rate, nitrogen removal efficiency, and phosphorus removal efficiency of the MBBR reactor.

[0075] The results showed that the in-situ manganese oxide MBBR reactor in this embodiment could achieve a COD removal rate of up to 80%, and TN and NO3 removal rates were also reduced. — The average removal rates of N were 72.19% and 76.38%, respectively, and NH4... + -N removal rate is higher than 90%, TP removal rate is higher than 85%, combined with Figure 2 to Figure 6 As shown, the in-situ manganese oxide MBBR reactor of this embodiment has excellent removal effects on various pollutants. The carbon reduction, nitrogen removal, and phosphorus removal process of the manganese oxide synergistic MBBR reactor prepared by the in-situ method provided by this invention can achieve effective carbon reduction, nitrogen removal, and phosphorus removal.

[0076] Any parts not mentioned in this invention can be achieved by referring to existing technologies.

[0077] Those skilled in the art should recognize that the above embodiments are merely illustrative of this application and are not intended to limit this application. Any appropriate changes and variations made to the above embodiments within the essential spirit and scope of this application should fall within the scope of protection of the claims of this application.

Claims

1. A process for carbon reduction, nitrogen removal, and phosphorus removal using manganese oxides prepared in situ in conjunction with an MBBR reactor, characterized in that, The steps are as follows: a. Prepare the required processing system The treatment system includes an influent tank, an MBBR reactor, a settling tank, and an effluent tank. The influent tank is used to supply wastewater and Mn to the MBBR reactor. 2+ The MBBR reactor contains a salt solution, with water entering from the lower side and exiting from the upper side; the settling tank is used to receive the effluent from the MBBR reactor; the packing material inside the MBBR reactor is cylindrical porous polyethylene packing material. b. Preparation of manganese-oxidizing mixed bacteria: Mn in the supernatant was prepared by targeted domestication of activated sludge. 2+ Manganese-oxidizing mixed bacteria at a concentration of 2-5 mg / L; c. Biofilm startup of the MBBR reactor: Preliminary biofilm formation: Activated sludge and manganese oxidation mixed bacteria are mixed at a mass ratio of 4 to 10:1 as inoculum sludge. The inoculum sludge is mixed with sewage at a ratio of 1:1 and filled into the MBBR reactor for aeration. N2 aeration is used to bring the MBBR reactor to an anaerobic state. After a certain period of aeration, the inoculum sludge is discharged. This step is repeated to complete the preliminary biofilm formation. sewage and Mn 2+ The salt solution is mixed and then enters the inlet tank, and then enters the MBBR reactor from the outlet of the inlet tank at a flow rate of 0.2~1.0 L / h. 10~30 mg of Mn is added to every 1 L of wastewater. 2+ Each water intake lasts 8–12 hours and continues for 5–10 days; sewage and Mn 2+ The salt solution is mixed and then enters the inlet tank, and then enters the MBBR reactor from the outlet of the inlet tank at a flow rate of 0.5~2.0 L / h. 10~30 mg of Mn is added to every 1 L of wastewater. 2+ The hydraulic retention time of the MBBR reactor was controlled at 2–6 hours, and after 5–7 days of operation, the effluent reached a stable state; Mn 2+ It exists in the MBBR reactor in the form of manganese oxide and is firmly loaded onto the packing material with microorganisms; d. Sewage and Mn 2+ The salt solution was mixed and then fed into the MBBR reactor, with 20-50 mg of Mn added to each 1 L of wastewater. 2+ As wastewater flows from bottom to top in the MBBR reactor, it passes through packing material that grows microorganisms and manganese oxides. During this process, the wastewater comes into full contact with the manganese oxide-loaded packing material to reduce carbon, nitrogen, and phosphorus. e. When Mn in the effluent of the MBBR reactor 2+ Stop adding Mn when its mass content exceeds 50% of the influent. 2+ The salt solution; carbon reduction, nitrogen removal and phosphorus removal are carried out by directly feeding wastewater into the MBBR reactor; In step b, the preparation steps of the manganese-oxidizing mixed bacteria are as follows: glucose is added to the wastewater as a culture carrier, with 10-50 mg of glucose added per 1 L of wastewater; activated sludge is used as inoculum; 10-30 mg / L of MnCl2 is added to the inoculum, and the mixture is anaerobically shaken and cultured at 35°C for 2-5 days until the Mn content in the supernatant increases. 2+ The concentration is 10~20 mg / L; Using acclimatized activated sludge as inoculum, repeat this step 2-5 times until Mn in the supernatant is found. 2+ A manganese-oxidizing mixed bacteria was obtained at a concentration of 2-5 mg / L; The MBBR reactor is cylindrical and wrapped with tin foil. A porous baffle is installed 5cm from the bottom of the MBBR reactor. The diameter of the packing is 10-50mm and the packing dosage is 70%. The water distribution zone is located below the porous baffle. The water inlet of the MBBR reactor is located on the side wall of the water distribution zone. An outlet is provided on the side wall 5cm from the top of the MBBR reactor, and the outlet is connected to the inlet of the sedimentation tank.

2. The process for carbon reduction, nitrogen removal, and phosphorus removal using manganese oxides prepared in situ in conjunction with an MBBR reactor according to claim 1, characterized in that: Mn 2+ The salt solution is a MnCl2 solution.

3. The process for carbon reduction, nitrogen removal, and phosphorus removal using manganese oxides prepared in situ in conjunction with an MBBR reactor according to claim 1, characterized in that: The sedimentation tank is equipped with a cone-shaped sludge hopper inside, with a sludge discharge port below the sludge hopper. The outlet of the sedimentation tank is 5cm from the top.

4. The process for carbon reduction, nitrogen removal, and phosphorus removal using manganese oxides prepared in situ in conjunction with an MBBR reactor according to claim 3, characterized in that: The effluent from the sedimentation tank enters the outlet tank through the outlet.

5. The process for carbon reduction, nitrogen removal, and phosphorus removal using manganese oxides prepared in situ in conjunction with an MBBR reactor according to claim 1, characterized in that: The inlet tank is connected to the sewage tank and Mn 2+ Reservoir tank.

6. The application of the in-situ prepared manganese oxide synergistically used in an MBBR reactor for carbon reduction, nitrogen removal, and phosphorus removal according to any one of claims 1 to 5 in the degradation of organic matter, characterized in that: The application is for the degradation of organic matter in rural sewage, sewage treatment plant effluent, or black and odorous water bodies.

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