CN102208668B - Liquid-solid fluidized bed microbial fuel cell hydrogen production device - Google Patents
Liquid-solid fluidized bed microbial fuel cell hydrogen production device Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 25
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- 239000000446 fuel Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 230000000813 microbial effect Effects 0.000 title claims abstract description 8
- 239000007787 solid Substances 0.000 title claims abstract description 8
- 239000010865 sewage Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 238000012360 testing method Methods 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 7
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- 238000003466 welding Methods 0.000 claims abstract description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 12
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- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 8
- 239000010802 sludge Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 230000002906 microbiologic effect Effects 0.000 claims description 6
- 238000005243 fluidization Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
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- 239000003795 chemical substances by application Substances 0.000 claims description 3
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- 241000894006 Bacteria Species 0.000 claims description 2
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- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
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- 238000010248 power generation Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
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- 239000000126 substance Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
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- 238000007731 hot pressing Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
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- 230000004083 survival effect Effects 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/33—Wastewater or sewage treatment systems using renewable energies using wind energy
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention belongs to the technical field of battery hydrogen production, and relates to a liquid-solid fluidized bed microbial fuel cell hydrogen production device. The bottom center of the device is provided with a sewage inlet, a sewage outlet is formed at the top of the side wall of an anode fluidized bed, and the upper part of the sewage inlet is provided with a pre-distribution chamber and connected with the anode fluidized bed through a flange; a liquid distribution plate is arranged between the pre-distribution chamber and the anode fluidized bed, and fluidized granules are filled in the inner lower part of the anode fluidized bed; a positive electrode of a graphite carbon rod is vertically placed inside the anode fluidized bed, one end of the bottom of the positive electrode is inserted into the fluidized granules, and the other end of the positive electrode and a carbon paper membrane cathode are connected through a welding lead and connected in series with a load and a stabilized voltage supply to form a closed loop; and 2 to 10 test ports are arranged vertically on the lower middle part of the side wall of the anode fluidized bed of organic glass in equal distance, and the side wall of the top of a cathode chamber is provided with a gas collecting outlet. The device has the advantages of low battery cost, high power generation performance, wide operating area, reliability in operation and good mass transfer effect of the anaerobic fluidized bed.
Description
Technical field:
The invention belongs to the auxiliary hydrogen technical field of producing of liquid-solid fluid bed reactor organisms fuel cell, relate to a kind of liquid-solid fluidized bed microbial fuel cell hydrogen production device, with liquid-solid fluid bed integrated for the waste water treatment occasion with microbe fuel, be specially adapted to the organic substance sewage disposal occasions such as beer industrial waste water, food processing wastewater, city domestic sewage.
Background technology:
At present, energy crisis and environmental pollution are increasingly serious, are threatening the mankind's survival and development.Renewable Energy Development is walked the focus that sustainable development path becomes various countries' scholar's research.But the intermittent and characteristics such as difficult storage and transportation due to regenerative resources such as solar energy, wind energies need a kind of energy carrier of high-efficiency cleaning as regenerative resource.Hydrogen Energy is acknowledged as following most potential energy carrier with its cleaning, efficient characteristics.Simultaneously, industrial development and population sharply expand resources and environment have been caused serious threat, make rational use of resources, and the recycling of realizing refuse is environmental emission reduction and the effective way of alleviating shortage of resources.microbiological fuel cell produces the hydrogen technology with organic glucose, the electronics that acetic acid etc. produce in anaerobism Mixed Microbes catalyst respiration with synchronize the proton that generates and adding under the condition of stabilized voltage power supply and be combined into hydrogen, this technology has the reaction condition gentleness, equipment is simple, easy to operate, operating cost is low, to advantages such as the organic matter of sewage removal effect are good, can realize the double effects of recuperated energy in sewage disposal, it is a kind of application prospect sewage disposal technology widely, it is investigated that asking this type of technology has not yet to see the tangible bibliographical information that changes on a large scale ripe application.Anaerobic fluidized bed anode microbiological fuel cell is that microbiological fuel cell is produced the mutually integrated a kind of novel reactor of hydrogen technology and fluidized-bed reactor, belongs to the technical scheme of the just to be developed and innovation of in the art research staff; And common batteries of the prior art (MFC) is applicable to the research in laboratory more, and the mode of the multiplex stirring of anode exists microbial profile inhomogeneous, and mass-transfer efficiency is low, is not easy to the outstanding shortcomings such as sewage disposal industry amplification.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seek to design and develop a kind of device of liquid-solid anaerobic fluidized bed microbiological fuel cell waste water treatment simultaneous hydrogen production, this device can add when realizing sewage disposal under the condition of stabilized voltage power supply and produce hydrogen, by regulation bed layer height, the discharge of sewage, waste strength and kind, liquid distribution hole yardstick, anaerobic sludge and the operating parameters such as carrier granular consumption and granularity, realize effective removal of chemical oxygen consumption of sewage (COD) pollutant and the raising of hydrogen output.
To achieve these goals, the agent structure of apparatus of the present invention comprises sewage inlet, outlet of sewer, sewage inlet pre-distributing chamber, liquid distributing board, anode fluidized bed body, fluid bed expanding reach, fluidized particles (filler), seal cover, gas collection outlet, test port, positive electrode, wire, negative electrode and load, cathode chamber and stabilized voltage power supply, and each parts formula structure forms anaerobic fluidized bed microbiological fuel cell device for producing hydrogen; The bottom of device center is shaped with sewage inlet, and outlet of sewer is placed in anode fluidized bed body sidewall apart from 30~80mm place, top, and sewage inlet top is shaped with pre-distributing chamber, and pre-distributing chamber is connected with the anode fluidized bed body by flange; Be shaped with liquid distributing board between pre-distributing chamber and anode fluidized bed body, in the anode fluidized bed body, the fluidized particles as filler is equipped with in the bottom, and fluidized particles is mixed by anaerobic sludge and carrier granular thereof and adds fluidized bed reaction zone; It is inboard that the vertical formula of the positive electrode of graphite carbon rod matter is placed in the anode fluidized bed body, one end of bottom inserts the electronics of drawing and conduct the organic matter degradation generation in fluidized particles (filler), the negative electrode of membrane type structure adopts and carries platinum carbon paper membrane structure, separate by proton exchange membrane between positive electrode and negative electrode, the wire that passes through to weld between the positive electrode other end of graphite carbon rod matter and carbon paper film negative electrode connects and series load is connected with stabilized voltage power supply forms the closed-loop path; The tactic test port in up and down is positioned at anode fluidized bed body lateral wall, is used for measuring bed layer pressure and fluidized particles flow velocity; The pre-distributing chamber of sewage inlet is evenly distributed bacterium liquid, realizes the abundant fluidisation of fluidized particles, improves water treatment effect, increases electrogenesis power, reduces internal resistance; Sewage is entered in the anode fluidized bed body through the pre-distributing chamber of sewage inlet and liquid distributing board successively by sewage inlet, and anaerobic sludge Mixed Microbes biofilm is in fluidized state on fluidized particles; Anode fluidized bed body top is provided with seal cover, and positive electrode is in sealing state and keeps anaerobic environment, and the seal cover downside is shaped with outlet of sewer; Between positive electrode and negative electrode, distance is 10mm-20mm; Negative electrode is for carrying the cathode construction of platinum carbon paper membrane type, and series resistance case between negative electrode and positive electrode uses stabilized voltage power supply to realize applied voltage on circuit, to overcome the catalysis electromotive force of negative electrode; The anode fluidized bed body sidewall middle and lower part of the polymethyl methacrylate matter structure that is arranged above and below equidistantly is shaped with 2-10 test port, with test envelope stressor layer and particle flow velocity; Between cathode chamber and anode fluidized bed body, flange form is connected, and it is shaped with the negative electrode that carries platinum carbon paper membrane type near cathode chamber side; Be shaped with the gas collection outlet on the top sidewall of cathode chamber.
The present invention compared with prior art has the following advantages: the one, and positive electrode chamber employing anaerobic organism fluid bed, the bottom-up bed that flows through of waste water makes filler be fluidized state, increased the contact area of interior biomembrane of unit interval with waste water, strengthen organic mass transfer in sewage, accelerated biochemical reaction rate; The 2nd, adopt stabilized voltage power supply that battery is made with voltage, make hydrogen proton and the electronics of the chamber generation of battery positive electrode be produced hydrogen at cathode chamber, obtain cleaning hydrogen as energy source; The 3rd, along bed axial height distribution negative electrode, reduce the proton transfer distance, improve proton transfer speed, thereby improve effect and the hydrogen output of waste water treatment; The 4th, anaerobic fluidized bed anode air cathode microbial fuel cell is simple in structure, volumetric power density is high, is easy to industry and amplifies; The present invention with waste water as battery fuel, take anaerobic sludge as the Mixed Microbes provenance, the battery cost is low, and electricity generation performance is high, the operating space field width, operation is reliable, anaerobic fluidized bed mass transfer effect is good, and biochemical reaction rate is fast, is easy to amplify and industrial applications, be widely used in the purified treatment of different chemical oxygen demand (COD) concentration sewage, and to the glucose wastewater treatment effect up to more than 97%.
Description of drawings:
Fig. 1 is the planar structure principle schematic of apparatus of the present invention.
Fig. 2 is the electron recovery rate change curve under the different applied voltage conditions of apparatus of the present invention.
Fig. 3 is the hydrogen recovery rate change curve under the different applied voltage conditions of apparatus of the present invention.
Embodiment:
Below in conjunction with drawings and Examples, apparatus of the present invention are further described.
Embodiment:
The agent structure of the present embodiment comprises sewage inlet 1, pre-distributing chamber 2, liquid distributing board 3, test port 4, positive electrode 5, anode fluidized bed body 6, fluid bed expanding reach 7, outlet of sewer 8, seal cover 9, stabilized voltage power supply 10, load 11, wire 12, gas collection outlet 13, negative electrode 14, cathode chamber 15 and fluidized particles 16, and each component combination consists of anaerobic fluidized bed film cathode microbial fuel cell unit; Sewage inlet 1 is positioned at reactor bottom center, caliber Φ 15mm; Outlet of sewer 8 is positioned at anode fluidized bed body 6 sidewalls apart from 50mm place, top, caliber Φ 15mm; The diameter of pre-distributing chamber 2 is 40mm, and is connected with anode fluidized bed body 6 by flange; Liquid distributing board 3 opening diameter Φ 1.5-2.5mm, percent opening 10-15% guarantees that sewage evenly enters; Be placed in the diameter of phi 70mm of the catalyst granules baffle plate (accompanying drawing is for marking) in anode fluidized bed body 6, its plate face opening diameter Φ 2-3mm, percent opening 10-15%, and be fixed on fluid bed expanding reach 7, guarantee that catalyst granules or fluidized particles do not flow out the reaction zone of anode fluidized bed body 6 with sewage; Anode fluidized bed body 6 up-down structures are divided into fluidized bed reaction zone and fluid bed expanding reach 7, and wherein the structure of fluidized bed reaction zone is the polymethyl methacrylate cylinder, diameter 40mm, high 450mm; The diameter 70mm of fluid bed expanding reach 7, high 150mm; Fluidized particles (filler) 16 mixes with the absorbent charcoal carrier particle in proportion for anaerobism reflux section anaerobic sludge (taming 30 days), is filled in the fluidized bed reaction zone of anode fluidized bed body 6; Positive electrode 5 is diameter of phi 5mm, the graphite carbon rod of long 150mm, and carbon-point bottom is positioned at fluidized particles 16, and other end welding lead 12 is derived electronics; The negative electrode 14 of membrane type structure forms for nafion film and year platinum carbon paper hot pressing, with the epoxy glue sealing, and successively distributes to improve the electronics transmission efficiency along the axial height of anode fluidized bed body 6, increases treatment effeciency; Several test ports that are arranged above and below 4 (Φ 4mm) are positioned at the polymethyl methacrylate sidewall, are used for measuring bed layer pressure and particle flow velocity; Link by flange form between cathode chamber 15 and anode fluidized bed body 6, the negative electrode 14 that carries platinum carbon paper membrane type that the centre is shaped with hot pressing separates.
The pending synthetic sewage of the present embodiment enters water pre-distributing chamber 2 from sewage inlet 1 (caliber Φ 15mm), pass liquid distributing board 3 (the diameter of phi 40mm of porous type, plate face opening diameter Φ 1.5-2.5mm, percent opening 10-15%) enter the reaction zone (diameter of phi 40mm) of anode fluidized bed body 6; Mud and carrier granular are filled in reaction zone, fluidisation under the effect in sewage flow field, Mixed Microbes in mud is carbon dioxide and hydrogen proton as catalyst with the organic substance direct oxidation in sewage, the electronics that produces leads to negative electrode 14 by the positive electrode 5 of graphite carbon rod structure, the hydrogen proton arrives negative electrode 14 through proton exchange membrane, hydrogen proton and electronics generate hydrogen in negative electrode 14 places reaction, and soon in sewage, COD is converted into small-molecule substance CO2 and H2.Sewage process fluid bed expanding reach 7 (Φ 70mm) after processing, then flow out through outlet of sewer 8, be partly refluxed to the reaction zone of anode fluidized bed body 6; A plurality of test ports 4 (Φ 4mm) are used for measuring the interior bed layer pressure of anode fluidized bed body 6 and the flow velocity of fluidized particles or catalyst granules; Gas collection outlet 13 is positioned at cathode chamber top sidewall locations, caliber Φ 10mm.
The present embodiment has following technical characterictic in practicing: the one, and between the flow control 10ml/min-900ml/min of sewage, can cause bed to save the loss of gushing with fluidized particles, thereby reduce mass transfer effect and electron production and transmission; The 2nd, the effect of liquid pre-distributing chamber is the homogeneity that ensures drainage flow, thereby guarantees the fluidization uniformity of fluidized particles in fluidized bed body; The 3rd, fluidized particles and bed flow behavior have substantial connection, grain diameter be chosen in 0.2mm between 5mm; The 3rd, the negative electrode position distributes along the fluid bed axial height, reduces the proton transfer distance, improves proton transfer efficient; The 4th, device is under the condition of stabilized voltage power supply, and proton and electronics are at negative electrode position generation hydrogen.
The present embodiment is suitable for the sewage disposal of different COD concentration, and the COD clearance can reach 97%, and good wastewater treatment efficiency is arranged; Accompanying drawing 2 and accompanying drawing 3 are hydrogen yield and the electron recovery rate change curve under different applied voltage conditions; Being the active carbon of 0.2-1mm and cultured anaerobic sludge with grain diameter drops in anode reaction district in the anode fluidized bed body of anaerobism with the ratio of 6: 5, when system temperature moves under 28 ± 3 ℃ of conditions, start battery is very fast, when applied voltage 0.25V, system normal operation, cathode chamber are collected hydrogen gradually; Show the advantages such as feasibility that the present embodiment mass-transfer efficiency is high, start battery is fast, treatment effect is good and this device produces hydrogen, be conducive to obtain more biomass energy, realize the practical application of bioelectrogenesis and synchronous wastewater processing technology.
Claims (1)
1. liquid-solid fluidized bed microbial fuel cell hydrogen production device, agent structure comprises sewage inlet, outlet of sewer, the pre-distributing chamber of sewage inlet, liquid distributing board, the anode fluidized bed body, the fluid bed expanding reach, fluidized particles as filler, seal cover, the gas collection outlet, test port, positive electrode, wire, negative electrode and load, cathode chamber and stabilized voltage power supply, each parts formula structure is assembled into anaerobic fluidized bed microbiological fuel cell hydrogen production bioreactor, it is characterized in that the bottom of device center is shaped with sewage inlet, outlet of sewer is placed in anode fluidized bed body sidewall apart from 30~80mm place, top, sewage inlet top is shaped with pre-distributing chamber, pre-distributing chamber is connected with the anode fluidized bed body by flange, be shaped with liquid distributing board between pre-distributing chamber and anode fluidized bed body, in the anode fluidized bed body, the fluidized particles as filler is equipped with in the bottom, and fluidized particles is mixed by anaerobic sludge and carrier granular thereof and adds fluidized bed reaction zone, it is inboard that the vertical formula of the positive electrode of graphite carbon rod matter is placed in the anode fluidized bed body, one end of bottom inserts the electronics of drawing and conduct the organic matter degradation generation in fluidized particles, the negative electrode of membrane type structure adopts and carries platinum carbon paper membrane structure, separate the positive electrode other end of graphite carbon rod matter and the formation of carrying between platinum carbon paper membrane structure negative electrode that wire by welding connects and series load is connected with stabilized voltage power supply closed-loop path between positive electrode and negative electrode by proton exchange membrane, the tactic test port in up and down is positioned at anode fluidized bed body lateral wall, is used for measuring bed layer pressure and fluidized particles flow velocity, the pre-distributing chamber of sewage inlet is evenly distributed bacterium liquid, realizes the abundant fluidisation of fluidized particles, sewage is entered in the anode fluidized bed body through the pre-distributing chamber of sewage inlet and liquid distributing board successively by sewage inlet, and anaerobic sludge Mixed Microbes biofilm is in fluidized state on fluidized particles, anode fluidized bed body top is provided with seal cover, and positive electrode is in sealing state and keeps anaerobic environment, and the seal cover downside is shaped with outlet of sewer, between positive electrode and negative electrode, distance is 10mm-20mm and series resistance case, uses stabilized voltage power supply to realize applied voltage on circuit, to overcome the catalysis electromotive force of negative electrode, the anode fluidized bed body sidewall middle and lower part of the polymethyl methacrylate matter structure that is arranged above and below equidistantly is shaped with 2-10 test port, with test envelope stressor layer and particle flow velocity, between cathode chamber and anode fluidized bed body, flange form is connected, and it is shaped with the negative electrode that carries platinum carbon paper membrane type near cathode chamber side, be shaped with the gas collection outlet on the top sidewall of cathode chamber.
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CN1776950A (en) * | 2005-11-30 | 2006-05-24 | 哈尔滨工业大学 | Air cathode biological fuel cell for electric generation from organic waste water |
CN1874040A (en) * | 2005-06-03 | 2006-12-06 | 清华大学 | Single pond type microbiological cell by using organic wastewater as fuel |
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CN1874040A (en) * | 2005-06-03 | 2006-12-06 | 清华大学 | Single pond type microbiological cell by using organic wastewater as fuel |
CN1776950A (en) * | 2005-11-30 | 2006-05-24 | 哈尔滨工业大学 | Air cathode biological fuel cell for electric generation from organic waste water |
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