CN101794896B - Anaerobic ammonia oxidation microbiological fuel cell - Google Patents
Anaerobic ammonia oxidation microbiological fuel cell Download PDFInfo
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- CN101794896B CN101794896B CN2010101311387A CN201010131138A CN101794896B CN 101794896 B CN101794896 B CN 101794896B CN 2010101311387 A CN2010101311387 A CN 2010101311387A CN 201010131138 A CN201010131138 A CN 201010131138A CN 101794896 B CN101794896 B CN 101794896B
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- anaerobic ammonia
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an anaerobic ammonia oxidation microbiological fuel cell, which consists of a constant temperature stirring system, a reaction system and a data acquisition monitoring system, wherein the constant temperature stirring system is provided with a constant temperature magnetic stirrer body and a magnetic stirring bar; the reaction system is provided with a cylindrical reactor body and a sealing cover; the lower and upper parts of the cylindrical reactor body are provided with a water inlet pipe and a water outlet pipe respectively; an electricity generation matrix is arranged in the cylindrical reactor body; anaerobic ammonia oxidation bacteria and a film-formed anode and a film-formed cathode to which the anaerobic ammonia oxidation bacteria is attached are immersed in the electricity generation matrix; the upper part of the sealing cover is provided with an anode wire fixing tube, a cathode wire fixing tube, a sampling tube and a reference electrode fixing tube; a seal ring is arranged between and connected by flanges with the cylindrical reactor body and the sealing cover; and the data acquisition monitoring system is provided with a load, a wire, a data acquisition device and an on-line computer. The device of the invention has the advantages of simple structure, low manufacturing cost, small internal resistance, efficient and stable performance and capability of realizing synchronous wastewater denitrification and biological electricity generation.
Description
Technical field
The present invention relates to biological fuel cell, relate in particular to a kind of anaerobic ammonia oxidation microbiological fuel cell.
Background technology
Microbiological fuel cell (Microbial Fuel Cells, be called for short MFC) be a kind of be anode catalyst with the microbe, chemical energy is converted into the device of electric energy.Utilize microbiological fuel cell, not only can be directly with the organic matter degradation in water body or the mud, and can the electronics that produce in the organic metabolism process be converted into electric current, thus obtain electric energy.In recent years, under the dual-pressure of environmental pollution and energy crisis, because microbiological fuel cell can be handled waste water simultaneously and produce electric energy, this new technology is favored by people more and more, has become waste water treatment and new energy development hot research fields.
The operation principle of microbiological fuel cell is following: under the anode action of microorganisms, substrate decomposes generation electronics, proton and other metabolite; Portions of electronics is delivered to anode surface and arrives negative electrode through external circuit, and proton arrives negative electrode through electrogenesis matrix; At cathode surface, electronics, proton combine with electron acceptor and form electric current.Most microbiological fuel cells are electrogenesis matrix with the organic substance, and the electrogenesis microbe is a facultative anaerobe, and battery configuration has two types of two chambers and single chambers.There is following shortcoming in these microbiological fuel cells: (1) is in the amphimicrobian electrogenesis bacterium of having found; Except that corrupt Shiva Salmonella (Shewanella putrefaciens), several kinds of bacteriums such as bacillus (Geobacteraceae), iron vat red spirillum (Rhodoferax ferrireducens); The electron transport efficient of all the other electrogenesis bacterium is very low; Need extra interpolation dimethyl diaminophenazine chloride, 2, electron mediums such as 6-anthraquinone come the strengthening electronic transmission, and mediator is poisonous mostly and price is higher.(2) double-chamber microbiological fuel cell is divided into two utmost point chambers of yin, yang by PEM; The proton transfer ability of PEM can change the pH value of cathode and anode chamber; Weaken microbial activity and electron transport ability, and PEM costs an arm and a leg (4000～12000 yuans/m
2); The electronics that is delivered to negative electrode need add electron acceptor and combine, and electron acceptor has two kinds of supply modes, and a kind of mode is to utilize the iron cyanide and permanganate etc. to have the chemical substance of high oxidation activity; This method need not supported precious metal catalyst on negative electrode; But cost is high, regeneration difficult, be prone to cause secondary pollution, another kind of mode is as electron acceptor, though air is cheap and easy to get with air; But its redox speed is low, needs at noble metal catalysts such as cathode load platinum.(3) single-chamber microbial fuel cell does not have cathode chamber, but still needs PEM, and its negative electrode also needs supported precious metal catalyst but also needs complicated water-proofing treatment.(4) electrogenesis matrix is organic substance, and conductivity is low, and the internal resistance of cell is big, and electrogenesis efficient is low, needs extra interpolation inorganic ions to strengthen its conductivity sometimes.The low two big bottlenecks that become the existing microbiological fuel cell development of restriction and used with the cost height of electrogenesis efficient.
To the above-mentioned defective of existing microbiological fuel cell, the present invention is the electrogenesis bacterium with the anaerobic ammonia oxidizing bacteria, need not to add electron medium; With the inorganic wastewater that contains ammonia nitrogen and nitrite nitrogen is electrogenesis matrix, and yin, yang the two poles of the earth are in the homophase solution, need not to be provided with PEM; Nitrite can need not to provide in addition the cathode electronics acceptor directly as the cathode electronics acceptor in the electrogenesis matrix, and negative electrode adheres to the electrogenesis biomembrane, can improve electron transport efficient, need not supported precious metal catalyst; Electrogenesis matrix is inorganic ions, and the internal resistance of cell is low, and battery performance is good, and electrogenesis efficient is high.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of anaerobic ammonia oxidation microbiological fuel cell is provided.
Anaerobic ammonia oxidation microbiological fuel cell is made up of constant temperature stirring system, reaction system and data acquisition and monitoring system three parts, and the constant temperature stirring system is provided with constant temperature blender with magnetic force body and magnetic agitation; Reaction system is provided with tubular reactor body and seal cover; Tubular reactor body bottom is provided with water inlet pipe; Tubular reactor body top is provided with outlet pipe; Electrogenesis matrix is equipped with in tubular reactor body inside; Be soaked with free anaerobic ammonia oxidizing bacteria and extension film anode that adheres to anaerobic ammonia oxidizing bacteria and extension film negative electrode in the electrogenesis matrix, seal cover top is provided with positive wire stationary pipes, cathode wire stationary pipes, probe tube and reference electrode stationary pipes, is provided with sealing ring between tubular reactor body and the seal cover and also connects through flange; The data acquisition and monitoring system is provided with load, lead, data acquisition unit and line computer, and the load two ends link to each other with extension film negative electrode with extension film anode respectively through lead.
Described electrogenesis matrix is the inorganic wastewater that contains ammonia nitrogen and nitrite nitrogen, and the pH value is 7.0～7.5, wherein adds microelement concentrate I, each 1.25mL/L of microelement concentrate II, and the composition of microelement concentrate I is: EDTA 5g/L, FeSO
45g/L; The composition of microelement concentrate II is: EDTA 15g/L, H
3BO
40.014g/L, MnCl
24H
2O 0.99g/L, CuSO
45H
2O 0.025g/L, ZnSO
47H
2O 0.43g/L, NiCl
26H
2O 0.19g/L, NaSeO
410H
2O 0.21g/L, NaMoO
42H
2O 0.22g/L.
Described tubular reactor body ratio of height to diameter is 1～2: 1, and electrogenesis matrix volume accounts for 2/3～3/4 of tubular reactor body volume, and free anaerobic ammonia oxidizing bacteria volume accounts for 1/5～1/10 of electrogenesis matrix volume.
Described extension film anode is carbon paper, carbon cloth, carbon felt, graphite felt or graphite cake with the electric conducting material of hanging the film negative electrode; Hang the film anode and be attached with the anaerobic ammonia oxidizing bacteria biomembrane with extension film cathode surface; Hanging the film anode is 2～4cm with hanging under the film negative electrode bottom the end distance tubular reactor body; The distance of hanging the film anode and hanging between the film negative electrode is 3～6cm, and extension film anode or extension film cathode area are 9～40m with the ratio of tubular reactor body volume
2: 1m
3
The beneficial effect that the present invention has: (1) utilizes anaerobic ammonia oxidizing bacteria to carry out denitrogenation of waste water and biological electrogenesis, can realize that contaminated wastewater is controlled and electrical energy production is carried out simultaneously.(2) yin, yang the two poles of the earth are in the homophase solution, need not to add electron medium, need not PEM, and nitrite can be directly as the cathode electronics acceptor, and apparatus structure is simple, are easy to amplify and industrial applications.(3) electrogenesis matrix is inorganic ions, and the internal resistance of cell is low, and battery performance is good, and electrogenesis efficient is high, does not discharge the greenhouse gases carbon dioxide in the electricity generation process, is a kind of clean energy resource process units.
Description of drawings
Accompanying drawing 1 is a kind of anaerobic ammonia oxidizing bacteria microbiological fuel cell structural representation;
Accompanying drawing 2 is structural representations of seal cover;
Wherein: constant temperature blender with magnetic force body 1, magnetic agitation 2, water inlet pipe 3, free anaerobic ammonia oxidizing bacteria 4, extension film anode 5, extension film negative electrode 6, electrogenesis matrix 7, tubular reactor body 8, seal cover 9, flange 10, positive wire stationary pipes 11, probe tube 12, load 13, reference electrode stationary pipes 14, cathode wire stationary pipes 15, sealing ring 16, outlet pipe 17, lead 18, data acquisition unit 19, line computer 20.
Embodiment
Shown in accompanying drawing, anaerobic ammonia oxidation microbiological fuel cell is made up of constant temperature stirring system I, reaction system II and data acquisition and monitoring system III three parts, and constant temperature stirring system I is provided with constant temperature blender with magnetic force body 1 and magnetic agitation 2; Reaction system II is provided with tubular reactor body 8 and seal cover 9; Tubular reactor body 8 bottoms are provided with water inlet pipe 3; Tubular reactor body 8 tops are provided with outlet pipe 17; Electrogenesis matrix 7 is equipped with in tubular reactor body 8 inside; Be soaked with free anaerobic ammonia oxidizing bacteria 4 and extension film anode that adheres to anaerobic ammonia oxidizing bacteria 5 and extension film negative electrode 6 in the electrogenesis matrix 7, seal cover 9 tops are provided with positive wire stationary pipes 11, cathode wire stationary pipes 15, probe tube 12 and reference electrode stationary pipes 14, are provided with sealing ring 16 between tubular reactor body 8 and the seal cover 9 and also connect through flange 10; The III of data acquisition and monitoring system is provided with load 13, lead 18, data acquisition unit 19 and line computer 20, and load 13 two ends link to each other with extension film negative electrode 6 with extension film anode 5 respectively through lead 18.
Described electrogenesis matrix 7 is for containing the inorganic wastewater of ammonia nitrogen and nitrite nitrogen, and the pH value is 7.0～7.5, wherein adds microelement concentrate I, each 1.25mL/L of microelement concentrate II, and the composition of microelement concentrate I is: EDTA 5g/L, FeSO
45g/L; The composition of microelement concentrate II is: EDTA 15g/L, H
3BO
40.014g/L, MnCl
24H
2O 0.99g/L, CuSO
45H
2O 0.025g/L, ZnSO
47H
2O0.43g/L, NiCl
26H
2O 0.19g/L, NaSeO
410H
2O 0.21g/L, NaMoO
42H
2O 0.22g/L.
Described tubular reactor body 8 ratio of height to diameters are 1～2: 1, and electrogenesis matrix 7 volumes account for 2/3～3/4 of tubular reactor body 8 volumes, and free anaerobic ammonia oxidizing bacteria 4 volumes account for 1/5～1/10 of electrogenesis matrix 7 volumes.
Described extension film anode 5 is carbon paper, carbon cloth, carbon felt, graphite felt or graphite cake with the electric conducting material of hanging film negative electrode 6; Hang film anode 5 and the anaerobic ammonia oxidizing bacteria biomembrane is arranged with extension film negative electrode 6 surface attachment; Hanging film anode 5 is 2～4cm with hanging 6 times end distance tubulars of film negative electrode reactor body, 8 bottoms; The distance of hanging film anode 5 and hanging between the film negative electrode 6 is 3～6cm, and extension film anode 5 or extension film negative electrode 6 areas are 9～40m with the ratio of tubular reactor body 8 volumes
2: 1m
3
Open the constant temperature stirring system, anaerobic ammonia oxidizing bacteria is dispersed under stirring action in the tubular reactor body with the inorganic wastewater that contains ammonia nitrogen and nitrite nitrogen, and constant temperature can be the Anammox bacteria growing and the reaction of denitrogenation electrogenesis provides suitable temperature conditions.Ammonia nitrogen discharges electronics and proton under the effect of anaerobic ammonia oxidizing bacteria, and collect and be delivered to extension film negative electrode through the external circuit lead by the film anode by hanging for the electronics of release, hangs the film cathode surface; Electronics, proton and nitrite combine, and produce electric current and generate nitrogen, accomplish denitrogenation and electricity generation process thus; The signal of telecommunication that reaction system produces is collected by data acquisition unit; And be transferred in the line computer, through the change in electric ruuning situation of monitoring reaction system simultaneously, the process of being convenient to is in time regulated and control.
Claims (3)
1. anaerobic ammonia oxidation microbiological fuel cell; It is characterized in that it is made up of constant temperature stirring system (I), reaction system (II) and data acquisition and monitoring system (III) three parts, constant temperature stirring system (I) is provided with constant temperature blender with magnetic force body (1) and magnetic agitation (2); Reaction system (II) is provided with tubular reactor body (8) and seal cover (9); Tubular reactor body (8) bottom is provided with water inlet pipe (3); Tubular reactor body (8) top is provided with outlet pipe (17); Electrogenesis matrix (7) is equipped with in tubular reactor body (8) inside; Be soaked with free anaerobic ammonia oxidizing bacteria (4) in the electrogenesis matrix (7) and adhere to the extension film anode (5) of anaerobic ammonia oxidizing bacteria and hang film negative electrode (6), seal cover (9) top is provided with positive wire stationary pipes (11), cathode wire stationary pipes (15), probe tube (12) and reference electrode stationary pipes (14), is provided with sealing ring (16) between tubular reactor body (8) and the seal cover (9) and passes through flange (10) connection; Data acquisition and monitoring system (III) is provided with load (13), lead (18), data acquisition unit (19) and line computer (20), and load (13) two ends link to each other with extension film negative electrode (6) with extension film anode (5) respectively through lead (18); Described electrogenesis matrix (7) is for containing the inorganic wastewater of ammonia nitrogen and nitrite nitrogen, and the pH value is 7.0～7.5, wherein adds microelement concentrate I, each 1.25mL/L of microelement concentrate II, and the composition of microelement concentrate I is: EDTA 5g/L, FeSO
45g/L; The composition of microelement concentrate II is: EDTA 15g/L, H
3BO
40.014g/L, MnCl
24H
2O 0.99g/L, CuSO
45H
2O 0.025g/L, ZnSO
47H
2O 0.43g/L, NiCl
26H
2O 0.19g/L, NaSeO
410H
2O 0.21g/L, NaMoO
42H
2O 0.22g/L.
2. a kind of anaerobic ammonia oxidation microbiological fuel cell according to claim 1; It is characterized in that described tubular reactor body (8) ratio of height to diameter is 1～2: 1; Electrogenesis matrix (7) volume accounts for 2/3～3/4 of tubular reactor body (8) volume, and free anaerobic ammonia oxidizing bacteria (4) volume accounts for 1/5～1/10 of electrogenesis matrix (7) volume.
3. a kind of anaerobic ammonia oxidation microbiological fuel cell according to claim 1; The electric conducting material that it is characterized in that described extension film anode (5) and extension film negative electrode (6) is carbon paper, carbon cloth, carbon felt, graphite felt or graphite cake; Hang film anode (5) and hang film negative electrode (6) surface attachment the anaerobic ammonia oxidizing bacteria biomembrane is arranged; Hanging film anode (5) and hanging under the film negative electrode (6) is 2～4cm bottom the end distance tubular reactor body (8); The distance of hanging film anode (5) and hanging between the film negative electrode (6) is 3～6cm, and the ratio of hanging film anode (5) or extension film negative electrode (6) area and tubular reactor body (8) volume is 9～40m
2: 1m
3
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| CN2010101311387A CN101794896B (en) | 2010-03-23 | 2010-03-23 | Anaerobic ammonia oxidation microbiological fuel cell |
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| CN2010101311387A CN101794896B (en) | 2010-03-23 | 2010-03-23 | Anaerobic ammonia oxidation microbiological fuel cell |
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| CN101794896A CN101794896A (en) | 2010-08-04 |
| CN101794896B true CN101794896B (en) | 2012-06-13 |
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| CN102249424A (en) * | 2011-04-02 | 2011-11-23 | 大连民族学院 | Proton exchange membrane-free microbiological fuel cell sewage treatment system and application method thereof |
| CN102324544B (en) * | 2011-09-05 | 2013-07-31 | 浙江工商大学 | Microbiological fuel cell for removing nitrogen and phosphorus |
| CN102351312B (en) * | 2011-09-14 | 2013-06-05 | 中国科学院成都生物研究所 | Bioelectrochemical denitriding reactor and application method thereof |
| CN102557272B (en) * | 2011-12-31 | 2013-12-04 | 东北电力大学 | Microbial fuel cell three-level continuous type waste water nitrogen-removing treatment method and device |
| CN102800883B (en) * | 2012-08-15 | 2014-09-10 | 浙江大学 | Nitrification microbial fuel cell |
| CN103094597B (en) * | 2013-01-25 | 2015-01-28 | 浙江大学 | Microbial fuel cell with function of efficiently and synchronously removing nitrogen and carbon |
| CN103803697B (en) * | 2014-01-21 | 2015-05-06 | 浙江大学 | Pipeline bio-membrane reactor with detachable inner body |
| CN104961231A (en) * | 2015-06-25 | 2015-10-07 | 南昌大学 | Anaerobic ammonia oxidation reactor device |
| CN107180987A (en) * | 2017-05-13 | 2017-09-19 | 华南理工大学 | Couple the negative electrode efficient denitrification type microbiological fuel cell of Anammox technology |
| CN107345930B (en) * | 2017-08-10 | 2024-02-09 | 滨州学院 | Biosensor for online monitoring ammonia nitrogen concentration in water |
| CN109638327B (en) * | 2018-12-19 | 2021-05-18 | 大连理工大学 | Process for denitrification and power generation by using single-chamber anaerobic ammonia oxidation sludge-microbial fuel cell device |
| CN109650536A (en) * | 2019-01-03 | 2019-04-19 | 大连理工大学 | The device and method of ammonia nitrogen anaerobism in-situ treatment based on ferrikinetics driving |
| CN111807503A (en) * | 2020-07-20 | 2020-10-23 | 南京神克隆水务有限公司 | Oxygen-limited microbial desalting tank and wastewater treatment method |
| CN116239213B (en) * | 2023-02-23 | 2023-10-24 | 北京工业大学 | Electrochemical-anaerobic ammonia oxidation device and operation method thereof |
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2010
- 2010-03-23 CN CN2010101311387A patent/CN101794896B/en not_active Expired - Fee Related
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| CN101302059A (en) * | 2008-06-24 | 2008-11-12 | 大连理工大学 | Inverted denitrification process film bioreactor |
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