CN109680288A - Bioelectrochemistry produces hydrogen and collection device and system - Google Patents
Bioelectrochemistry produces hydrogen and collection device and system Download PDFInfo
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- CN109680288A CN109680288A CN201811617911.3A CN201811617911A CN109680288A CN 109680288 A CN109680288 A CN 109680288A CN 201811617911 A CN201811617911 A CN 201811617911A CN 109680288 A CN109680288 A CN 109680288A
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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
- 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
- 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
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- 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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- 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
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- 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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Abstract
The present invention provides a kind of bioelectrochemistries to produce hydrogen and collection device and system, is close to the first hydrophobic permeable membrane in the device on rear side of cathode；First gas collecting tube is set on rear side of cathode, is accordingly used in collecting the hydrogen of cathode side；Second gas collecting tube is set on front side of cathode, and end is equipped with the second hydrophobic permeable membrane and lays and is accordingly used in collecting hydrogen remaining in electrolyte in the electrolytic solution；Negative pressure pump is by applying negative pressure, and airbag is by negative pressure pump for collecting and storing hydrogen；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 of the invention, 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, achieve the purpose that quickly to collect the hydrogen that microorganism electrolysis generates, to inhibit methanation；In addition, cathode and anode exist together a Room in the system, system internal resistance is reduced, coulombic efficiency is improved, achievees the purpose that efficient, lasting H2-producing capacity.
Description
Technical field
The invention belongs to debirs/waste water technology fields, and in particular to a kind of bioelectrochemistry produces hydrogen and collection device
And system.
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 vast potential for future development in debirs/waste water process field.Bioelectrochemistry system for producing hydrogen is divided into double
Room and single chamber two major classes collect hydrogen by gas natural diffuseness.The anode and cathode of dual chamber bioelectrochemistry system for producing hydrogen
It being ion exchanged film and is separated into two Room, methanogen is more difficult to touch hydrogen, also it is less competitive than electricity production bacterium in substrate use aspects,
Therefore Methanation 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.It is single
The anode and cathode of room bioelectrochemistry 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,
As Developing mainstream；But hydrogen easily diffuses in electrolyte, and methanogen consumes hydrogen methane phase by methyl coenzyme M, causes
Methanogen is largely proliferated, and methanation phenomenon is serious, and H2-producing capacity is gradually reduced.Currently, inhibiting bioelectrochemistry system for producing hydrogen
Methanation has following methods:
1. physical method: 1) introducing air and inhibit methanogen activity, but the activity of electricity production bacterium can be reduced in this way；2) it mentions
High applied voltage is to 0.7V or more, this method is only effective in the early stage, and reactor is run in a fortnight, still with methane phase
Based on；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) ultraviolet
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, it is purple
External exposure will no longer function；5) change reactor configuration, install a polytetrafluoroethylene film additional between a cathode and an anode and carry out
Separating, 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, reduces coulombic efficiency, H2-producing capacity is poor, simultaneously
The problems such as with the fouling membrane caused by Ion transfer and fouling.
2. chemical method: 1) adding acid reduces the pH of electrolyte, inhibits methanogen activity, but can also reduce production in this way
The activity of electric bacterium；2) coenzyme M analog is added as methane 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 and irritation,
For 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 present invention are to provide a kind of bioelectrochemistry and produce hydrogen and collection device.
A second object of the present invention is to provide a kind of bioelectrochemistries for realizing above-mentioned apparatus to produce hydrogen and collection system.
In order to achieve the above objectives, solution of the invention is:
A kind of bioelectrochemistry produces hydrogen and collection device comprising electrolysis chamber 1, anode 2, cathode 3, the first hydrophobic, air-permeability
Film 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 are gentle
Bag 13.
Wherein, it is electrolysed chamber 1, is used to accommodate 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 the electrolytic solution, 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, 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, sludge anaerobic fermentation 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 in Stainless Steel net, graphene modified electrode, palladium modified electrode and platinum modified electrode one
Kind or more.
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 bioelectrochemistry produces hydrogen and the bioelectrochemistry of collection device produces hydrogen and collection system, also wrap
Include 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.
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, 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.
Detailed description of the invention
Fig. 1 is the bioelectrochemistry production hydrogen of the embodiment of the present invention 1 and embodiment 2 and the structural schematic diagram of collection system.
Fig. 2 is that the bioelectrochemistry of the embodiment of the present invention 3 produces the structural schematic diagram of hydrogen and collection system.
Fig. 3 is the production hydrogen effect signal that bioelectrochemistry of the invention produces each embodiment and comparative example in hydrogen and collection system
Figure.
Specific embodiment
The present invention provides a kind of bioelectrochemistries to produce hydrogen and collection device and system.
<bioelectrochemistry produces hydrogen and collection device>
A kind of bioelectrochemistry produces hydrogen and collection device, as shown in Figure 1 comprising electrolysis chamber 1, anode 2, cathode 3, the
One hydrophobic permeable membrane 4, the second hydrophobic permeable membrane 6, the second gas collecting tube 10, third gas collecting tube 11, threeway 8, is born first gas collecting tube 9
Press pump 12 and airbag 13.
Wherein, electrolysis chamber 1 is for accommodating electrolyte；Electrolyte is selected from the mixed liquor containing low molecular organic acids, contains low point
Sub- organic acid can produce electricity bacterium by anode and quickly utilize, to mean quickly to generate free electron and H+, not only improve
The chemical property of the device, and also accelerate the generation of hydrogen；Electrolyte includes but is not limited to organic waste anaerobic fermentation
The low molecular organic acids mixed liquor etc. of liquid, organic waste water anaerobic fermentation liquid, sludge anaerobic fermentation liquid and carbochain number within 12, easily
It is utilized by the electricity production bacterium in anode biomembrane, is further conducive to anode and continues, steadily supply 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 adhering to for microorganism, the electrode of large specific surface area, the anode 2 in the present invention is the electricity production bacterium biomembrane anode tamed, from
And is conducive to anode and continues, steadily supply free electron and H+, the chemical property of the device is not only increased, is also accelerated
Hydrogen generates.
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 net,
Graphene modified electrode, palladium modified electrode and platinum modified electrode etc., are conducive to free electron and H+It is combined in cathode 3 and forms hydrogen
Gas, 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
Funnel structure, the endface of the funnel structure are equipped with the second hydrophobic permeable membrane 6, and the second hydrophobic permeable membrane 6 is laid in the electrolytic solution,
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, bioelectrochemistry produces the course of work of hydrogen and collection device are as follows: bioelectrochemistry produces hydrogen and collection device
Interior anode biomembrane discharges electronics and H during degradation of organic substances+, electronics reaches cathode 3 through external circuit, and in cathode 3
With H+In conjunction with generation hydrogen；Negative pressure pump 12 collects the production of cathode 3 by threeway 8 out of the first gas collection chamber 5 from the first gas collecting tube 9
Raw hydrogen, and strengthen out of the second gas collection chamber 7 from the second gas collecting tube 10 collect hydrogen remaining in electrolyte simultaneously, make
Methanogen in electrolyte is difficult to contact with hydrogen, and methanogen is avoided to generate methane using methyl coenzyme M consumption hydrogen, because
This inhibits methanation.
<bioelectrochemistry produces hydrogen and collection system>
A kind of bioelectrochemistry produces hydrogen and collection system comprising bioelectrochemistry produces the building and life of hydrogen and collection system
Object electrochemistry produces the operation of hydrogen and collection system.
Wherein, as shown in Figure 1, it includes: electrolysis chamber 1, anode (domestication that bioelectrochemistry, which produces hydrogen and the building of collection system,
Good electricity production bacterium biomembrane anode), cathode 3, the first hydrophobic permeable membrane 4, the first gas collection chamber 5, the second hydrophobic permeable membrane 6, the
It is two gas collection chambers 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.
Bioelectrochemistry produces hydrogen and the operation of collection system includes the following steps: to fill electrolyte in electrolysis chamber 1, leads to
Crossing pressure stabilizing external power supply and controlling the voltage of the system is 0.3-1.8V, while starting negative pressure pump 12, by threeway 8 from the first gas collection
It is collected in hydrogen to airbag 13 respectively in the second gas collection chamber 7 at the first gas collection chamber 5, the second gas collecting tube 10 at pipe 9；If
It is denoted as a cycle of operation, and more when data collector shows the electric current of the system lower than 0.1mA with sequence batch mode operation
Change fresh electrolyte；If being run with continuous stream mode, the flow velocity by adjusting electrolyte makes the electric current of system not less than 0.1mA.
The present invention is further illustrated with reference to embodiments.
Embodiment 1:
The bioelectrochemistry of the present embodiment produces hydrogen and the structure of collection system is as shown in Figure 1 comprising electrolysis chamber 1, sun
Pole 2 (the electricity production bacterium biomembrane anode tamed), cathode 3, the first hydrophobic permeable membrane 4, the first gas collection chamber 5, second are hydrophobic
Air film 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,
Inside is equipped with the cylindrical cavity (cavity volume is about 39ml, and effective liquid volume is 30ml) that height is 5.5cm, diameter is 3cm,
Anode 2 using 3cm × 3cm conductive carbon brush, by conducting wire that carbon fiber and diameter are 1mm according to helical form test tube brush sample preparation and
At negative pressure pump 12 is BT-100L flow type Lange negative pressure pump.
The bioelectrochemistry of the present embodiment produces the operational process of hydrogen and collection system are as follows: using sludge anaerobic fermentation liquid as sun
Pole substrate applies voltage (0.8V) in the two sides of microorganism electrolysis cell, while starting negative pressure pump to apply negative pressure is 0.01MPa, should
The production hydrogen rate (hydrogen output/total gas production) of system is as shown in curve a in Fig. 3.
Embodiment 2
The bioelectrochemistry of the present embodiment produces hydrogen and the structure of collection system is as shown in Figure 1 comprising electrolysis chamber 1, sun
Pole 2 (the electricity production bacterium biomembrane anode tamed), cathode 3, the first hydrophobic permeable membrane 4, the first gas collection chamber 5, second are hydrophobic
Air film 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,
Inside is equipped with the cylindrical cavity (cavity volume is about 39ml, and effective liquid volume is 30ml) that height is 5.5cm, diameter is 3cm,
Anode 2 using 3cm × 3cm conductive carbon brush, by conducting wire that carbon fiber and diameter are 1mm according to helical form test tube brush sample preparation and
At negative pressure pump 12 is BT-100L flow type Lange negative pressure pump.
The bioelectrochemistry of the present embodiment produces the operational process of hydrogen and collection system are as follows: using sludge anaerobic fermentation liquid as sun
Pole substrate applies voltage (0.8V) in the two sides of microorganism electrolysis cell, after running ten periods, restarts negative pressure pump and applies negative pressure
For 0.01MPa, the production hydrogen rate (hydrogen output/total gas production) of the system is as shown in curve b in Fig. 3.
Embodiment 3:
The bioelectrochemistry of the present embodiment produces hydrogen and collection system is based on common single chamber bioelectrochemistry system for producing hydrogen upper
It states and has made a kind of simplification on the basis of embodiment, structure is as shown in Figure 2 comprising electrolysis chamber 1, anode 2 (have been tamed
Produce electricity bacterium biomembrane anode), cathode 3, collection port 4, hydrophobic permeable membrane 5, the first conducting wire 6, external power supply 7, the second conducting wire 8, electricity
Resistance 9, privates 10, collector 11, gas collecting tube 12, negative pressure pump 13, pipeline 14 and airbag 15, electrolysis chamber 1 are organic glass
The cuboid that material is processed into, inside be equipped with height be 5.5cm, cylindrical cavity that diameter is 3cm (cavity volume is about 39ml,
Effective liquid volume is 30ml), anode 2 using 3cm × 3cm conductive carbon brush, by carbon fiber and diameter be 1mm conducting wire according to
Helical form test tube brush sample preparation forms, and hydrophobic permeable membrane 5 is close on rear side of cathode 3, for collecting the hydrogen of 3 side of cathode, negative pressure pump 13
It is connect by the other end of gas collecting tube 12 with the collection port 4 that microorganism electrolysis cell upper end is arranged, for applying in gas collecting tube 12
Negative pressure, negative pressure pump 13 are BT-100L flow type Lange negative pressure pump；Negative pressure pump 13 including but not limited to vacuum pump and suction pump etc.,
The hydrogen that cathode 3 generates is collected by negative pressure, contact of the methanogen in electrolyte with hydrogen is reduced, effectively delays methanation
Process makes system have good lasting H2-producing capacity.
Wherein, airbag 15 is connected by pipeline 14 and negative pressure pump 13 with the other end of gas collecting tube 12, for collecting and storing
Hydrogen.
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 bioelectrochemistry of the present embodiment produces the operational process of hydrogen and collection system are as follows: using sludge anaerobic fermentation liquid as sun
Pole substrate applies voltage (0.8V) in the two sides of microorganism electrolysis cell, while starting negative pressure pump to apply negative pressure is 0.01MPa, should
The production hydrogen rate (hydrogen output/total gas production) of system is as shown in curve c in Fig. 3.
Comparative example 1:
The bioelectrochemistry of this comparative example produces hydrogen and the structure of collection system is as shown in Figure 1 comprising electrolysis chamber 1, sun
Pole 2 (the electricity production bacterium biomembrane anode tamed), cathode 3, the first hydrophobic permeable membrane 4, the first gas collection chamber 5, second are hydrophobic
Air film 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,
Inside is equipped with the cylindrical cavity (cavity volume is about 39ml, and effective liquid volume is 30ml) that height is 5.5cm, diameter is 3cm,
Anode 2 using 3cm × 3cm conductive carbon brush, by conducting wire that carbon fiber and diameter are 1mm according to helical form test tube brush sample preparation and
At negative pressure pump 12 is BT-100L flow type Lange negative pressure pump.
The bioelectrochemistry of this comparative example produces the operational process of hydrogen and collection system are as follows: using sludge anaerobic fermentation liquid as sun
Pole substrate applies voltage (0.8V) in the two sides of microorganism electrolysis cell, does not start negative pressure pump, run 20 periods, the system
Production hydrogen rate (hydrogen output/total gas production) as shown in curve d in Fig. 3.
In summary, the bioelectrochemistry of comparative example 1 produces hydrogen and collection system does not utilize negative pressure pump to apply negative pressure (i.e. without negative
Press strip part), system produces hydrogen rate and is decreased obviously, therefore illustrates that methane phase reaction is increasingly becoming leading reaction in the system, the system
Generated hydrogen is captured by methanogen mostly and is utilized, so that the production hydrogen rate of system declines；Methanation is inhibited to arrange if not taking
It applies, system will be difficult to keep efficient, lasting H2-producing capacity.Just start negative pressure pump application simultaneously when the system starting of embodiment 1
Negative pressure, therefore the production hydrogen rate of the system is always held at higher level, shows that there is the system good methanation to inhibit consumption,
System can be made to keep efficient, lasting H2-producing capacity.The bioelectrochemistry of embodiment 2 is prolonged again after producing hydrogen and collection system starting
Starting negative pressure pump applies negative pressure late, and in the negative pressure pump inactive stage, the production hydrogen rate of the system is decreased obviously, therefore is illustrated in system
Methane phase reaction in portion's is increasingly becoming leading reaction, consumes generated hydrogen so as to cause the decline of hydrogen rate is produced；After applying negative pressure,
It reruns ten periods, the production hydrogen rate of the system is gone up rapidly；Therefore have obviously for having there is the system of methanation phenomenon
Inhibition methanation effect, ensure that the system high efficiency, lasting H2-producing capacity.Bioelectrochemical of the embodiment 3 to embodiment 1
It learns production hydrogen and collection system has done simplification, most of hydrogen of cathode generation can be collected, effectively delay methanation, keep good
Continue hydrogen production potential；But remaining Hydrogen collection is limited in hydrogen and electrolyte due to generating for cathode both ends, effect
Fruit is slightly worse than embodiment 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 (9)
1. a kind of bioelectrochemistry produces hydrogen and collection device comprising electrolysis chamber (1), anode (2) and cathode (3), in which: electricity
It solves 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 the second hydrophobic permeable membrane (6), and second hydrophobic permeable membrane (6) is laid in the electrolytic solution, second gas collection
Pipe (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)
The third gas collecting tube (11) and the threeway (8) to applying respectively in first gas collecting tube (9), second gas collecting tube (10)
Add negative pressure；
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.
2. bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: first hydrophobic, air-permeability
Film (4), second hydrophobic permeable membrane (6) are selected from one of polytetrafluoroethylene film, polyvinylidene fluoride film and polyethylene film
More than.
3. bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: the electrolyte, which is selected from, to be contained
The mixed liquor of low molecular organic acids.
4. bioelectrochemistry according to claim 3 produces hydrogen and collection device, it is characterised in that: described organic containing low molecule
The mixed liquor of acid is selected from organic waste anaerobic fermentation liquid, organic waste water anaerobic fermentation liquid, sludge anaerobic fermentation liquid and carbochain number and exists
One or more of low molecular organic acids mixed liquor within 12.
5. bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: the anode (2) is selected from
One or more of carbon brush, carbon felt, graphite felt and carbon cloth.
6. bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: the cathode (3) is selected from
One or more of Stainless Steel net, graphene modified electrode, palladium modified electrode and platinum modified electrode.
7. bioelectrochemistry according to claim 1 produces hydrogen and collection device, it is characterised in that: negative pressure pump (12) choosing
From one or more of vacuum pump and suction pump.
8. a kind of realize that the described in any item bioelectrochemistries of claim 1-7 produce hydrogen and the bioelectrochemistry of collection device 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).
9. bioelectrochemistry according to claim 8 produces hydrogen and collection system, it is characterised in that: the external power supply (14)
Voltage be 0.3-1.8V.
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| CN110777389A (en) * | 2019-12-03 | 2020-02-11 | 武汉理工大学 | Tubular membrane electrode microbial electrochemical device |
| WO2022231196A1 (en) * | 2021-04-29 | 2022-11-03 | Lg Electronics Inc. | Filter for water treatment device |
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