Advanced treatment process of manganese redox-driven organic matter removal and microbial denitrification

Abstract

The application discloses a deep treatment process of manganese redox-driven organic matter removal and synergistic microbial denitrification, and relates to the technical field of wastewater treatment. The process comprises the following steps: preparing and installing a required treatment system, wherein the treatment system comprises a water inlet tank, an upflow biological reactor, a water outlet tank, an online automatic water quality detector and a computer terminal; preparing functional fillers, which are active MnO2 composite fillers and / or Bio-MnOx composite fillers; mixing the functional fillers with natural manganese ore, and filling the mixed fillers in a filler area; preparing a functional biological agent and adding the agent into the upflow biological reactor to carry out biofilm formation and start-up; when the COD concentration of effluent is higher than 15 mg / L or the TN concentration of effluent is higher than 5 mg / L, extending HR for treatment; and when the extended HR is still not up to the effluent requirements after 24 hours, adding a reinforcing agent Mn 2+ The application has low energy consumption and cost, and belongs to a green and low-carbon technology.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of wastewater treatment, in particular to a deep treatment process for removing organic matter and denitrification of microorganisms driven by manganese redox. BACKGROUND

[0002] With the acceleration of urbanization, water resource shortage problem is increasingly prominent, at the same time, due to poor water quality caused by "water pollution type of water shortage" further aggravates the scarcity of water resources, and the treatment and reuse of wastewater can alleviate water shortage to some extent, which is also an important way to supplement water conservation. However, with the improvement of urbanization level and the continuous advancement of industrialization process in China, the discharge of urban domestic sewage and industrial wastewater is increasing, and the secondary effluent of the domestic wastewater treatment plant still contains some organic matter that is difficult to be biodegraded. Among them, the residual humic substances are a kind of macromolecular polycyclic aromatic compounds containing phenolic hydroxyl, carboxyl and other functional groups, which are also the key precursors of disinfection by-products. If it is discharged directly without treatment, it will lead to eutrophication of water body and cause irreversible pollution to water environment. Therefore, in order to protect the water quality and ecological safety of water system, the urban wastewater needs to be treated strictly before being discharged into the receiving water body.

[0003] At present, the advanced treatment technology of secondary effluent mainly covers physical and chemical treatment and biological treatment. The physical and chemical treatment methods include advanced oxidation method, membrane separation method and coagulation sedimentation, which can effectively remove pollutants, but have high energy consumption, large investment and are not conducive to low-carbon development. Biological treatment technology mainly includes biofilm method, biological filter and constructed wetland. The effluent produced by biofilm method usually contains a large amount of easily precipitated biofilm pieces and small biological fragments, which may cause turbidity of effluent due to the lack of biological flocculation ability similar to activated sludge. In contrast, biological filter and constructed wetland, as a kind of green ecological technology, are widely used in municipal wastewater treatment due to their low energy consumption and meeting the low-carbon emission target. However, this kind of technology still faces the challenges of poor biodegradability of influent, difficulty in long-term stable operation and single type of filling substrate in the treatment process, which limits its effect and durability in large-scale application.

[0004] For the above problems, the prior art has made relevant research, and the relevant patent applications are as follows:

[0005] The application number 201810286726.4 proposes an integrated device for sewage ultra-low emission efficient deep treatment, which uses an integrated high-speed sedimentation tank and an electrochemical enhanced denitrification filter to effectively realize the gradient deep removal of nitrogen, phosphorus, organic matter and suspended solids, but this process requires high power, increasing the energy consumption cost of deep treatment. Biological treatment methods generally have the advantages of simple operation and green ecology. The application number 201210031269.7 proposes a method for natural manganese ore-microorganism synergistic treatment of refractory micro-pollutants, which uses an anaerobic bioreactor with natural manganese ore as the filling layer to achieve effective removal of refractory organic pollutants such as persistent organic pollutants (POPs), precursors of trihalomethane (THMFP), endocrine disruptors (EDCs) and pharmaceutical and personal care products (PPCPs) in wastewater, but the high-valence manganese content in the natural manganese ore filler that actually plays a role is low, and the treatment effect is limited. The application number 202310304420.8 discloses a method and reactor for manganese cycle coupled denitrification simultaneous removal of refractory organic matter, which uses MnO2 loaded on modified corn cobs as functional filler, and realizes efficient removal of nitrate and refractory organic matter in water body through microbial driven manganese oxidation-reduction cycle coupled denitrification. However, the loading capacity of the corn cob loaded MnO2 filler is limited, and the preparation cost is high, which is not conducive to large-scale use.

[0006] Therefore, the prior art needs to be further improved. SUMMARY

[0007] The purpose of the present application is to provide a manganese oxidation-reduction driven organic matter removal and microbial denitrification deep treatment process. The refractory organic matter in wastewater is oxidized by high-valence manganese to improve its biological availability, and the oxidized organic matter and reduced manganese ions can be used as electron donors for microbial denitrification, thereby realizing the removal of refractory organic matter and deep denitrification of wastewater, and realizing manganese cycle under the action of biochemistry

[0008] In order to achieve the above purpose, the following technical solutions are adopted in the present application:

[0009] A manganese oxidation-reduction driven organic matter removal and microbial denitrification deep treatment process, comprising the following steps:

[0010] a. Preparation of functional filler

[0011] The functional filler is active MnO2 composite filler and / or Bio-MnOx composite filler, and x is 1-2;

[0012] b. Preparation of required treatment system

[0013] The processing system comprises a water inlet tank, an upflow bioreactor, a water outlet tank, an online automatic water quality detector and a computer terminal, the online automatic water quality detector is connected with the water inlet tank and the water storage tank respectively; the water inlet tank is connected with the water inlet of the lower part of the upflow bioreactor, and the water outlet tank is connected with the water outlet of the upper part of the upflow bioreactor; the upflow bioreactor comprises a reactor body, the reactor body is in a cylindrical shape, a porous partition is arranged in the reactor body, the upper part of the porous partition is a filler area, and the lower part of the porous partition is a water distribution area;

[0014] The functional filler is mixed with the natural manganese ore at a volume ratio of 1:5-10 and filled in the filler area;

[0015] c. Preparation of functional biological agent

[0016] c1. Directional domestication of manganese oxidizing bacteria: using municipal sewage to be treated added with glucose as a culture carrier, anaerobic activated sludge as inoculum, and adding 30-50 mg / L of MnCl2, anaerobic oscillation culture is carried out for 2-5 days, until the Mn 2+ concentration in the supernatant is 5-15 mg / L, then the directional domestication is successful;

[0017] c2. Directional domestication of manganese reducing bacteria: using municipal sewage to be treated added with glucose as a culture carrier, anaerobic activated sludge as inoculum, and adding 0.6-1 g / L of MnO2, anaerobic oscillation culture is carried out for 2-5 days, until the Mn 2+ concentration in the supernatant is 10-15 mg / L, then the directional domestication is successful;

[0018] The manganese oxidizing bacteria and the manganese reducing bacteria are mixed at a volume ratio of 1:1 to obtain the functional biological agent;

[0019] d. The functional biological agent is added to the upflow bioreactor for biofilm formation and start-up;

[0020] e. When the pH of the water to be treated is 4.0-9.0, the water temperature is 5-30℃, the water is fed through the water inlet of the upflow bioreactor, the HRT is 4-24 h, and the COD and TN concentrations of the system effluent are maintained at 5-15 mg / L and 1-5 mg / L respectively;

[0021] When the COD concentration of the effluent is higher than 15 mg / L or the TN concentration of the effluent is higher than 5 mg / L, the value of HRT is prolonged for treatment, and when the value is prolonged to 24 h and still does not meet the effluent requirements, a reinforcing agent Mn 2+ .

[0022] The preparation method of the active MnO2 composite filler in step a is as follows: under room temperature, a carrier is added into a mixed solution of 0.1-0.2M KMnO4 and 0.1-0.42M NaOH, and stirred constantly; after 10-30 minutes, 0.1-0.2M MnCl2 solution is added dropwise into the obtained mixed system, and reacted; after the reaction is completed, the system is left to stand for 3-6 hours, and then diluted and washed, and left to dry, and the active MnO2 composite filler is obtained.

[0023] The carrier is a natural manganese ore or a porous matrix, and the porous matrix is a porous volcanic rock or a porous filler; the volume ratio of the carrier to the mixed solution of KMnO4 and NaOH is 0.2-1:1, and the volume ratio of KMnO4, NaOH and MnCl2 is 12:4:3.

[0024] The preparation method of the Bio-MnO x The preparation method of the composite filler is as follows: LB culture medium is configured, and manganese oxidizing bacteria Pseudomonas putida MnB6 is introduced into the LB culture medium under 28℃, and cultured under 120rpm shaking for 6-8 hours, and then 5-15mg / L Mn 2+ is added, and then a certain amount of carrier is added for impregnation for 24-48 hours, and then taken out and washed twice with pH=7 biological phosphate buffer, and the composite filler is obtained.

[0025] The upflow bioreactor is made of organic glass, the distance between the porous partition plate and the bottom of the reactor body is 10cm, the height of the filler layer in the filler area is 70cm, and the water storage layer is above the filler area, and the height of the water storage layer is 20cm.

[0026] The COD and TN of the water inlet tank and the water outlet tank are detected by an online automatic water quality detector, and the online automatic water quality detector is connected with a computer terminal.

[0027] The particle size of the mixed filler is 0.5-2cm; the removal rate of the treatment system to COD reaches 60-95%, and the removal rate of the treatment system to TN reaches 65-90%.

[0028] The deep treatment process of the manganese redox-driven organic matter removal and microbial denitrification synergy, in step d, the biofilm formation and start-up comprises: (1) the muffled exposure stage, the activated sludge of the sewage plant is mixed with the functional biological agent as the inoculated sludge, the volume ratio of the activated sludge and the functional biological agent is 10:1, the inoculated sludge is filled in the up-flow biological reactor, after the muffled exposure for 24-48h, the sludge in the up-flow biological reactor is emptied, the activated sludge is filled in the up-flow biological reactor again, the process is repeated for 4-7d, and the preliminary biofilm formation is completed; (2) the outlet of the water inlet tank supplies water to the up-flow biological reactor at 0.2-1.0L / h, and the operation is performed for 8-12h, and the operation is continuously performed for 4-7d; (3) the outlet of the water inlet tank supplies water to the up-flow biological reactor at 0.5-2.0L / h, and the operation is performed for 15d, the biological membrane is loaded on the filler, and the biofilm formation is completed.

[0029] The deep treatment process of the manganese redox-driven organic matter removal and microbial denitrification synergy, the amount of the added reinforcing agent Mn 2+ needs to ensure that the Mn 2+ concentration at the water outlet is ≤0.1mg / L.

[0030] The deep treatment process of the manganese redox-driven organic matter removal and microbial denitrification synergy, a peristaltic pump is arranged on the water inlet pipeline connected between the water inlet tank and the up-flow biological reactor.

[0031] Compared with the prior art, the present application has the following beneficial technical effects:

[0032] (1) The present application provides a deep treatment process of manganese redox-driven organic matter removal and microbial denitrification synergy, wherein the functional filler is added in the up-flow biological reaction tank, the functional filler is active MnO2 composite filler and / or Bio-MnO x 2 composite filler, the functional filler has strong oxidation capacity, can improve the biodegradability of refractory organic matter and release manganese ions, which can make the microorganisms utilize the refractory organic matter in the sewage and the released manganese ions as electron donors to carry out the denitrification reaction, so as to realize the synchronous removal of the refractory organic matter and total nitrogen. In addition, the natural manganese ore has a high specific surface area and contains a large amount of high-valence manganese, so it has strong adsorption and oxidation capacity, and can provide microbial attachment sites and remove part of the refractory organic matter by adsorption and high-valence manganese oxidation. The carrier for preparing the functional filler, such as the natural manganese ore / porous matrix, is rich in resources, has a suitable price, and has good adsorption and oxidation efficiency.

[0033] (2) The functional biological agent is obtained by domesticating anaerobic activated sludge of a sewage plant, and the mixed sludge of the functional biological agent and the anaerobic activated sludge is used for biofilm formation, the mixed sludge contains indigenous bacteria and enriched functional bacteria (manganese oxidizing bacteria agent and manganese reducing bacteria agent), without additional bacteria source, the microorganism can quickly adapt to the environment and play a role, thereby shortening the reactor starting time and improving the reaction efficiency.

[0034] (3) The multivalent change of manganese elements is realized under the biochemical action No secondary pollution is generated, and the upflow biological reactor is suitable for large-scale treatment. The water inlet tank and the water outlet tank of the upflow biological reactor are provided with online automatic water quality detectors, the water quality (COD and TN) of inlet and outlet water is monitored in real time, visual operation can be performed, and management is facilitated.

[0035] (4) The method realizes online monitoring of the water quality of the water inlet tank and the water outlet tank through the online automatic water quality detector, is beneficial to operation and management, has low treatment energy consumption and low cost, and belongs to green and low-carbon technology. BRIEF DESCRIPTION OF DRAWINGS

[0036] The application will be further described below in combination with the drawings:

[0037] Figure 1 The application is a required treatment system structure schematic diagram.

[0038] Figure 2 The application is a required treatment system structure schematic diagram.

[0039] Figure 3 The application is a required treatment system structure schematic diagram.

[0040] Figure 4 The application is a required treatment system structure schematic diagram.

[0041] Figure 5 The application is a required treatment system structure schematic diagram.

[0042] Figure 6 The application is a required treatment system structure schematic diagram.

[0043] In the figure: 1, peristaltic pump, 2, porous partition, 3, filler layer, 4, exhaust pipe, 5, valve, 6, online automatic water quality detector, 7, water inlet tank, 8, water outlet tank. DETAILED DESCRIPTION

[0044] The application provides a deep treatment process of manganese redox-driven organic matter removal and synergistic microbial denitrification.

[0045] It can be understood that the connection relationship described in the application refers to direct or indirect connection. For example, A is connected with B, which can be direct connection between A and B, or indirect connection between A and B through one or more other electrical components. For example, A and C can be directly connected, and C and B can be directly connected, so that A and B are connected through C. It can also be understood that "A is connected with B" described in the application can be direct connection between A and B, or indirect connection between A and B through one or more other electrical components.

[0046] In the description of the application, unless otherwise specified, " / " represents the meaning of "or", for example, A / B can represent A or B. "And / or" in this paper is only a description of the association between the associated objects, which means that there can be three kinds of relationships, for example, A and / or B, which can represent three cases: A exists alone, A and B exist together, and B exists alone.

[0047] The main technical idea of the application is that by using self-made functional fillers, the organic matter can be better degraded and the total nitrogen can be removed synchronously in the upflow bioreactor; in addition, the functional biological agent is obtained by domesticating anaerobic activated sludge in a sewage plant, so that the microorganism can quickly adapt to the environment and play its role without adding external bacteria source; the on-line automatic water quality detector connected by the water inlet tank and the water storage tank can realize on-line monitoring of the COD and TN of the inlet and outlet water.

[0048] The "carrier" described in the application is a natural manganese ore or a porous matrix, and the porous matrix is a porous volcanic rock or a porous filler.

[0049] As Figure 1As shown, the present application is a kind of manganese redox driven organic matter removal and microbial denitrification synergistic advanced treatment system, including up-flow bioreactor, peristaltic pump 1, porous partition 2, filler layer 3, exhaust pipe 4, valve 5, online automatic water quality detector 6, water inlet tank 7, water outlet tank 8. The up-flow bioreactor includes reactor body, which is made of organic glass, 100cm high, 25cm in diameter, and the porous partition 2 is arranged in the reactor body, which is 10cm away from the bottom of the reactor body. The water distribution area is below the porous partition, and the water inlet of the reactor body is located on the side wall of the reactor body below the porous partition, that is, the water is fed from the bottom. The peristaltic pump 1 is arranged on the pipeline connecting the water inlet of the reactor body and the water inlet tank 7; the filler area is above the porous partition, and the height of the filler layer in the filler area is 70cm. The functional filler prepared by the present application is used in the filler layer, and a water storage layer with a height of 20cm is left above the filler layer. In addition, the water inlet tank and the water outlet tank are connected to the online automatic water quality detector 6 for online water quality (COD, TN) detection.

[0050] The present application will be further described in combination with the above-mentioned system.

[0051] Example 1:

[0052] This embodiment can be applied to municipal sewage with COD (chemical oxygen demand) concentration of 15-25mg / L, TN (total nitrogen) concentration of 10-20mg / L, pH range of 6.5-7.5, water temperature (15-25℃) of the municipal sewage to be treated, and the concentrations of COD and TN in the system effluent are 1-3mg / L and 1-3mg / L respectively. The removal rate of COD reaches 88-95%, and the removal rate of TN reaches 83-90%, achieving deep purification of municipal sewage.

[0053] The structure of the advanced treatment system required in this embodiment is shown in Figure 1 .

[0054] A kind of manganese redox driven organic matter removal and microbial denitrification synergistic advanced treatment process, comprising the following steps:

[0055] a, preparation of functional filler

[0056] The functional filler is active MnO2 composite filler: under room temperature conditions, 0.1-0.2M KMnO4 and 0.1-0.42M NaOH mixed solution is added to natural manganese ore / porous substrate (the volume ratio of natural manganese ore / porous substrate to mixed solution is 0.2-1:1), and continuous stirring, 10-30min, 0.1-0.2M MnCl2 solution (volume ratio of KMnO4: NaOH: MnCl2 = 12:4:3) is added dropwise to the mixed system. After reaction, the mixed system is placed for 3-6h. Dilution washing, and drying after standing.

[0057] b. Preparation and installation of the above treatment system

[0058] Mix the functional filler with the natural manganese ore at a volume ratio of 1:5-10 and fill it in the filler zone;

[0059] c. Preparation of functional biological agent

[0060] c1. Directional domestication of manganese oxidizing bacteria: use the municipal wastewater to be treated added with 30-50 mg / L glucose as the culture carrier, anaerobic activated sludge as the inoculum (20%-50%, v / v), and add 30-50 mg / L MnCl2, and cultivate under anaerobic oscillation at 35°C for 2-5 days, until the Mn 2+ concentration in the supernatant is 5-15 mg / L, then the directional domestication is successful;

[0061] c2. Directional domestication of manganese reducing bacteria: use the municipal wastewater to be treated added with 30-50 mg / L glucose as the culture carrier, anaerobic activated sludge as the inoculum (20%-50%, v / v), and add 0.6-1 g / L MnO2, and cultivate under anaerobic oscillation at 35°C for 2-5 days, until the Mn 2+ concentration in the supernatant is 10-15 mg / L, then the directional domestication is successful;

[0062] Mix the manganese oxidizing bacteria and the manganese reducing bacteria at a volume ratio of 1:1 to obtain the functional biological agent;

[0063] d. Add the functional biological agent to the upflow bioreactor for biofilm formation and start-up;

[0064] The system biofilm formation and start-up is divided into three stages: the first stage is the smothering stage. Use the anaerobic activated sludge from the wastewater treatment plant mixed with the functional biological agent at a volume ratio of 10:1 as the inoculum, and fill the upflow bioreactor. After smothering for 24-48 h, empty the sludge in the upflow bioreactor, and fill it with activated sludge again, repeat this process for about 4-7 days to complete the preliminary biofilm formation.

[0065] The second stage is the continuous water feeding stage with small flow rate. The water to be fed is the municipal wastewater to be treated, and the outlet of the water feeding tank supplies water to the upflow bioreactor at a flow rate of 0.2-1.0 L / h, continuously running for 8-12 h, and this stage lasts for about 3-7 days. In the early stage of biofilm formation, the microbial load is not firm, and too large flow rate can easily lead to the shedding of the biofilm loaded on the filler in the smothering stage, affecting the biofilm formation effect.

[0066] The third stage is to run the acclimation stage under the design parameter range. The influent is the municipal sewage to be treated, a large influent flow is set to continuously run (the flow is controlled in the effective running range, and the flow should not be too large, and the HRT of the upflow bioreactor is set to 2-6h), the microorganisms in the upflow bioreactor are further multiplied and acclimated, the system runs for about 15d, and the effluent reaches a stable state. At this time, the biofilm load on the filler can be seen in the system, that is, the biofilm formation is successful.

[0067] e. Water treatment regulation:

[0068] The pH of the municipal sewage to be treated is 6.5-7.5, the water temperature is 20-25℃, the influent is introduced through the influent port of the upflow bioreactor, the HRT is 6-24h, and the concentrations of the effluent COD and TN are maintained at 15-25mg / L and 10-20mg / L, respectively.

[0069] When the concentration of the effluent COD is higher than 15mg / L or the concentration of the effluent TN is higher than 5mg / L, the value of the HRT is prolonged for treatment, and when the HRT is prolonged to 24h and still does not meet the effluent requirements, the reinforcing agent Mn 2+ is added to the influent tank at 5-15mg / L Mn(II) (it is required to ensure that the effluent Mn(II) is not more than 0.1mg / L) to improve the treatment efficiency of the upflow bioreactor. After the treatment efficiency meets the effluent requirements and is stable for 3-5d, the addition of the reinforcing agent Mn 2+ is stopped to maintain the high-efficiency operation of the upflow bioreactor.

[0070] The specific steps for building and starting the treatment system of the embodiment are as follows:

[0071] Step 1: The active MnO2 composite filler is prepared. Under room temperature conditions, 10-15mm natural manganese ore is added to a mixed solution of 0.2M KMnO4 and 0.42M NaOH (the volume ratio of the natural manganese ore to the mixed solution is 1:1), and continuous stirring is performed for 30min. Then, 0.2M MnCl2 solution is added dropwise to the mixed system (the volume ratio of KMnO4:NaOH:MnCl2 is 12:4:3), and continuous stirring is continued for 1h. After the reaction, the mixed system is left to stand for 6h. Then, tap water is used for washing until the pH of the leaching solution approaches neutrality, and the active MnO2 composite filler is dried at room temperature for 48h to obtain the active MnO2 composite filler.

[0072] Step 2: The active MnO2 composite filler prepared in the previous step is mixed with 10-15mm natural manganese ore at a volume ratio of 1:5, and is loaded into the filler layer of the upflow bioreactor to form a manganese oxidation-reduction driven organic matter removal and microbial denitrification system.

[0073] Step 3: The functional biological bacterial agent is prepared.

[0074] Step 3a: Using the municipal sewage to be treated with the addition of 50 mg / L glucose as the culture carrier, the anaerobic activated sludge from the sewage treatment plant as the inoculum (50%, the volume ratio of the culture carrier to the inoculum being 1:1), after mixing the culture carrier with the inoculum, 30 mg / L of MnCl2 solution was added thereto, and the mixture was cultured anaerobically at 35°C for 2-5 days until the Mn 2+ concentration in the supernatant was 5-15 mg / L, then the directional domestication was successful, and the manganese oxidizing bacterial agent was obtained;

[0075] Step 3b: Using the municipal sewage to be treated with the addition of 50 mg / L glucose as the culture carrier, the anaerobic activated sludge as the inoculum (50%, the volume ratio of the culture carrier to the inoculum being 1:1), and 1 g / L of MnO2 was added, and the mixture was cultured anaerobically at 35°C for 2-5 days until the Mn 2+ concentration in the supernatant was 10-15 mg / L, then the directional domestication was successful, and the manganese reducing bacterial agent was obtained;

[0076] Step 3c: The manganese oxidizing bacterial agent and the manganese reducing bacterial agent were mixed according to the volume ratio of 1:1 to obtain the functional biological bacterial agent.

[0077] Step 4: The anaerobic activated sludge from the sewage plant was mixed with the functional biological bacterial agent according to the volume ratio of 10:1 to obtain the inoculated sludge.

[0078] Step 5: The manganese oxidation-reduction driven organic matter removal and microbial denitrification system was started and operated.

[0079] Step 5a: The inoculated sludge in step 4 was used to start the biofilm formation of the upflow bioreactor, and the upflow bioreactor was started by means of the smothering culture, the continuous water feeding at a small flow rate of 1 L / h and a large flow rate of 2 L / h, and the manganese oxide-microbial immobilization stage.

[0080] The experimental water was the effluent from the secondary sedimentation tank of a sewage plant, and the water quality indexes were as shown in Table 1:

[0081] Table 1

[0082]

[0083] Step 6: After the upflow bioreactor was successfully started, during the stable operation, the experimental water in the water feeding tank was introduced into the upflow bioreactor by means of the peristaltic pump, and the upflow bioreactor was continuously operated in the laboratory at 20-30°C, and the hydraulic retention time was 12 h.

[0084] Step 7: After the upflow bioreactor was stably operated, the changes of pollutants such as COD and TN and the organic matter removal rate and denitrification efficiency of the manganese oxidation-reduction driven organic matter removal and microbial denitrification system were monitored on-line and periodically.

[0085] Step 8: After the manganese redox-driven organic matter removal synergistic microbial denitrification system has been running for 300 days, if the treatment effect deteriorates, add 10 mg / L Mn(II) (prepared from MnCl2) to the influent tank (ensuring that the effluent Mn(II) does not exceed 0.1 mg / L) to improve the treatment efficiency of the upflow bioreactor. Stop adding the Mn enhancer after the treatment efficiency meets the effluent requirements and stabilizes for 3 days. 2+ This maintains the efficient operation of the upflow bioreactor. The water treatment control results are as follows: Figure 6 As shown.

[0086] The results showed that the average removal rate of COD by the upflow bioreactor in this embodiment reached 87%, and the average removal rate of TN was over 86%. Figures 2 to 5 As shown, this embodiment demonstrates that the manganese redox-driven organic matter removal synergistic microbial denitrification system exhibits excellent removal capabilities for various pollutants. When the treatment efficiency of the upflow bioreactor decreased, the addition of Mn(II) enhancer restored the original treatment efficiency and continued to function stably. Figure 6 As shown, this illustrates the effectiveness of the water treatment control method.

[0087] Example 2:

[0088] The difference between this embodiment and Embodiment 1 is that:

[0089] The functional packing material used is Bio-MnO. x The composite filler, with x taking values ​​from 1 to 2, is prepared as follows:

[0090] Step 1: Prepare LB medium. Introduce the manganese-oxidizing bacterium *Pseudomonas putida* MnB6 (BCCM / LMG 2322) into the LB medium at 28°C and culture for 6–8 h with shaking at 120 rpm. Then, introduce 15 mg / L Mn(II) followed by a certain amount of natural manganese ore with a particle size of 10–15 mm (the volume ratio of natural manganese ore to LB medium is 1:1). After soaking for 24–48 h, remove the natural manganese ore and wash twice with 10 mM biological phosphate buffer (pH = 7) to obtain Bio-MnO. x Composite packing material.

[0091] Step 2: The Bio-MnO prepared in the previous step... x The composite packing material is mixed with 10-15mm natural manganese ore at a volume ratio of 1:5 and then filled into the packing layer of an upflow bioreactor to form a manganese oxidation-reduction driven organic matter removal synergistic microbial denitrification system.

[0092] The results showed that the average removal rate of COD by the upflow bioreactor in this embodiment reached over 90%, and the average removal rate of TN reached as high as 87%. Figures 2 to 5 As shown, this embodiment demonstrates that the manganese redox-driven organic matter removal synergistic microbial denitrification system exhibits excellent removal capabilities for various pollutants.

[0093] Example 3:

[0094] The difference between this embodiment and Embodiment 1 is that:

[0095] The functional filler used is a mixture of active MnO2 composite filler and Bio-MnOx composite filler; its preparation process is as follows:

[0096] Step 1: Preparation of activated MnO2 composite filler. At room temperature, natural manganese ore with a particle size of 10-15 mm (volume ratio of natural manganese ore to the mixture is 1:1) was added to a mixture of 0.2 M KMnO4 and 0.42 M NaOH. After stirring continuously for 30 min, 0.2 M MnCl2 solution (volume ratio of KMnO4:NaOH:MnCl2 = 12:4:3) was added dropwise to the mixture. Stirring was continued for 1 h. After the reaction, the mixture was allowed to stand for 6 h. Then, it was washed with tap water until the pH of the leachate was close to neutral, and then dried at room temperature for 48 h to obtain the activated MnO2 composite filler.

[0097] Step 2: Prepare LB medium. Introduce the manganese-oxidizing bacterium *Pseudomonas putida* MnB6 (BCCM / LMG 2322) into the LB medium at 28°C and culture for 6–8 hours with shaking at 120 rpm. Then, introduce 15 mg / L Mn(II) followed by a certain amount of natural manganese ore with a particle size of 10–15 mm (natural manganese ore to LB medium volume ratio 1:1). After soaking for 24–48 hours, remove the natural manganese ore and wash twice with 10 mM biological phosphate buffer (pH = 7) to obtain Bio-MnO. x Composite packing material.

[0098] Step 3: The active MnO2 composite filler and Bio-MnO2 prepared in Step 1 and Step 2 are then processed together. x The composite packing material is mixed with 10-15mm natural manganese ore in a volume ratio of 1:1:10 and then filled into the packing layer of an upflow bioreactor to form a manganese oxidation-reduction driven organic matter removal synergistic microbial denitrification system.

[0099] The results showed that the average removal rate of COD by the upflow bioreactor in this embodiment reached 89%, and the average removal rate of TN reached 87%. Figures 2 to 5The removal effects of the biological denitrification system of Comparative Example 1 on various pollutants are significantly poorer than those of the manganese redox-driven organic matter removal and microbial denitrification systems of Example 1, Example 2 and Example 3.

[0100] Comparative Example 1:

[0101] Comparative Example 1 differs from Example 1 in that the filler used is natural manganese ore with a particle size of 10-15 mm, and the specific system setup steps are as follows:

[0102] Step 1: Fill the 10-15 mm natural manganese ore into the filler layer of the upflow bioreactor to form the microbial denitrification system.

[0103] The results show that the average removal rate of the upflow bioreactor of Comparative Example 1 on COD is only 70%, and the average removal rate of TN is 68%, combined with the fact that the removal rate of TN is lower than that of COD, it can be seen that the removal effect of the upflow bioreactor of Comparative Example 1 on TN is poor. Figures 2 to 5 The removal effects of the biological denitrification system of Comparative Example 1 on various pollutants are significantly poorer than those of the manganese redox-driven organic matter removal and microbial denitrification systems of Example 1, Example 2 and Example 3.

[0104] Comparative Example 2:

[0105] Comparative Example 2 differs from Example 1 in that the inoculated sludge is unacclimated anaerobic activated sludge from a sewage plant, and the specific system startup steps are as follows: Step 1: Use the anaerobic activated sludge from the sewage plant as the inoculated sludge to start the biofilm formation of the upflow bioreactor, and through the muffled exposure culture, continuously feed water at a small flow rate of 1 L / h and a large flow rate of 2 L / h, and a fixed phase to start the upflow bioreactor.

[0106] The results show that the average removal rate of the upflow bioreactor of Comparative Example 2 on COD is only 75%, and the average removal rate of TN is 73%, combined with the fact that the removal rate of TN is lower than that of COD, it can be seen that the removal effect of the upflow bioreactor of Comparative Example 2 on TN is poor. Figures 2 to 5 The removal effects of the biological denitrification system of Comparative Example 2 on various pollutants are significantly poorer than those of the manganese redox-driven organic matter removal and microbial denitrification systems of Example 1, Example 2 and Example 3.

[0107] The removal effects of the upflow bioreactors of Example 1, Example 2, Example 3, Comparative Example 1 and Comparative Example 2 on the COD and TN of the experimental water during the 30-day continuous and stable operation are shown in Table 2:

[0108] Table 2

[0109]

[0110] According to the results of the above examples and comparative examples, the manganese redox-driven organic matter removal and microbial denitrification deep treatment process proposed by the present application can be started up by using the self-made active MnO2 composite filler and Bio-MnO2 microbial denitrification system, and the removal effects of the system on various pollutants are excellent. xThe composite filler and the functional bacteria agent make the upflowing biological reactor better and more efficient in degrading organic matters and synchronously removing total nitrogen. In addition, the functional filler prepared in the application has suitable price, good adsorption and oxidation efficiency, and the mixed sludge of the functional biological bacteria agent and the anaerobic active sludge is used for biofilm formation, the mixed sludge contains indigenous bacteria and enriched functional bacteria groups, can make the microorganisms quickly adapt to the environment and play the role, thereby shortening the reactor starting time and improving the reaction efficiency. In summary, the application has the advantages of good treatment effect, low energy consumption, low cost and belongs to the green low-carbon technology.

[0111] The parts not mentioned in the application can be realized by referring to the prior art.

[0112] Those skilled in the art should recognize that the above embodiments are only used to illustrate the present application, and are not used as a limitation on the present application, and as long as the above embodiments are appropriately changed and changed within the scope of the spirit of the present application, they should fall within the scope of protection of the claims of the present application.

Claims

1. A deep treatment process of manganese redox-driven organic matter removal and synergistic microbial denitrification, characterized in that, The method comprises the following steps: a. preparing functional filler The functional filler is active MnO2 composite filler and / or Bio-MnOx composite filler, wherein x is 1-2; b. preparing a required treatment system The treatment system comprises a water inlet tank, an up-flowing biological reactor, a water outlet tank, an online automatic water quality detector and a computer terminal. The online automatic water quality detector is connected with the water inlet tank and the water storage tank respectively. The water inlet tank is connected with the water inlet of the lower part of the up-flowing biological reactor, and the water outlet tank is connected with the water outlet of the upper part of the up-flowing biological reactor. The up-flowing biological reactor comprises a reactor body which is in a cylindrical shape. A porous partition is arranged in the reactor body. The filler area is above the porous partition, and the water distribution area is below the porous partition. The functional filler is mixed with natural manganese ore at a volume ratio of 1:5-10 and filled in the filler area. c. preparing functional biological agent c1. Directional domestication of manganese oxidizing bacteria: municipal sewage to be treated with added glucose as culture carrier, anaerobic activated sludge as inoculum, and 30-50 mg / L of MnCl2, anaerobic oscillation culture for 2-5 days, until the Mn 2+ concentration in the supernatant is 5-15 mg / L, then the directional domestication is successful; c2. Directional domestication of manganese-reducing bacteria: using the municipal sewage to be treated with glucose as the culture carrier, anaerobic activated sludge as the inoculum, and adding 0.6-1 g / L of MnO2, the anaerobic oscillation culture is carried out for 2-5 days, until the Mn 2+ concentration in the supernatant is 10-15 mg / L, then the directional domestication is successful; The manganese oxidizing bacteria agent and the manganese reducing bacteria agent are mixed at a volume ratio of 1:1 to obtain the functional biological agent. d. adding the functional biological agent into the up-flowing biological reactor to start the biofilm formation e. When the pH of the water to be treated is 4.0-9.0, the water temperature is 5-30℃, the water is fed into the up-flowing biological reactor through the water inlet, the HRT is 4-24h, and the COD and TN concentrations of the system outlet water are maintained at 5-15mg / L and 1-5mg / L respectively. When the effluent COD concentration is higher than 15 mg / L or the effluent TN concentration is higher than 5 mg / L, the HRT is extended for treatment, and when it is still not in conformity with the effluent requirements after being extended to 24 h, the enhancer Mn is added 2+ .

2. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 1, characterized in that: In step a, the active MnO2 composite filler is prepared by adding a carrier into a mixed solution of 0.1-0.2M KMnO4 and 0.1-0.42M NaOH under room temperature, continuously stirring, adding 0.1-0.2M MnCl2 solution drop by drop into the obtained mixed system, reacting, standing for 3-6h after the reaction is completed, diluting and washing, and placing for drying.

3. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 2, characterized in that: The carrier is natural manganese ore or porous matrix. The porous matrix is porous volcanic rock or porous filler. The volume ratio of the carrier to the mixed solution of KMnO4 and NaOH is 0.2-1:1, and the volume ratio of KMnO4, NaOH and MnCl2 is 12:4:

3.

4. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 1, characterized in that: Bio-MnO x The preparation method of the composite filler is as follows: configuring LB culture medium, introducing manganese oxidizing bacteria Pseudomonas putida MnB6 into the LB culture medium at 28℃, culturing for 6-8h under 120rpm shaking, then introducing 5-15mg / L Mn 2+ , then adding a certain amount of carrier for impregnation for 24-48h, taking out, washing twice with pH=7 biological phosphate buffer solution, and obtaining the composite filler.

5. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 1, characterized in that: The up-flowing biological reactor is made of organic glass. The distance between the porous partition and the bottom of the reactor body is 10cm. The height of the filler layer in the filler area is 70cm. The area above the filler area is the water storage layer, and the height of the water storage layer is 20cm.

6. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 1, characterized in that: The COD and TN of the water inlet tank and the water outlet tank are detected by the online automatic water quality detector which is connected with the computer terminal.

7. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 1, characterized in that: The particle size of the mixed filler is 0.5-2cm. The removal rate of the treatment system for COD is 60-95%, and the removal rate for TN is 65-90%.

8. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 1, characterized in that: The biofilm starting-up in step d comprises: (1) a phase of mummification, mixing the activated sludge in the sewage plant with the functional biological agent as the inoculated sludge, the volume ratio of the activated sludge to the functional biological agent is 10:1, filling the up-flowing biological reactor with the inoculated sludge, emptying the sludge in the up-flowing biological reactor after mummification for 24-48 hours, filling the up-flowing biological reactor with the activated sludge again, repeating the process for 4-7 days, and completing the preliminary biofilm formation; (2) supplying water to the up-flowing biological reactor from the outlet of the water inlet tank at 0.2-1.0 / L, operating for 8-12 hours, and continuing for 4-7 days; (3) supplying water to the up-flowing biological reactor from the outlet of the water inlet tank at 0.5-2.0 / L, operating for 15 days, loading the biological membrane on the filler, and completing the biofilm formation.

9. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 1, characterized in that: The amount of the reinforcing agent Mn 2+ must be ensured that the Mn 2+ concentration at the water outlet is ≤ 0.1 mg / L.

10. The advanced treatment process for removing organic matter and denitrification by synergistic microorganisms driven by manganese redox according to claim 1, characterized in that: A peristaltic pump is arranged on the water inlet pipeline connecting the water inlet tank and the up-flowing biological reactor.

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