CN111530267B - Device and method for denitration of flue gas by combining microbial fuel cell with microbial electrolytic cell - Google Patents

Device and method for denitration of flue gas by combining microbial fuel cell with microbial electrolytic cell Download PDF

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CN111530267B
CN111530267B CN202010355687.6A CN202010355687A CN111530267B CN 111530267 B CN111530267 B CN 111530267B CN 202010355687 A CN202010355687 A CN 202010355687A CN 111530267 B CN111530267 B CN 111530267B
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mfc
mec
cathode
flue gas
anode
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CN111530267A (en
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黄少斌
黄行柱
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South China University of Technology SCUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/005—Combined electrochemical biological processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/812—Electrons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a device and a method for denitration of flue gas by combining a microbial fuel cell and a microbial electrolysis cell, wherein the cathode of an MFC is connected to the anode of an MEC through a lead, the anode of the MFC is connected to the cathode of the MEC through a lead, and the anode chamber and the cathode chamber of the MFC and the MEC are separated by a proton exchange membrane; a flue gas inlet and a nutrient solution outlet are formed in the bottom of the MFC cathode, a flue gas outlet and a nutrient solution inlet are formed in the top of the MFC cathode, and a nutrient solution circulation loop is arranged between the cathode chamber of the MFC and the cathode chamber of the MEC; electrons generated by the MFC are used as a power supply to act on the MEC, and the flue gas denitration is realized under the double strengthening action of the MEC and the MFC. The invention has low cost and low energy consumption, NOx in the flue gas is transferred to a liquid phase through the chemical absorbent, and the pollutants are removed and the absorbent is activated through the MFC-MEC combined technology, so that the high-efficiency and green denitration of the medium-temperature flue gas can be realized.

Description

Device and method for denitration of flue gas by combining microbial fuel cell with microbial electrolytic cell
Technical Field
The invention belongs to the technical field of engineering, and particularly relates to a device and a method for removing nitrogen oxides at medium temperature by combining a microbial fuel cell with a microbial electrolytic cell.
Background
According to the data statistics of the national ministry of environmental protection, the smoke emission of China is increased year by year, and the total emission amount is only increased but not reduced. The traditional flue gas treatment technologies at present comprise selective catalytic reduction, selective non-catalytic reduction, biological methods and chemical absorption methods. In all the technologies, the application prospect of the biological flue gas denitration method is wide, wherein the new biological electrochemical flue gas denitration technology promotes the development direction of flue gas denitration. The bioelectrochemical system includes a Microbial Fuel Cell (MFC), a Microbial Electrolysis Cell (MEC), and the like. MEC is a method in which a voltage is applied to degrade or reduce a harmful substance, and at the same time, a voltage is applied to achieve redox of a target substance.
BER (bio-membrane electrode reactor) or cab (chemical adsorption bio-membrane electrode reactor) belong to one of MECs, SCI research has reported for cab flue gas denitration, and cab electrolysis technology causes flue gas denitration, which needs to consume a large amount of electricity and energy. The MFC-MEC combined technology has only been reported in the research on hydrogen production in the beginning of the 21 st century, and now, the technology has been greatly developed from the initial MFC-MEC hydrogen production to wastewater treatment, metal substance recovery and the like. On the other hand, the activation effect of the MFC flue gas absorption liquid has been reported, and the MEC flue gas efficient denitration process has been researched, verified and published. However, the MFC-MEC combined technology is an innovative technology in the aspect of waste gas treatment, and the blank area of the technology is urgently needed to be taken into consideration. The microbial fuel cell also has similar patents CN102324544B, CN103123976B, CN105032152B and CN107376631A in the flue gas circulating liquid treatment technology. These several microbial fuel cells are of a dual chamber construction. Similar studies have been made on the denitration of MFC flue gas, and the Research on the two-chamber MFC reduction flue gas circulating liquid (Journal of chemical technology and biological technology 2015; 90: 1692-. However, in the prior art, CABER flue gas denitration consumes energy and has high cost; MFC flue gas denitration, only accomplish the activation of circulating fluid, do not relate to in the aspect of MFC direct reduction of flue gas; the MEC flue gas denitration has the shortcoming of power consumption, and is with high costs, directly uses the power in addition, has the electric current big, makes the conductor temperature rise easily, will increase shortcomings such as safety measure.
Therefore, it is very important to establish a method for direct flue gas denitration by combining a microbial fuel cell with a microbial electrolysis cell.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a method for denitrating medium-temperature flue gas by combining a microbial fuel cell with a microbial electrolysis cell, which is low in cost and energy consumption, so as to realize high-efficiency and green denitration of the medium-temperature flue gas. The process transfers NOx in flue gas to the liquid phase by means of chemical absorbents, removes such pollutants by means of MFC-MEC combined technology and activates the absorbents.
The purpose of the invention is realized by the following technical scheme:
a device for denitrating smoke by combining a microbial fuel cell with a microbial electrolysis cell, wherein a cathode of an MFC is connected to an anode of an MEC through a lead, an anode of the MFC is connected to a cathode of the MEC through a lead, and an anode chamber and a cathode chamber of the MFC and the MEC are separated by a proton exchange membrane; a flue gas inlet and a nutrient solution outlet are formed in the bottom of the MFC cathode, a flue gas outlet and a nutrient solution inlet are formed in the top of the MFC cathode, and a nutrient solution circulation loop is arranged between the cathode chamber of the MFC and the cathode chamber of the MEC; electrons generated by the MFC are used as a power supply to act on the MEC, and the flue gas denitration is realized under the double strengthening action of the MEC and the MFC.
Preferably, the MEC anode is a graphite rod, the MEC cathode is an electrode consisting of the graphite rod and graphite particles, the graphite particles are also used as fillers, the graphite particles are in good contact with each other, and the graphite particles are obtained by cutting after being polished by a graphite rod.
Preferably, the MFC anode is a carbon brush and the MFC cathode consists of a graphite rod and a graphite felt filler.
Preferably, the MFC and the MEC are respectively a double-cylinder sleeve structure, the carbon brush is a cylinder, the diameter D of the carbon brush is less than D, and D is the diameter of the inner wall of the anode chamber of the MFC.
Preferably, the number of graphite rods of the MFC and MEC cathodes is 4-12, and the graphite rods are arranged around the anode chamber. When the cylindrical reactor is relatively large, the number of graphite rods is correspondingly increased in order to ensure that the distance between the graphite rod electrodes is relatively short.
Preferably, the top and the bottom of the MFC cathode are provided with water distribution sieve holes. The nutrient solution of MFC cathode chamber drip, be the velocity of flow that the control nutrient solution supplied with through the peristaltic pump, under low velocity of flow, MFC cathode chamber top liquid is intermittent trickle state, after nutrient solution whereabouts to the sieve mesh, homodisperse, under the action of gravity nutrient solution is from top to bottom, flows on the filler surface to collect at the bottom.
Preferably, the graphite particle filler has a porosity of 0.4-0.8 and a graphite felt filler size of 1 x 2-2 x 4 cm.
The method for denitration of flue gas by using the device comprises the following steps:
(1) inoculating the microorganisms: adding electrogenic bacteria into the MFC anode chamber and the MEC anode chamber, and hanging aerobic denitrifying bacteria in the filler biomembranes of the MFC cathode chamber and the MEC cathode chamber;
(2) flue gas enters from the bottom of the MFC cathode chamber, and nutrient solution is added from the top of the MFC cathode chamber; nutrient solution and flue gas are in gas-liquid countercurrent in the MFC cathode chamber, the flue gas passes through a filler with a wet biological membrane, meets the nutrient solution trickling from top to bottom, is absorbed by the nutrient solution containing ferrous complexing absorbent, the treated gas is discharged from the top of the MFC, the nutrient solution is discharged from the bottom of the MFC and enters the MEC, a graphite rod and graphite particles of the MEC cathode are soaked in the nutrient solution, and the nutrient solution circularly flows between the MFC cathode chamber and the MEC cathode chamber.
Preferably, activated sludge of a secondary sedimentation tank after fermentation of an anaerobic tank of a sewage treatment plant is also added into the MFC anode chamber and the MEC anode chamber; the electrogenic bacteria are Geobacter (Geobacter), and the aerobic denitrifying bacteria are Pseudomonas (Pseudomonas sp). Pseudomonas (Pseudomonas) can utilize both Fe (II) EDTA-NO and Fe (III) EDTA as electron acceptors.
Preferably, the complexing absorbent is selected from a combination of two of: ferrous iron ethylene diamine tetraacetic acid (Fe (II) EDTA) and ferrous iron citric acid (Fe (II) Cit), wherein the final concentration of ferrous iron in the nutrient solution is 4-60 mmol/L.
Preferably, the carbon source of the culture medium of the MFC anode chamber and the MEC anode chamber is one or more than two of sodium formate, sodium acetate and sodium lactate, or sewage of a secondary sedimentation tank of a slaughter wastewater sewage plant.
All biofilms in the MFCs and MECs described can be derived from acclimation and are neutralized with phosphate buffer.
The mesophilic electrogenic bacteria in the MFC anode chamber are mainly Geobacter such as Geobacter and the like, can be purchased from the China common microorganism preservation management center, and have the CGMCC number of No1.12536 and the GenBank accession number of KF 006333. Address: xilu No. 1 Hospital No. 3, Beijing, Chaoyang, North.
The complex NOx and the ferric iron complexing agent in the nutrient solution are respectively reduced in the MFC, in the MEC cathode chamber, in addition to the fact that the complex NO receives electrons of the MFC anode to be reduced, on the other hand, under the action of aerobic denitrifying bacteria, the ferric iron complexing agent is also promoted to be reduced.
The ferric complexing agent is formed by reacting oxygen in smoke with a ferrous complexing agent to form the ferric complexing agent without NOx absorption, and the reaction formula is as follows:
4Fe(Ⅱ)(EDTA)+2O2+4H+→4Fe(Ⅲ)(EDTA)+H2O
the MFC cathode chamber reduction means that NOx in flue gas is absorbed by a complexing agent, enters liquid and is acted by microorganisms in the process of flowing through a biological membrane, and the complexing NOx and ferric iron complexing agent receive electrons of an MEC anode to obtain reduction.
The MEC cathode chamber is reduced, hydrogen is generated at the MEC cathode under the action of electrons provided by the MFC anode, and the ferric iron complexing agent is reduced under the action of aerobic denitrifying bacteria.
In the invention, the voltmeter needs to monitor the electricity generation condition of the MFC on line, when the electricity generation is reduced rapidly, the anode culture medium of the MFC and the MEC needs to be replaced, the original volume is changed, and a new carbon source is added.
In the invention, the flue gas denitration efficiency is directly influenced by the ferrous iron complexing agent, and in the reaction process, the ferrous iron complexing agent is influenced by oxygen gas of flue gas inlet on one hand, and on the other hand, the ferrous iron complexing agent Fe (II) directly reacts with the complexing state NO, the NO is reduced into nitrogen, and the ferrous iron is oxidized into ferric iron. Traditionally, MFC has been widely found to produce hydrogen on MECs, i.e. the electrons produced by MFC combine with protons in the cathode of the MEC to form hydrogen. Meanwhile, the aerobic denitrifying bacteria can use hydrogen as energy to reduce the Fe (III) complex. The divalent iron complex is increased to ensure the high-efficiency denitration efficiency of the flue gas.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention applies the electric energy generated by the microbial fuel cell to a microbial electrolytic cell as an external power supply and can generate voltage of 300 plus 600 mV.
(2) The carbon source can be effectively utilized, the reduction of the complexing NOx and ferric iron complexing agent is promoted under the action of the cathode chamber of the microbial fuel cell MFC, and on the other hand, electrons in electric energy generated by the MFC are efficiently utilized to promote the reduction of the complexing NOx and Fe (III) complexing agent again.
(3) The invention can realize flue gas denitration quickly and efficiently, can promote the degradation of wastewater pollutants, and improves the tolerance of the ferrous iron complexing agent to oxygen under the strengthening action of MEC.
(4) The process reduces NOx to non-polluting N2The process method is reasonable, the occupied area is small, and no secondary pollution is generated.
Drawings
FIG. 1 is a schematic view of a microbial fuel cell-microbial electrolysis cell flue gas denitration device of the invention.
In the figure: 1 silicone tube for supplying nutrient solution to MFC; 2 Microbial Electrolysers (MECs); 3MEC cathode electrode graphite rod; 4MEC anode electrode graphite rod; 5 refluxing the nutrient solution to a silicone tube of the MEC; 6 copper wire connecting MFC and MEC; 7 anode (carbon brush) of microbial fuel cell MFC; 8 cathode of microbial fuel cell MFC; 9MFC treated gas outlet; 10 Microbial Fuel Cells (MFCs); 11 an air inlet; 12 a peristaltic pump; 13 sieve pores for water distribution; 14, a voltmeter; 15 a heat preservation device; 16 a temperature controller; 17, insulating a gas tank; 18 a gas mass regulator; 19 a gas flow meter; 20 flue gas tank.
FIG. 2 is a diagram showing the denitration effect of example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
MFC-MEC flue gas denitrification facility, as shown in figure 1, MFC and MEC structure size are the same, and both are telescopic structure, anode is inside, the cathode is in the outer loop, MFC inside anode chamber internal diameter is 5.4cm, high 20cm, MFC cathode chamber internal diameter is 10cm, high 20cm, wrap up on foraminiferous cylinder with proton exchange membrane (PEM, Nafion117, Dupont, USA), the cylinder external diameter is 6cm, high 20 cm. As shown in the figure, the MFC has a hollow chamber on the upper and lower sides, the height of the hollow chamber is 7cm, and the inner diameter is 10 cm. The anode and the cathode are respectively arranged on the two devices, the diameter of an MFC anode carbon brush is 5cm, the diameter of a cathode graphite rod and graphite particles is 6mm, the length of the graphite particles is 10cm, and graphite felt packing is 1 x 2 cm.
The cathode 8 of the MFC is connected to the anode 4 of the MEC through a copper wire, the anode 7 of the MFC is connected to the cathode 3 of the MEC through a copper wire, and the anode chamber and the cathode chamber of the MFC and the MEC are separated by a proton exchange membrane; the bottom of the MFC cathode is provided with an air inlet 11 and a nutrient solution outlet, the top of the MFC cathode is provided with a gas outlet 9 and a nutrient solution inlet, and a nutrient solution circulating pipeline is arranged between the cathode chamber of the MFC and the cathode chamber of the MEC.
A small amount of activated sludge and water sample are taken from a secondary sedimentation tank behind an anaerobic tank of a certain municipal sewage plant in Guangzhou city and inoculated into an MFC reactor anode, a small amount of bacteria liquid of mesophilic electrogenic bacteria is added into an MFC anode chamber and an MEC anode chamber at the same time, the formation of complex electrogenic flora can be accelerated by adopting a method of mixing the activated sludge and the electrogenic bacteria, the mesophilic electrogenic bacteria are Geobacter such as Geobacter, and the like, can be purchased from the China general microbiological culture Collection center (CGMCC No1.12536), and are provided with culture medium, and the basic culture medium (L per liter) of the anode chamber is Na2HPO4·12H2O，17.10g，K2HPO4，3.00g，NaCl，0.50g，NH4Cl, 1.00g, yeast extract, 0.50g, C3H5NaO3，2.24g。
Inoculating activated sludge of a secondary sedimentation tank behind an anaerobic tank of a certain municipal sewage plant in Guangzhou city into an MEC cathode chamber, wherein the activated sludge carries a small amount of Pseudomonas, and preparing a basic culture medium, wherein the basic culture medium of the cathode chamber consists of the following substances (per liter): glucose, 5.00g, K2HPO4，5.00g，KH2PO4，1.00g，MgCl2，0.05g，GaCl2，0.0111g，FeSO4·7H20.005g of O, 1mL of vitamin and 1mL of trace element. The trace elements contained the following components (per liter): nitrilotriacetic acid, 1.50g, MgSO4·7H2O，3.00g，MnSO4·H2O，0.50g，NaCl，1.00g，FeSO4·7H2O，0.10g，CoSO4·7H2O，0.18g，CaCl2·2H2O，0.10g，ZnSO4·7H2O，0.18g，CuSO4·5H2O，0.01g，KAl(SO4)2·12H2O，0.02g，H3BO3，0.01g，Na2MoO4·2H2O，0.01g，NiCl2·6H2O，0.03g，Na2SeO3·5H2O，0.30mg，Na2WO4·2H2O, 0.40 mg. Vitamins for bacterial growth include the following (per liter): biotin, 2.00mg, folic acid, 2.00mg, pyridoxine-HCl, 10.00mg, thiamine-HCl-2H 2O, 5.00mg, riboflavin, 5.00mg, nicotinic acid, 5.00mg, D-Ca-pantothenate, 5.00mg, vitamin B12, 0.10mg, p-aminobenzoic acid, 5.00mg, lipoic acid, 5.00mg, distilled water, 1000.00 ml.
1. Domestication culture of mesophilic electrogenic bacteria on MFC anode and MEC anode
Connecting the leads of the MFC-MEC device, starting the heat preservation device, keeping the temperature at 55 ℃, connecting a voltmeter to anodes and cathodes at two ends of the microbial fuel cell, monitoring the power generation condition of the MFC, continuously supplying flue gas in an MFC-MEC flue gas denitration system, starting domestication, replacing the culture medium of the anode once a week, wherein the replacement volume is general, the voltmeter shows weak voltage after 10 days and the generated voltage is unstable, the MFC generates stable voltage after 100 days, the voltage is higher than 300mV, and the power generation bacteria formation of the MFC-MEC system is stable.
2. MFC cathode chamber and MEC cathode chamber filler biofilm formation
The method comprises the steps of synchronously domesticating the cathode chamber biofilm formation and the anode chamber electrogenesis bacteria, wherein when a culture medium in an MFC cathode is initially added, the concentration of a glucose solution is 5g/L, the culture medium contains a Fe (II) EDTA absorbent, when the MFC electrogenesis is rapidly reduced and the electrogenesis is very low, the anode carbon source sodium acetate is completely consumed, the culture medium in a reactor is replaced, the replacement volume is half of the volume of an MEC cathode chamber, a divalent iron complexing agent is contained in a new culture medium, meanwhile, 50mL of activated sludge is continuously inoculated, the glucose concentration is gradually reduced when the culture medium is replaced each time, the glucose concentration is gradually reduced from 5-5-4-4-3-3-2-2-1g/L, and finally the glucose concentration of 1g/L is kept. When a tan biological film can be seen on MFC graphite felt filler and MEC graphite rod particles, film hanging on MFC cathode graphite felt filler and MEC cathode graphite particles is completed, the flue gas denitration efficiency is monitored, and the stable and continuous 7d denitration efficiency is higher than 75% of the successful denitration microorganism domestication.
3. Device operation test
The artificial synthetic smoke comprises the following components: 1.5% NO + 20% air + 78% N2. Clean tap water is taken, and MFC and MEC anode carbon sources adopt sodium acetate, so that the final concentration of the sodium acetate is 3 g/L. The solution is added to the anode compartment 7 of the microbial fuel cell. Taking clean tap water, removing oxygen for 30 minutes, preparing a culture medium, adding Fe (II) EDTA complexing agent to enable the final concentration to be 5mmol/L, adding glucose solution to enable the final concentration to be 1g/L, and filling the solution into a cathode chamber of a microbial electrolytic cell. And (3) opening the peristaltic pump 12, introducing test gas into the microbial fuel cell, wherein the temperature of the device is 55 ℃, the flow of the gas is adjusted to be 0.25L/min, the effective retention time is 240s, and the effective test time is 7 d. The result shows that the NOx removal efficiency can reach 85% within the test time, the power generation can reach 300mV, 5g/L of glucose needs to be added periodically, and the NOx removal device can be recycled for half a year.
Example 2
The present embodiment is different from embodiment 1 in that:
(1) the artificial synthetic waste gas NOx 450-750mg/m3 is introduced into the flue gas for running for 8 hours every day, and the flow rate of the flue gas is 60m 3/h.
(2) Inoculating the cultured strain on the filler, periodically measuring the NOx removal efficiency, starting the cyclic biofilm formation for about 115 days, and measuring that the waste gas removal efficiency can reach 80 percent and the biofilm formation is successful. The denitration efficiency can be finally maintained at 85% after the device runs for 150 days.
Example 3
The flow rate of flue gas of a certain coal-fired boiler is 45000m3H, NO content 500mg/m3The process according to the invention is as follows:
(1) according to the components of waste gas, the denitration tower is a cylindrical sleeve type microbial fuel cell, the diameter of the microbial fuel cell tower is 9m, the height of the microbial fuel cell tower is 20m, the diameter of an internal anode cylinder is 5m, the height of the internal anode cylinder is 20m, the anode adopts a carbon brush, and the diameter of bristles of the carbon brush is 4 m. The diameter of the inner wall of the external reactor is 9m, the cathode adopts graphite rods and carbon felt packing, the grain diameter of the packing is 2cm, the length of the packing is 3 cm, 12 graphite rods are inserted into the packing, the graphite rods are arranged at equal intervals and surround the anode for a circle, and the diameter of the graphite rods is 2cm, and the length of the graphite rods is 10 m. In the embodiment, the carbon source of the anode is sewage of a secondary sedimentation tank of a slaughter wastewater sewage plant, a glucose solution is used as the cathode by 5g/L, Fe (II) EDTA is used as an absorbent in the absorption process, and the concentration of Fe (II) EDTA is 10mmol/L as a complexing agent. Microbial fuel cells employ a proton exchange membrane (PEM, Nafion117, Dupont, USA) to separate the anode and cathode.
(2) The microbial electrolysis cell adopts graphite particle packing, the microbial electrolysis cell tower has the diameter of 5m and the height of 10m, the anode and the cathode are separated by a clapboard with a proton exchange membrane sieve pore, the anode and the cathode both adopt graphite rods, and the diameter and the length of the graphite rods are 2cm and 10 m.
(3) The temperature of the microbial fuel cell and the microbial electrolysis cell device is kept between 45 and 60 ℃.
(4) During the acclimatization period, a large amount of a bacterial solution of an electrogenic bacterium is added.
The device is operated for 3 months, and NO in the gas leaving the microbial fuel cell tower is 100mg/Nm3And the denitration efficiency is 80%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. An apparatus for denitrating flue gas by combining a microbial fuel cell and a microbial electrolysis cell, wherein a cathode of an MFC is connected to an anode of an MEC through a lead, an anode of the MFC is connected to a cathode of the MEC through a lead, and an anode chamber and a cathode chamber of the MFC and the MEC are separated by a proton exchange membrane; a flue gas inlet and a nutrient solution outlet are formed in the bottom of the MFC cathode, a flue gas outlet and a nutrient solution inlet are formed in the top of the MFC cathode, and a nutrient solution circulation loop is arranged between the cathode chamber of the MFC and the cathode chamber of the MEC; electrons generated by the MFC are used as a power supply to act on the MEC, and the flue gas denitration is realized under the double strengthening action of the MEC and the MFC; the MFC anode is a carbon brush, and the MFC cathode consists of a graphite rod and graphite felt filler; the MFC is a double-cylinder sleeve structure, the carbon brush is a cylinder, the diameter D of the carbon brush is smaller than D, and D is the diameter of the inner wall of the anode chamber of the MFC.
2. The apparatus of claim 1,
the MEC anode is a graphite rod, the MEC cathode is a composite electrode consisting of the graphite rod and graphite particles, and the graphite particles are coarse and are in good contact.
3. The apparatus of claim 2, wherein the MEC is a double cylindrical sleeve structure.
4. The flue gas denitration method by using the device of any one of claims 1 to 3, characterized by comprising the following steps:
(1) inoculating the microorganisms: adding electrogenic bacteria into the MFC anode chamber and the MEC anode chamber, and hanging aerobic denitrifying bacteria in the filler biomembranes of the MFC cathode chamber and the MEC cathode chamber;
(2) flue gas enters from the bottom of the MFC cathode chamber, and nutrient solution is added from the top of the MFC cathode chamber; nutrient solution and flue gas are in gas-liquid countercurrent in the MFC cathode chamber, the flue gas passes through a filler with a wet biological membrane, meets the nutrient solution trickling from top to bottom, is absorbed by the nutrient solution containing ferrous complexing absorbent, the treated gas is discharged from the top of the MFC, the nutrient solution is discharged from the bottom of the MFC and enters the MEC, a graphite rod and graphite particles of the MEC cathode are soaked in the nutrient solution, and the nutrient solution circularly flows between the MFC cathode chamber and the MEC cathode chamber.
5. The method according to claim 4, characterized in that the MFC anode chamber and the MEC anode chamber are further added with activated sludge of a secondary sedimentation tank after fermentation of an anaerobic tank of a sewage treatment plant.
6. The method according to claim 4 or 5, wherein the electrogenic bacteria are Geobacter (Geobacter) and the aerobic denitrifying bacteria are Pseudomonas (Pseudomonas), Paracoccus (Paracoccus), Alcaligenes (Alcaligenes).
7. The method according to claim 4 or 5, wherein the complexing absorbent is selected from the group consisting of: ferrous iron ethylenediaminetetraacetic acid (Fe (II) EDTA), ferrous iron citric acid (Fe (II) Cit).
8. The method as claimed in claim 4 or 5, wherein the carbon source of the MFC anode chamber and MEC anode chamber culture medium is one or more of sodium formate, sodium acetate and sodium lactate, or sewage of secondary sedimentation tank of slaughter wastewater sewage plant.
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CN111607532B (en) * 2020-04-28 2021-09-07 福建农林大学 Method for driving denitrification of alcaligenes faecalis
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102553434A (en) * 2012-03-06 2012-07-11 浙江大学 Device and method for purifying nitrogen oxides in flue gas by utilizing electrode biological membrane
CN105032152A (en) * 2015-07-24 2015-11-11 大连理工大学 Chemical absorption and microbial fuel cell combined synchronous flue gas desulfurization and denitration technology
CN105032168A (en) * 2015-07-13 2015-11-11 华南理工大学 Device and method for removing nitrogen oxides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102553434A (en) * 2012-03-06 2012-07-11 浙江大学 Device and method for purifying nitrogen oxides in flue gas by utilizing electrode biological membrane
CN105032168A (en) * 2015-07-13 2015-11-11 华南理工大学 Device and method for removing nitrogen oxides
CN105032152A (en) * 2015-07-24 2015-11-11 大连理工大学 Chemical absorption and microbial fuel cell combined synchronous flue gas desulfurization and denitration technology

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
MFC-MEC 耦合系统产电性能及处理含镉重金属废水的研究;潘璐璐 等;《化工学报》;20191231;第70卷(第1期);第242-250页 *
中温烟气的生物脱硝工艺及生物电化学强化效果研究;黄行柱;《中国优秀硕士学位论文全文数据库，工程科技Ⅰ辑》;20200215;第B027-1113页 *
微生物燃料电池再生NOX特异性吸收产物和同步产电研究;易鹏;《中国优秀硕士学位论文全文数据库，工程科技Ⅰ辑》;20140815;第B027-444页 *
微生物电解池效能及其与微生物燃料电池的联合运行探索;谢倍珍 等;《环境科学与技术》;20140930;第37卷(第9期);第59-64页 *
生物电化学系统处理废气的研究进展;黄行柱;《微生物学通报》;20190225;第1115-1126页 *

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