CN109680290A - Manifold type bioelectrochemistry produces hydrogen and collection device, system and produces hydrogen methods - Google Patents
Manifold type bioelectrochemistry produces hydrogen and collection device, system and produces hydrogen methods Download PDFInfo
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- CN109680290A CN109680290A CN201811618595.1A CN201811618595A CN109680290A CN 109680290 A CN109680290 A CN 109680290A CN 201811618595 A CN201811618595 A CN 201811618595A CN 109680290 A CN109680290 A CN 109680290A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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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
Hydrogen and collection device, system are produced the present invention provides a kind of manifold type bioelectrochemistry and produce hydrogen methods, first hydrophobic permeable membrane and the second hydrophobic permeable membrane are respectively placed in rear side and the front side of cathode in the device, hydrogen remaining in cathode side and electrolyte is collected respectively, to play synergistic effect, so that negative pressure pump realizes double negative pressure gas collections, airbag is connected by negative pressure pump and pipeline with the other end of third gas collecting tube, for collecting and storing hydrogen, achieve the purpose that quickly to collect the hydrogen generated in the system, the methanogen in electrolyte is made to be difficult to contact with hydrogen；Methanation inhibitor is added in electrolyte simultaneously, so that the methyl coenzyme M chemical inactivation of methanogen, avoids methanogen from generating methane using methyl coenzyme M consumption hydrogen, to inhibit methanation；Cathode and anode exist together a Room in system of the invention, reduce system internal resistance, improve coulombic efficiency, further achieve the purpose that system high efficiency, lasting H2-producing capacity.
Description
Technical field
The invention belongs to debirs/waste water technology fields, and in particular to a kind of manifold type bioelectrochemistry produces hydrogen and receipts
Acquisition means, system and production hydrogen methods.
Background technique
Bioelectrochemistry system for producing hydrogen can convert hydrogen for the chemical energy in debirs/waste water, realize their money
Sourceization utilizes, and has broad based growth prospect in debirs/waste water process field.Bioelectrochemistry system for producing hydrogen divide dual chamber and
Single chamber two major classes, collect hydrogen by gas diffusion.The anode and cathode of dual chamber bioelectrochemistry system for producing hydrogen is handed over by ion
It changes film and is separated into two Room, methanogen is more difficult to touch hydrogen, is also less competitive than electricity production bacterium, therefore methane in substrate use aspects
Change degree is low；But anode and cathode in two Room, causes system internal resistance big respectively, and coulombic efficiency is low, and H2-producing capacity is poor.Single chamber bioelectricity
The anode and cathode of chemical system for producing hydrogen exists together a Room, and system internal resistance is low, and coulombic efficiency is high, and H2-producing capacity is good, it has also become development
Mainstream；But hydrogen easily diffuses in electrolyte, and methanogen consumes hydrogen methane phase by methyl coenzyme M, leads to methanogen
A large amount of proliferation, methanation phenomenon is serious, and H2-producing capacity is gradually reduced.Currently, the methanation of bioelectrochemistry system for producing hydrogen is inhibited to have
Following methods:
1, it physical method: 1) introduces air and inhibits methanogen activity, but can also reduce the activity of electricity production bacterium in this way；2)
Applied voltage is improved to 0.7V or more, this method is only effective in the early stage, and reactor is run in a fortnight, still to produce first
Based on alkane；3) 4 DEG C are reduced the temperature to, methane backeria is totally constrained, but can also reduce reaction rate in this way, increases energy consumption；4) purple
Outer light irradiation, this method is only effective to the system that methanation does not occur, once firm methane phase system is set up in system,
Ultraviolet irradiation will no longer function；5) change reactor configuration, between a cathode and an anode install additional a polytetrafluoroethylene film into
Row separates, and cathode is tightly attached to the other side of film, and negative pressure pump is arranged in reactor end, though hydrogen is effectively prevented to electrolyte
Side diffusion, but the presence of film increases system internal resistance between anode and cathode electrode, reduces coulombic efficiency, and H2-producing capacity is poor,
Simultaneously with the fouling membrane caused by Ion transfer and fouling the problems such as.
2, chemical method: 1) adding acid reduces electrolyte pH, inhibits methanogen activity, but can also reduce electricity production in this way
The activity of bacterium；2) coenzyme M analog is added as methanation inhibitor, and effective coenzyme M analog has 2- bromoethane sulphur at present
Apparent inhibitory effect can be observed in hydrochlorate, and concentration need to could completely inhibit methane phase close to 0.6mM, meanwhile, 2- bromoethane
Sulfonate has certain toxicity, can stimulate eyes, respiratory system and skin, and in N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid
(BES) it will not degrade substantially in；3) halogenated aliphatic hydrocarbon, wherein the chloroform in chloromethane has the structure similar with methyl
And the stronger C-H bond of activity, the biological effect of the functional enzymes such as methyl coenzyme M can be inhibited, but it is with toxicity, irritation
Suspecious carcinogen.
Summary of the invention
For methanation existing for bioelectrochemistry system for producing hydrogen in the prior art, internal resistance is big and performance is gradually reduced etc.
Deficiency, primary and foremost purpose of the invention are to provide a kind of manifold type bioelectrochemistry and produce hydrogen and collection device.
A second object of the present invention is to provide a kind of manifold type bioelectrochemistries for realizing above-mentioned apparatus to produce hydrogen and collection
System.
Third object of the present invention is to provide a kind of production hydrogen methods using above system.
In order to achieve the above objectives, solution of the invention is:
A kind of manifold type bioelectrochemistry produces hydrogen and collection device comprising electrolysis chamber 1, anode 2, cathode 3, first are dredged
Water ventilated membrane 4, the first gas collecting tube 9, the second hydrophobic permeable membrane 6, the second gas collecting tube 10, third gas collecting tube 11, threeway 8, negative pressure pump
12 and airbag 13.
Wherein, it is electrolysed chamber 1, is used to accommodate electrolyte.Methanation inhibitor is added in electrolyte.
Anode 2 is used to supply electronics and H+。
Cathode 3 is used to generate hydrogen, and the first hydrophobic permeable membrane 4 is close on rear side of cathode 3.
First gas collecting tube 9, one end runs through the side wall of the first gas collection chamber 5 and is set to 3 rear side of cathode, for collecting cathode
The hydrogen of 3 sides.
Second gas collecting tube 10, one end is through the side wall for being electrolysed chamber 1 and is set to 3 front side of cathode, and end is equipped with second
Hydrophobic permeable membrane 6, the second hydrophobic permeable membrane 6 are laid in electrolyte, and the second gas collecting tube 10 is remaining in electrolyte for collecting
Hydrogen.
Threeway 8 is used to connect the other end of the first gas collecting tube 9, the other end and third gas collecting tube of the second gas collecting tube 10
11 one end.
Negative pressure pump 12 connect by the other end of third gas collecting tube 11 with threeway 8, be used to pass through third gas collecting tube 11 and
Threeway 8 to applying negative pressure in the first gas collecting tube 9, the second gas collecting tube 10 respectively.
Airbag 13 is connected, for collecting and storing with the other end of third gas collecting tube 11 by negative pressure pump 12 and pipeline
Hydrogen.
Preferably, the first hydrophobic permeable membrane 4, the second hydrophobic permeable membrane 6 are selected from polytetrafluoroethylene film, polyvinylidene fluoride film
One or more of with polyethylene film.
Preferably, methanation inhibitor is 3- nitro ester -1- propyl alcohol, and concentration is 5.0 × 10-6-5.0×10-3mol/L。
Preferably, electrolyte is selected from the mixed liquor containing low molecular organic acids.
Preferably, the mixed liquor containing low molecular organic acids is selected from organic waste anaerobic fermentation liquid, organic waste water anaerobic fermentation
One or more of the low molecular organic acids mixed liquor of liquid and carbochain number within 12.
Preferably, anode 2 is selected from one or more of carbon brush, carbon felt, graphite felt and carbon cloth.
Preferably, cathode 3 is selected from Stainless Steel felt, Graphene electrodes, carbon nanotube electrode, palladium modified electrode and platinum modification electricity
One or more of pole.
Preferably, negative pressure pump 12 is selected from one or more of vacuum pump and suction pump.
It is a kind of to realize that above-mentioned manifold type bioelectrochemistry produces hydrogen and the manifold type bioelectrochemistry of collection device produces hydrogen and receipts
Collecting system further includes external power supply 14, resistance 15 and collector 16.
Wherein, external power supply 14 is pressure stabilizing external power supply, is used to adjust the voltage of the system；External power supply 14 is by leading
Line 17 is separately connected anode 2 and cathode 3.
Collector 16 is digital acquisition device, is used to show the electric current of the system；Digital acquisition device passes through conducting wire 17 and electricity
The both ends of resistance 15 are connected.
Preferably, the voltage of external power supply 14 is 0.3-1.8V.
A method of hydrogen is produced according to above-mentioned manifold type bioelectrochemistry and collection system is realized and produces hydrogen comprising following step
It is rapid:
(1) anode is cultivated under microbiological fuel cell mode produce electricity bacterium
By culture medium, 1:1 is mixed by volume with inoculum, is removed dissolved oxygen therein, is then added to Microbial fuel
In battery；Resistance is accessed in closed circuit system, with the operation of static basis, when the voltage at resistance both ends is more than 0.1V
Afterwards, it no longer needs to use inoculum, culture medium is added directly in microbiological fuel cell, repeated at least three periods, until micro-
Biological fuel cell stablizes output maximum voltage, thinks that anode electricity production bacterium has been enriched with completion at this time；
(2) hydrogen manufacturing under microorganism electrolysis cell mode
Anode biomembrane starts microorganism electrolysis cell after taming, and the cathode of microbiological fuel cell is replaced with microorganism
The cathode of electrolytic cell, is transferred to microorganism electrolysis cell mode under the applied voltage of 0.3-1.8V, anode (2) by conducting wire with it is external
The anode of power supply (14) is connected, and cathode (3) is connected by conducting wire with the cathode of external power supply (14), and anode (2) is organic in degradation
Electronics, H are discharged during object+And carbon dioxide, electronics reach cathode (3) through external circuit, and in cathode (3) and H+In conjunction with generation
Hydrogen, while adding methanation inhibitor in the electrolyte of the electrolytic cell and stirring electrolyte, with the operation of static basis；
When electric current is lower than 0.1mA in microorganism electrolysis cell, fresh electrolyte is replaced, is denoted as a cycle of operation, repeats multiple periods,
Until microorganism electrolysis cell starts to produce hydrogen.
Preferably, methanation inhibitor is 3- nitro ester -1- propyl alcohol, and concentration is 5.0 × 10-6-5.0×10-3mol/L。
Preferably, culture medium is made of sodium acetate, phosphate buffer, electrolytes and minerals.
Preferably, inoculum is selected from one or more of excess sludge and anaerobic sludge.
Preferably, the mode of stirring be selected from turbine stirring, impeller stirring, paddle stirring, anchor formula stirring, pusher stirring and
One or more of magnetic agitation.
By adopting the above scheme, the beneficial effects of the present invention are:
The first, the first hydrophobic permeable membrane and the second hydrophobic permeable membrane are respectively placed in the rear side of cathode in system of the invention
And front side, hydrogen remaining in cathode side and electrolyte is collected respectively, to play synergistic effect, i.e., negative pressure pump passes through the first collection
Tracheae collects the hydrogen of cathode side, and hydrogen remaining in electrolyte is collected by the second gas collecting tube, so that negative pressure pump is realized
Double negative pressure gas collections achieve the purpose that quickly to collect the hydrogen generated in the system, are difficult to the methanogen in electrolyte and hydrogen
Gas contact avoids methanogen from generating methane using methyl coenzyme M consumption hydrogen, to inhibit methanation.
The second, the present invention adds 5.0 × 10 in the production hydrogen methods of bioelectrochemistry-6-5.0×10-3The methane of mol/L
Change inhibitor 3-NOP, so that the methyl coenzyme M chemical inactivation of methanogen, avoids methanogen and consume by methyl coenzyme M
Hydrogen has cut off the metabolic pathway of methanogen, the purpose for inhibiting methanation is furthermore achieved, to significantly enhance system
H2-producing capacity so that bioelectrochemistry system for producing hydrogen has more application and popularization value.
Cathode and anode exist together a Room in third, system of the invention, reduce system internal resistance, improve coulombic efficiency,
Further achieve the purpose that system high efficiency, lasting H2-producing capacity.
Detailed description of the invention
Fig. 1 is that the manifold type bioelectrochemistry production hydrogen of the embodiment of the present invention 1 and comparative example and the structure of collection system are shown
It is intended to.
Fig. 2 is that the manifold type bioelectrochemistry of the embodiment of the present invention 2 produces the structural schematic diagram of hydrogen and collection system.
Fig. 3 is the production hydrogen effect that manifold type bioelectrochemistry of the invention produces each embodiment and comparative example in hydrogen and collection system
Fruit schematic diagram.
Specific embodiment
Hydrogen and collection device, system are produced the present invention provides a kind of manifold type bioelectrochemistry and produce hydrogen methods.
<manifold type bioelectrochemistry produces hydrogen and collection device>
A kind of manifold type bioelectrochemistry produces hydrogen and collection device, as shown in Figure 1 comprising electrolysis chamber 1, anode 2, yin
Pole 3, the first hydrophobic permeable membrane 4, the first gas collecting tube 9, the second hydrophobic permeable membrane 6, the second gas collecting tube 10, third gas collecting tube 11, three
Logical 8, negative pressure pump 12 and airbag 13.
Wherein, for electrolysis chamber 1 for accommodating electrolyte, the methanation inhibitor added in electrolyte is 3- nitro ester -1-
Propyl alcohol (3-NOP), concentration are 5.0 × 10-6-5.0×10-3Mol/L not only can guarantee effective inhibition to methanogen, but also not
The activity for reducing electricity production bacterium achievees the purpose that improve coulombic efficiency, to guarantee system high efficiency, lasting H2-producing capacity.
Therefore, methanation inhibitor 3-NOP is introduced in electrolyte can result in the methyl coenzyme M chemistry mistake of methanogen
It is living, methanogen is avoided by methyl coenzyme M and consumes hydrogen generation methane, has been cut off the metabolic pathway of methanogen, has been realized
The purpose for inhibiting methanation, to enhance the H2-producing capacity of system.3-NOP mainly passes through targeting methyl coenzyme M reduction
The active site of enzyme blocks the eubolism of methanogen, and organism nonhazardous is acted on.And has use 3-NOP at present
In the research for inhibiting ruminant tumor gastric discharge of methane, 3-NOP can effectively reduce in cow rumen about 30% methane row
High-volume, and toxic action is not generated to milk cow.
Electrolyte is selected from the mixed liquor containing low molecular organic acids, can produce electricity bacterium quickly by anode containing low molecular organic acids
It utilizes, to mean quickly to generate free electron and H+, the chemical property of the device is not only increased, and also accelerate
The generation of hydrogen；Electrolyte includes but is not limited to that organic waste anaerobic fermentation liquid, organic waste water anaerobic fermentation liquid and carbochain number exist
Low molecular organic acids mixed liquor within 12 etc. is easily utilized by the electricity production bacterium in anode biomembrane, is further conducive to sun
Pole 2 continues, steadily supplies free electron and H+。
Anode 2 is for supplying electronics and H+；Anode 2 includes but is not limited to carbon brush, carbon felt, graphite felt and carbon cloth etc., anode 2
Easily adhere to for microorganism, the electrode of large specific surface area, is conducive to anode and continues, steadily supply free electron and H+, not only mention
The high chemical property of the device, also accelerates hydrogen generation.
Cathode 3 is close to the first hydrophobic permeable membrane 4 for generating hydrogen, rear side, and the length of the first hydrophobic permeable membrane 4 is greater than
The length of cathode 3, the first hydrophobic permeable membrane 4 divide for major part and secondary part, the major part of the first hydrophobic permeable membrane 4
Length is identical as the length of cathode 3, and the secondary part of the first hydrophobic permeable membrane 4 is 3 liang of end sides of cathode and the side wall for being electrolysed chamber 1
The part of formation, the major part of the first hydrophobic permeable membrane 4 collect the hydrogen of 3 side of cathode, the secondary mian part of the first hydrophobic permeable membrane 4
Divide and not only collects the hydrogen of 3 side of cathode but also collect hydrogen remaining in electrolyte, the major part of the first hydrophobic permeable membrane 4
Synergistic effect is played with the secondary part of the first hydrophobic permeable membrane 4, the hydrogen near collected both cathode 3；Wherein, the first gas collection
Pipe 9 is used to collect the hydrogen of 3 side of cathode, runs through the side wall of the first gas collection chamber 5 and is set to 3 rear side of cathode, thus after cathode 3
First hydrophobic permeable membrane 4 of side electrolysis chamber 1 adjacent thereto forms the first gas collection chamber that hydrogen is collected for the first gas collecting tube 9
5, in order to the quick collection of hydrogen；Low, alkali corrosion resistance the electrode for hydrogen-evolution overpotential of cathode 3, including but not limited to Stainless Steel felt,
Graphene electrodes, carbon nanotube electrode, palladium modified electrode or platinum modified electrode etc., are conducive to free electron and H+In 3 knot of cathode
Conjunction forms hydrogen, to improve the H2-producing capacity of the device.
Second gas collecting tube 10 is through the side wall for being electrolysed chamber 1 and is set to 3 front side of cathode, and the lower end of the second gas collecting tube 10 is inverted
The endface of funnel structure, the funnel structure is equipped with the second hydrophobic permeable membrane 6, and the second hydrophobic permeable membrane 6 is laid in electrolyte,
The second gas collection chamber 7 that hydrogen is collected for the second gas collecting tube 10 is formed between second hydrophobic permeable membrane 6 and upside down funnel structure, because
What this second gas collecting tube 10 was collected is hydrogen remaining in electrolyte.
Threeway 8 is for connecting the other end of the first gas collecting tube 9, the other end of the second gas collecting tube 10 and third gas collecting tube 11
One end.
Negative pressure pump 12 is connect by the other end of third gas collecting tube 11 with threeway 8, for passing through third gas collecting tube 11 and three
Apply negative pressure respectively in logical 8 pair of first gas collecting tube 9, the second gas collecting tube 10；Negative pressure pump 12 includes but is not limited to vacuum pump and suction
Pump etc. collects the hydrogen that 3 electrode of cathode generates by subatmospheric negative pressure, the methanogen in electrolyte is made to be difficult to contact
To hydrogen, methanogen is avoided using methyl coenzyme M consumption hydrogen and generates methane, realizes the purpose for inhibiting methanation, from
And it ensure that system high efficiency, lasting H2-producing capacity.
In summary, the first hydrophobic permeable membrane 4 and the second hydrophobic permeable membrane 6 are respectively placed in rear side and the front side of cathode 3, point
Hydrogen that Shou Ji be not remaining in 3 side of cathode and electrolyte, while also functioning to synergistic effect, i.e., negative pressure pump 12 passes through the first gas collecting tube
The 9 main hydrogen for collecting 3 side of cathode, also collect hydrogen remaining in electrolyte, thus negative pressure pump 12 by the second gas collecting tube 10
It realizes double negative pressure gas collections, achievees the purpose that quickly to collect the hydrogen generated in the device, be difficult to the methanogen in electrolyte
It is contacted with hydrogen, avoids methanogen from generating methane using methyl coenzyme M consumption hydrogen, to inhibit methanation；In addition, anode
2 and the Room that exists together of cathode 3 to reduce system internal resistance improve coulombic efficiency, further reach system high efficiency, constantly
The purpose of H2-producing capacity.
Airbag 13 is connected by pipeline and negative pressure pump 12 with the other end of third gas collecting tube 11, for collecting and storing hydrogen
Gas.
Specifically, manifold type bioelectrochemistry produces the course of work of hydrogen and collection device are as follows: manifold type bioelectrochemistry produces
Methanation inhibitor 3-NOP is added in electrolyte in hydrogen and collection device, anode biomembrane is released during degradation of organic substances
Electric discharge and H+, electronics reaches cathode 3 through external circuit, and in cathode 3 and H+In conjunction with generation hydrogen；Negative pressure pump 12 by threeway 8 from
The hydrogen that cathode 3 generates is collected in the first gas collection chamber 5 at first gas collecting tube 9, and the from the second gas collecting tube 10 simultaneously
Strengthen in two gas collection chambers 7 and collect hydrogen remaining in electrolyte, makes the methanogen in electrolyte be difficult to contact with hydrogen, keep away
Exempt from methanogen and generate methane using methyl coenzyme M consumption hydrogen, therefore inhibits methanation.
<manifold type bioelectrochemistry produces hydrogen and collection system>
A kind of manifold type bioelectrochemistry produces hydrogen and collection system comprising manifold type bioelectrochemistry produces hydrogen and collects system
The building of system and manifold type bioelectrochemistry produce the operation of hydrogen and collection system.
Wherein, manifold type bioelectrochemistry produce the building of hydrogen and collection system include: electrolysis chamber 1, anode 2, cathode 3,
First hydrophobic permeable membrane 4, the first gas collection chamber 5, the second hydrophobic permeable membrane 6, the second gas collection chamber 7, threeway 8, the first gas collecting tube
9, the second gas collecting tube 10, third gas collecting tube 11, negative pressure pump 12, airbag 13, external power supply 14, resistance 15, collector 16 and conducting wire
17。
Wherein, external power supply 14 is pressure stabilizing external power supply, for adjusting the voltage of the system；External power supply 14 passes through conducting wire
17 are separately connected anode 2 and cathode 3；The voltage of external power supply 14 is 0.3-1.8V.
Collector 16 is digital acquisition device, for showing the electric current of the system；Digital acquisition device passes through conducting wire 17 and resistance
15 both ends are connected.
The system is integrally fixed by bolts, and respectively sentences rubber stopper or seal with elastometic washer, junction epoxy resin coating with
Guarantee the leakproofness of whole system.
Manifold type bioelectrochemistry produces hydrogen and the operation of collection system includes the following steps: to fill electricity in electrolysis chamber 1
Liquid is solved, adds methanation inhibitor 3-NOP in electrolyte, is 0.3- by the voltage that pressure stabilizing external power supply controls the system
1.8V, while starting negative pressure pump 12, by threeway 8 from from the first gas collecting tube 9 the first gas collection chamber 5,10 at the second gas collecting tube
The second gas collection chamber 7 in collected in hydrogen to airbag 13 respectively, that is, the hydrogen generated under the negative pressure that negative pressure pump is applied, warp
First hydrophobic permeable membrane 4 and the second hydrophobic permeable membrane 6 are collected into airbag 13 from 3 quick separating of cathode；If with sequence batch side
Formula operation is denoted as a cycle of operation, and replace fresh electricity when data collector shows the electric current of the system lower than 0.1mA
Solve liquid；If being run with continuous stream mode, the flow velocity by adjusting electrolyte makes the electric current of system not less than 0.1mA.
<producing hydrogen methods>
The present invention carries out electricity production bacterium enrichment, micro- life to anode electrode first with microbiological fuel cell (MFC) mode operation
Object fuel cell top end opening, cathode carried catalyst side are directly directly exposed to air with electrolyte contacts, the other side；Its
It is secondary be transferred to microorganism electrolysis cell (MEC) mode operation after, microorganism electrolysis cell top end opening sealing, cathode electrode side directly with
Electrolyte contacts, the other side are close to hydrophobic permeable membrane, are connected by gas collecting tube with negative pressure pump, then pass through gas collecting tube and airbag phase
Even.
Specifically, hydrogen is produced using above-mentioned manifold type bioelectrochemistry and collection system is realized and produces hydrogen methods comprising as follows
Step:
(1) anode is cultivated under microbiological fuel cell mode produce electricity bacterium
By culture medium, 1:1 is mixed by volume with inoculum, the dissolution for being passed through high pure nitrogen stripping 10min to go in water removal
Then oxygen is added in microbiological fuel cell；Resistance is accessed in closed circuit system, is run with static basis, when
After the voltage at resistance both ends is more than 0.1V, no longer need to culture medium is added directly in microbiological fuel cell, weight with inoculum
Multiple at least three periods think that anode electricity production bacterium has been enriched with until microbiological fuel cell stablizes output maximum voltage at this time
At；
(2) hydrogen manufacturing under microorganism electrolysis cell mode
Anode biomembrane starts microorganism electrolysis cell after taming, and the cathode of microbiological fuel cell is replaced with microorganism
The cathode of electrolytic cell, is transferred to microorganism electrolysis cell (MEC) mode under the applied voltage of 0.3-1.8V, anode 2 by conducting wire with
The anode of external power supply 14 is connected, and cathode 3 is connected by conducting wire with 14 cathode of external power supply, and anode 2 is in degradation of organic substances process
Middle release electronics, H+And carbon dioxide, electronics reach cathode 3 through external circuit, and in cathode 3 and H+In conjunction with generation hydrogen, while
Methanation inhibitor is added in the electrolyte of the electrolytic cell and stirs electrolyte, with the operation of static basis；When microorganism electricity
When electric current is lower than 0.1mA in Xie Chi, fresh electrolyte is replaced, is denoted as a cycle of operation, multiple periods are repeated, until microorganism
Electrolytic cell starts to produce hydrogen, while starting negative pressure pump, quickly collects in the hydrogen to airbag 13 that cathode 3 generates.
Wherein, methanation inhibitor is 3- nitro ester -1- propyl alcohol, and concentration is 5.0 × 10-6-5.0×10-3mol/L。
Culture medium is made of sodium acetate, phosphate buffer, electrolytes and minerals.
Inoculum is selected from one or more of excess sludge or anaerobic sludge.
The agitating mode of electrolyte includes but is not limited to turbine stirring, impeller stirring, paddle stirring, anchor formula stirring, promotes
Formula stirring or magnetic agitation etc. reach and reduce concentration polarization influence, accelerate H+From 2 electrode of anode to 3 electrode transfer of cathode.Pass through
On the one hand the stirring of electrolyte guarantees electrolyte homogeneous to the full extent, reduce anode nearby concentration and electricity in electrolysis chamber 1
The difference of liquid concentration is solved, and then can reduce concentration polarization；On the other hand be conducive to H+Migration in the electrolytic solution, to promote
Cathode generates hydrogen；In addition, interior circulation can also make the low molecular organic acids in electrolyte be fully utilized.
The present invention is further illustrated with reference to embodiments.
Embodiment 1:
The manifold type bioelectrochemistry of the present embodiment produces hydrogen and the structure of collection system is as shown in Figure 1 comprising electrolyte chamber
Room 1, anode 2, cathode 3, the first hydrophobic permeable membrane 4, the first gas collection chamber 5, the second hydrophobic permeable membrane 6, the second gas collection chamber 7,
Threeway 8, the first gas collecting tube 9, the second gas collecting tube 10, third gas collecting tube 11, negative pressure pump 12, airbag 13, external power supply 14, resistance
15, collector 16 and conducting wire 17, electrolysis chamber 1 are the cuboid that pmma material is processed into, and inside is equipped with height and is
5.5cm, the cylindrical cavity that diameter is 3cm (cavity volume is about 39ml, and effective liquid volume is 30ml), the use of anode 2 3cm ×
The conductive carbon brush of 3cm is formed by the conducting wire that carbon fiber and diameter are 1mm according to helical form test tube brush sample preparation, and cathode is stainless steel
The conducting wire that felt, anode 2 and cathode 3 are all made of 0.5mm diameter is connected with external circuit, and negative pressure pump 12 is BT-100L flow type Lange
Negative pressure pump.
The production hydrogen methods of the present embodiment specifically comprise the following steps:
(1) anode is cultivated under microbiological fuel cell (MFC) mode produce electricity bacterium
Culture medium (being made of sodium acetate, phosphate buffer, vitamin and microelement) and inoculum is (remaining dirty
Mud is derived from the sludge of secondary sedimentation tank of sewage treatment work) 1:1 is mixed by volume, and is passed through high pure nitrogen stripping 10min to go to remove water
In dissolved oxygen, be then added in microbiological fuel cell；1000 Ω resistance are accessed, in closed circuit system with static state batch
Secondary mode is run, and after the voltage when resistance both ends is more than 0.1V, no longer needs to use inoculum, culture medium is added directly microorganism
It in fuel cell, repeated at least three periods, until microbiological fuel cell stablizes output maximum voltage, thinks that anode produces at this time
Electric bacterium has been enriched with completion；
(2) hydrogen manufacturing under microorganism electrolysis cell mode
The cathode of microbiological fuel cell is replaced with to the cathode of microorganism electrolysis cell, using sludge anaerobic fermentation liquid as sun
Pole substrate, in the applied voltage of 0.8V, (carbon brush anode is connected by conducting wire with the anode of external power supply, stainless steel felt cathode electrode
Be connected by conducting wire with the cathode of external power supply) under be transferred to microorganism electrolysis cell mode, with static basis operation；When micro- life
When electric current is lower than 0.1mA in object electrolytic cell, replaces fresh electrolyte, be denoted as a cycle of operation, each cycle run for 24 hours, until
Microorganism electrolysis cell can start success after stablizing, and start to produce hydrogen.
The operational process of the manifold type bioelectrochemistry system for producing hydrogen of the present embodiment are as follows: using sludge anaerobic fermentation liquid as sun
Pole substrate when the two sides of microorganism electrolysis cell apply voltage (0.8V), while starting negative pressure pump and applying negative pressure 0.01MPa,
And add methanation inhibitor 3-NOP stirring electrolyte into the electrolyte of the electrolytic cell and carry out producing hydrogen reaction, the system
Hydrogen rate (hydrogen output/total gas production) is produced as shown in curve a in Fig. 3.
Embodiment 2:
The manifold type bioelectrochemistry of the present embodiment produces hydrogen and collection system based on common single chamber MEC in above-described embodiment
On the basis of made a kind of simplification, structure is as shown in Figure 2 comprising electrolysis chamber 1, anode 2, cathode 3, collection port 4, hydrophobic
Ventilated membrane 5, the first conducting wire 6, external power supply 7, the second conducting wire 8, resistance 9, privates 10, collector 11, gas collecting tube 12, negative pressure
Pump 13, pipeline 14 and airbag 15, electrolysis chamber 1 are the cuboid that pmma material is processed into, and inside is equipped with height and is
5.5cm, the cylindrical cavity that diameter is 3cm (cavity volume is about 39ml, and effective liquid volume is 30ml), the use of anode 2 3cm ×
The conductive carbon brush of 3cm is formed according to helical form test tube brush sample preparation by the conducting wire that carbon fiber and diameter are 1mm, is close on rear side of cathode 3
Hydrophobic permeable membrane 5, for collecting the hydrogen of 3 side of cathode, cathode is stainless steel felt, and anode 2 and cathode 3 are all made of 0.5mm diameter
Conducting wire be connected with external circuit, the collection port that negative pressure pump 13 passes through the other end of gas collecting tube 12 and the setting of microorganism electrolysis cell upper end
4 connections, for negative pressure is applied in gas collecting tube 12, negative pressure pump 13 to be BT-100L flow type Lange negative pressure pump；Negative pressure pump 13 includes
But be not limited to vacuum pump and suction pump etc., the hydrogen that 3 electrode of cathode generates is collected by subatmospheric negative pressure, makes electrolyte
In methanogen be difficult to touch hydrogen, avoid methanogen using methyl coenzyme M consumption hydrogen generate methane, realize
The purpose for inhibiting methanation, to ensure that system high efficiency, lasting H2-producing capacity.
Wherein, airbag 15 is connected by pipeline and negative pressure pump 13 with the other end of gas collecting tube 12, for collecting and storing hydrogen
Gas.
External power supply 7 is pressure stabilizing external power supply, for adjusting the voltage of the system；External power supply 7 by the first conducting wire 6,
Second conducting wire 8 and privates 10 are separately connected anode 2 and cathode 3；The voltage of external power supply 7 is 0.3-1.8V.
Collector 11 is digital acquisition device, for showing the electric current of the system；Digital acquisition device passes through the second conducting wire 8, the
Three wires 10 are connected with the both ends of resistance 9.
The system is integrally fixed by bolts, and respectively sentences rubber stopper or seal with elastometic washer, junction epoxy resin coating with
Guarantee the leakproofness of whole system.
The production hydrogen methods of the present embodiment are the same as embodiment 1.
The operational process of the manifold type bioelectrochemistry system for producing hydrogen of the present embodiment are as follows: using sludge anaerobic fermentation liquid as sun
Pole substrate when the two sides of microorganism electrolysis cell apply voltage (0.8V), while starting negative pressure pump and applying negative pressure 0.01MPa,
And add methanation inhibitor 3-NOP stirring electrolyte into the electrolyte of the electrolytic cell and carry out producing hydrogen reaction, the system
Hydrogen rate (hydrogen output/total gas production) is produced as shown in curve b in Fig. 3.
Comparative example 1:
The manifold type bioelectrochemistry of this comparative example produces hydrogen and the structure of collection system is as shown in Figure 1 comprising electrolyte chamber
Room 1, anode 2, cathode 3, the first hydrophobic permeable membrane 4, the first gas collection chamber 5, the second hydrophobic permeable membrane 6, the second gas collection chamber 7,
Threeway 8, the first gas collecting tube 9, the second gas collecting tube 10, third gas collecting tube 11, negative pressure pump 12, airbag 13, external power supply 14, resistance
15, collector 16 and conducting wire 17, electrolysis chamber 1 are the cuboid that pmma material is processed into, and inside is equipped with height and is
5.5cm, the cylindrical cavity that diameter is 3cm (cavity volume is about 39ml, and effective liquid volume is 30ml), the use of anode 2 3cm ×
The conductive carbon brush of 3cm is formed by the conducting wire that carbon fiber and diameter are 1mm according to helical form test tube brush sample preparation, and cathode is stainless steel
The conducting wire that felt, anode 2 and cathode 3 are all made of 0.5mm diameter is connected with external circuit, and negative pressure pump 12 is BT-100L flow type Lange
Negative pressure pump.
The production hydrogen methods of this comparative example are the same as embodiment 1.
The operational process of the manifold type bioelectrochemistry system for producing hydrogen of this comparative example are as follows: using sludge anaerobic fermentation liquid as sun
Pole substrate only starts negative pressure pump 12 and applies negative pressure 0.01MPa when the two sides of microorganism electrolysis cell apply voltage (0.8V),
Methanation inhibitor 3-NOP is not added into the electrolyte of the electrolytic cell, runs 20 periods, the production hydrogen rate of the system (produces
Hydrogen amount/total gas production) as shown in curve c in Fig. 3.
Comparative example 2:
The manifold type bioelectrochemistry of this comparative example produces hydrogen and the structure of collection system is as shown in Figure 1 comprising electrolyte chamber
Room 1, anode 2 (, cathode 3, the first hydrophobic permeable membrane 4, the first gas collection chamber 5, the second hydrophobic permeable membrane 6, the second gas collection chamber 7,
Threeway 8, the first gas collecting tube 9, the second gas collecting tube 10, third gas collecting tube 11, negative pressure pump 12, airbag 13, external power supply 14, resistance
15, collector 16 and conducting wire 17, electrolysis chamber 1 are the cuboid that pmma material is processed into, and inside is equipped with height and is
5.5cm, the cylindrical cavity that diameter is 3cm (cavity volume is about 39ml, and effective liquid volume is 30ml), the use of anode 2 3cm ×
The conductive carbon brush of 3cm is formed by the conducting wire that carbon fiber and diameter are 1mm according to helical form test tube brush sample preparation, and cathode is stainless steel
The conducting wire that felt, anode 2 and cathode 3 are all made of 0.5mm diameter is connected with external circuit, and negative pressure pump 12 is BT-100L flow type Lange
Negative pressure pump.
The production hydrogen methods of this comparative example are the same as embodiment 1.
The operational process of the manifold type bioelectrochemistry system for producing hydrogen of this comparative example are as follows: using sludge anaerobic fermentation liquid as sun
Pole substrate when the two sides of microorganism electrolysis cell apply voltage (0.8V), while not starting negative pressure pump 12, only to the electrolytic cell
Added in electrolyte methanation inhibitor 3-NOP stirring electrolyte and carry out produce hydrogen reaction, the system production hydrogen rate (hydrogen output/
Total gas production) as shown in curve d in Fig. 3.
In summary, the manifold type bioelectrochemistry of comparative example 1 produces hydrogen and collection system in the case where there is condition of negative pressure, the system
Production hydrogen rate be maintained at higher level in initial operating stage, illustrate in the electrolyte that methane phase reaction is suppressed, system is to produce hydrogen
Key reaction；After running some cycles, there is downward trend in the production hydrogen rate of system, illustrates that methane backeria is adapting to negative pressure in the system
Growth and breeding is started again at after low hydrogen condition, so that the production hydrogen rate of system declines；The manifold type bioelectrochemistry of comparative example 2
When producing hydrogen and collection system and not starting negative pressure pump and only add methanation inhibitor 3-NOP, the production hydrogen rate of the system can be maintained always
In higher level, illustrate that its internal methane phase reaction is suppressed, there is only less hydrogen consumptions；The system of embodiment 1 starts
When just start negative pressure pump simultaneously and apply and negative pressure and add methanation inhibitor into electrolyte, therefore the production hydrogen rate of the system is always
Be maintained at higher level, and be higher than comparative example 1, in comparative example 2 system production hydrogen rate, show method in the embodiment compared to
Simple postposition negative pressure pump apply negative pressure or it is simple add methanation inhibitor 3-NOP, inhibit with good methanation
Consumption, can make system keep efficient, lasting H2-producing capacity.Embodiment 2 produces hydrogen and collection to the bioelectrochemistry of embodiment 1
System has done simplification, can collect most of hydrogen of cathode generation, effectively delays methanation, keeps good and persistently produces Hydrogen Energy
Power；But remaining Hydrogen collection is limited in hydrogen and electrolyte due to generating for cathode both ends, and effect is slightly worse than real
Apply example 1.
The above-mentioned description to embodiment is that this hair can be understood and used for the ease of those skilled in the art
It is bright.Those skilled in the art obviously readily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiments, without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments.
Those skilled in the art's principle according to the present invention, not departing from improvement that scope of the invention is made and modification all should be at this
Within the protection scope of invention.
Claims (10)
1. a kind of manifold type bioelectrochemistry produces hydrogen and collection device comprising electrolysis chamber (1), anode (2) and cathode (3),
Wherein: electrolysis chamber (1) is used to accommodate electrolyte；
Anode (2), is used to supply electronics and H+；
Cathode (3), is used to generate hydrogen；
It is characterized by: its further include: the first hydrophobic permeable membrane (4), the first gas collecting tube (9), the second hydrophobic permeable membrane (6),
Two gas collecting tubes (10), third gas collecting tube (11), threeway (8), negative pressure pump (12) and airbag (13)；
It is close to the first hydrophobic permeable membrane (4) on rear side of the cathode (3)；
First gas collecting tube (9), one end run through the side wall of the first gas collection chamber (5) and are set on rear side of the cathode (3), use
In the hydrogen for collecting cathode (3) side；
Second gas collecting tube (10), one end is through the side wall for being electrolysed chamber (1) and is set on front side of the cathode (3),
Its end is equipped with second hydrophobic permeable membrane (6), and second hydrophobic permeable membrane (6) is laid in electrolyte, and described second
Gas collecting tube (10) is for collecting hydrogen remaining in electrolyte；
The threeway (8), be used to connect the other end of first gas collecting tube (9), second gas collecting tube (10) it is another
The one end at end and the third gas collecting tube (11)；
The negative pressure pump (12) is connect, for passing through with the threeway (8) by the other end of the third gas collecting tube (11)
Third gas collecting tube (11) and threeway (8) to applying negative pressure in first gas collecting tube (9), second gas collecting tube (10) respectively；
Airbag (13) is connected, for collecting with the other end of the third gas collecting tube (11) by negative pressure pump (12) and pipeline
And store hydrogen；
Methanation inhibitor is added in the electrolyte.
2. manifold type bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: described first dredges
Water ventilated membrane (4), the second hydrophobic permeable membrane (6) are selected from one in polytetrafluoroethylene film, polyvinylidene fluoride film and polyethylene film
Kind or more.
3. manifold type bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: the methanation
Inhibitor is 3- nitro ester -1- propyl alcohol, and concentration is 5.0 × 10-6-5.0×10-3mol/L。
4. manifold type bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: the electrolyte
Selected from the mixed liquor containing low molecular organic acids；
Preferably, the mixed liquor containing low molecular organic acids is selected from organic waste anaerobic fermentation liquid, organic waste water anaerobic fermentation
The low molecular organic acids mixed liquor of liquid and carbochain number within 12 more than one.
5. manifold type bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: the anode
(2) selected from one or more of carbon brush, carbon felt, graphite felt and carbon cloth；
Preferably, the cathode (3) is selected from Stainless Steel felt, Graphene electrodes, carbon nanotube electrode, palladium modified electrode and platinum modification
One or more of electrode.
6. manifold type bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: the negative pressure pump
(12) one or more of vacuum pump and suction pump are selected from.
7. a kind of realize that manifold type bioelectrochemistry described in any one of claims 1-6 produces hydrogen and the manifold type of collection device is raw
Object electrochemistry produces hydrogen and collection system, it is characterised in that: it further includes external power supply (14), resistance (15) and collector (16)；
The external power supply (14) is pressure stabilizing external power supply, is used to adjust the voltage of the system；The external power supply (14) is logical
It crosses conducting wire (17) and is separately connected anode (2) and cathode (3)；
The collector (16) is digital acquisition device, is used to show the electric current of the system；The digital acquisition device passes through conducting wire
(17) it is connected with the both ends of the resistance (15).
8. bioelectrochemistry according to claim 7 produces hydrogen and collection system, it is characterised in that: the external power supply (14)
Voltage be 0.3-1.8V.
9. a kind of manifold type bioelectrochemistry according to claim 7 produces hydrogen and collection system realizes the method for producing hydrogen,
Be characterized in that: it includes the following steps:
(1) anode is cultivated under microbiological fuel cell mode produce electricity bacterium
By culture medium, 1:1 is mixed by volume with inoculum, is removed dissolved oxygen therein, is then added to microbiological fuel cell
It is interior；Resistance is accessed in closed circuit system, with the operation of static basis, after the voltage when resistance both ends is more than 0.1V, nothing
Inoculum need to be used again, the culture medium is added directly in microbiological fuel cell, repeated at least three periods, until micro- life
Object stable fuel cell exports maximum voltage, thinks that anode electricity production bacterium has been enriched with completion at this time；
(2) hydrogen manufacturing under microorganism electrolysis cell mode
Anode biomembrane starts microorganism electrolysis cell after taming, and the cathode of microbiological fuel cell is replaced with microorganism electrolysis
The cathode in pond, is transferred to microorganism electrolysis cell mode under the applied voltage of 0.3-1.8V, and anode (2) passes through conducting wire and external power supply
(14) anode is connected, and cathode (3) is connected by conducting wire with the cathode of external power supply (14), and anode (2) is in degradation of organic substances mistake
Electronics, H are discharged in journey+And carbon dioxide, electronics reach cathode (3) through external circuit, and in cathode (3) and H+In conjunction with generate hydrogen,
Methanation inhibitor is added in the electrolyte of the electrolytic cell and stirs the electrolyte simultaneously, with the operation of static basis；
When electric current is lower than 0.1mA in microorganism electrolysis cell, fresh electrolyte is replaced, is denoted as a cycle of operation, repeats multiple periods,
Until microorganism electrolysis cell starts to produce hydrogen.
10. according to the method described in claim 9, it is characterized by: the methanation inhibitor be 3- nitro ester -1- propyl alcohol,
Its concentration is 5.0 × 10-6-5.0×10-3mol/L；
Preferably, the culture medium is made of sodium acetate, phosphate buffer, electrolytes and minerals；
Preferably, the inoculum is selected from one or more of excess sludge and anaerobic sludge；
Preferably, the mode of the stirring be selected from turbine stirring, impeller stirring, paddle stirring, anchor formula stirring, pusher stirring and
One or more of magnetic agitation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110367426A (en) * | 2019-07-03 | 2019-10-25 | 浙江大学 | A kind of ultrasound-electrode-nano-porous films coupled hydrogen making disinfection system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2241846A1 (en) * | 1997-06-27 | 1998-12-27 | Mario De Souza | Hydrogen generating apparatus |
| CN102400169A (en) * | 2011-11-01 | 2012-04-04 | 浙江大学 | Method for producing hydrogen by alkalescent microbe electrolysis |
| US20150233001A1 (en) * | 2010-03-17 | 2015-08-20 | Board Of Trustees Of Michigan State University | Microbial electrochemical cells and methods for producing electricity and bioproducts therein |
| CN106011176A (en) * | 2016-07-01 | 2016-10-12 | 河海大学 | Method for producing hydrogen from residual sludge by anaerobic fermentation and microbial electrolysis cell coupling |
| CN106115864A (en) * | 2016-08-18 | 2016-11-16 | 福州品行科技发展有限公司 | A kind of hydrogen-rich water tumbler |
-
2018
- 2018-12-28 CN CN201811618595.1A patent/CN109680290B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2241846A1 (en) * | 1997-06-27 | 1998-12-27 | Mario De Souza | Hydrogen generating apparatus |
| US20150233001A1 (en) * | 2010-03-17 | 2015-08-20 | Board Of Trustees Of Michigan State University | Microbial electrochemical cells and methods for producing electricity and bioproducts therein |
| CN102400169A (en) * | 2011-11-01 | 2012-04-04 | 浙江大学 | Method for producing hydrogen by alkalescent microbe electrolysis |
| CN106011176A (en) * | 2016-07-01 | 2016-10-12 | 河海大学 | Method for producing hydrogen from residual sludge by anaerobic fermentation and microbial electrolysis cell coupling |
| CN106115864A (en) * | 2016-08-18 | 2016-11-16 | 福州品行科技发展有限公司 | A kind of hydrogen-rich water tumbler |
Non-Patent Citations (4)
| Title |
|---|
| PA OCHOA GARCIA: "MITIGACION DE LA EMISION DE METANO EN LA FERMENTACION RUMINAL, MEDIANTE EL USO DE ACIDO 3-NITRO-1-PROPINICO", 《MAESTRÍA THESIS, UNIVERSIDAD AUTONOMA DE CHIHUAHUA.》 * |
| 蒋阳月 等: "微生物电解池制氢技术的研究进展", 《现代化工》 * |
| 路璐: "生物质微生物电解池强化产氢及阳极群落结构环境响应", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 陈小粉 等: "微生物电解产氢新技术研究现状与进展", 《环境科学与技术》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110367426A (en) * | 2019-07-03 | 2019-10-25 | 浙江大学 | A kind of ultrasound-electrode-nano-porous films coupled hydrogen making disinfection system |
| CN110367426B (en) * | 2019-07-03 | 2022-03-18 | 浙江大学 | Ultrasonic-electrode-nano porous membrane coupling hydrogen production sterilization system |
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