CN110078225A - A kind of microorganism electrolysis cell and oxidation operation are degraded synchronous CO2Methanation process - Google Patents
A kind of microorganism electrolysis cell and oxidation operation are degraded synchronous CO2Methanation process Download PDFInfo
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- CN110078225A CN110078225A CN201910413809.XA CN201910413809A CN110078225A CN 110078225 A CN110078225 A CN 110078225A CN 201910413809 A CN201910413809 A CN 201910413809A CN 110078225 A CN110078225 A CN 110078225A
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 244000005700 microbiome Species 0.000 title claims abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 10
- 230000003647 oxidation Effects 0.000 title claims abstract description 9
- 230000001360 synchronised effect Effects 0.000 title claims description 8
- 230000008569 process Effects 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 239000002861 polymer material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005273 aeration Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 11
- 239000005416 organic matter Substances 0.000 claims description 8
- 239000010865 sewage Substances 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000002906 microbiologic effect Effects 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 239000007836 KH2PO4 Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910018890 NaMoO4 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims description 3
- 238000011081 inoculation Methods 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 4
- 230000000644 propagated effect Effects 0.000 abstract description 4
- 238000005728 strengthening Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Biodiversity & Conservation Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Treatment Of Sludge (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
It degrades the invention discloses a kind of microorganism electrolysis cell and its oxidation operation and synchronizes CO2Methanation process, its main feature is that the anode and cathode of electrolytic cell is the compound bio electrode that several graphite felts are axially arranged in carbon electrode, anode chamber is connected to by the pipeline of setting proton cross-film peristaltic pump with cathode chamber；The graphite felt is that the electrode with three-dimensional structure is made in conduction high polymer material, and oxidation operation, which is degraded, synchronizes CO2Methanation process includes: the configuration of electrolyte and anode chamber's matrix, the transmission of proton cross-film and constant potential electrochemical degradation step.The present invention has the formation of the apposition growth, biomembrane of strengthening electrically active function bacterium and the conduction of electronics compared with prior art, preferably resolves PEM in reactor operational process and pollutes and lead to proton H+The problem of transmission is obstructed, avoids cathode chamber CH4Generation efficiency is low, improves proton H+Propagated flux is conducive to improve CH4Generation efficiency has wide application prospect.
Description
Technical field
The present invention relates to field of microbial electromechanical technology, especially a kind of microorganism electrolysis cell and its reinforcing organic matter oxygen
Change the synchronous CO that degrades2Methanation process.
Background technique:
Microorganism electrolysis cell (MEC) technology is low in external source to be enriched in the electrically active function bacterium of cathode surface as biocatalyst
Under the driving of potential, breaks through overpotential and interior resistance limits, with CO2For carbon source, CH is catalyzed and synthesized4Etc. a variety of low-carbon fuel, thus
Realize CO2Emission reduction and increasing value and reutilizing.In reaction chamber anode, inoculating active microorganism is anodic oxygen agent, is catalyzed electron donor
Oxidation reaction occurs for (water, small molecular organic acid and macromolecular carbohydrate etc.), discharges electronics and proton H+, wherein electricity
Son reaches cathode via external circuit, is utilized in cathode by reduction reaction；Proton H+Proton through two reacting chamber spaces is handed over
Film (PEM) is changed into cathode, participates in methanogenesis reaction.
Currently, being mostly used water as electronics/proton H in the anode chamber of MEC+Donor, but hydrone cracking needed for
Theoretical electrode potential is higher (+0.820 V vs. SHE), and excessively high decomposition electric potential will increase required external source voltage, cuts down electricity
The total energy source efficiency of methane system, and may cause electrode corrosion, decompose, or even interrupt electronics/proton H+Supply.In view of
This, is used as electronics/proton H using abandoned biomass etc.+Donor can improve CH4While the stability of synthesis process, realize high
Imitate degradation of organic substances.
The organic matter degradation of the prior art is synchronous to realize CO2In the research of bioelectricity methanation, with prolonging for reaction time
Long, proton exchange membrane is likely to occur different degrees of pollution, the adventitious deposit resistance of anode current donor and electrically active function bacterium
Proton H is filled in+Toward the access of cathode transmitting, its transmission efficiency is reduced, cathode methanogenesis process is caused to be obstructed.In response to this problem
Preferable solution is not suggested that, only based on short-term batch experiment, to avoid there is this problem.But short-term batch is tried
For testing, though there are advantage in terms of the timeliness for verifying expected conclusion, there are still it is some inevitably it is not perfect it
Place.On the one hand, in view of the urgency of experimental period, the high efficiency and high stability of electrically active function bacterium are living during short-term experiment
Dynamic it is expected, this will improve requirement to electrically active function bacterium；On the other hand, whether the result that short-term research obtains is enough to prop up
The conclusion suitable for engineering is held, still needs to further probe into.Therefore, continue efficient CO to realize2Emission reduction and conversion recycle first
Alkane, it is necessary to propose a kind of effectively reinforcing proton cross-film transmission method.
Summary of the invention
The purpose of the present invention is a kind of microorganism electrolysis cells and oxidation operation that design in view of the deficiencies of the prior art
Degrade synchronous CO2Methanation process loads electrically active function bacterium and CO using compound bio electrode surface2The microorganism electricity of aeration
The proton transport for solving pool structure and proton cross-film anode chamber and cathode chamber, under applying electrical potential effect, anode electrically active function
The pre- matrix degradation of bacterium degradation, generates proton H+And electronics, proton H+Enter cathode by proton exchange membrane (PEM), in bioelectricity
Chemical synthesis CH4In the process microorganism from electrode surface receive electronics by expose into CO2It is reduced to CH4, thus realize carbon emission reduction with
Increasing value and reutilizing realizes that cathode chamber efficiently restores CO2Synthesize CH4Proton is provided, cathode chamber methane recovery efficiency is strengthened, structure is simple,
Methane recovery is high-efficient, has preferable Social benefit and economic benefit.
The object of the present invention is achieved like this: a kind of microorganism electrolysis cell, including is equipped with potentiostat and electric current record
The double-chamber microbiological electrolytic cell of instrument is equipped with proton exchange membrane between anode chamber and cathode chamber, its main feature is that being equipped with sun in anode chamber
Pole compound bio electrode, cathode chamber is interior to be equipped with cathode compound bio electrode, CO2Aeration tube and reference electrode, anode chamber is by being arranged
The pipeline of proton cross-film peristaltic pump is connected to cathode chamber；The anode compound bio electrode and cathode compound bio electrode are carbon-point
Several graphite felts that electrode is axially arranged；The graphite felt be cloth strip superposition be wrapped on carbon electrode, and by carbon filament by its
It is coated and fixed；The potentiostat and galvo-recorder simultaneously connect, and anode is electrically connected with anode compound bio electrode, cathode with
Cathode compound bio electrode and reference electrode are electrically connected；The cathode chamber is equipped with the outlet conduit and first of water outlet peristaltic pump connection
The outlet of alkane gas；The anode chamber is equipped with the water inlet line of water inlet peristaltic pump connection.
The graphite felt is that the electrode with three-dimensional structure is made in conduction high polymer material.
A kind of synchronous CO of oxidation operation degradation of microorganism electrolysis cell2Methanation process, its main feature is that this method is specific
The following steps are included:
A, the configuration of electrolyte
Electrolyte presses NaHCO3: KH2PO4: K2HPO4: NH4Cl: CaCl2•2H2O: MgCl2•6H2O:Na2S•9H2O: micro
Solution=1.25g/L:0.85g/L:1.09g/L:0.63g/L:0.19g/L:0.5g/L:0.5 mL:0.5 mL configuration, it is described micro-
It measures solution and presses MnCl2•2H2O: NiCl2•6H2O:CuCl2•2H2O:H3BO3: CoCl2•6H2O: FeCl2•4H2O: NaMoO4•
2H2O=1.25:0.01:0.0068:0.015:0.0425:0.5: 0.0063 configuration.
B, the configuration of anode chamber's matrix
The activated sludge for being derived from sewage plant takes supernatant after centrifugal treating six minutes, and with the electrolyte of above-mentioned configuration by COD
Content is adjusted to be used as anode chamber's matrix after 2000 ~ 4000mg/L, and the centrifugal rotational speed is 6000 revs/min.
C, the electrochemical degradation of organic matter
It is four days by water inlet peristaltic pump and the hydraulic detention time for being discharged peristaltic pump control anode chamber, and is wriggled by proton cross-film
For pump by the organic matter degradation electrolyte circulation of anode chamber to cathode chamber, the cathode chamber inoculation liquid is derived from the activity of sewage treatment plant
Sludge；The CO2Purity is 99.999%, and aeration flow velocity is 0.3 L/ minutes, and aeration time is 30 minutes/day.
D, the control of constant potential
Apply -0.6 V potential to cathode compound bio electrode by potentiostat and galvo-recorder.
The present invention has following advantageous effects compared with prior art:
(1), CO is realized using double-chamber microbiological electrolytic cell reactor2Methanation can effectively reduce microorganism for single chamber
It with the intersection of final product, improves product purity and avoids short circuit, so that improving methane generates performance.
(2), carbon-point-graphite felt materials are attached to as the two poles of the earth compound bio electrode, sufficiently benefit using electrically active function bacterium
Three-dimensional structure and excellent electric conductivity with graphite felt, to strengthen the formation of the apposition growth, biomembrane of electrically active function bacterium
And the conduction of electronics.
(3), by CO2Membrane interface liquid can be achieved along the tangentially-arranged progress source the C supply in PEM membrane face, this setting in air inlet
Microfluidization, enhancing film surface shearing washes away, reduce film surface incrustation and film resistance, improve proton H+Propagated flux is conducive to improve CH4
Generation efficiency.
(4), proton cross-film transmission pump can realize matter by pumping out and being pumped into cathode chamber for the matrix after anodic degradation
The reinforcing of sub- cross-film transmission avoids leading to proton H due to PEM pollutes in reactor operational process+Transmission is obstructed, to avoid yin
Pole room CH4Generation efficiency is low.
(5), adapt to different flooded condition and processing requirement, occupied area is small, it can be achieved that operation steady in a long-term, have compared with
Broad application prospect.
(6), high degree of automation, it is convenient for installation and maintenance, it is stable, operator is required low.
Detailed description of the invention
Fig. 1 is schematic structural view of the invention；
Fig. 2 is compound bio electrode scheme of installation.
Specific embodiment
Refering to attached drawing 1, a kind of reinforcing oxidation operation degradation synchronization CO provided by the present invention2The microorganism electricity of methanation
Xie Chi, including the double-chamber microbiological electrolytic cell (dual chamber MEC reactor) 1 separated by proton exchange membrane (PEM) 3, in anode chamber
Equipped with anode compound bio electrode 2, it is equipped with cathode compound bio electrode 7, reference electrode 11 in cathode chamber and is arranged in bottom
CO2Aeration tube 6, the cathode compound bio electrode 7 are arranged in CO26 top of aeration tube, and it is logical with anode compound bio electrode 2
Oversampling circuit is electrically connected with potentiostat 4 with galvo-recorder 5；The anode chamber bottom is equipped with the water inlet of connection water inlet peristaltic pump 8
Pipeline, the pipeline that upper portion of anode chamber is equipped with connection proton cross-film peristaltic pump 9 are connected to cathode chamber bottom；The water inlet peristaltic pump 8
Pre- matrix degradation is sent into the anode chamber of the double-chamber microbiological electrolytic cell 1；The proton cross-film peristaltic pump 9 will with after anodic degradation
Matrix pump out and be pumped into cathode chamber, realize the reinforcing of proton cross-film transmission, avoid because in reactor operational process, due to
Proton transport is obstructed caused by PEM pollution, eventually leads to cathode chamber CH4Generation efficiency is low.
Refering to attached drawing 2, the anode compound bio electrode 2 and cathode compound bio electrode 7 include: being arranged in carbon electrode
Two graphite felts 22 at 21 centers, the graphite felt 22 is superimposed respectively is wrapped in 21 periphery of carbon electrode, and is coated by carbon filament 23
It is fixed.
Application method of the present invention is specifically includes the following steps: electrolyte added by anode chamber and cathode chamber is formulated as follows (g/
L): NaHCO31.25；KH2PO40.85；K2HPO41.09；NH4Cl 0.63；CaCl2•2H2O 0.19；MgCl2•6H2O
0.5；Na2S•9H20.5 mL(0.25 g/L of O) and 0.5 mL of micro solution.The micro solution is formulated as follows (g/L):
MnCl2•2H2O 0.125；NiCl2•6H2O 0.01；CuCl2•2H2O 0.0068；H3BO30.015；CoCl2•6H2O
0.0425；FeCl2•4H2O 0.5 and NaMoO4•2H2O 0.0063。
Anode chamber's organic matter to be processed is derived from sewage plant activated sludge, after 6 minutes centrifugation (6000 revs/min),
Take supernatant with above-mentioned electrolyte dilution to its COD concentration for 2000 ~ 4000mg/L, as anode chamber's matrix.Pass through daily
Controlling control anode chamber's hydraulic detention time into (out) water peristaltic pump 8(10) is four days, while real by proton cross-film peristaltic pump 9
Now daily from anode chamber toward the continuous transfer medium of cathode chamber.Cathode chamber inoculation liquid is derived from sewage treatment plant residual active sludge, leads to
The circuit control for crossing potentiostat 4 applies -0.6 V potential to cathode compound bio electrode 7.Daily ultra-pure CO2(99.999%)
Aeration flow velocity is set as 0.3 L/ minutes, and aeration time control is 30 minutes/day.The proton exchange membrane (PEM) 3 and dual chamber
After MEC longtime running, the polluted possibility of PEM, therefore by CO2Air inlet is along the tangentially-arranged progress source the C benefit of film surface
It gives, the Microfluidization of membrane interface liquid is realized in this change, and enhancing film surface shearing washes away, reduces film surface incrustation and film resistance, improve
Proton H+Propagated flux is conducive to improve CH4Generation efficiency, while anode is gone out into water-based circulation and fills into cathode chamber, improve cathode chamber
Proton H+It fills into, finally improves CO2Electric methane combined coefficient.
Below with specific embodiments of the present invention, and the synchronous CO of oxidation operation degradation of proton transport is not strengthened2First
The comparative example of alkanisation, the invention will be further described.
Comparative example 1
Anode chamber's organic matter to be processed is again taken from sewage plant activated sludge, after being centrifuged (8000r/min) through 6 min, takes
Supernatant reaches 6383.1 mg/L with above-mentioned electrolyte dilution to COD concentration, as anode chamber's matrix, controls anode chamber's water
The power residence time is 4 d, applies -0.6 V potential to cathode by the circuit control of potentiostat 4.CO2Aeration flow velocity is set as
0.3 L/min, aeration time control are 30 min/d, CH in cathode chamber4Yield is 5.80 mL/L/d, COD drop in anode water outlet
Solution rate is 79.2%.
Embodiment 1
Refering to attached drawing 1, anode is prepared with electrolyte added in cathode, micro solution and application method is identical as comparative example 1, training
The dual chamber MEC reactor 1 that device uses 520 mL is supported, wherein anode chamber and each 260 mL of cathode chamber, includes 200 mL reactants
Product and 60 mL of headspace collected for biogas.Average distance between anode and cathode is 4.0 centimetres, passes through outside
The two poles of the earth are connected to potentiostat 4 by circuit, and to provide -0.6 required V potential, two electrode material used is by graphite felt 22
The carbon electrode 21 of winding.Anode chamber's matrix is the sludge supernatant by electrolyte dilution, and COD concentration is 3070.2 mg/L,
As anode chamber's matrix.Cathode chamber is directly added into electrolyte and 5 mL seed sludges, and by the electrolyte pH in two Room of yin, yang
7.0 are adjusted to the growth of suitable electrically active function bacterium, ultra-high purity CO2(99.999%) as function bacterium carbon source with 0.3 L/
The flow velocity of minute blasts cathode reaction chambers (30 minute/day).It realizes daily by proton cross-film peristaltic pump 9 from anode chamber simultaneously
Toward the continuous transfer medium of cathode chamber.At regular intervals, the life of certain volume is taken out from the headspace of cathode cavity with syringe
Object gas (CH4), it is analyzed by the gas chromatograph equipped with thermal conductivity detector (TCD).COD degradation rate is measured with national standard method, double
After room MEC reactor 1 is run 78 days, which, which degrades, synchronizes CO2The cathode chamber CH of methanation4Yield is up to
20.80 mL/L/d, 5.80 mL/L/d in more above-mentioned comparative example 1 improve 258.6%, while COD degradation rate in anode water outlet
Up to 95.6%, 79.2% in more above-mentioned comparative example 1 improves 20.7%.Simultaneously as CO2The change for filling into mode, reduces film
Area dirt and film resistance, after reaction, there is not contamination phenomenon in PEM.
The present invention realizes CO using double-chamber microbiological electrolytic cell 12For methanation is compared with single chamber, can effectively reduce microorganism and
The intersection of final product improves product purity and avoids short circuit.Meanwhile anode compound bio electrode 2 and cathode compound bio are electric
Pole 7 is made of carbon electrode 21, graphite felt 22 and loading microorganisms, has good three-dimensional structure conducive to microorganism attachment.
Also, by CO2 The miniflow of membrane interface liquid can be achieved along the tangentially-arranged progress source the C supply in PEM membrane face, this setting in air inlet
State, enhancing film surface shearing wash away, reduce film surface incrustation and film resistance, improve proton H+Propagated flux is conducive to improve CH4Generate effect
Rate.Anode is gone out into water-based circulation simultaneously and fills into cathode chamber, improves cathode chamber proton H+It fills into, finally improves CO2Electric methane synthesis
Efficiency.
Above only the present invention will be further described, and not to limit this patent, all is equivalence enforcement of the present invention,
It should be contained within the scope of the claims of this patent.
Claims (3)
1. a kind of microorganism electrolysis cell, the double-chamber microbiological electrolytic cell including being equipped with potentiostat and galvo-recorder, anode chamber
Proton exchange membrane is equipped between cathode chamber, it is characterised in that be equipped with anode compound bio electrode in anode chamber, set in cathode chamber
There are cathode compound bio electrode, CO2Aeration tube and reference electrode, anode chamber by setting proton cross-film peristaltic pump pipeline and cathode
Room connection；The anode compound bio electrode and cathode compound bio electrode are several graphite felts that carbon electrode is axially arranged；
The graphite felt is that the superposition of cloth strip is wrapped on carbon electrode, and is coated and fixed by carbon filament；The potentiostat and electricity
Stream recorder simultaneously connects, and anode is electrically connected with anode compound bio electrode, cathode and cathode compound bio electrode and reference electricity
Pole is electrically connected；The cathode chamber is equipped with outlet conduit and the methane gas outlet of water outlet peristaltic pump connection；The anode chamber is equipped with
The water inlet line that peristaltic pump of intaking connects.
2. microorganism electrolysis cell according to claim 1, it is characterised in that the graphite felt is made of conduction high polymer material
Electrode with three-dimensional structure.
The synchronous CO 3. a kind of oxidation operation of microorganism electrolysis cell described in claim 1 is degraded2The method of methanation, feature
Be this method specifically includes the following steps:
A, the configuration of electrolyte
Electrolyte presses NaHCO3: KH2PO4: K2HPO4: NH4Cl: CaCl2•2H2O: MgCl2•6H2O:Na2S•9H2O: micro
Solution=1.25g/L:0.85g/L:1.09g/L:0.63g/L:0.19g/L:0.5g/L:0.5 mL:0.5 mL configuration, it is described micro-
It measures solution and presses MnCl2•2H2O: NiCl2•6H2O:CuCl2•2H2O:H3BO3: CoCl2•6H2O: FeCl2•4H2O: NaMoO4•
2H2O=1.25:0.01:0.0068:0.015:0.0425:0.5: 0.0063 configuration；
B, the configuration of anode chamber's matrix
The activated sludge for being derived from sewage plant takes supernatant after centrifugal treating six minutes, and with the electrolyte of above-mentioned configuration by COD
Content is adjusted to be used as anode chamber's matrix after 2000 ~ 4000mg/L, and the centrifugal rotational speed is 6000 revs/min；
C, the electrochemical degradation of organic matter
Controlling anode chamber's hydraulic detention time by water inlet peristaltic pump and water outlet peristaltic pump is four days, and by proton cross-film peristaltic pump
By the organic matter degradation electrolyte circulation of anode chamber to cathode chamber, the activity that the cathode chamber inoculation liquid is derived from sewage treatment plant is dirty
Mud；The CO2Purity is 99.999%, and aeration flow velocity is 0.3 L/ minutes, and aeration time is 30 minutes/day；
D, the control of constant potential
Apply -0.6 V potential to cathode compound bio electrode by potentiostat and galvo-recorder.
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| CN113398716A (en) * | 2021-05-14 | 2021-09-17 | 上海电力大学 | Biological methanation system for capturing carbon dioxide in renewable energy hydrogen production coupled power plant |
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| CN111180773A (en) * | 2019-12-31 | 2020-05-19 | 福建农林大学 | Double-chamber microbial fuel cell and preparation method thereof |
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| CN114196534A (en) * | 2021-12-10 | 2022-03-18 | 哈尔滨工业大学 | Carbon-based emission reduction of CO2Device and method for biologically synthesizing methane |
| CN114699908A (en) * | 2022-01-20 | 2022-07-05 | 中国环境科学研究院 | Activated sludge coupled device and method for fixing carbon dioxide by driving microorganisms with electric energy |
| CN115583718A (en) * | 2022-09-07 | 2023-01-10 | 齐鲁工业大学 | Bioelectrochemical reactor and method for treating wastewater by same |
| CN115583718B (en) * | 2022-09-07 | 2023-12-29 | 齐鲁工业大学 | Bioelectrochemical reactor and method for treating wastewater by same |
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