CN112479507B - Method for enrichment culture of anaerobic methane-oxidizing bacteria by using coupled biological-membrane-electrochemical waste gas and wastewater co-treatment device - Google Patents
Method for enrichment culture of anaerobic methane-oxidizing bacteria by using coupled biological-membrane-electrochemical waste gas and wastewater co-treatment device Download PDFInfo
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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
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- C02F3/005—Combined electrochemical biological processes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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
- C02F2101/00—Nature of the contaminant
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- C02F2101/101—Sulfur compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/166—Nitrites
Abstract
The invention provides a method for enriching and culturing anaerobic methane-oxidizing bacteria by using a coupled biological-membrane-electrochemical waste gas and wastewater synergistic treatment device, belonging to the technical field of environmental engineering. The method comprises the following steps: the device comprises a main reactor and a membrane separator, wherein the main reactor comprises a biological-electrochemical reaction area, and an aeration membrane component, a cathode plate and an anode plate are arranged in the biological-electrochemical reaction area. The method combines biological-electrochemical reaction with membrane separation, and adopts a membrane aeration mode to improve the mass transfer rate of methane from a gas phase to a liquid phase, thereby providing sufficient substrates for the growth and metabolism of anaerobic methane-oxidizing bacteria. By the auxiliary means of an external power supply, the electron transfer is enhanced, and the metabolic activity of the anaerobic methane-oxidizing bacteria is improved. Moreover, the invention adopts the membrane separator to effectively intercept anaerobic methane-oxidizing bacteria, and the biomass of the reaction system is retained to the maximum extent.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a coupled biological-membrane-electrochemical waste gas and wastewater co-treatment device, a co-treatment method and application thereof.
Background
In the solid waste treatment and disposal processes of refuse landfill, compost, sludge concentration, anaerobic sludge digestion and the like, a large amount of volatile organic compounds are released. Volatile organic compounds seriously damage human health and the ecological environment. Most volatile organic compounds have peculiar smell, such as styrene, dichloromethane and triethylamine, which irritate olfactory organs of human bodies and cause unpleasant sense. High concentrations of volatile organic compounds cause respiratory, skin, and conjunctival damage. Some volatile organic compounds have mutagenic, carcinogenic and teratogenic 'triple-triggering' effects, and belong to the priority control pollutants published by the U.S. Environmental Protection Agency (EPA). Prolonged exposure to benzene-containing air can lead to blood abnormalities and even leukemia. Methylene chloride mainly damages the human nervous system and can cause nausea, headache, epileptic seizures, and even respiratory arrest in the expositive. Chlorobenzene has inhibitory and anesthetic effects on the central nervous system, and is irritant to the skin and mucous membranes. Exposure to chlorobenzene at high concentrations can cause anesthetic symptoms and even coma. The volatile organic compounds dissipated into the atmosphere can generate photochemical reaction with nitrogen oxide, hydrocarbon and the like in the atmosphere under the irradiation of sunlight to generate photochemical smog.
Leachate and digested sludge dewatering liquid generated by landfill and composting contain high-concentration ammonia nitrogen, nitrate and sulfate. Excessive ammonia nitrogen is discharged into the water body to cause water eutrophication, and the ornamental value of the water body is reduced. Nitrate and nitrite which are oxidation products of ammonia nitrogen can also influence the normal growth of aquatic organisms; excessive intake of nitrite by humans can also cause blood hypoxia and cause cancer. Sulfate in the wastewater can cause acidification of the water body, and the conversion product hydrogen sulfide is corrosive and can corrode water pipelines. The fertilizer is discharged to the ground surface, the soil structure is damaged, and the soil fertility is reduced.
Therefore, the treatment of volatile organic compounds in the air and the denitrification and desulfurization of wastewater have been receiving much attention. The research on effective volatile organic compounds and nitrogen-containing and sulfur-containing wastewater treatment technology has important significance for ecological environment safety and human health.
The removal of volatile organic compounds in the air and the denitrification and desulfurization of wastewater are mainly converted into harmless or low-harmful substances such as carbon dioxide, water, nitrogen and the like through the following oxidation-reduction reaction. The essence of the redox reaction is the transfer of electrons. The oxidation of volatile organics can provide electrons, and the reduction of nitrates, nitrites, and sulfates requires the acquisition of electrons, schematically represented by the equations (1-4). Therefore, nitrate, nitrite and sulfate can be reduced by utilizing electrons provided by the oxidation process of the volatile organic compounds, so that the cooperative treatment of the volatile organic compounds and the wastewater containing nitrogen and sulfur is realized, and the schematic reaction formula is shown as (5-7).
CxHyOz→CO2+H2O+e- (1)
NO2 -+e-+H+→H2O+N2 (2)
NO3 -+e-+H+→CO2+H2O+N2 (3)
SO4 2-+e-+H+→CO2+H2O+S2-/S (4)
CxHyOz+NO3 -+H+→CO2+H2O+N2 (5)
CxHyOz+NO2 -+H+→CO2+H2O+N2 (6)
CxHyOz+SO4 2-+H+→CO2+H2O+S2-/S (7)
The biological method for treating volatile organic compounds is widely researched and applied due to the characteristics of low investment, low operating cost, no secondary pollution and the like. However, for volatile organic compounds that are hydrophobic or difficult to degrade, the treatment effect of conventional biological treatment techniques is often not ideal.
Disclosure of Invention
The invention provides a coupled biological-membrane-electrochemical cooperative treatment device for waste gas and waste water, a cooperative treatment method and application, which combine biological-electrochemical reaction and membrane separation and effectively improve the removal effect of volatile organic compounds in waste gas and nitrate, nitrite and sulfate in waste water. Meanwhile, the device can be used for enrichment culture of anaerobic methane-oxidizing bacteria.
The invention provides a method for enriching and culturing anaerobic methane-oxidizing bacteria by using a coupling type biological-membrane-electrochemical device for co-processing volatile organic compounds and wastewater containing nitrogen and sulfur, which comprises the following steps:
the device comprises a main reactor and a membrane separator, wherein the main reactor comprises a biological-electrochemical reaction area, and an aeration membrane component, a cathode plate and an anode plate are arranged in the biological-electrochemical reaction area;
adding an inoculum containing anaerobic methane-oxidizing bacteria and a culture solution into the biological-electrochemical reaction zone to obtain a mixed solution; wherein the inoculum further comprises at least one of denitrifying bacteria or sulfate reducing bacteria; the culture solution comprises at least one of nitrate, nitrite or sulfate;
methane is added into the biological-electrochemical reaction area through an aeration membrane component; during the enrichment culture period, anaerobic methane-oxidizing bacteria are attached to the anode to oxidize methane into carbon dioxide; denitrifying bacteria are attached to the cathode to reduce nitrate and nitrite into nitrogen; sulfate reducing bacteria are attached to the cathode to reduce sulfate into sulfur ions or elemental sulfur;
and after the mixed liquor is treated by the biological-electrochemical reaction, the mixed liquor enters a membrane separator for filtration, the filtered filtrate is directly discharged outside the membrane separator, and the filtered organisms are collected, wherein the organisms comprise anaerobic methane-oxidizing bacteria after enrichment culture, and the organisms further comprise at least one of denitrifying bacteria and sulfate reducing bacteria.
Further, the device also comprises a gas diversion area and a tail gas purification area, wherein the unconsumed methane in the biological-electrochemical reaction area and the gas generated by the metabolism of the microorganisms escape from the liquid phase to the gas phase, pass through the gas diversion area to reach the tail gas purification area, and are discharged after being adsorbed and purified by the filler.
Further, surplus methane in the bio-electrochemical reaction zone is utilized by being recycled into the bio-electrochemical reaction zone.
Further, the pH of the bio-electrochemical reaction zone is maintained at 7.0 to 7.5.
Preferably, the temperature of the bio-electrochemical reaction zone is controlled to be 10-38 ℃.
Further, the air supply pressure of the aeration membrane component is 0.01-0.06 MPa;
the aeration membrane component adopts a bubble-free aeration mode to carry out aeration.
Further, the anaerobic methane-oxidizing bacteria include anaerobic methane-oxidizing archaea, anaerobic methane-oxidizing bacteria;
further, in the mixed liquor of the bio-electrochemical reaction zone: the ratio of anaerobic methane oxidation archaea to total archaea is 0.5-95%, and the abundance is 1.0 × 102-5.0×1014copies L-1(ii) a The anaerobic methane-oxidizing bacteria account for 0-100% of the total bacteria, and have an abundance of 5.0 × 103-2.0×1014copies L-1(ii) a The denitrifying bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 2.0 × 102-1.0×1014copies L-1(ii) a The ratio of sulfate reducing bacteria to total bacteria is 0.5-95%, and the abundance is 5.0 × 102-2.0×1014copies L-1。
Further, the mixed solution comprises nutrient solution;
the nutrient solution comprises the following components: KHCO3 0.1-1.8g/L；CaCl2·2H2O 0.10-0.35g/L； MgSO4·7H2O 0.05-0.25g/L；KH2PO40.01-0.6 g/L; 0.1-1.5ml/L of trace elements;
preferably, the composition of the trace elements is: FeSO4·7H2O 2.85g/L；CoCl2·6H2O 0.120g/L； CuSO4 0.320g/L；H3BO3 0.015g/L；ZnSO4·7H2O 0.070g/L；MnCl2·4H2O 0.500g/L； NiCl2·6H2O 0.10g/L；SeO2 0.070g/L；Na2WO4·2H2O 0.050g/L；Na2MoO4 0.250g/L。
Further, in the enrichment culture process, the nutrient solution is added separately, and the adding frequency is 1-2 times per month.
Further, the apparatus comprises: a main reactor and a membrane separator;
the inner lower part of the main reactor is a biological-electrochemical reaction zone; an aeration membrane component for controlling the gas to be treated to enter and exit is arranged on one side in the biological-electrochemical reaction area, and a cathode plate and an anode plate which are connected with an external power supply are arranged on the other side in the biological-electrochemical reaction area;
the upper part in the main reactor is provided with a gas diversion area and a tail gas purification area; the upper part and the lower part in the main reactor are separated by a horizontal clapboard, and a first gap for conveying the gas after the biological-electrochemical reaction into a gas guide area is arranged between the horizontal clapboard and the inner wall of the main reactor; at least one vertical baffle plate is arranged between the gas guiding area and the tail gas purification area, and a second gap for conveying gas into the tail gas purification area is arranged between the vertical baffle plate and the inner wall of the main reactor or the horizontal partition plate; the tail gas purification area is internally provided with a filler;
the membrane separator is arranged on the outer side of the main reactor and is used for filtering and separating liquid treated by the main reactor.
The invention has the following advantages:
(1) the invention provides a coupled biological-membrane-electrochemical waste gas and wastewater cooperative treatment device, which combines biological-electrochemical reaction with membrane separation, and is provided with a main reactor and a membrane separator, wherein a biological-electrochemical reaction zone, a gas diversion zone and a tail gas purification zone are arranged in the main reactor; an aeration membrane component, a cathode plate and an anode plate are arranged in the biological-electrochemical reaction zone, waste gas enters the biological-electrochemical reaction zone through the aeration membrane component, waste water directly enters the biological-electrochemical reaction zone through a water inlet pipe, meanwhile, microorganisms in mixed liquid in the biological-electrochemical reaction zone can grow on the anode plate and the cathode plate respectively, auxiliary voltage can promote electron transfer, oxidation-reduction reaction is facilitated, and therefore the conversion effect of organic matters, nitrate, nitrite and sulfate is remarkably improved. Then, after being separated by a membrane separator, the waste water can be discharged. And the gas generated after the biological-electrochemical reaction can be purified through the gas guiding area and the tail gas purifying area, so that the environmental pollution is effectively reduced. The device is an integrated device formed by combining a coupling type biological-electrochemical conversion container and a solid-liquid membrane separation container, and has the advantages of compact structure, scientific structure and simple operation and maintenance.
(2) The method for the synergistic treatment of the volatile organic compounds and the wastewater containing nitrogen and sulfur combines the coupled biological-electrochemical conversion container and the solid-liquid film, and adopts a film aeration mode to effectively improve the mass transfer rate from the gas phase to the liquid phase. By the aid of an external power supply, electron transfer is enhanced, the conversion effect of organic matters, nitrate, nitrite and sulfate is improved, and the problem of poor waste water and waste gas removal effect is solved.
(3) The invention also provides a method for enrichment culture of anaerobic methane-oxidizing bacteria by using the coupled biological-membrane-electrochemical waste gas and wastewater synergistic treatment device, which combines biological-electrochemical reaction with membrane separation, improves the mass transfer rate of methane from a gas phase to a liquid phase by adopting a membrane aeration mode, and provides sufficient substrates for the growth and metabolism of the anaerobic methane-oxidizing bacteria. By the auxiliary means of an external power supply, the electron transfer is enhanced, and the metabolic activity of the anaerobic methane-oxidizing bacteria is improved. Moreover, the invention adopts the membrane separator to effectively intercept anaerobic methane-oxidizing bacteria, and the biomass of the reaction system is retained to the maximum extent.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural diagram of an apparatus according to an embodiment of the present invention;
description of reference numerals:
1-a main reactor;
11-biological-electrochemical reaction area, 111-cathode plate, 112-anode plate, 113-aeration membrane component, 114-air inlet pipe, 115-circulating air control valve, 116-air inlet control valve, 117-pressure gauge, 118-water inlet pipe, 119-pH and temperature monitoring composite electrode;
12-gas flow directing zone, 120-horizontal partition, 121-first gap, 122-second gap, 123-first vertical baffle, 124-second vertical baffle;
13-tail gas purification area, 131-gas distribution plate, 132-filler and 133-gas outlet;
2-a membrane separator;
20-circulating pump, 21-membrane separation element, 22-drain pipe and 23-sludge discharge port.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict. In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. The terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. The terms "mounted," "connected," and "coupled" are to be construed broadly and may, for example, be fixedly coupled, detachably coupled, or integrally coupled; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. When an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
In the prior art, when the waste gas containing volatile organic compounds and the wastewater containing nitrogen and sulfur are treated, the volatile organic compounds are in a gas phase, while nitrate, nitrite and sulfate are in a liquid phase, and the volatile organic compounds in the gas phase are converted by using the nitrate, nitrite and sulfate in the liquid phase, the processes of mass transfer from the gas phase to the liquid phase, diffusion in the liquid phase, microbial absorption and degradation and the like are often needed, wherein the gas/liquid mass transfer is the rate-limiting step of the whole process. In the case of hydrophobic substances such as methane, styrene, and methylene chloride, the mass transfer rate from the gas phase to the liquid phase is slow, and thus in practice, a problem of poor removal effect often arises.
The embodiment of the invention provides a coupled biological-membrane-electrochemical waste gas and wastewater cooperative treatment device, which combines biological-electrochemical reaction and membrane separation, and is provided with a main reactor and a membrane separator, wherein a biological-electrochemical reaction area, a gas diversion area and a tail gas purification area are arranged in the main reactor; an aeration membrane component, a cathode plate and an anode plate are arranged in the biological-electrochemical reaction area, waste gas enters the biological-electrochemical reaction area through the aeration membrane component, waste water directly enters the biological-electrochemical reaction area through a water inlet pipe, meanwhile, microorganisms (volatile organic matter oxidizing bacteria, anaerobic methane oxidizing archaea, anaerobic methane oxidizing bacteria, sulfate reducing bacteria and denitrifying bacteria with electric activity) in mixed liquid in the biological-electrochemical reaction area can respectively grow on the anode plate and the cathode plate, auxiliary voltage can promote electron transfer, redox reaction is facilitated, and therefore the conversion effect of organic matters, nitrate, nitrite and sulfate is remarkably improved. Then, after being separated by a membrane separator, the waste water can be discharged. And the gas generated after the biological-electrochemical reaction can be purified through the gas guiding area and the tail gas purifying area, so that the environmental pollution is effectively reduced.
The coupled biological-membrane-electrochemical waste gas and wastewater cooperative treatment device provided by the embodiment of the invention is an integrated device formed by combining a coupled biological-electrochemical conversion container and a solid-liquid membrane separation container, and has the advantages of compact structure, scientific structure and simple operation and maintenance.
The embodiment of the invention provides a device for coupled biological-membrane-electrochemical synergistic treatment of volatile organic compounds and nitrogen-containing and sulfur-containing wastewater, which comprises a main reactor 1 and a membrane separator 2;
the inner lower part of the main reactor 1 is a biological-electrochemical reaction zone 11; an aeration membrane assembly 113 for controlling the gas to be treated to enter and exit is arranged on one side in the biological-electrochemical reaction zone 11, and a cathode plate 111 and an anode plate 112 connected with an external power supply are arranged on the other side in the biological-electrochemical reaction zone 11;
the upper part in the main reactor 1 is provided with a gas diversion area 12 and a tail gas purification area 13; the upper part and the lower part in the main reactor 1 are separated by a horizontal clapboard 120, and a first gap 121 for conveying the gas after the biological-electrochemical reaction into the gas guiding area 12 is arranged between the horizontal clapboard 120 and the inner wall of the main reactor; at least one vertical baffle plate is arranged between the gas guiding area 12 and the tail gas purification area 13, and a second gap 122 for conveying gas into the tail gas purification area 13 is arranged between the vertical baffle plate and the inner wall of the main reactor 1 or the horizontal partition plate 120; the tail gas purification area 13 is internally provided with a filler 132;
the membrane separator 2 is arranged outside the main reactor 1 and is used for filtering and separating the liquid treated by the main reactor 1.
As shown in fig. 1, in some embodiments of the present invention, within the bio-electrochemical reaction zone 11:
the air inlet end of the aeration membrane module 113 is connected with an external air source through an air inlet pipe 114. Specifically, an intake control valve 116 and a pressure gauge 117 are provided on the intake pipe 114.
The air outlet end of the aeration membrane module 113 is connected with an air inlet pipe 114 through a first circulating pipeline. And a circulation gas control valve 115 for controlling gas circulation is arranged on the first circulation pipeline.
The membrane of the aeration membrane module 113 may be a hollow fiber membrane, a flat sheet membrane, a tubular membrane or a spiral membrane. The membrane aperture of the aeration membrane component is 0.01-50 μm. The membrane material of the aeration membrane module 113 may be polyvinylidene fluoride, polypropylene, or the like. When aeration membrane module 113 is a hollow fiber membrane, the membrane specific surface of the hollow fiber membrane may be 15 to 25m2 m-3. The aeration membrane component mainly realizes the aeration function, and microorganisms are not easy to attach to the aeration membrane component.
And a pH and temperature monitoring composite electrode 119 is also arranged in the biological-electrochemical reaction zone 11. The pH and temperature monitoring composite electrode can be used for detecting the pH and the temperature of the mixed liquid in the biological-electrochemical reaction zone 11.
Specifically, the cathode plate 111 is positioned above the anode plate 112. The distance between the cathode plate 111 and the anode plate 112 is 1-50 cm.
The anode plates 112 are one or more groups. The anode plate is in a net or rectangular shape and can be folded or bent. The included angle between the anode plate and the bottom plane is 0-60 degrees. The anode plate is made of materials including but not limited to titanium, carbon cloth and carbon felt. Preferably, the anode is made of a combination of a titanium mesh as a support of the carbon cloth and a carbon cloth bent and folded to increase the attachment area of microorganisms.
The cathode plate 111 is one or more groups. The cathode plate is in the shape of a mesh or a rectangle and can be folded or bent. The included angle between the cathode plate and the bottom plane is 0-60 degrees. The material of the cathode plate includes but is not limited to titanium, carbon cloth and carbon felt. Preferably, the cathode is made of a combination of a titanium mesh as a support of the carbon cloth and a carbon cloth bent and folded to increase the microorganism attachment area.
A mixed liquid is arranged in the biological-electrochemical reaction zone 11; the mixed liquid includes electroactive microorganisms. The electroactive microorganisms comprise volatile organic matter oxidizing bacteria, anaerobic methane oxidizing archaea, anaerobic methane oxidizing bacteria, sulfate reducing bacteria and denitrifying bacteria with electrical activity; wherein the volatile organic compound oxidizing bacteria are microorganisms which oxidize conventional non-methane organic compounds.
It is to be noted that an electroactive microorganism is in particular a microorganism capable of transferring electrons across a cell membrane, both from the inside to the outside of the cell and from the outside to the inside of the cell.
In the embodiment of the invention, the electroactive biomembrane growing on the anode plate can exchange electrons with the conductive material through oxidation reaction; the electroactive biomembrane growing on the cathode plate can perform electron transfer with the electrode and reduce nitrate, nitrite and sulfate. The electron transfer is enhanced by applying an external power supply to the anode plate and the cathode plate, so that the conversion effect of the refractory volatile organic compounds is enhanced.
Specifically, volatile organic matter oxidizing bacteria, anaerobic methane oxidizing archaea and anaerobic methane oxidizing bacteria with electric activity are attached to the anode plate. The ratio of anaerobic methane oxidation archaea to total archaea is 0.5-95%, and the abundance is 1.0 × 105-5.0×1015copies g-1(ii) a The anaerobic methane-oxidizing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 5.0 × 105-2.0×1015copies g-1。
Sulfate reducing bacteria and denitrifying bacteria with electric activity are attached to the negative plate. The denitrifying bacteria accounts for 0.5-95% of the total bacteria,the abundance ratio is 2.0 × 105-1.0×1015copies g-1(ii) a The sulfate reducing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 1.0 × 105-8.0×1015copies g-1。
In the mixed liquid of the biological-electrochemical reaction zone: the ratio of anaerobic methane oxidation archaea to total archaea is 0.5-95%, and the abundance is 1.0 × 102-5.0×1014copies L-1(ii) a The anaerobic methane-oxidizing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 5.0 × 103-2.0×1014copies L-1(ii) a The denitrifying bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 2.0 × 102-1.0×1014copies L-1(ii) a The sulfate reducing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 5.0 × 102-2.0×1014copies L-1。
Because the microbial strains are complex, the mixed liquor also comprises microorganisms without electric activity and part of conventional strains. That is, the above microorganisms include all of volatile organic matter oxidizing bacteria, anaerobic methane-oxidizing archaea, anaerobic methane-oxidizing bacteria, denitrifying bacteria, sulfate-reducing bacteria, etc. in the mixed liquor, including electrically active and non-electrically active microorganisms.
The mixed solution also comprises nutrient solution. The nutrient solution comprises KHCO3 0.1-1.8g/L； CaCl2·2H2O 0.10-0.35g/L；MgSO4·7H2O 0.05-0.25g/L；KH2PO40.01-0.6 g/L; 0.1-1.5ml/L of trace elements.
The mixed solution also comprises nitrogen-sulfur wastewater to be treated and the like which are added into a biological-electrochemical reaction zone of the main reactor.
The main reactor 1 can be made of plexiglas plate or plastic plate.
As shown in FIG. 1, in some embodiments of the present invention, the lower portion of the main reactor 1 is a bio-electrochemical reaction zone 11; the upper part is a gas diversion area 12 and a tail gas purification area 13, which specifically comprises the following components:
one end of the horizontal partition 120 is fixedly connected with the inner wall of the main reactor 1, and a first gap 121 is arranged between the other end of the horizontal partition 120 and the inner wall of the main reactor 1.
The vertical baffles include a first vertical baffle 123 and a second vertical baffle 124; the first vertical baffle 123 is fixed to the horizontal partition 120, and the second vertical baffle 122 is adjacent to the packing 132 and fixed to the inner wall of the main reactor 1.
The bottom of the packing 132 is provided with a gas distribution plate 131. The gas distribution plate 131 is provided with openings. The gas distribution plate 131 is mainly used to disperse the gas from the gas guiding area 12 into the exhaust gas purifying area 13. The aperture of the gas distribution plate is 1-300 mm; preferably, the gas distribution plate 131 has a hole diameter of 2 to 100 mm. The top of the main reactor 1 is provided with a gas outlet 133, the gas outlet 133 is positioned at the top of the tail gas purification area, and the gas treated by the filler 132 is discharged from the gas outlet 133.
The filler can comprise one or more than two of active carbon, molecular sieve, volcanic rock, perlite, polyurethane foam, Raschig rings and polyethylene plastic balls. Preferably, the filler is a rough and porous material with a specific surface area of 150-2(ii)/g, porosity of 30-99%.
As shown in fig. 1, in some embodiments of the present invention, the main reactor 1 is in communication with the membrane separator 2, specifically:
the water inlet on the membrane separator 2 is connected with the water outlet on the main reactor 1 and positioned in the biological-electrochemical reaction area through a connecting pipe; preferably, a circulation pump 20 is provided on the connection pipe.
The bottom of the membrane separator 2 is provided with a sludge discharge port 23, and the sludge discharge port 23 is communicated with a water inlet pipe 118 arranged on the main reactor 1 through a second circulating pipeline. The water inlet pipe 118 is provided with a water pump for pumping the water to be treated into the bio-electrochemical reaction zone 11.
A membrane separation element 21 is provided in the membrane separator 2. Further, the membrane separation element 21 is a hollow fiber membrane, a flat membrane, a tubular membrane or a spiral membrane. Furthermore, the membrane material is polyvinylidene fluoride or polysulfone, and the membrane aperture of the membrane separation component is 0.02-0.45 μm.
The water outlet end of the membrane separation element 21 discharges the treated liquid out of the membrane separator 2 through a drain 22. And a water outlet pump is arranged on the water outlet pipe 22.
Furthermore, the external power supply is a direct current stabilized power supply and can provide 0-1.6V voltage. In the embodiment of the invention, the membrane separation component can effectively intercept microorganisms in the mixed solution, the degradation function of volatile organic compounds, the growth generation period of denitrifying bacteria and sulfate reducing bacteria is long, and the microorganism enrichment difficulty is high. By adopting the membrane separation technology, functional microorganisms can be effectively intercepted, the growth of the microorganisms is facilitated, the biomass in a biological reaction zone is maintained, and the treatment effect is ensured. Meanwhile, macromolecular substances can be filtered out, and the effluent quality is greatly improved.
The embodiment of the invention also provides a method for cooperatively treating volatile organic compounds and nitrogen-containing and sulfur-containing wastewater by using the device, which comprises the following steps:
adding nitrogen-sulfur containing wastewater to be treated and microorganisms into a biological-electrochemical reaction zone to form a mixed solution; the microorganisms comprise volatile organic matter oxidizing bacteria, anaerobic methane oxidizing archaea, anaerobic methane oxidizing bacteria, sulfate reducing bacteria and denitrifying bacteria;
an aeration membrane component, a cathode plate and an anode plate are arranged in the biological-electrochemical reaction area; after entering the biological-electrochemical reaction zone through the aeration membrane component, the volatile organic compounds are diffused to the anode plate and oxidized by the volatile organic compound oxidizing bacteria, anaerobic methane oxidizing archaea and anaerobic methane oxidizing bacteria with electric activity attached to the anode plate; nitrate radical and nitrite radical in the nitrogen-containing and sulfur-containing wastewater are reduced into nitrogen by the denitrifying bacteria with electrical activity attached to the negative plate, and sulfate in the nitrogen-containing and sulfur-containing wastewater is reduced into hydrogen sulfide or sulfur simple substance by the sulfate reducing bacteria with electrical activity attached to the negative plate;
in the mixed liquid in the biological-electrochemical reaction zone, volatile organic matter oxidizing bacteria, anaerobic methane oxidizing archaea and anaerobic methane oxidizing bacteria convert the volatile organic matter, denitrifying bacteria reduce nitrate radical and nitrite radical as nitrogen by taking the volatile organic matter as an electron donor, and sulfate reducing bacteria reduce sulfate radical to hydrogen sulfide or elemental sulfur by taking the volatile organic matter as the electron donor;
the mixed solution is treated by a biological-electrochemical reaction and then enters a membrane separator for filtration; and directly discharging the filtered filtrate to the outside of the membrane separator, and refluxing the filtered organisms to a biological-electrochemical reaction zone for reuse or collection, wherein the organisms comprise a mixture formed by volatile organic matter oxidizing bacteria, anaerobic methane oxidizing archaea, anaerobic methane oxidizing bacteria, denitrifying bacteria and sulfate reducing bacteria.
Furthermore, microorganisms are attached to the filler for growth, and volatile organic compounds are further degraded and purified by the microorganisms attached to the filler. The microorganism to be attached for growth may be Sporothrix (Sporothrix), Rhodococcus (Rhodococcus), (Pseudomonas), Bacillus (Bacillus), Geobacter (Geobacter), etc.
Further, the pH of the bio-electrochemical reaction zone is maintained at 7.0 to 7.5.
Further, the temperature of the bio-electrochemical reaction zone is controlled at 10-38 ℃.
Furthermore, the biological-electrochemical reactor area can not be filled with oxygen, and the liquid is blown off by 99.99 percent of high-purity nitrogen for not less than 20min before entering, so that the water inlet is ensured to be anaerobic.
Furthermore, the cathode plate and the anode plate are connected with an external power supply, the external power supply is a direct current stabilized power supply, and the direct current stabilized power supply can provide 0-1.6V voltage.
Further, the air supply pressure of the aeration membrane component is 0.01-0.06 MPa.
Furthermore, the aeration membrane component adopts a micro-bubble or bubble-free mode for aeration.
Further, the mixed liquor also comprises nutrient solution.
Further, the nutrient solution composition comprises KHCO3 0.1-1.8g/L；CaCl2·2H2O 0.10-0.35g/L； MgSO4·7H2O 0.05-0.25g/L；KH2PO40.01-0.6 g/L; 0.1-1.5ml/L of trace elements;
the composition of the trace elements comprises: FeSO4·7H2O 2.85g/L；CoCl2·6H2O 0.120g/L； CuSO40.320g/L；H3BO3 0.015g/L；ZnSO4·7H2O 0.070g/L；MnCl2·4H2O 0.500g/L； NiCl2·6H2O 0.10g/L；SeO2 0.070g/L；Na2WO4·2H2O 0.050g/L；Na2MoO4 0.250g/L。
Further, anaerobic methane-oxidizing archaea and anaerobic methane-oxidizing bacteria are mainly attached to the anode, the anaerobic methane-oxidizing archaea accounts for 0.5-95% of the total archaea, and the abundance is 1.0 multiplied by 105-5.0×1015copies g-1(ii) a The anaerobic methane-oxidizing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 5.0 × 105-2.0×1015copies g-1；
Further, denitrifying bacteria are attached to the cathode, accounting for 0.5-95% of the total bacteria, and the abundance is 2.0 × 105-1.0×1015copies g-1(ii) a Sulfate reducing bacteria attached to the cathode in the ratio of 0.5-95% and abundance of 1.0 × 105-8.0×1015copies g-1；
Further, in the mixed liquor of the bio-electrochemical reaction zone: the ratio of anaerobic methane oxidation archaea to total archaea is 0.5-95%, and the abundance is 1.0 × 102-5.0×1014copies L-1(ii) a The anaerobic methane-oxidizing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 5.0 × 103-2.0×1014copies L-1(ii) a The denitrifying bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 2.0 × 102-1.0×1014copies L-1(ii) a The sulfate reducing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 5.0 × 102-2.0×1014copies L-1。
Further, the filtrate is pumped out of the membrane separator 2 through a water discharge pipe 22 by a water discharge pump, which may be continuous or intermittent; the flow rate of the effluent is 0.01-50L/min.
Further, the volatile organic compounds include styrene, dichloromethane, triethylamine, styrene, benzene, chlorobenzene, ethyl acetate, toluene, methyl mercaptan, monomethylamine, dimethylamine, trimethylamine, ethylenediamine, and the like.
Further, the nitrogen-containing and sulfur-containing wastewater comprises ammonia nitrogen, nitrate, nitrite, sulfate, thiosulfate and the like.
Specifically, the method for cooperatively treating volatile organic compounds and wastewater containing nitrogen and sulfur by using the device for cooperatively treating volatile organic compounds and wastewater containing nitrogen and sulfur by using the coupled biological-membrane-electrochemical method comprises the following steps:
adding nitrogen-sulfur containing wastewater to be treated and microorganisms into a biological-electrochemical reaction zone to form a mixed solution; the microorganisms comprise volatile organic matter oxidizing bacteria, anaerobic methane oxidizing archaea, anaerobic methane oxidizing bacteria, sulfate reducing bacteria and denitrifying bacteria;
the volatile organic compounds enter the aeration membrane module 113 through the air inlet pipe 114, and enter the biological-electrochemical reaction area 11 through the aeration membrane module 113; in the biological-electrochemical reaction zone 11, volatile organic compounds diffuse to the anode plate and are oxidized by the volatile organic compound oxidizing bacteria with electric activity attached to the anode plate;
the wastewater containing nitrogen and sulfur enters the biological-electrochemical reaction zone 11 through the water inlet pipe 118, nitrate radicals and nitrite radicals in the wastewater are reduced into nitrogen by the denitrifying bacteria with electrical activity attached to the cathode plate, and sulfate in the wastewater is reduced into hydrogen sulfide or elemental sulfur by the sulfate reducing bacteria with electrical activity;
in the mixed liquid in the biological-electrochemical reaction zone 11, the volatile organic matter oxidizing bacteria convert the volatile organic matter, the denitrifying bacteria reduce nitrate radical and nitrite radical as nitrogen by taking the volatile organic matter as an electron donor, and the sulfate reducing bacteria reduce sulfate radical to hydrogen sulfide or sulfur simple substance by taking the volatile organic matter as the electron donor.
The mixed liquor is biologically purified through the biological-electrochemical reaction and is pumped to the membrane separator 2 through the circulating pump 20 for filtration; the filtered filtrate is pumped out of the membrane separator 2 by a water pump through a water discharge pipe 22; the organisms comprise a mixture formed by volatile organic matter oxidizing bacteria, denitrifying bacteria and sulfate reducing bacteria, and are discharged from the sludge discharge port 23 and returned to the biological-electrochemical reaction zone 11 through the circulating pipeline II or directly discharged.
The surplus volatile organic compound gas in the aeration membrane module 113 enters the biological-electrochemical reaction area 11 again through the circulating pipeline and the air inlet pipe 114 for conversion; the volatile organic compounds which enter the biological-electrochemical reaction zone 11 through the aeration membrane module 113 and are not completely oxidized and other gases generated by the metabolism of microorganisms enter the gas phase, enter the gas flow guide zone 12 through the first gap 121 upwards, pass through the second gap 122 from the gas flow guide zone 12, and enter the tail gas purification zone 13 through the gas flow distribution plate 131; after being purified by the packing 132, the exhaust gas is discharged from the gas outlet 133.
The embodiment of the invention also provides a method for carrying out enrichment culture on anaerobic methane-oxidizing bacteria by using the device for the coupled biological-membrane-electrochemical synergistic treatment of volatile organic compounds and nitrogen-containing and sulfur-containing wastewater.
In the prior art, anaerobic methane-oxidizing bacteria have harsh growth conditions, are sensitive to the environment, grow slowly and have long generation period, so the domestication and enrichment are long in time consumption and difficult.
By adopting the coupled biological-membrane-electrochemical waste gas and wastewater cooperative treatment device provided by the embodiment of the invention, the biological-electrochemical reaction and the membrane separation are combined, the mass transfer rate of methane from a gas phase to a liquid phase is improved by adopting a membrane aeration mode, and a sufficient substrate is provided for the growth and metabolism of anaerobic methane-oxidizing bacteria. By the auxiliary means of an external power supply, the electron transfer is enhanced, and the metabolic activity of the anaerobic methane-oxidizing bacteria is improved. Moreover, the invention adopts the membrane separator to effectively intercept anaerobic methane-oxidizing bacteria, and the biomass of the reaction system is retained to the maximum extent.
The embodiment of the invention also provides a method for carrying out enrichment culture on anaerobic methane-oxidizing bacteria by using the device for the coupled biological-membrane-electrochemical synergistic treatment of volatile organic compounds and nitrogen-containing and sulfur-containing wastewater, which comprises the following steps:
the device comprises a main reactor and a membrane separator, wherein the main reactor comprises a biological-electrochemical reaction area, and an aeration membrane component, a cathode plate and an anode plate are arranged in the biological-electrochemical reaction area;
adding an inoculum containing anaerobic methane-oxidizing bacteria and a culture solution into the biological-electrochemical reaction zone to obtain a mixed solution; wherein the inoculum further comprises at least one of denitrifying bacteria or sulfate reducing bacteria; the culture solution comprises at least one of nitrate, nitrite or sulfate;
methane is added into the biological-electrochemical reaction area through an aeration membrane component; during the enrichment culture period, anaerobic methane-oxidizing bacteria are attached to the anode to oxidize methane into carbon dioxide; denitrifying bacteria are attached to the cathode to reduce nitrate and nitrite into nitrogen; sulfate reducing bacteria are attached to the cathode to reduce sulfate into sulfur ions or elemental sulfur;
and after the mixed liquor is treated by the biological-electrochemical reaction, the mixed liquor enters a membrane separator for filtration, the filtered filtrate is directly discharged outside the membrane separator, and the filtered organisms are collected, wherein the organisms comprise anaerobic methane-oxidizing bacteria after enrichment culture, and the organisms further comprise at least one of denitrifying bacteria and sulfate reducing bacteria.
Further, the device also comprises a gas diversion area and a tail gas purification area, wherein the unconsumed methane in the biological-electrochemical reaction area and the gas generated by the metabolism of the microorganisms escape from the liquid phase to the gas phase, pass through the gas diversion area to reach the tail gas purification area, and are discharged after being adsorbed and purified by the filler.
Further, surplus methane in the bio-electrochemical reaction zone is utilized by being recycled into the bio-electrochemical reaction zone.
Further, the pH of the bio-electrochemical reaction zone is maintained at 7.0 to 7.5.
Preferably, the temperature of the bio-electrochemical reaction zone is controlled to be 10-38 ℃.
Furthermore, the air supply pressure of the aeration membrane component is 0.01-0.06 MPa.
Furthermore, the aeration membrane component adopts a micro-bubble or bubble-free mode for aeration.
Further, the anaerobic methane-oxidizing bacteria include anaerobic methane-oxidizing archaea, anaerobic methane-oxidizing bacteria.
Further, in the mixed liquor of the bio-electrochemical reaction zone: the ratio of anaerobic methane oxidation archaea to total archaea is 0.5-95%Abundance ratio of 1.0X 102-5.0×1014copies L-1(ii) a The anaerobic methane-oxidizing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 5.0 × 103-2.0×1014copies L-1(ii) a The denitrifying bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 2.0 × 102-1.0×1014copies L-1(ii) a The sulfate reducing bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 5.0 × 102-2.0×1014copies L-1。
Further, the mixed solution comprises nutrient solution;
the nutrient solution comprises the following components: KHCO3 0.1-1.8g/L；CaCl2·2H2O 0.10-0.35g/L； MgSO4·7H2O 0.05-0.25g/L；KH2PO40.01-0.6 g/L; 0.1-1.5ml/L of trace elements;
preferably, the composition of the trace elements is: FeSO4·7H2O 2.85g/L；CoCl2·6H2O 0.120g/L； CuSO4 0.320g/L；H3BO3 0.015g/L；ZnSO4·7H2O 0.070g/L；MnCl2·4H2O 0.500g/L； NiCl2·6H2O 0.10g/L；SeO2 0.070g/L；Na2WO4·2H2O 0.050g/L；Na2MoO4 0.250g/L。
Further, in the enrichment culture process, the nutrient solution is added separately, and the adding frequency is 1-2 times per month. The nutrient solution is added regularly, so that the environmental disturbance is reduced, and a proper and stable environment is provided for the growth of anaerobic methane-oxidizing bacteria.
Further, the apparatus comprises: a main reactor 1 and a membrane separator 2;
the inner lower part of the main reactor 1 is a biological-electrochemical reaction zone 11; an aeration membrane assembly 113 for controlling the gas to be treated to enter and exit is arranged on one side in the biological-electrochemical reaction zone 11, and a cathode plate 111 and an anode plate 112 connected with an external power supply are arranged on the other side in the biological-electrochemical reaction zone 11;
the upper part in the main reactor 1 is provided with a gas diversion area 12 and a tail gas purification area 13; the upper part and the lower part in the main reactor 1 are separated by a horizontal clapboard 120, and a first gap 121 for conveying the gas after the biological-electrochemical reaction into the gas guiding area 12 is arranged between the horizontal clapboard 120 and the inner wall of the main reactor; at least one vertical baffle plate is arranged between the gas guiding area 12 and the tail gas purification area 13, and a second gap 122 for conveying gas into the tail gas purification area 13 is arranged between the vertical baffle plate and the inner wall of the main reactor 1 or the horizontal partition plate 120; the tail gas purification area 13 is internally provided with a filler 132;
the membrane separator 2 is arranged outside the main reactor 1 and is used for filtering and separating the liquid treated by the main reactor 1.
The present invention will be described in detail with reference to examples.
Example 1Culture method of denitrifying anaerobic methane-oxidizing bacteria
Fig. 1 is a diagram of a processing apparatus structure adopted in this embodiment. A device for the coupled biological-membrane-electrochemical synergistic treatment of volatile organic compounds and nitrogen-containing and sulfur-containing wastewater, which is made of organic glass, has the length, width and height of 15cm, 9cm and 20cm respectively. The inoculum is sludge containing denitrifying anaerobic methane-oxidizing bacteria (ANME-2d, M.oxyfera) cultured in the early stage of a laboratory. The applied auxiliary voltage is 0-1.6 v. The air supply pressure of the aeration membrane component is 0.03MPa, and the air supply is methane standard gas (concentration CH)495% of CO25%). The nitrite concentration in the system is detected two to three times every week, and the concentration is maintained between 0 and 40mg to N L-1。
Continuously running for 120d, and removing nitrogen at a rate of 30-150mg-N L-1d-1The oxidation rate of methane is 0.4-1.5mmol L-1d-1. The anode biomembrane denitrifying anaerobic methane oxidation archaea (ANME-2d) accounts for 5-88% of the total archaea, and the abundance is 1.2 multiplied by 108-5.3×109The ratio of copies/g, denitrifying anaerobic methane-oxidizing bacteria (M.oxyfera) to total bacteria is 6% -65%, and the abundance is 1.2X 108-1.2×109copies/g. The cathode biofilm denitrifying bacteria (Hypotrophium, Denitrisoma, Thiobacillus) accounts for 2% -50% of the total bacteria, and the abundance is 7.5 × 109-9.5×109The ratio of copies/g, denitrifying anaerobic methane oxidation archaea (ANME-2d) to total archaea is 1% -26%, and the abundance is 2.1X 107-5.3×109copies/g, denitrifying anaerobic methane-oxidizing bacteria (M. oxypera) account for 25% of the total bacteria, and the abundance is 3.7X 109copies/g。
Example 2Method for culturing sulfate type methane oxidation microorganisms
Fig. 1 is a diagram of a processing apparatus structure adopted in this embodiment. A device for the coupled biological-membrane-electrochemical synergistic treatment of volatile organic compounds and nitrogen-containing and sulfur-containing wastewater, which is made of organic glass, has the length, width and height of 15cm, 9cm and 20cm respectively. Taking anaerobic digestion sludge of a sewage treatment plant as domesticated inoculation sludge, adding the domesticated inoculation sludge into a serum bottle, and adding potassium sulfate into the serum bottle, wherein the sulfate radical concentration is 5000mg L-1And carrying out anaerobic culture for three months to obtain the domesticated sludge. Transferring the domesticated sludge to equipment for co-processing volatile organic compounds and nitrogen-containing and sulfur-containing wastewater by coupling type biology-membrane-electrochemistry. The applied auxiliary voltage was 1.1 v. The air supply pressure of the aeration membrane component is 0.05MPa, and the air supply is methane standard gas (CH)4Concentration 60% and He concentration 40%). The sulfate radical concentration in the initial reaction system was 3200mg L-1The concentration of sulfuric acid in the system was measured two to three times per week.
After continuous culture for 150 days, the sulfate concentration is reduced by 1323mg L-1. The anode biological membrane has the abundance of methane oxidation functionalized archaea (ANME-1, ANME-3) of 8.6 multiplied by 107copies/g, abundance of methane-oxidizing bacteria (Methylococcus, Methylomonas) is 1.3 × 108copies/g. The percentage of the cathode biological membrane sulfate reducing bacteria in the total bacteria is 36 percent, and the abundance is 6.2 multiplied by 108copies/g。
Example 3Culture method for co-culturing denitrifying and sulfate type methane oxidation microorganisms
Fig. 1 is a diagram of a processing apparatus structure adopted in this embodiment. A device for the coupled biological-membrane-electrochemical synergistic treatment of volatile organic compounds and nitrogen-containing and sulfur-containing wastewater, which is made of organic glass, has the length, width and height of 15cm, 9cm and 20cm respectively. Place for taking sewageTreating anaerobic digestion sludge as domesticated inoculating sludge, adding into a serum bottle, adding potassium sulfate into the serum bottle, wherein the sulfate radical concentration is 5000mg L-1And carrying out anaerobic culture for three months to obtain the domesticated sludge. Domesticated sludge and sludge containing denitrifying methane anaerobic oxidation microorganisms cultured in a laboratory are transferred into a device for the coupled biological-membrane-electrochemical co-treatment of volatile organic compounds and wastewater containing nitrogen and sulfur. The applied auxiliary voltage was 0.5 v. The air supply pressure of the aeration membrane component is 0.04MPa, and the air supply is methane standard gas (CH)4Concentration 60% and He concentration 40%). In the case of nitrite and sulfate as electron acceptors, the initial concentrations were 1165.76mg/L and 1930.75mg/L, respectively.
And continuously culturing for 180 d. Detecting the composition of an electrode biomembrane community, wherein the anode biomembrane comprises methane oxidation functionalized archaea (ANME-1, ANME-2d, Methanobacter, Methanosarcina) accounting for 60.4 percent of the total archaea, and the abundance of the archaea is 8.6 multiplied by 108The ratio of the archaea with the carbalkoxy function (ANME-2d) is 1.2 percent; the content of methane oxidation resisting bacteria (M.oxypera) in the total bacteria is 2.2%, and the abundance ratio is 2.3X 107copies/g. The sulfate reducing bacteria (Desucoccus) of the cathode biomembrane accounts for 6% of the total bacteria, and the abundance is 6.2 multiplied by 108copies/g。
Example 4Method for cooperatively treating methane, nitrate and nitrite
Fig. 1 is a diagram of a processing apparatus structure adopted in this embodiment. The length, width and height of the coupling type biological-membrane-electrochemical cooperative treatment equipment for volatile organic compounds and nitrogen-containing and sulfur-containing wastewater, which is made of plastic plates, are respectively 1.5m, 0.90m and 2.0 m. The air supply pressure of the aeration membrane component is 0.03MPa, and the methane inlet concentration is 3.58 multiplied by 104mg/m3, the inflow rate is 2L/min, the concentration of nitrate in the inflow water is 20mg-N/L, and the concentration of nitrite is 15mg N/L.
The methane concentration of the outlet gas is 6.5 multiplied by 103mg/m3The removal rate is 81.8 percent, and the emission of methane is lower than the pollutant emission standard of a national urban sewage treatment plant. The concentration of nitrate radical in the effluent is 1.2mg-N/L, the concentration of nitrate radical is 0.6mg-N/L, the removal rates are respectively 94.0 percent and 96.0 percentAnd the outlet gas concentration reaches the air pollutant emission standard established by the state. The ratio of anode biomembrane denitrifying anaerobic methane oxidation archaea (ANME-2d) to total archaea is 66%, and the abundance is 5.3 multiplied by 109copies/g, denitrifying anaerobic methane-oxidizing bacteria (M. oxypera) account for 35% of the total bacteria, and the abundance is 1.2X 109copies/g. The cathode biofilm denitrifying bacteria (Hypotrophium, Ignavobacterium, Rhodococcus, Thiobacillus) account for 50% of the total bacteria, and the abundance is 7.5 × 109The ratio of copies/g, denitrifying anaerobic methane oxidation archaea (ANME-2d) to total archaea is 26%, and the abundance is 5.3 multiplied by 108copies/g, denitrifying anaerobic methane-oxidizing bacteria (M. oxypera) account for 25% of the total bacteria, and the abundance is 3.7X 109copies/g。
Example 5Method for cooperatively treating methane, benzene, nitrate and sulfate
Fig. 1 is a diagram of a processing apparatus structure adopted in this embodiment. The device for the coupled biological-membrane-electrochemical synergistic treatment of volatile organic compounds and nitrogen-containing and sulfur-containing wastewater, which is made of organic glass, has the length, width and height of 1.0m, 0.60m and 1.8m respectively. The air supply pressure of the aeration membrane component is 0.05MPa, the inlet concentration of benzene and methane is 42.78mg/m3, 2.69 multiplied by 104mg/m3The flow rate of inlet water is 1.8L/min, the concentration of nitrate in inlet water is 30mg-N/L, and the concentration of sulfate radical is 260 mg/L.
The benzene and methane concentrations of the outlet gas are respectively 9.66mg/m3And 5.7X 103mg/m3The removal rates were 77.4% and 78.8%. The concentration of nitrate in effluent is 2mg-N/L, the removal rate is 93.3%, the concentration of sulfate is 101 mg/L, and the removal rate is 61.5%. The anode biomembrane anaerobic methane oxidation archaea (ANME-2, ANME-3, ANME-2d) accounts for 36% of the total archaea, and the abundance is 8.7 × 108copies/g, denitrifying anaerobic methane-oxidizing bacteria (M. oxypera) account for 5% of the total bacteria, and the abundance is 2.3X 108The bacillus (Geobacter) accounts for 10% of the total bacteria, and the abundance is 4.5 × 108The Bacillus (Bacillus) accounts for 10 percent of the total bacteria in the copies/g, and the abundance is 4.5 multiplied by 108copies/g. The total content of cathode biofilm denitrifying bacteria (Hyphomicbium) isThe ratio of bacteria is 8%, and the abundance is 3.2X 109copies/g, sulfate reducing bacteria (Desulfuripora, Desulfovibrio, Desulsporsinus) account for 10% of the total bacteria, with an abundance of 3.2 × 109The ratio of copies/g of archaea (ANME-2, ANME-3, ANME-2d) to total archaea is 2%, and the abundance is 5.3 × 108copies/g, denitrifying anaerobic methane-oxidizing bacteria (M. oxypera) account for 1% of the total bacteria, and the abundance is 3.7X 108copies/g。
Example 6Method for cooperatively treating methane, toluene, styrene, nitrate and sulfate
Fig. 1 is a diagram of a processing apparatus structure adopted in this embodiment. The length, width and height of the device for the coupled biological-membrane-electrochemical synergistic treatment of volatile organic compounds and nitrogen-containing and sulfur-containing wastewater, which is made of a glass steel plate, are respectively 1.6m, 1.0m and 2.1 m. The air supply pressure of the aeration membrane component is 0.04MPa, and the inlet concentration of methane, benzene and toluene is 7.69 multiplied by 104mg/m3,50.67mg/m3，39.76mg/m3. The flow rate of the inlet water is 2.5L/min, the concentration of nitrate in the inlet water is 63mg-N/L, and the concentration of sulfate radical in the inlet water is 320 mg/L.
The concentrations of methane, benzene and toluene in the discharged gas are respectively 7.7 multiplied by 103mg/m3，9.96mg/m3，8.65mg/m3The removal rates were 89.9%, 80.34% and 78.2%, respectively. The concentration of nitrate in the effluent is 2mg-N/L, the removal rate is 96.8%, the concentration of sulfate is 112mg/L, and the removal rate is 65.0%. The ratio of anode biomembrane denitrifying anaerobic methane oxidation archaea (ANME-1, ANME-2d) to total archaea is 16%, and the abundance is 1.7 multiplied by 108copies/g, denitrifying anaerobic methane-oxidizing bacteria (M. oxypera) account for 0.9% of the total bacteria, and the abundance is 3.6X 108The bacillus (Geobacter) accounts for 6% of the total bacteria, and the abundance is 2.3 × 109copies/g, the proportion of Pseudomonas (Pseudomonas) in the total bacteria is 8.1 percent, and the abundance is 3.2 multiplied by 109copies/g. The negative biomembrane denitrifying bacteria (Ignavibacter, Hyphomicrobium, Thiobacillus) account for 10.2% of the total bacteria, and the abundance is 5.6 multiplied by 109The total bacteria content of copies/g and sulfate reducing bacteria (Desulfovibrio, Desulfuripora) is 15.6%, and the abundance is 8.3 × 109The ratio of copies/g, denitrifying anaerobic methane oxidation archaea (ANME-2d) to total archaea is 0.3%, and the abundance is 1.3 multiplied by 107copies/g, denitrifying anaerobic methane-oxidizing bacteria (M. oxypera) account for 0.1% of the total bacteria, and the abundance is 5.7X 107copies/g。
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for enriching and culturing anaerobic methane-oxidizing bacteria by using a coupling type biological-membrane-electrochemical device for coprocessing volatile organic compounds and wastewater containing nitrogen and sulfur is characterized by comprising the following steps:
the device used in the method comprises a main reactor and a membrane separator, wherein the main reactor comprises a biological-electrochemical reaction area, and an aeration membrane component, a cathode plate and an anode plate are arranged in the biological-electrochemical reaction area;
adding an inoculum containing anaerobic methane-oxidizing bacteria and a culture solution into the biological-electrochemical reaction zone to obtain a mixed solution; wherein the inoculum further comprises at least one of denitrifying bacteria or sulfate reducing bacteria; the culture solution comprises at least one of nitrate, nitrite or sulfate;
methane is added into the biological-electrochemical reaction area through an aeration membrane component; during the enrichment culture period, anaerobic methane-oxidizing bacteria are attached to the anode to oxidize methane into carbon dioxide; denitrifying bacteria are attached to the cathode to reduce nitrate and nitrite into nitrogen; sulfate reducing bacteria are attached to the cathode to reduce sulfate into sulfur ions or elemental sulfur;
the mixed liquor enters a membrane separator for filtration after being treated by biological-electrochemical reaction, the filtered filtrate is directly discharged outside the membrane separator, and the filtered organism is collected, wherein the organism comprises anaerobic methane-oxidizing bacteria after enrichment culture, and the organism also comprises at least one of denitrifying bacteria and sulfate reducing bacteria;
the device used by the method specifically comprises the following steps: a main reactor and a membrane separator;
the inner lower part of the main reactor is a biological-electrochemical reaction zone; an aeration membrane component for controlling the gas to be treated to enter and exit is arranged on one side in the biological-electrochemical reaction area, and a cathode plate and an anode plate which are connected with an external power supply are arranged on the other side in the biological-electrochemical reaction area; the cathode plate (111) is positioned above the anode plate (112);
the upper part in the main reactor is provided with a gas diversion area and a tail gas purification area; the upper part and the lower part in the main reactor are separated by a horizontal clapboard, and a first gap for conveying the gas after the biological-electrochemical reaction into a gas guide area is arranged between the horizontal clapboard and the inner wall of the main reactor; at least one vertical baffle plate is arranged between the gas guiding area and the tail gas purification area, and a second gap for conveying gas into the tail gas purification area is arranged between the vertical baffle plate and the inner wall of the main reactor or the horizontal partition plate; the tail gas purification area is internally provided with a filler;
the membrane separator is arranged on the outer side of the main reactor and is used for filtering and separating liquid treated by the main reactor.
2. The method of claim 1,
the device also comprises a gas diversion area and a tail gas purification area, wherein the unconsumed methane in the biological-electrochemical reaction area and the gas generated by the metabolism of the microorganism are dissipated into the gas phase from the liquid phase, pass through the gas diversion area to reach the tail gas purification area, and are discharged after being adsorbed and purified by the filler.
3. The method of claim 1,
excess methane in the bio-electrochemical reaction zone is utilized by recycling into the bio-electrochemical reaction zone.
4. The method of claim 1,
the pH of the bio-electrochemical reaction zone is maintained at 7.0-7.5,
the temperature of the biological-electrochemical reaction zone is controlled at 10-38 ℃.
5. The method of claim 1,
the air supply pressure of the aeration membrane component is 0.01-0.06 Mpa;
the aeration membrane component adopts a bubble-free aeration mode to carry out aeration.
6. The method of claim 1,
the anaerobic methane-oxidizing bacteria include anaerobic methane-oxidizing archaea and anaerobic methane-oxidizing bacteria.
7. The method of claim 1,
in the mixed liquid of the biological-electrochemical reaction zone: the ratio of anaerobic methane oxidation archaea to total archaea is 0.5-95%, and the abundance is 1.0 × 102-5.0×1014copies L-1(ii) a The anaerobic methane-oxidizing bacteria account for 0-100% of the total bacteria, and have an abundance of 5.0 × 103-2.0×1014copies L-1(ii) a The denitrifying bacteria accounts for 0.5-95% of the total bacteria, and the abundance is 2.0 × 102-1.0×1014copies L-1(ii) a The ratio of sulfate reducing bacteria to total bacteria is 0.5-95%, and the abundance is 5.0 × 102-2.0×1014copies L-1。
8. The method of claim 1,
the mixed solution comprises nutrient solution;
the nutrient solution comprises the following components: KHCO3 0.1-1.8g/L；CaCl2·2H2O 0.10-0.35g/L；MgSO4·7H2O 0.05-0.25g/L；KH2PO40.01-0.6 g/L; 0.1-1.5ml/L of trace elements;
the trace elements comprise the following components: FeSO4·7H2O 2.85g/L；CoCl2·6H2O 0.120g/L；CuSO4 0.320g/L；H3BO3 0.015g/L；ZnSO4·7H2O 0.070g/L；MnCl2·4H2O 0.500g/L；NiCl2·6H2O 0.10g/L；SeO2 0.070g/L；Na2WO4·2H2O 0.050g/L；Na2MoO4 0.250g/L。
9. The method of claim 8,
in the enrichment culture process, the nutrient solution is added independently, and the adding frequency is 1-2 times per month.
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