CN110284150A - A method of promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase - Google Patents
A method of promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase Download PDFInfo
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- CN110284150A CN110284150A CN201910680322.8A CN201910680322A CN110284150A CN 110284150 A CN110284150 A CN 110284150A CN 201910680322 A CN201910680322 A CN 201910680322A CN 110284150 A CN110284150 A CN 110284150A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The present invention relates to a kind of methods for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase, the following steps are included: 1) building includes the microorganism electrolysis cell of cathode pool and anode pool, working electrode and reference electrode are equipped in cathode pool, it is equipped in anode pool to electrode, is separated between cathode pool and anode pool by proton exchange membrane；2) methanogen culture medium is added in cathode pool and anode pool；3) redox materials are added in cathode pool；4) it is inoculated with methane phase bacterium solution in cathode pool and cultivates；5) cathode pool on-load voltage；6) by cathode pool headspace enrichment methane.Compared with prior art, the present invention promotes electronics by the transmitting of electrode to methanogen, thus improves methane phase rate by the way that redox materials are added in cathode pool using its own continuous redox reaction；The present invention have many advantages, such as easy to operate, methane production is high, without other by-products.
Description
Technical field
The invention belongs to Resources of Carbon Dioxide technical fields, are related to a kind of promotion microorganism electrochemical chemical recycling of carbon dioxide
The method of methane phase.
Background technique
Since the industrial revolution, the production activity of the mankind is a significant increase CO in atmosphere2Content.CO2As main
One of greenhouse gases, the growth of content may cause global warming in an atmosphere and weather extreme event increases.How to reduce
CO in atmosphere2Content, or even be translated into high added value chemicals become one the whole world research hot spot.Common turns
Change method includes chemical conversion and bioconversion.Chemical method generally requires high temperature and pressure and catalyst, in contrast, bioconversion
It can occur under room temperature condition of normal pressure, reaction condition is mild, has broad application prospects.
Using microorganism by CO2Be electrochemically transformed is methane existing research and report.Hara et al. (Mechanism of
Electromethanogenic Reduction of CO2by a Thermophilic Methanogen,Energy
Procedia, 2013,37:7021-7028) use the carbon paper wrapped up by carbon-coating as working electrode, thermophilic methanogen mode
For bacterial strain as inoculum, methane phase rate is about 0.0163 μm of ol/ (cm2·h)；Lohner et al. (Hydrogenase-
independent uptake and metabolism of electrons by the archaeon Methanococcus,
The ISME Journal, 2014,8:1673-1681) using graphite rod as working electrode, Methanococcus
For the pure bacterium of maripaludis as inoculum, methane phase rate is about 0.051 μm of ol/ (cm2·h)；Pascal et al.
(Selective microbial electrosynthesis of methane by a pure culture of a
Marine lithoautotrophic archaeon, Bioelectrochemistry, 2015,102:50-55) use graphite
As working electrode, the Methanobacterium-like pure bacterium of archaeon strain IM1 is as inoculum, methane phase speed
Rate is 0.0146 μm of ol/ (cm2·h)。
Chinese patent CN109022495A discloses a kind of method of micro-reduction carbon dioxide methane phase, including following
Step: 1) building includes the microorganism electrolysis cell of cathode pool and anode pool, includes working electrode, reference electrode in cathode pool；Sun
Pole pond includes to electrode；It is separated between cathode pool and anode pool with proton exchange membrane；2) production first is added in cathode pool and anode pool
Alkane bacterium culture medium；3) 1.5-5.0% methanogen bacterium solution is inoculated in cathode pool；It cultivates at room temperature；4) cathode pool load-
0.6V (vs SHE) voltage；5) methane is harvested by cathode pool head space.78 hours methane productions of this method can accumulate 8.453 μ
Mol, the methane production of carbon cloth electrode can accumulate the methane phase speed to 6.370 μm of ol, after being promoted on the whole under the same terms
Rate is 0.0181 μm of ol/ (cm2·h)。
It can be seen that prior art methane phase rate is still very low, this has become one of technology commercialization application
Key constraints.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of promotion microorganism electricity
The method of chemical conversion carbon dioxide methane phase.
The present invention is directed to CO2It is electrochemically transformed the low problem of conversion rate for generating methane and the micro- life of a kind of promotion proposed
Object is electrochemically transformed CO2The method of methane phase.The present invention, which mainly passes through, introduces the generating rate that redox materials improve methane.
The purpose of the present invention is establish a kind of microorganism electrochemical reduction CO2The method of methane phase, by being gone back using oxidation
Original matter improves bioelectrochemistry conversion CO as electron transmission medium2The rate of methane phase, redox materials used
Be naturally occurring in nature or can be secreted by microorganism itself, thus relative to by concentrate microbial or
In the method that anode is added additional catalyst or improved methane phase rate using special electrode, the cost of this method is relatively
It is low.
The purpose of the present invention can be achieved through the following technical solutions:
A method of promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase, comprising the following steps:
1) building includes the microorganism electrolysis cell of cathode pool and anode pool, and graphite felt electrode or carbon cloth electricity are equipped in cathode pool
Pole is equipped with platinum as working electrode, Ag/AgCl electrode to electrode as reference electrode, in anode pool, cathode pool and anode pool it
Between separated by N117 proton exchange membrane；
2) methanogen culture medium is added in cathode pool and anode pool；
3) redox materials are added in cathode pool；
4) it is inoculated with 10-50% methane phase bacterium solution in cathode pool and cultivates；
5) voltage of cathode pool load -0.6V extremely -1.0V (vs SHE)；
6) by cathode pool headspace enrichment methane, and methane content in headspace gas is detected with gas chromatograph.
Further, the formula of the methanogen culture medium is as follows: 0.3-0.4g/L K2HPO4、0.2-0.25g/L
KH2PO4、0.4-0.6g/L NH4Cl、0.4-0.6g/L MgSO4·7H2O、0.2-0.3g/L CaCl2、2-2.5g/L NaCl、
0.5-1g/L NaHCO3, 8-12mL/L trace element solution and 0.5-2mL/L vitamin solution；
The formula of the trace element solution is as follows: 1000-2000mg/L FeCl2·4H2O、50-80mg/L
ZnCl2、80-120mg/L MnCl2·4H2O、4-8mg/L HBO3、150-220mg/L CoCl2·6H2O、1.5-3mg/L
CuCl2·H2O、20-30mg/L NiCl2·6H2O、30-40mg/L NaMo4·2H2O and 8-13mL/L HCL aqueous solution；It is described
HCL aqueous solution be HCL aqueous solution that mass percent is 20-30%；
The formula of the vitamin solution is as follows: 1-3mg/L biotin, 1-3mg/L folic acid, 8-13mg/L vitamin
B6,3-8mg/L vitamin B1,3-8mg/L vitamin B2,3-8mg/L niacin, 3-8mg/L pantothenic acid, 0.05-0.15mg/L dimension
Raw element B12,3-8mg/L aminobenzoic acid and 3-8mg/L lipoic acid.
Further, in step 3), the redox materials include anthraquinone -2,6- disulfonic acid sodium salt, anthraquinone -2- carboxylic
One or more of acid, anthraquinone-2-sodium or thionine, concentration of the redox materials in cathode pool are 0.1-
0.75mmol/L, the concentration are the effective concentration ranges determined on the basis of many experiments, if beyond in the concentration range,
It, can be unobvious to the facilitation effect of methane phase after redox materials then are added.
The redox materials first carry out high-temperature sterilization before being added as a preferred technical solution,.
Further, in step 4), the methanogen includes Pasteur's sarcina methanica (Methanosarcina
Barkeri), Bu Shi methane backeria (Methanobacterium byrantti) or Heng Shi methanospirillum (Methanospirillum
One or more of hungatei).
Further, in step 4), the inoculum concentration of methane phase bacterium solution is 10-50%.Through a large number of studies show that, use microorganism
Promote CO2The experiment of conversion is that 10-50% is more suitable in bacterium solution inoculum concentration, connects bacterium amount if increasing, it is excessively high to will lead to cost.
The methane phase bacterium solution is methanogen single bacterium as a preferred technical solution, to avoid other products are generated.
Further, conversion process is in room temperature to carrying out at 37 DEG C.Room temperature to 37 DEG C be methanogen growth most thermophilic
Degree, when too high or too low for temperature, the metabolism of microorganism can slow down, or even dead.
Further, the voltage of cathode pool load -0.6V extremely -1.0V (vs SHE).When voltage is higher than the range, electronics
Transmitting is mostly direct electron transfer approach, and the chance for using redox materials is less；When voltage is lower than the range, first is produced
The activity of alkane bacterium can gradually decrease, and be unfavorable for CO2Conversion.
Before conversion process, CO is filled with to the head space of microorganism electrolysis cell2Gas；After conversion process, gas-chromatography is used
Instrument detects methane content in headspace gas.
Compared with prior art, the invention has the characteristics that:
1) present invention is promoted by the way that redox materials are added in cathode pool using its own continuous redox reaction
Into electronics by the transmitting of electrode to methanogen, methane phase rate is thus improved；
2) present invention have many advantages, such as easy to operate, methane production is high, without other by-products.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of microorganism electrolysis cell in embodiment 1.
Description of symbols in figure:
Electrode, 3-reference electrodes, 4-working electrodes, 5-methanogen culture mediums, 6-protons are handed in 1-power supply, 2-
Change film, 7-methanogens.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1:
The embodiment is divided into experimental group A and control group B while carrying out.
Experimental group A is as shown in Figure 1.Microorganism electrolysis cell includes cathode pool and anode pool, and reference is wherein equipped in cathode pool
Electrode 3, working electrode 4, methanogen 7 and methanogen culture medium 5, anode pool is interior to be equipped with to electrode 2, cathode pool and anode pool
Between be equipped with N117 proton exchange membrane 6, be additionally provided with power supply 1 and be separately connected reference electrode 3, working electrode 4 and to electrode 2.At this
Methanogen 7 is Methanosarcina barkeri in example.Reference electrode 3 is Ag/AgCl electrode, is platinum pair to electrode 2
Electrode 2, working electrode 4 are graphite felt electrode.
The formula of methanogen culture medium 5 is as follows: 0.35g/L K2HPO4、0.23g/L KH2PO4、0.5g/L NH4Cl、
0.5g/L MgSO4·7H2O、0.25g/L CaCl2、2.25g/L NaCl、0.85g/L NaHCO3, 10mL/L microelement it is molten
Liquid and 1mL/L vitamin solution.
Wherein, the formula of trace element solution is as follows: 1500mg/L FeCl2·4H2O、70mg/L ZnCl2、100mg/L
MnCl2·4H2O、6mg/L HBO3、190mg/L CoCl2·6H2O、2mg/L CuCl2·H2O、24mg/L NiCl2·6H2O、
36mg/L NaMo4·2H2O and 10mL/L 20-30%HCl aqueous solution；The formula of vitamin solution is as follows: 2mg/L biotin,
2mg/L folic acid, 10mg/L vitamin B6,5mg/L vitamin B1,5mg/L vitamin B2,5mg/L niacin, 5mg/L pantothenic acid,
0.1mg/L vitamin B12,5mg/L aminobenzoic acid and 5mg/L lipoic acid.
CO is restored using above-mentioned apparatus2It is as follows for the method for methane:
In experimental group A, 40mL methanogen culture medium 5 is first added in cathode pool, then in methanogen culture medium 5
The middle anthraquinone 2,6 disulfonic acid sodium that the 0.50mmol/L by high-temperature sterilization is added；20mL (inoculum concentration is accessed in cathode pool
33%) Methanosarcina barkeri bacterium solution, head space are full of CO2Gas, working electrode 4 are graphite felt electrode.By work
The potential for making electrode 4 is adjusted to -0.85V (vs SHE), is reacted at room temperature.
In control group B, 40mL methanogen culture medium 5 is added in cathode pool, anthraquinone -2 is added not in cathode pool,
6- disulfonic acid sodium salt；Then the Methanosarcina barkeri bacterium solution of 20mL (33%) is accessed in cathode pool, head space fills
Full CO2Gas.Working electrode 4 is graphite felt electrode.The potential of working electrode 4 is adjusted to -0.85V (vs SHE), in room temperature
Under reacted.
The headspace gas ingredient of two groups of experiments uses gas chromatograph for determination after 96 hours.It as a result is the methane production of A group
For 79.15 μm of ol, average methane phase rate is 0.14 μm of ol/ (cm2·h)；The methane production of B group is 24.98 μm of ol, average
Methane phase rate be 0.043 μm of ol/ (cm2·h).It can be seen that under the same conditions, the present invention improves methane phase rate.
Embodiment 2:
The example is divided into experimental group A and control group B while carrying out.
Experimental group A is as shown in Figure 1.50mL methanogen culture medium 5 is added in cathode pool, then in methanogen culture
The anthraquinone-2-sodium of the 0.25mmol/L by high-temperature sterilization is added in base 5；10mL (inoculum concentration is accessed in cathode pool
16.7%) Methanobacterium byrantti bacterium solution, head space are full of CO2Gas.Working electrode 4 is carbon cloth electrode.It will
The potential of working electrode 4 is adjusted to -0.6V (vs SHE), is reacted at 32 DEG C.
In control group B, 50mL methanogen culture medium 5 is added in cathode pool, anthraquinone -2- is added not in cathode pool
Sodium sulfonate；Then the Methanobacterium byrantti bacterium solution of 10mL (16.7%) is accessed in cathode pool, head space is full of
CO2Gas.Working electrode 4 is carbon cloth electrode.The potential of working electrode 4 is adjusted to -0.6V (vs SHE), is carried out at 32 DEG C
Reaction.
The headspace gas ingredient of two groups of experiments uses gas chromatograph for determination after 96 hours.It as a result is the methane production of A group
For 42.35 μm of ol, average methane phase rate is 0.074 μm of ol/ (cm2·h)；The methane production of B group is 10.25 μm of ol, is put down
Equal methane phase rate is 0.018 μm of ol/ (cm2·h).It can be seen that under the same conditions, the present invention improves methane phase speed
Rate.
Embodiment 3:
The example is divided into experimental group A and control group B while carrying out.
Experimental group A is as shown in Figure 1.30mL methanogen culture medium 5 is added in cathode pool, then in methanogen culture
The anthraquinone-2-carboxylic acid of the 0.10mmol/L by high-temperature sterilization is added in base 5；30mL (inoculum concentration 50%) is accessed in cathode pool
Methanosarcina barkeri bacterium solution, head space be full of CO2Gas.Working electrode 4 is graphite felt electrode.By working electrode
4 potential is adjusted to -0.95V (vs SHE), is reacted at 35 DEG C.
In control group B, 30mL methanogen culture medium 5 is added in cathode pool, not anthraquinone -2- the carboxylic in cathode pool addition
Acid；Then the Methanosarcina barkeri bacterium solution of 30mL (50%) is accessed in cathode pool, head space is full of CO2Gas.
Working electrode 4 is graphite felt electrode.The potential of working electrode 4 is adjusted to -0.95V (vs SHE), is reacted at 35 DEG C.
The headspace gas ingredient of two groups of experiments uses gas chromatograph for determination after 96 hours.It as a result is the methane production of A group
For 124.35 μm of ol, average 0.22 μm of ol/ (cm of methane phase rate2·h)；The methane production of B group is 20.54 μm of ol, average
Methane phase rate be 0.036 μm of ol/ (cm2·h).It can be seen that under the same conditions, the present invention improves methane phase rate.
Embodiment 4:
The example is divided into experimental group A and control group B while carrying out.
Experimental group A is as shown in Figure 1.54mL methanogen culture medium 5 is added in cathode pool, then in methanogen culture
The anthraquinone 2,6 disulfonic acid sodium of the 0.50mmol/L by high-temperature sterilization is added in base 5；6mL (inoculum concentration is accessed in cathode pool
10%) Methanosarcina barkeri bacterium solution, head space are full of CO2Gas.Working electrode 4 is carbon cloth electrode.By work
The potential of electrode 4 is adjusted to -1.0V (vs SHE), is reacted at room temperature.
In control group B, 54mL methanogen culture medium 5 is added in cathode pool, anthraquinone -2 is added not in cathode pool,
6- disulfonic acid sodium salt；Then the Methanosarcina barkeri bacterium solution of 6mL (10%) is accessed in cathode pool, head space is full of
CO2Gas.Working electrode 4 is carbon cloth electrode.The potential of working electrode 4 is adjusted to -1.0V (vs SHE), is carried out at room temperature
Reaction.
The headspace gas ingredient of two groups of experiments uses gas chromatograph for determination after 96 hours.It as a result is the methane production of A group
For 66.43 μm of ol, average methane phase rate is 0.12 μm of ol/ (cm2·h)；The methane production of B group is 25.26 μm of ol, average
Methane phase rate be 0.044 μm of ol/ (cm2·h).It can be seen that under the same conditions, the present invention improves methane phase rate.
Embodiment 5:
The example is divided into experimental group A and control group B while carrying out.
Experimental group A is as shown in Figure 1.40mL methanogen culture medium 5 is added in cathode pool, then in methanogen culture
The thionine of the 0.75mmol/L by high-temperature sterilization is added in base 5；It is accessed in cathode pool 20mL (inoculum concentration 33%)
Methanospirillum hungatei bacterium solution, head space are full of CO2Gas.Working electrode 4 is graphite felt electrode.By work electricity
The potential of pole 4 is adjusted to -0.9V (vs SHE), is reacted at room temperature.
In control group B, 40mL methanogen culture medium 5 is added in cathode pool, does not add thionine in cathode pool；So
The Methanospirillum hungatei bacterium solution of 20mL (33%) is accessed in cathode pool afterwards, head space is full of CO2Gas.Work
Making electrode 4 is graphite felt electrode.The potential of working electrode 4 is adjusted to -0.9V (vs SHE), is reacted at room temperature.
The headspace gas ingredient of two groups of experiments uses gas chromatograph for determination after 96 hours.It as a result is the methane production of A group
For 22.68 μm of ol, average methane phase rate is 0.039 μm of ol/ (cm2·h)；The methane production of B group is 21.55 μm of ol, is put down
Equal methane phase rate is 0.037 μm of ol/ (cm2·h).It can be seen that under the same conditions, the present invention improves methane phase speed
Rate.
Embodiment 6:
The example is divided into experimental group A and control group B while carrying out.
Experimental group A is as shown in Figure 1.40mL methanogen culture medium 5 is added in cathode pool, then in methanogen culture
The 0.10mmol/L anthraquinone-2-carboxylic acid for passing through high-temperature sterilization is added in base 5；It is accessed in cathode pool 20mL (inoculum concentration 33%)
Methanosarcina barkeri bacterium solution, head space are full of CO2Gas.Working electrode 4 is carbon cloth electrode.By working electrode 4
Potential is adjusted to -0.80V (vs SHE), is reacted at 37 DEG C.
In control group B, 40mL methanogen culture medium 5 is added in cathode pool, anthraquinone -2- is added not in cathode pool
Carboxylic acid；Then the Methanosarcina barkeri bacterium solution of 20mL (33%) is accessed in cathode pool, head space is full of CO2Gas
Body.Working electrode 4 is carbon cloth electrode.The potential of working electrode 4 is adjusted to -0.80V (vs SHE), is carried out at 37 DEG C anti-
It answers.
The headspace gas ingredient of two groups of experiments uses gas chromatograph for determination after 96 hours.It as a result is the methane production of A group
For 101.59 μm of ol, average methane phase rate is 0.18 μm of ol/ (cm2·h)；The methane production of B group is 21.98 μm of ol, is put down
Equal methane phase rate is 0.038 μm of ol/ (cm2·h).It can be seen that under the same conditions, the present invention improves methane phase speed
Rate.
Embodiment 7:
Microorganism electrolysis cell includes cathode pool and anode pool, and reference electrode 3 is wherein equipped in cathode pool, working electrode 4, is produced
Methane backeria 7 and methanogen culture medium 5, anode pool is interior to be equipped with to electrode 2, and N117 proton is equipped between cathode pool and anode pool and is handed over
Film 6 is changed, power supply 1 is additionally provided with and is separately connected reference electrode 3, working electrode 4 and to electrode 2.Methanogen 7 is in this example
Methanosarcina barkeri.Reference electrode 3 is Ag/AgCl electrode, is platinum to electrode 2 to electrode 2, working electrode 4 is
Graphite felt electrode.
The formula of methanogen culture medium 5 is as follows: 0.3g/L K2HPO4、0.2g/L KH2PO4、0.4g/L NH4Cl、
0.4g/L MgSO4·7H2O、0.2g/L CaCl2、2g/L NaCl、0.5g/L NaHCO3, 8mL/L trace element solution and
0.5mL/L vitamin solution；
The formula of trace element solution is as follows: 1000mg/L FeCl2·4H2O、50mg/L ZnCl2、80mg/L
MnCl2·4H2O、4mg/L HBO3、150mg/L CoCl2·6H2O、1.5mg/L CuCl2·H2O、20mg/L NiCl2·
6H2O、30mg/L NaMo4·2H2O and 8mL/L 20%HCl aqueous solution；
The formula of vitamin solution is as follows: 1mg/L biotin, 1mg/L folic acid, 8mg/L vitamin B6,3mg/L vitamin
B1,3mg/L vitamin B2,3mg/L niacin, 3mg/L pantothenic acid, 0.05mg/L vitamin B12,3mg/L aminobenzoic acid and
3mg/L lipoic acid.
CO is restored using above-mentioned apparatus2It is as follows for the method for methane:
40mL methanogen culture medium 5 is first added in cathode pool, is then added in methanogen culture medium 5 through excessively high
Anthraquinone -2,6- sodium disulfonate of temperature sterilizing and the equimolar mixture of anthraquinone-2-sodium, form the oxidation of 0.50mmol/L also
Former substance solution；The Methanosarcina barkeri bacterium solution of 20mL (inoculum concentration 33%) is accessed in cathode pool, head space fills
Full CO2Gas, working electrode 4 are graphite felt electrode.The potential of working electrode 4 is adjusted to -0.85V (vs SHE), in room temperature
Under reacted.
The headspace gas ingredient of two groups of experiments uses gas chromatograph for determination after 96 hours.As a result, methane production is 70.5 μ
Mol, average methane phase rate are 0.12 μm of ol/ (cm2·h)。
Embodiment 8:
Microorganism electrolysis cell includes cathode pool and anode pool, and reference electrode 3 is wherein equipped in cathode pool, working electrode 4, is produced
Methane backeria 7 and methanogen culture medium 5, anode pool is interior to be equipped with to electrode 2, and N117 proton is equipped between cathode pool and anode pool and is handed over
Film 6 is changed, power supply 1 is additionally provided with and is separately connected reference electrode 3, working electrode 4 and to electrode 2.Methanogen 7 is in this example
Methanosarcina barkeri.Reference electrode 3 is Ag/AgCl electrode, is platinum to electrode 2 to electrode 2, working electrode 4 is
Graphite felt electrode.
The formula of methanogen culture medium 5 is as follows: 0.4g/L K2HPO4、0.25g/L KH2PO4、0.6g/L NH4Cl、
0.6g/L MgSO4·7H2O、0.3g/L CaCl2、2.5g/L NaCl、1g/L NaHCO3, 12mL/L trace element solution and
2mL/L vitamin solution；.
The formula of trace element solution is as follows: 2000mg/L FeCl2·4H2O、80mg/L ZnCl2、120mg/L
MnCl2·4H2O、8mg/L HBO3、220mg/L CoCl2·6H2O、3mg/L CuCl2·H2O、30mg/L NiCl2·6H2O、
40mg/L NaMo4·2H2O and 13mL/L 30%HCl aqueous solution；
The formula of vitamin solution is as follows: 3mg/L biotin, 3mg/L folic acid, 13mg/L vitamin B6,8mg/L vitamin
B1,8mg/L vitamin B2,8mg/L niacin, 8mg/L pantothenic acid, 0.15mg/L vitamin B12,8mg/L aminobenzoic acid and
8mg/L lipoic acid.
CO is restored using above-mentioned apparatus2It is as follows for the method for methane:
40mL methanogen culture medium 5 is first added in cathode pool, is then added in methanogen culture medium 5 through excessively high
The equimolar mixture of anthraquinone -2,6- disulfonic acid sodium salt, anthraquinone-2-carboxylic acid and anthraquinone-2-sodium that temperature sterilizes, forms
The redox materials solution of 0.50mmol/L；The Methanosarcina of 20mL (inoculum concentration 33%) is accessed in cathode pool
Barkeri bacterium solution, head space are full of CO2Gas, working electrode 4 are graphite felt electrode.The potential of working electrode 4 is adjusted to-
0.85V (vs SHE), is reacted at room temperature.
The headspace gas ingredient of two groups of experiments uses gas chromatograph for determination after 96 hours.As a result, methane production is 67.05
μm ol, average methane phase rate are 0.11 μm of ol/ (cm2·h)。
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase, which is characterized in that this method includes following
Step:
1) building includes the microorganism electrolysis cell of cathode pool and anode pool, and working electrode and reference electrode, sun are equipped in cathode pool
It is equipped in the pond of pole to electrode, is separated between cathode pool and anode pool by proton exchange membrane；
2) methanogen culture medium is added in cathode pool and anode pool；
3) redox materials are added in cathode pool；
4) it is inoculated with methane phase bacterium solution in cathode pool and cultivates；
5) cathode pool on-load voltage；
6) by cathode pool headspace enrichment methane.
2. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 1, feature
It is, in step 1), the working electrode is graphite felt electrode or carbon cloth electrode, and the reference electrode is Ag/AgCl electricity
Pole, described is platinum to electrode to electrode.
3. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 1, feature
It is, in step 1), the proton exchange membrane is N117 proton exchange membrane.
4. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 1, feature
It is, in step 2), the formula of the methanogen culture medium is as follows: 0.3-0.4g/L K2HPO4、0.2-0.25g/L
KH2PO4、0.4-0.6g/L NH4Cl、0.4-0.6g/L MgSO4·7H2O、0.2-0.3g/L CaCl2、2-2.5g/L NaCl、
0.5-1g/L NaHCO3, 8-12mL/L trace element solution and 0.5-2mL/L vitamin solution.
5. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 4, feature
It is, the formula of the trace element solution is as follows: 1000-2000mg/L FeCl2·4H2O、50-80mg/L ZnCl2、
80-120mg/L MnCl2·4H2O、4-8mg/L HBO3、150-220mg/L CoCl2·6H2O、1.5-3mg/L CuCl2·
H2O、20-30mg/L NiCl2·6H2O、30-40mg/L NaMo4·2H2O and 8-13mL/L HCL aqueous solution；
The formula of the vitamin solution is as follows: 1-3mg/L biotin, 1-3mg/L folic acid, 8-13mg/L vitamin B6,3-
8mg/L vitamin B1,3-8mg/L vitamin B2,3-8mg/L niacin, 3-8mg/L pantothenic acid, 0.05-0.15mg/L vitamin
B12,3-8mg/L aminobenzoic acid and 3-8mg/L lipoic acid.
6. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 1, feature
It is, in step 3), the redox materials include anthraquinone -2,6- disulfonic acid sodium salt, anthraquinone-2-carboxylic acid, anthraquinone -2- sulphur
One of sour sodium or thionine are a variety of, and concentration of the redox materials in cathode pool is 0.1-0.75mmol/L.
7. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 1, feature
It is, in step 4), the methanogen includes in Pasteur's sarcina methanica, Bu Shi methane backeria or Heng Shi methanospirillum
It is a kind of.
8. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 1, feature
It is, in step 4), the inoculum concentration of the methane phase bacterium solution is 10-50%.
9. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 1, feature
It is, in step 5), the voltage of the cathode pool load is -0.6V to -1.0V (vs SHE).
10. a kind of method for promoting microorganism electrochemical chemical recycling of carbon dioxide methane phase according to claim 1, feature
It is, conversion process is in room temperature to carrying out at 37 DEG C.
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