CN115259376A - Biological autotrophic nitrogen removal device under charging and discharging of sulfur battery and sewage treatment method thereof - Google Patents
Biological autotrophic nitrogen removal device under charging and discharging of sulfur battery and sewage treatment method thereof Download PDFInfo
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- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 12
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2853—Anaerobic digestion processes using anaerobic membrane bioreactors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention discloses a biological autotrophic nitrogen removal device under charging and discharging of a sulfur battery and a sewage treatment method thereof, belonging to the technical field of sewage treatment. The device comprises an anaerobic membrane bioreactor (AnMBR) and a Membrane Aeration Biofilm Reactor (MABR) which are communicated with each other. The sulfur redox process and the denitrification process are coupled, and electrons in organic matters are transferred to sulfides in an AnMBR to complete the charging process of the sulfur battery; in the MABR, the electrons in the sulfide are further transferred to nitrate or nitrite, and the sulfide is oxidized again to sulfate, completing the discharge process of the sulfur cell. Through the charging and discharging process of the sulfur battery, organic matters and ammonia nitrogen in the sewage are completely removed. The denitrification process completely depends on the autotrophic microorganisms and the membrane biofilm process, so that the sludge yield is low, the energy consumption is extremely low, the occupied area is small, the modularization is realized, and the operation is flexible.
Description
Technical Field
The invention relates to a sewage treatment process, in particular to a biological autotrophic nitrogen removal device under charging and discharging of a sulfur battery and a sewage treatment method thereof.
Background
The traditional sewage treatment process greatly improves the water environment quality and plays an irreplaceable role in the urbanization process of China. But the method has the problems of high energy consumption, large floor area, high residual sludge yield and the like. Data statistics show that every 1 ten thousand tons of sewage can be treated to generate 5-10 tons of sludge with water content of 80%. With the improvement of the sewage treatment rate in China, the amount of the excess sludge is also continuously increased, and the estimated amount of the excess sludge reaches 7538 ten thousand tons in 2025. The cost of sludge treatment and disposal is extremely high. Normally, the treatment cost accounts for about 50% of the operation cost of sewage plants. The existing sludge reduction technology, including pyrolysis, ultrasonic treatment, anaerobic digestion and the like, has high cost and large occupied area, and cannot solve the problems fundamentally.
In order to reduce the generation of excess sludge from the source, both patent CN200810217944.9 and patent CN202111016586.7 disclose a sulfate reduction, autotrophic denitrification and nitrification integrated process (SANI). The process is based on the valence state circulation of sulfur elements, adopts sulfur autotrophic denitrifying bacteria to replace traditional heterotrophic bacteria to realize denitrification, adopts an anaerobic process to replace an aerobic process to realize organic matter removal, and further radically solves the problem of high sludge yield. However, in the application of the SANI process, the conventional aeration mode separates nitrification and denitrification processes, so that the reduction of the occupied area is limited, and the removal of nitrate nitrogen needs to be realized by refluxing, and the system complexity and the aeration and refluxing energy consumption are not effectively reduced.
Disclosure of Invention
The invention aims to develop a SANI process substitution process, which can greatly reduce energy consumption, reduce process sections, improve integration level of a reaction process and simplify system complexity while further reducing the source yield of excess sludge, thereby meeting the requirements of carbon reduction and consumption reduction of current sewage treatment, and providing a novel biological autotrophic nitrogen removal device under charging and discharging of a sulfur battery and a sewage treatment method thereof.
The invention adopts the following specific technical scheme:
in a first aspect, the invention provides a bioautotrophic denitrification device under charging and discharging of a sulfur battery, which comprises an anaerobic membrane bioreactor for sulfate reduction and a membrane aeration biofilm reactor for realizing synchronous nitrification and sulfur autotrophic denitrification; and the water outlet of the anaerobic membrane bioreactor is communicated with the water inlet of the membrane aeration biomembrane reactor and is used for introducing sulfate reduction products in the wastewater into the membrane aeration biomembrane reactor.
Preferably, the sulfate reduction product is one or more of sulfide, soluble elemental sulfur, thiosulfate and sulfite.
Preferably, the anaerobic membrane bioreactor and the membrane aeration biofilm reactor are both provided with sewage circulating pipelines for enabling sewage in the reactors to be in a complete mixing state.
Preferably, the upper part of the membrane-aeration biomembrane reactor is provided with an overflow water outlet for discharging the treated water.
Preferably, the water outlet of the anaerobic membrane bioreactor is communicated with the membrane aeration biomembrane reactor through a pipeline provided with a suction water pump.
Preferably, the biomembrane attached to the microporous membrane in the membrane-aerated biomembrane reactor has a layered structure to simultaneously perform nitrification and sulfur autotrophic denitrification processes; the inner layer of the biological membrane is an aerobic layer, and the outer layer is an anoxic or anaerobic layer.
In a second aspect, the present invention provides a method for treating wastewater by using the bioautotrophic denitrification apparatus under charge and discharge of the sulfur battery in the first aspect, comprising:
introducing sewage to be treated containing organic matters, ammonia nitrogen and sulfate radicals into an anaerobic membrane bioreactor, reducing the sulfate radicals in the sewage into a sulfate reduction product through a sulfate reduction process, transferring electrons in the organic matters to the sulfate reduction product, and finishing the charging and decarburization processes of a sulfur battery; the sulfate reduction product is one or more of sulfide, soluble sulfur simple substance, thiosulfate and sulfite;
introducing the sewage treated by the anaerobic membrane bioreactor into a membrane aeration biomembrane reactor; in the membrane aeration biomembrane reactor, ammonia nitrogen is oxidized into nitrate or nitrite by nitrifying bacteria positioned in the inner layer of the biomembrane through synchronous nitrification-sulfur autotrophic denitrification reaction by means of the layered biomembrane structure on the microporous membrane; the generated nitrate or nitrite is reduced into nitrogen by sulfur autotrophic denitrifying bacteria positioned on the outer layer of the biological membrane, and then is discharged and removed from the device, electrons in the sulfate reduction product are further transferred to nitrate or nitrite, the discharge of a sulfur battery and denitrification reaction are completed, and the treatment of sewage is realized.
Preferably, the sewage to be treated is municipal sewage with the sulfate radical concentration of less than 100mg S/L or industrial wastewater with the sulfate radical concentration of more than 200mg S/L.
Preferably, when the sewage to be treated is municipal sewage with sulfate radical concentration less than 100mg S/L, the effluent part of the membrane aeration biomembrane reactor is refluxed into the anaerobic membrane bioreactor through a reflux pipeline, so that the molar ratio of sulfur and nitrogen in the influent water of the anaerobic membrane bioreactor is maintained to be more than 0.9.
Preferably, the dissolved oxygen concentration of the sewage in the membrane-aerated biofilm reactor is controlled between 0.2 and 0.5 mg/L.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention realizes the biological autotrophic nitrogen removal of the sewage by means of the charging and discharging process of the sulfur battery, the yield of the excess sludge is low, and meanwhile, the AnMBR (anaerobic membrane bio-membrane reactor) and the MABR (membrane aeration bio-membrane reactor) are membrane bio-membrane processes, so that the production of the excess sludge can be further reduced.
(2) The invention realizes the synchronous nitrification-sulfur autotrophic denitrification process by the MABR technology, integrates two biochemical reactions in one space, greatly reduces the occupied area, avoids the energy consumption caused by reflux and reduces the process complexity.
(3) The invention adopts MABR bubble-free aeration, greatly reduces the aeration energy consumption and has outstanding economic advantages.
(4) According to the invention, the AnMBR is adopted to realize the sulfate reduction process, the sludge concentration is high, the volume load is large, the problem of sludge loss is avoided, and the influence of effluent microorganisms on the subsequent reaction process is effectively avoided.
(5) The AnMBR and the MABR can be operated in a modularized mode, different treatment capacity requirements can be met by simply connecting modules in series, and the distributed sewage treatment method can effectively adapt to the existing distributed sewage treatment mode.
Drawings
FIG. 1 is a schematic diagram of a process of biological autotrophic nitrogen removal under charging and discharging of a sulfur battery;
FIG. 2 is a schematic diagram of the structure of a bioautotrophic denitrification device under charging and discharging of a sulfur battery in the embodiment of the invention;
FIG. 3 is a graph showing the effect of sulfide concentration on ammonia nitrogen and sulfide removal in the MABR reactor in the examples;
FIG. 4 is a graph of the effect of sulfide concentration on total nitrogen removal in an MABR reactor in the examples;
FIG. 5 is a schematic view showing the overall operation of the apparatus in the embodiment;
FIG. 6 is the biofilm microbial community composition of the MABR reactor performing the simultaneous nitrification-sulfur autotrophic denitrification process of the example.
The drawings in the figures are illustrated as: the anaerobic membrane biofilm reactor 21, the air bag 210, the first membrane module 211, the first reactor 212, the water inlet pump 213, the water production pump 214, the membrane aeration biofilm reactor 22, the sealing cock 220, the second reactor 221, the second membrane module 222, the internal circulation pump 223, the pressure reducing valve 224 and the oxygen bottle 225.
Detailed Description
The invention is further illustrated and described below with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
As shown in fig. 1, the bioautotrophic denitrification device for charging and discharging sulfur batteries provided by the invention comprises an anaerobic membrane bioreactor (AnMBR) 21 for sulfate reduction in a charging process, and a membrane-aerated biofilm reactor (MABR) 22 for synchronous nitrification-sulfur autotrophic denitrification (SNAD) in a discharging process. The water outlet of the anaerobic membrane bioreactor 21 is communicated with the water inlet of the membrane-aerated biofilm reactor 22 and is used for introducing sulfate reduction products in the wastewater into the membrane-aerated biofilm reactor 22. Transferring electrons in organic matters to a sulfate reduction product by the AnMBR through a sulfate reduction process to complete the charging of a sulfur battery and the removal of COD; and the AnMBR effluent is in communication with the MABR feed water to introduce sulfate-reduction products into the MABR. The MABR has a layered biomembrane structure, the inner layer is an aerobic nitrification layer, the outer layer is an anoxic autotrophic denitrification layer, and electrons in a sulfate reduction product are further transferred to nitrate or nitrite through an SNAD process, so that the discharge of a sulfur battery and the removal of total nitrogen are completed. Wherein, the sulfate reduction product refers to one or more of sulfide, soluble sulfur simple substance, thiosulfate and sulfite.
In practical application, a sewage circulating pipeline is arranged in the AnMBR to ensure that the reactor is in a complete mixing state, and a suction water pump is arranged in the reactor and used for injecting the sulfate-containing reduction product sewage into the MABR. The MABR is provided with a sewage circulating pipeline to ensure that the reactor is in a complete mixing state, and an overflow water outlet is arranged above the circulating pipeline and used for discharging and treating purified water. The MABR has a layered biomembrane structure, namely, the inner layer of the biomembrane is an aerobic layer, and the outer layer of the biomembrane is an anoxic or anaerobic layer, and can carry out nitrification and sulfur autotrophic denitrification processes at the same time.
During charging of the sulfur battery, the sulfate reduction product may be dissolved elemental sulfur, thiosulfate, sulfite, in addition to sulfide. During the discharge of the sulfur cell, the sulfide or soluble elemental sulfur or thiosulfate or sulfite is reduced to sulfate again, and the electron acceptor is nitrate or nitrite or oxygen.
The reaction apparatus will be specifically described with reference to examples.
As shown in fig. 2, the bioautotrophic denitrification apparatus for sulfur battery charging and discharging according to the embodiment of the present invention includes an anaerobic membrane biofilm reactor (AnMBR) 21 and a Membrane Aerated Biofilm Reactor (MABR) 22. The anaerobic membrane biofilm reactor 21 is composed of a first reactor 212 made of cylindrical organic glass, the effective volume is 2.35L,wherein a first membrane module 211 is provided. The first membrane module 211 consists of 38 microfiltration membranes having a length of 70 cm. The first reactor 212 is also provided with an air bag 210 which is communicated with the interior of the first reactor 212 through a silicone tube. The gas bag 210 is filled with a part of nitrogen gas for equalizing the pressure inside the first reactor 212. While a 5 watt submersible pump (not shown) is provided in the first reactor 212 to ensure that the liquids therein are in a fully mixed state. Sewage is pumped from the bottom of the first reactor 212 by a water inlet pump 213, sulfate radicals in the sewage are reduced into sulfate reduction products under the action of Sulfate Reducing Bacteria (SRB) in the anaerobic membrane biological membrane reactor 21, and COD is converted into bicarbonate radical (HCO) as an electron donor in the sulfate reduction process 3 - ) Is removed, and the sulfur battery is charged. The sulphate reduction product rich effluent is filtered through a first membrane module 211 and pumped into a Membrane Aerated Biofilm Reactor (MABR) 22 by a water production pump 214. The membrane-aerated biofilm reactor 22 comprises two cylindrical second reactors 221 made of glass and having an effective volume of 62mL. The second reactors 221 are each provided with a second membrane module 222 having one end closed and the other end penetrating therethrough. The second membrane module 222 is composed of 35 polypropylene (PP) dense hollow fiber membranes having a length of 33 cm, and an effective membrane area of 155.4 cm square. The seal cock 220 fixes the second membrane module 222 to the second reactor 221, and seals the second reactor 221. An oxygen cylinder 225 communicates with the second membrane module 222 through a pressure relief valve 224 for providing oxygen within the membrane cavity. The sulfate-containing reduction product wastewater entering the membrane-aerated biofilm reactor 22 is rapidly and completely mixed in the second reactor 221 under the action of the internal circulation pump 223. The biofilm is attached to the surface of the fibrous membrane of the second membrane module 222. Wherein, the inner biomembrane is an aerobic layer, and oxidizes ammonia nitrogen in the sewage into nitrite nitrogen or nitrate nitrogen under the action of nitrobacteria; the outer biomembrane is anoxic or even anaerobic layer, and under the action of sulfur autotrophic denitrifying bacteria, the sulfate reduction product is used as an electron donor to reduce nitrite nitrogen or nitrate nitrogen into nitrogen gas, thereby achieving complete denitrification. In this process, the sulfate reduction product is further oxidized to sulfate, completing the sulfur cell discharge process. Through film exposureAfter the synchronous nitrification-sulfur autotrophic denitrification process (SNAD) treatment of the gas biofilm reactor 22, the sewage is discharged through an overflow port (not shown in the figure).
In this example, the composition of the wastewater used to carry out the process of the invention was as follows: KH (Perkin Elmer) 2 PO 4 53mg/L；K 2 HPO 4 18mg/L；CaCl 2 53.6mg/L；NH 4 Cl 191mg/L；MgCl 2 ·6H 2 O 100mg/L；CH 3 COONa 382.5mg/L；Na 2 SO 4 443.8mg/L, and the trace elements are as follows: feCl 3 ·6H 2 O 3.03mg/L；H 3 BO 3 0.3mg/L；CuSO 4 ·5H 2 O 0.06mg/L；KI 0.06mg/L；MnCl 2 ·4H 2 O 0.24mg/L；Na 2 MoO 4 ·2H 2 O 0.12mg/L；ZnSO 4 ·7H 2 O 0.24mg/L；CoCl 2 ·6H 2 O0.3 mg/L. In the sewage, the COD concentration is about 200mg/L, and sulfate ions SO 4 2- The concentration of (A) is about 100mg S/L, and the concentration of ammonia nitrogen is about 50mg N/L. Wherein the COD is determined by rapid digestion spectrophotometry. Sulfate, nitrate and nitrite were determined by ion chromatography. Ammonia nitrogen and sulfide were measured by colorimetric method.
In specific implementation, the anaerobic membrane biofilm reactor 21 and the membrane aeration biofilm reactor 22 are inoculated with a certain amount of sludge taken from a secondary sedimentation tank of a certain sewage treatment plant, and then domestication and biofilm formation are respectively carried out. For AnMBR, sewage containing COD, ammonia nitrogen and sulfate radicals is continuously introduced, the Hydraulic Retention Time (HRT) is kept for 12 hours, and enrichment culture of sulfate reducing bacteria is carried out. After the AnMBR is stably operated, the AnMBR generally needs 30-40 days, effluent is successfully enriched with sulfide, and COD is kept at a low level.
For MABR, separate acclimation culture was also performed first. Firstly, continuously introducing sewage only containing ammonia nitrogen into the sewage to construct an inner layer of the nitrifying biological membrane. Then, sewage containing sulfide and ammonia nitrogen is introduced into the sewage, and an outer sulfur autotrophic denitrification biological film is constructed. The aeration pressure is adjusted to keep the dissolved oxygen concentration of the liquid phase main body of the reactor below 0.5mg/L so as to keep the activity of the sulfur autotrophic denitrifying bacteria. The concentrations of the inlet water sulfide and ammonia nitrogen are kept at 20mg S/L and 20mg N/L in the initial stage, the HRT is continuously shortened to 1 hour, and the concentrations of the outlet water sulfide and ammonia nitrogen are lower than 1mg/L after about 60 days. And then maintaining the HRT for 1 hour, and continuously increasing the sulfide concentration of the MABR feed water, wherein the removal conditions of the MABR on ammonia nitrogen, sulfide and total nitrogen under different feed water sulfide concentrations are respectively shown in a figure 3 and a figure 4. As can be seen from the figure, as the concentration of the sulfide in the feed water is increased from 20mg S/L to 50mg S/L, the removal of the sulfide is basically not influenced, and the removal rate is stabilized at 100 percent. The removal of ammonia nitrogen is inhibited to a certain extent at the initial stage, but the inhibition is gradually eliminated along with time, the final ammonia nitrogen of the effluent is still lower than 2mg/L, and the removal rate reaches more than 90%. This indicates that the biofilm in the MABR has formed a better layered membrane structure. The sulfur autotrophic denitrifying bacteria positioned on the outer layer effectively protect the nitrifying bacteria on the inner layer from being poisoned by sulfides, so that the MABR keeps high-efficiency nitrification capability. The total nitrogen removal was low at a feed water sulfide of 20mg S/L, around 30%. With the increase of the concentration of the sulfide to 50mg S/L, the total nitrogen removal rate reaches over 90 percent, and the total nitrogen of effluent is lower than 2mg/L. This indicates that the nitrogen removal efficiency is greatly affected by the sulfur-nitrogen ratio, and the sulfur-nitrogen ratio is preferably higher than 0.9 (molar ratio). At the moment, the MABR already has high-efficiency synchronous nitrification-sulfur autotrophic denitrification capability, and can efficiently remove ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the sewage. Meanwhile, sulfur balance analysis and spectral analysis show that when the concentration of the inlet water sulfide is 50mg S/L, elemental sulfur accumulation exists in the biological membrane. In-situ batch experiments prove that the elemental sulfur can be used as an electron donor again to promote the sulfur autotrophic denitrification when sulfide is deficient as an electron and energy storage body.
In the next stage, the AnMBR effluent with stable operation is introduced into the MABR, and the operation efficiency of the whole system is measured. At this time, the influent of the AnMBR contained 200mg/L COD,100mg S/L sulfate, 50mg N/L ammonia nitrogen. FIG. 5 shows COD and total nitrogen removal for the AnMBR-MABR system. The results show that the system has high-efficiency COD and total nitrogen removal capacity, the average COD and total nitrogen removal rate reaches over 85 percent and 75 percent, the effluent COD is lower than 40mg/L, and the total nitrogen is lower than 12mg/L. The denitrification load reaches 0.9kg N/m 3 And d. The total nitrogen in the effluent is in the form of nitrate nitrogen as the main nitrogen, and the proportion of the total nitrogen is more than 95 percent. At the moment, the carbon-nitrogen ratio of inlet water is about 4, and the quality of outlet water reaches the first grade A standard in discharge Standard of pollutants for municipal wastewater treatment plant (GB 18918-2002). The average electron utilization efficiency in the denitrification process reaches about 60 percent. The biological autotrophic nitrogen removal process under the charging and discharging of the sulfur battery has advantages in the treatment of the saline wastewater with low carbon-nitrogen ratio.
Calculating the sludge yield of the reaction system shown in the figure 2, wherein the sludge yield of the sulfate reduction process performed by the AnMBR is 0.25g VSS/g COD; the sludge yield of the SNAD process executed by the MABR is 0.024g VSS/g TN, which is far lower than that of the traditional activated sludge treatment process. While the overflow of the MABR is substantially free of suspended solids.
Further, the microbial community structure analysis was performed on the biofilm in the MABR, and the results are shown in fig. 6. Thiobacillus is the major sulfide oxidizing bacterium. The bacteria can use oxygen as an electron acceptor, and can also use nitrate or nitrite as an electron donor. Nitrospira is the major ammonia oxidizing bacterium. In the SNAD process performed by the MABR, nitrospira and Thiobacillus perform a nitrification process and a sulfur autotrophic denitrification process, respectively. Meanwhile, a large number of heterotrophic bacteria such as Denitratisoma, defluviii monas and the like are found in the biofilm. This suggests that in MABR there may also be a heterotrophic denitrification process, contributing to the removal of total nitrogen.
The results show that the biological autotrophic nitrogen removal process and the method thereof under the charge and discharge of the sulfur battery carry out a sulfate reduction process through the AnMBR to remove COD, complete a charging process, store electrons in sulfides, then the sulfides enter the MABR to carry out a synchronous nitrification-sulfur autotrophic denitrification process, ammonia nitrogen and generated nitrate or nitrite are synchronously removed, the sulfides are further oxidized into sulfate, and a discharging process is completed. The sludge yield in the whole denitrification process is extremely low, and the sludge treatment cost is effectively reduced. And meanwhile, an MABR bubble-free aeration technology is adopted, so that the aeration energy consumption is greatly reduced, and the upper layered biomembrane structure of the MABR ensures that nitrification and denitrification are carried out in the same space, so that the backflow energy consumption is avoided, and the occupied land is further saved. AnMBR and MABR are the membrane technology, can carry out the modularization operation, and the technology integrated level is high, can to a great extent satisfy future sewage treatment demand.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (10)
1. A biological autotrophic nitrogen removal device under the charge and discharge of a sulfur battery is characterized by comprising an anaerobic membrane bioreactor (21) for sulfate reduction and a membrane aeration biomembrane reactor (22) for realizing synchronous nitrification and sulfur autotrophic denitrification; the water outlet of the anaerobic membrane bioreactor (21) is communicated with the water inlet of the membrane aeration biomembrane reactor (22) and is used for introducing sulfate reduction products in the wastewater into the membrane aeration biomembrane reactor (22).
2. The bioautotrophic denitrification device with charging and discharging of sulfur batteries according to claim 1, wherein the sulfate reduction product is one or more of sulfide, soluble elemental sulfur, thiosulfate, and sulfite.
3. The bioautotrophic denitrification device under charge and discharge of sulfur batteries according to claim 1, characterized in that a sewage circulation pipeline for enabling sewage in the anaerobic membrane bioreactor (21) and the membrane aeration biofilm reactor (22) to be in a completely mixed state is arranged in each of the anaerobic membrane bioreactor and the membrane aeration biofilm reactor.
4. The bioautotrophic denitrification apparatus for sulfur battery charging and discharging according to claim 1, characterized in that the upper part of the membrane-aerated biofilm reactor (22) is provided with an overflow outlet for discharging treated purified water.
5. The bioautotrophic denitrification apparatus with charging and discharging of sulfur battery as recited in claim 1, wherein the water outlet of the anaerobic membrane bioreactor (21) is communicated with the membrane aeration biofilm reactor (22) through a pipeline provided with a suction water pump.
6. The bioautotrophic denitrification device under charge and discharge of sulfur batteries according to claim 1, characterized in that the biofilm attached to the microporous membrane of the membrane-aerated biofilm reactor (22) has a layered structure to simultaneously perform nitrification and sulfur autotrophic denitrification processes; the inner layer of the biological membrane is an aerobic layer, and the outer layer is an anoxic or anaerobic layer.
7. A method for treating sewage by using the bioautotrophic denitrification apparatus under charge and discharge of the sulfur battery according to any one of claims 1 to 6, comprising:
introducing sewage to be treated containing organic matters, ammonia nitrogen and sulfate radicals into an anaerobic membrane bioreactor (21), reducing the sulfate radicals in the sewage into a sulfate reduction product through a sulfate reduction process, transferring electrons in the organic matters to the sulfate reduction product, and completing the charging and decarbonization processes of a sulfur battery; the sulfate reduction product is one or more of sulfide, soluble sulfur simple substance, thiosulfate and sulfite;
introducing the sewage treated by the anaerobic membrane bioreactor (21) into a membrane aeration biomembrane reactor (22); in a membrane aeration biomembrane reactor (22), ammonia nitrogen is oxidized into nitrate or nitrite by nitrifying bacteria positioned on the inner layer of the biomembrane through synchronous nitrification-sulfur autotrophic denitrification reaction by means of a layered biomembrane structure on a microporous membrane; the generated nitrate or nitrite is reduced into nitrogen by sulfur autotrophic denitrifying bacteria positioned on the outer layer of the biological membrane, and then is discharged and removed from the device, electrons in the sulfate reduction product are further transferred to nitrate or nitrite, the discharge of a sulfur battery and denitrification reaction are completed, and the treatment of sewage is realized.
8. The method according to claim 7, wherein the sewage to be treated is municipal sewage having a sulfate concentration of < 100mg S/L or industrial wastewater having a sulfate concentration of > 200mg S/L.
9. The sewage treatment method according to claim 7, wherein when the sewage to be treated is municipal sewage with sulfate concentration less than 100mg S/L, the effluent part of the membrane aeration bio-membrane reactor (22) is returned to the anaerobic membrane bioreactor (21) through a return line so that the molar ratio of sulfur to nitrogen in the influent water of the anaerobic membrane bioreactor (21) is maintained above 0.9.
10. The wastewater treatment method according to claim 7, wherein the dissolved oxygen concentration of wastewater in the membrane-aerated biofilm reactor (22) is controlled to be between 0.2 and 0.5 mg/L.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070163952A1 (en) * | 2004-01-30 | 2007-07-19 | Scheier Etal | Dissimilatory sulfate reduction as a process to promote denitrification in marine recirculating aquaculture systems |
| CN202849154U (en) * | 2012-09-19 | 2013-04-03 | 北京格瑞奥环境科技有限公司 | Novel anaerobic membrane bioreactor for treating high-sulfate organic wastewater |
| CN105565594A (en) * | 2015-12-16 | 2016-05-11 | 哈尔滨工业大学 | Device for removing carbon, nitrogen and sulfur in pharmaceutical wastewater through two MBBRs (moving bed bio-film reactors) and method utilizing device to treat pharmaceutical wastewater |
| CN108503026A (en) * | 2018-04-19 | 2018-09-07 | 中国矿业大学 | City secondary effluent sulfenyl matter recycles autotrophic denitrification method |
| CN112028237A (en) * | 2020-09-07 | 2020-12-04 | 北京理工大学 | Preparation of H by using anaerobic membrane bioreactor2Method for treating heavy metal wastewater and contaminated acid by using S |
| CN112723546A (en) * | 2021-01-29 | 2021-04-30 | 光大环保技术研究院（深圳）有限公司 | Biological treatment device for high-sulfate high-ammonia nitrogen content wastewater |
| CN113716689A (en) * | 2021-08-11 | 2021-11-30 | 中国长江三峡集团有限公司 | Mixed nutrition type denitrification method based on sulfur reduction and sulfur autotrophic denitrification |
| CN114751515A (en) * | 2022-05-05 | 2022-07-15 | 浙江大学 | Stable and efficient short-cut denitrification method and treatment device |
-
2022
- 2022-08-08 CN CN202210942625.4A patent/CN115259376A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070163952A1 (en) * | 2004-01-30 | 2007-07-19 | Scheier Etal | Dissimilatory sulfate reduction as a process to promote denitrification in marine recirculating aquaculture systems |
| CN202849154U (en) * | 2012-09-19 | 2013-04-03 | 北京格瑞奥环境科技有限公司 | Novel anaerobic membrane bioreactor for treating high-sulfate organic wastewater |
| CN105565594A (en) * | 2015-12-16 | 2016-05-11 | 哈尔滨工业大学 | Device for removing carbon, nitrogen and sulfur in pharmaceutical wastewater through two MBBRs (moving bed bio-film reactors) and method utilizing device to treat pharmaceutical wastewater |
| CN108503026A (en) * | 2018-04-19 | 2018-09-07 | 中国矿业大学 | City secondary effluent sulfenyl matter recycles autotrophic denitrification method |
| CN112028237A (en) * | 2020-09-07 | 2020-12-04 | 北京理工大学 | Preparation of H by using anaerobic membrane bioreactor2Method for treating heavy metal wastewater and contaminated acid by using S |
| CN112723546A (en) * | 2021-01-29 | 2021-04-30 | 光大环保技术研究院（深圳）有限公司 | Biological treatment device for high-sulfate high-ammonia nitrogen content wastewater |
| CN113716689A (en) * | 2021-08-11 | 2021-11-30 | 中国长江三峡集团有限公司 | Mixed nutrition type denitrification method based on sulfur reduction and sulfur autotrophic denitrification |
| CN114751515A (en) * | 2022-05-05 | 2022-07-15 | 浙江大学 | Stable and efficient short-cut denitrification method and treatment device |
Non-Patent Citations (1)
| Title |
|---|
| 庞庆庄等: "《农村污水处理技术及应用》", 辽宁科学技术出版社, pages: 7 - 9 * |
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