CN114196534A - Carbon-based emission reduction of CO2Device and method for biologically synthesizing methane - Google Patents
Carbon-based emission reduction of CO2Device and method for biologically synthesizing methane Download PDFInfo
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 122
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 32
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Chemical group O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
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- 239000001257 hydrogen Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 3
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- 230000003570 biosynthesizing effect Effects 0.000 claims 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
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- 238000011084 recovery Methods 0.000 abstract description 3
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- 230000015572 biosynthetic process Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
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- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
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Abstract
Carbon-based emission reduction of CO2A device and a method for biologically synthesizing methane belong to the fields of carbon emission reduction and energy recovery. The main body of the biological filter tank is an annular tank body, the outer layer tank body of the annular tank body is a clean water tank, a biological anode, a porous matrix and a biological cathode are sequentially arranged in the inner layer tank body of the annular tank body from bottom to top, the inner layer tank body, the biological anode, the porous matrix and the biological cathode are combined to form the biological electrolytic tank filter tank, and the biological anode and the biological cathode are connected with an external circuit through copper wires; the one-way drain pipe fixedly penetrates through the upper part of the side wall of the biological electrolytic cell filter, the biological electrolytic cell filter is communicated with the clean water tank through the one-way drain pipe, the treated water drain pipe fixedly penetrates through the upper part of the side wall of the clean water tank, and the upper part of the biological electrolytic cell filter is communicated with the exhaust flue; one end of the water inlet pipeline passes through the clean water tank and the side wall of the biological electrolytic tank filter chamber and is communicated with the lower area of the biological anode. The invention utilizes CO2And the carbon source of the organic pollutants in the sewage is used for producing methane, so that the purposes of energy recovery and carbon emission reduction are achieved.
Description
Technical Field
The invention belongs to the field of carbon emission reduction and energy recovery, and provides a method for catalyzing CO by using a bioelectrochemical means2A technology for preparing methane, in particular to CO emission reduction based on carbon2An apparatus and method for the biosynthesis of methane.
Background
In recent years, the massive use of fossil energy has led to atmospheric CO2The content is increased, which causes a series of problems, and the urgent need is to solve the problem of greenhouse gas emission, namely CO2Is an important one of them. By using CO2Methane production is an effective technical means.
The traditional methane production device adopts the technical means of anaerobic digestion, and the means mainly utilizes acetic acid to produce methane and less utilizes CO2The purpose of carbon emission reduction cannot be achieved, the methane production efficiency is low, and actual detection shows that 0.42-0.45 Nm is generated by degrading 1kgCOD under the anaerobic condition3The methane content of the methane is about 60 percent, and the heat value of the methane is 21.52 multiplied by 103kJ/m3Left and right. The reason for the poor methane yield is: the anaerobic digestion process has the problem of acid accumulation, which affects methane bacteriaActivity; in the conventional anaerobic digestion process, raw material CO2Derived from decomposition of long-chain organic compounds, CO2The production is slow, and the methane production reaction can not be promoted; in the process of methane production by anaerobic digestion, most of the methane production reaction processes are subjected to CO production2、H2The methane bacterium further converts the intermediate product CO2、H2Conversion to methane, and CO2、H2The gas is difficult to participate in the reaction of methane bacteria for converting methane. According to the research of related personnel, reactants utilized by methane bacteria can be classified into three categories: acetic acid nutritional type; a methylotrophic form; h2、CO2And (4) nutrition type. The anaerobic digestion means mainly utilizes acetotroph methane bacteria to produce methane, but the acetotroph methane bacteria flora part of the strains still need to decompose the acetic acid into CO2、H2Is applied to directly utilize H2、CO2Few methane production approaches of nutritional methane bacteria have been studied. The MEC method introduced in recent years is used for producing methane, the anaerobic digestion process is strengthened, particularly the generation of hydrogen is strengthened, the problem of acid accumulation is solved, and a raw material is provided for methane bacteria. But for H2、CO2The method achieves high-efficiency utilization with corresponding methanobacteria, and particularly, the corresponding biological cathode has no relevant research.
Disclosure of Invention
The invention aims to utilize CO aiming at the traditional methane production device2Can not achieve the problems of carbon emission reduction and energy recycling, and provides a carbon emission reduction-based CO2An apparatus and method for the biosynthesis of methane.
The invention strengthens metabolism of methane bacteria by physical, chemical, biological, bioelectrochemical and other composite means, mainly utilizes the methane bacteria to realize the conversion of carbon dioxide and hydrogen protons to methane, achieves the purposes of carbon emission reduction and energy recycling, has the advantages of low operation cost, clean operation, high efficiency, environmental protection, carbon emission reduction and the like, and can better realize the aim of carbon emission reduction.
The invention uses methane bacteria as catalyst, and uses flue gas and organic waste water to produce methane, which is energy gas, to achieve the purpose of synchronously purifying flue gas, recycling organic waste water energy, and purifying outlet flue gas and organic waste water.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
carbon-based emission reduction of CO2The device for biologically synthesizing the methane comprises a biological filter main body, wherein the biological filter main body is an annular filter body, and an outer layer filter body of the annular filter body is a clean water tank; carbon-based CO emission reduction2The device for biologically synthesizing methane also comprises a water inlet unit and an exhaust and drainage unit; the exhaust and drainage unit comprises a one-way drainage pipe, a one-way valve I, an exhaust flue and a treated water drainage pipe; the water inlet unit comprises a water inlet pipeline;
the inner-layer tank body of the annular tank body is internally provided with a biological anode, a porous matrix and a biological cathode from bottom to top in sequence, the inner-layer tank body, the biological anode, the porous matrix and the biological cathode are combined to form a biological electrolytic tank filter, and the biological anode and the biological cathode are respectively connected with an external circuit through copper wires;
the one-way drain pipe fixedly penetrates through the upper part of the side wall of the biological electrolytic cell filter, the biological electrolytic cell filter is communicated with the clean water tank through the one-way drain pipe, the one-way drain pipe drains the treated water in the biological electrolytic cell filter into the clean water tank, a one-way valve I is arranged on the one-way drain pipe, the treated water drain pipe fixedly penetrates through the upper part of the side wall of the clean water tank, and the upper part of the biological electrolytic cell filter is communicated with the exhaust flue; one end of the water inlet pipeline passes through the side wall of the filter tank of the clean water tank and the biological electrolytic tank and is communicated with the lower area of the biological anode; the side wall of the biological electrolytic tank filter chamber is provided with a flue gas inlet communicated with the biological cathode.
Carbon-based emission reduction of CO2Carbon-based emission reduction CO realization of device for biologically synthesizing methane2A method for the biosynthesis of methane, said method comprising the steps of:
the method comprises the following steps: the organic wastewater flows into the bottom of a filter tank of the biological electrolytic cell through a water inlet pipeline and is distributed with water to run in an upflow manner;
step two: the organic wastewater passes through a biological anode, a porous matrix and a biological cathode from bottom to top, nitrobacteria on the biological anode convert ammonia nitrogenThe nitrate nitrogen and the acetic acid and the methyl compound are produced by the dominant flora of the acetic acid bacteria by using organic pollutants C O2Providing a precursor for methane bacteria, decomposing ammonia nitrogen and organic pollutants, and generating electric charge to be transferred to a biological anode;
step three: the organic wastewater flows through the biological cathode, methane bacteria and hydrogen bacteria on the biological cathode obtain electrons through the biological cathode, and H is extracted2、CO2And converting the methane into methane to realize the recycling of energy.
Compared with the prior art, the invention has the beneficial effects that:
1. by adopting the device, carbon and energy in the flue gas and the organic wastewater are recycled, methane is used as an energy source gas, and sustainable recycling of resources is realized;
2. the problem of low efficiency of the existing anaerobic fermentation methane production process is solved, and the methane yield is enhanced based on an electrochemical principle and electrode design;
3. solves the problem of raw material source of the prior anaerobic fermentation methane production process, and utilizes the flue gas mainly containing a large amount of CO2The gas is used as a carbon source to achieve the purpose of emission reduction.
4. The invention combines the water inlet unit, the exhaust and drainage unit and the biological electrolytic cell filter tank and cooperates with each other in function, and the invention can cooperatively recover the flue gas to produce methane and purify waste water and waste gas.
5. The biological anode is embedded with nitrifying and vulcanizing bacteria dominant flora, and the biological cathode is embedded with methane bacteria dominant flora; the biological cathode is a graphite felt wrapped array aeration iron-zinc oxide modified nickel tube electrode body which is hollow in the nickel tube electrode body, the nickel tube electrode body is formed by combining a nickel tube electrode tube plate and a plurality of aeration pore tubes which are arranged on the nickel tube electrode tube plate in an array mode, and CO is introduced into the nickel tube electrode body in the operation process through electrodeposition2Aerating to achieve the purpose of efficiently utilizing CO by methane bacteria2And the purpose of improving the energy recycling efficiency is achieved.
6. The biological cathode is a graphite felt wrapped array aeration iron zinc oxide modified nickel tube electrode body, and the methane production efficiency of the biological electrolytic tank filter is effectively improved.
7. The device of the invention adopts a modular design, and has convenient installation and simple replacement.
Drawings
FIG. 1 is carbon-based CO abatement of the present invention2A front view of a device for biosynthesis of methane;
FIG. 2 is a cross-sectional view of section B-B of FIG. 1;
FIG. 3 is a cross-sectional view of section D-D of FIG. 1;
fig. 4 is a partially enlarged view of fig. 1 at a.
The names and reference numbers of the components referred to in the above figures are as follows:
the device comprises a water inlet pipeline 1-1, a pump I1-2, a valve 1-3, a biological anode 2-1, a porous substrate 2-2, a copper wire 2-3, a biological cathode 2-4, a nickel tube electrode 2-5, an aeration hole tube 2-6, a graphite felt 2-7, a pump II 2-8, a one-way valve II 2-9, a flue gas inlet 2-10, a one-way drain pipe 3-1, a one-way valve I3-2, an exhaust flue 3-3 and a treated water drain pipe 3-4.
Detailed Description
The first embodiment is as follows: as shown in FIGS. 1-4, the present embodiment discloses a carbon-based CO emission reduction2The device for biologically synthesizing the methane comprises a biological filter main body, wherein the biological filter main body is an annular filter body, and an outer layer filter body of the annular filter body is a clean water tank; carbon-based CO emission reduction2The device for biologically synthesizing methane also comprises a water inlet unit and an exhaust and drainage unit; the exhaust and drainage unit comprises a one-way drainage pipe 3-1, a one-way valve I3-2, an exhaust flue 3-3 and a treated water drainage pipe 3-4; the water inlet unit comprises a water inlet pipeline 1-1;
the inner layer of the annular tank body is internally provided with a biological anode 2-1 (the biological anode 2-1 is used for inoculating predominant bacteria flora of acetic acid bacteria and nitrobacteria), a porous substrate 2-2 (the porous substrate 2-2 is made of cheap porous material, can be selected from any one of carbon fiber balls, multi-layer carbon felts, volcanic rock particles, carbon sponges and ceramic particles, and can also be selected from other materials with similar functions), the porous substrate 2-2 provides buffer for a biological cathode 2-4 and the biological anode 2-1, provides an inoculation space for the biological cathode 2-4 and the biological anode 2-1 bacteria and plays a part of water purification function), and the biological cathode 2-4 (the biological cathode 2-4 is used for inoculating predominant bacteria flora of methane bacteria, the organic wastewater flows upwards and sequentially passes through the biological anode 2-1, the biological anode 2-1 and the porous substrate 2-2, The porous substrate 2-2 and the biological cathode 2-4 finish the work of acetic acid production, methane production and decontamination), the inner layer cell body, the biological anode 2-1, the porous substrate 2-2 and the biological cathode 2-4 are combined to form a biological electrolytic cell filter, the biological anode 2-1 and the biological cathode 2-4 are respectively connected with an external circuit through a copper wire 2-3 (the external circuit provides about 0.4V potential and provides electrons to participate in the cathode reaction of the biological cathode 2-4 for methane production);
the one-way drain pipe 3-1 is fixedly penetrated through the upper part of the side wall of the biological electrolytic cell filter, the biological electrolytic cell filter is communicated with a clean water tank through the one-way drain pipe 3-1, the one-way drain pipe 3-1 discharges the treated water in the biological electrolytic cell filter into the clean water tank, the one-way drain pipe 3-1 is provided with a one-way valve I3-2, the treated water discharge pipe 3-4 is fixedly penetrated through the upper part of the side wall of the clean water tank (the settled treated water (clean water) is discharged into a water tank, a water source or a next-stage treatment device through the treated water discharge pipe 3-4), and the upper part of the biological electrolytic cell filter is communicated with an exhaust flue 3-3 (methane gas is collected by a methane collection device after overflowing from the exhaust flue 3-3); one end of the water inlet pipeline 1-1 passes through the side wall of the filter tank of the clean water tank and the biological electrolytic tank and is communicated with the lower area of the biological anode 2-1; the side wall of the biological electrolytic tank filter is provided with a flue gas inlet 2-10 communicated with the biological cathode 2-4.
The second embodiment is as follows: as shown in FIG. 1, this embodiment is a further description of the first embodiment, in which the height of the one-way drain pipe 3-1 is lower than the height of the treated water drain pipe 3-4 (to prevent methane gas from leaking out of the one-way drain pipe 3-1 and all of the gas enters the methane collection device).
The third concrete implementation mode: as shown in fig. 1, the present embodiment is a further description of the first embodiment, and the biocathode 2-4 includes a plurality of nickel tube electrodes 2-5, a plurality of exposure hole tubes 2-6, and graphite felts 2-7; the nickel tube electrode plate is characterized in that the nickel tube electrodes 2-5 are horizontally arranged and communicated to form a nickel tube electrode tube plate, a plurality of exposure hole tubes 2-6 are arrayed on the nickel tube electrode tube plate, the exposure hole tubes 2-6 are nickel tubes, and the exposure hole tubes 2-6 are connected with the nickel tube electrodes 2-5The upper sides of the plurality of the exposure hole pipes 2-6 extend upwards, the lower sides extend downwards, the nickel pipe electrode body is formed by combining a plurality of nickel pipe electrodes 2-5 and a plurality of the exposure hole pipes 2-6, and the outer surface of the nickel pipe electrode body is modified with ZnO and Fe3O4The nickel tube electrode body is wrapped in the graphite felt 2-7, and a plurality of air exposure hole tubes 2-6 are penetrated into the graphite felt 2-7.
The biological cathode 2-4 is filled with CO2The flue gas provides raw materials for methane bacteria, and ensures CO under the action of the aeration hole pipes 2-6 arranged in an array2Is fully utilized by methane bacteria; the nickel tube electrode body of the biological cathode 2-4 adopts Fe3O4And Zn O modification, wherein the modification method is electrochemical deposition. The biological cathode 2-4 can be designed by introducing raw material CO2The liquid phase environment around the biological cathode 2-4 is synchronously stirred, the mass transfer efficiency of the biological cathode 2-4 is enhanced, and the methane production capacity is improved. Meanwhile, the biological cathode 2-4 obtains electrons from the biological anode 2-1 through an external circuit to carry out hydrogen ion reduction and methanogenesis reactions, and the overall reaction of the biological cathode 2-4 is
Hydrogen ion reduction equation of 2H++2e-→H2(ii) a The formula of methane production by methane bacteria is CH3COOH→CH4+CO2And 4H2+CO2→CH4+2H2And O. Under the combined action of the biological cathode 2-4 electrode half-reaction, the biological cathode 2-4 can solve the problem of acid accumulation in the traditional anaerobic digestion methanogenesis process, and convert H ions into H2Participating in a methanogenesis reaction; by CO aeration2Replaces CO derived from decomposition of long-chain organic compounds in the original anaerobic digestion process2Improving the raw material C O2The supply amount of the methane production is increased, and the purposes of decarburization and emission reduction are achieved.
The fourth concrete implementation mode: as shown in fig. 1, this embodiment is a further description of the third embodiment, and the inner diameter of the nickel tube electrode 2-5 is 32 mm; the thickness of the biological cathode 2-4 (namely the thickness of the graphite felt 2-7) is 300 mm; the inner diameter of the aeration hole pipes 2-6 is 10 mm.
The fifth concrete implementation mode: as shown in fig. 1, this embodiment is a further description of a third embodiment, and the plurality of aeration holes of the aeration hole pipes 2 to 6 are arranged in a staggered manner.
The sixth specific implementation mode: as shown in FIG. 1, this embodiment is a further description of the first embodiment, the bioanode 2-1 is made of a modular porous filler with electrical conductivity (besides serving as an electrode to provide or absorb electrons, the porous filler also provides a large specific surface area for microorganisms to attach to form a membrane), the bioanode 2-1 has a thickness of 0.1m (materials include but are not limited to graphene aerogel, carbon sponge, foam copper, etc. taking graphene as an example, the parameters are as follows: the specific surface area is 400-1000m2The specific capacitance is 144F/g, the impedance is 0.65Ohm, the resistivity of the graphene is 0.001 omega-m, and the material has good specific surface area and conductivity, and is beneficial to inoculating microorganisms and transferring electrons to an external circuit).
The seventh embodiment: as shown in fig. 1, the first embodiment is further described, and the water inlet unit further includes a pump 1-2 and a valve 1-3; the pump I1-2 and the valve 1-3 are both arranged on the water inlet pipeline 1-1 (the water inlet pipeline 1-1 is controlled by the pump I1-2 and the valve 1-3 to control the flow of wastewater, and the water inlet is controlled according to the aeration quantity of the biological cathode 2-4 and the activity of methane bacteria, and the pump I1-2 and the valve 1-3 ensure the normal and stable operation of the device together).
The specific implementation mode is eight: as shown in fig. 1, this embodiment further illustrates a third embodiment, wherein a second pump 2-8 and a second check valve 2-9 are installed on the nickel tube electrode 2-5. Pumping CO by the second pump 2-82And liquid is prevented from flowing backwards into the nickel tube electrode body.
The specific implementation method nine: as shown in FIG. 1, this embodiment is a further description of the third embodiment, in which ZnO and Fe are modified on the surface of the nickel tube electrode of the biocathodes 2-43O4The specific method comprises the following steps:
firstly, ultrasonic cleaning is carried out on a nickel tube electrode body in three cleaning solutions of acetone, ethanol and deionized water in sequence, the cleaning temperature is 50-70 ℃, the power is 40KHZ, and the cleaning time in each cleaning solution is 5min, then blowing by using nitrogen; putting a nickel tube electrode body into a tube electrode body containing 0.01mol/L of Zn2+、
Na+In the electrolyte with pH value of 5, a platinum or graphite electrode is used as an auxiliary electrode, the distance between the auxiliary electrode and a nickel tube electrode body is 10cm, the constant potential of the nickel tube electrode body is set to be-1.5V, the current intensity is controlled to be 2-10 mA, the electrolyte is electrified for 15min, and the electrolyte passes through an electrode reaction equation
Zn2++2OH-→Zn(OH)2，Zn(OH)2→ZnO+H2O finishes the modification of the ZnO to the nickel tube electrode body; then cleaning and drying in acetone, ethanol and deionized water in the same way; putting a nickel tube electrode body into a furnace body containing 0.02mol/L Fe3+、
Na+Controlling the current intensity to be 2-10 mA in the electrolyte with the pH value of 3, electrifying for 15min, and reacting Fe through a nickel tube electrode body3++2e-→ Fe, iron simple substance is attached on the nickel tube electrode body, and Fe of trivalent iron is carried out due to local pH value increase near the nickel tube electrode body caused by hydrogen production reaction around the nickel tube electrode body3++3OH-→Fe(OH)3，3Fe(OH)3+H++e-＝Fe3O4+5H2Reacting Fe with O, Ni tube electrode3O4Attaching; finally, the nickel tube electrode body is placed on flame for roasting for 1-2min, the flame temperature is 500-800 ℃, and the conversion of Fe elementary substance into Fe is finished3O4Conversion to thereby complete ZnO and Fe3O4And (5) modifying the nickel tube electrode body.
The detailed implementation mode is ten: as shown in FIGS. 1-4, the present embodiment discloses a method for reducing CO emission based on carbon by using the apparatus according to any one of the first to ninth embodiments2A method for the biosynthesis of methane, said method comprising the steps of:
the method comprises the following steps: the organic wastewater flows into the bottom of a filter tank of the biological electrolytic cell through a water inlet pipeline 1-1 and is distributed with water to run in an upflow manner;
step two: the organic wastewater passes through a biological anode 2-1, a porous substrate 2-2 and a biological cathode 2-4 from bottom to top, nitrobacteria on the biological anode 2-1 convert ammonia nitrogen into nitrate nitrogen, and an acetate dominant flora (attached to the biological anode 2-1) produces acetic acid, methyl compounds and CO by utilizing organic pollutants2Providing a precursor for methane bacteria, decomposing ammonia nitrogen and organic pollutants, and generating electric charge to be transferred to the biological anode 2-1;
step three: the organic wastewater flows through the biological cathode 2-4, methane bacteria and hydrogen bacteria on the biological cathode 2-4 pass through the biological cathode 2-4 to obtain electrons, and H is separated2、CO2And converting the methane into methane to realize the recycling of energy.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and its inventive concept within the technical scope of the present invention.
Claims (10)
1. Carbon-based emission reduction of CO2The device for biologically synthesizing the methane comprises a biological filter main body, wherein the biological filter main body is an annular filter body, and an outer layer filter body of the annular filter body is a clean water tank; the method is characterized in that: carbon-based CO emission reduction2The device for biologically synthesizing methane also comprises a water inlet unit and an exhaust and drainage unit; the exhaust and drainage unit comprises a one-way drainage pipe (3-1), a one-way valve I (3-2), an exhaust flue (3-3) and a treated water drainage pipe (3-4); the water inlet unit comprises a water inlet pipeline (1-1);
the inner-layer tank body of the annular tank body is internally provided with a biological anode (2-1), a porous matrix (2-2) and a biological cathode (2-4) from bottom to top in sequence, the inner-layer tank body, the biological anode (2-1), the porous matrix (2-2) and the biological cathode (2-4) are combined to form a biological electrolytic tank filter, and the biological anode (2-1) and the biological cathode (2-4) are respectively connected with an external circuit through copper leads (2-3);
the one-way drain pipe (3-1) fixedly penetrates through the upper part of the side wall of the biological electrolytic tank filter, the biological electrolytic tank filter is communicated with the clean water tank through the one-way drain pipe (3-1), the one-way drain pipe (3-1) drains the treated water in the biological electrolytic tank filter into the clean water tank, a one-way valve I (3-2) is arranged on the one-way drain pipe (3-1), the treated water drain pipe (3-4) fixedly penetrates through the upper part of the side wall of the clean water tank, and the upper part of the biological electrolytic tank filter is communicated with the exhaust flue (3-3); one end of the water inlet pipeline (1-1) passes through the side wall of the clean water tank and the biological electrolytic tank and is communicated with the lower area of the biological anode (2-1); the side wall of the biological electrolytic tank filter is provided with a flue gas inlet (2-10) communicated with the biological cathode (2-4).
2. Carbon-based CO emission reduction according to claim 12The device for biologically synthesizing methane is characterized in that: the height of the one-way drain pipe (3-1) is lower than that of the treated water drain pipe (3-4).
3. Carbon-based CO emission reduction according to claim 12The device for biologically synthesizing methane is characterized in that: the biological cathode (2-4) comprises a plurality of nickel tube electrodes (2-5), a plurality of aeration hole tubes (2-6) and a graphite felt (2-7); the nickel tube electrode comprises a plurality of nickel tube electrodes (2-5), a plurality of nickel tube electrode tube plates are horizontally arranged and communicated, a plurality of exposure hole tubes (2-6) are arrayed on the nickel tube electrode tube plates, the plurality of exposure hole tubes (2-6) are nickel tubes, the plurality of exposure hole tubes (2-6) are communicated with the nickel tube electrodes (2-5), the plurality of exposure hole tubes (2-6) extend upwards and downwards, a nickel tube electrode body is formed by combining the plurality of nickel tube electrodes (2-5) and the plurality of exposure hole tubes (2-6), and ZnO and Fe are modified on the outer surface of the nickel tube electrode body3O4The nickel tube electrode body is wrapped in the graphite felt (2-7), and a plurality of air hole tubes (2-6) penetrate into the graphite felt (2-7).
4. Carbon-based CO abatement according to claim 32The device for biologically synthesizing methane is characterized in that: the inner diameter of the nickel tube electrode (2-5) is 32 mm; the thickness of the biocathode (2-4)Is 300 mm; the inner diameter of the aeration hole pipe (2-6) is 10 mm.
5. Carbon-based CO abatement according to claim 32The device for biologically synthesizing methane is characterized in that: the aeration holes of the aeration hole pipes (2-6) are arranged in a staggered mode.
6. Carbon-based CO emission reduction according to claim 12The device for biologically synthesizing methane is characterized in that: the biological anode (2-1) is made of modular porous filler with electric conductivity, and the thickness of the biological anode (2-1) is 0.1 m.
7. Carbon-based CO emission reduction according to claim 12The device for biologically synthesizing methane is characterized in that: the water inlet unit also comprises a first pump (1-2) and a valve (1-3); the first pump (1-2) and the valve (1-3) are both arranged on the water inlet pipeline (1-1).
8. Carbon-based CO abatement according to claim 32The device for biologically synthesizing methane is characterized in that: and a second pump (2-8) and a second one-way valve (2-9) are arranged on the nickel tube electrode (2-5).
9. Carbon-based CO abatement according to claim 32The device for biologically synthesizing methane is characterized in that: the surface of the nickel tube electrode body of the biological cathode (2-4) is modified with ZnO and Fe3O4The specific method comprises the following steps:
firstly, ultrasonically cleaning a nickel tube electrode body in three cleaning solutions of acetone, ethanol and deionized water in sequence, wherein the cleaning temperature is 50-70 ℃, the power is 40KHZ, the cleaning time in each cleaning solution is 5min, and then, drying by using nitrogen; putting a nickel tube electrode body into a tube electrode body containing 0.01mol/L of Zn2+、0.1mol/L
Na+In the electrolyte with pH 5, a platinum or graphite electrode is used as an auxiliary electrode, and the auxiliary electrode and nickel are mixedThe distance between the electrode bodies is 10cm, the constant potential of the nickel electrode body is set to-1.5V, the current intensity is controlled to be 2-10 mA, the current is electrified for 15min, and the electrode reaction equation is obtained
Zn2++2OH-→Zn(OH)2，Zn(OH)2→ZnO+H2O finishes the modification of the ZnO to the nickel tube electrode body; then cleaning and drying in acetone, ethanol and deionized water in the same way; putting a nickel tube electrode body into a furnace body containing 0.02mol/L Fe3+、0.1mol/L
Na+Controlling the current intensity to be 2-10 mA in the electrolyte with the pH value of 3, electrifying for 15min, and reacting Fe through a nickel tube electrode body3++2e-→ Fe, iron simple substance is attached on the nickel tube electrode body, and ferric iron is carried out by the equation Fe of local pH value increase near the nickel tube electrode body caused by hydrogen production reaction around the nickel tube electrode body3++3OH-→Fe(OH)3，3Fe(OH)3+H++e-＝Fe3O4+5H2Reacting Fe with O, Ni tube electrode3O4Attaching; finally, the nickel tube electrode body is placed on flame for roasting for 1-2min, the flame temperature is 500-800 ℃, and the conversion of Fe elementary substance into Fe is finished3O4Conversion to thereby complete ZnO and Fe3O4And (5) modifying the nickel tube electrode body.
10. Carbon-based CO emission reduction using the device of any one of claims 1 to 92A method of biosynthesizing methane, comprising: the method comprises the following steps:
the method comprises the following steps: the organic wastewater flows into the bottom of a filter tank of the biological electrolytic cell through a water inlet pipeline (1-1) and is distributed with water to run in an upflow manner;
step two: the organic wastewater passes through a biological anode (2-1), a porous substrate (2-2) and a biological cathode (2-4) from bottom to top, nitrobacteria on the biological anode (2-1) convert ammonia nitrogen into ammonia nitrogenThe organic pollutants are utilized by nitrate nitrogen and acetic acid bacteria dominant flora to produce acetic acid, methyl compounds and CO2Precursor is provided for methane bacteria, and electric charge is generated and transferred to a biological anode (2-1) while pollutants ammonia nitrogen and organic pollutants are decomposed;
step three: the organic wastewater flows through the biological cathode (2-4), methane bacteria and hydrogen bacteria on the biological cathode (2-4) obtain electrons through the biological cathode (2-4), and H is removed2、CO2And converting the methane into methane to realize the recycling of energy.
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