CN110078225B - Microbial electrolytic cell and synchronous CO for organic oxidative degradation 2 Methanation process - Google Patents
Microbial electrolytic cell and synchronous CO for organic oxidative degradation 2 Methanation process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 20
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- 230000001360 synchronised effect Effects 0.000 title claims abstract description 12
- 238000010525 oxidative degradation reaction Methods 0.000 title claims abstract description 11
- 230000008569 process Effects 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 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
- 230000015556 catabolic process Effects 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
- 239000005416 organic matter Substances 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 239000002861 polymer material Substances 0.000 claims abstract description 3
- 229920001940 conductive polymer Polymers 0.000 claims abstract 2
- 239000012528 membrane Substances 0.000 claims description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000010802 sludge Substances 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 239000010865 sewage Substances 0.000 claims description 8
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- 230000014759 maintenance of location Effects 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000011081 inoculation Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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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
- 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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Abstract
The invention discloses a microbial electrolytic cell and synchronous CO for organic oxidative degradation thereof 2 The methanation method is characterized in that the anode and the cathode of the electrolytic cell are composite bioelectrodes with a plurality of graphite felts axially arranged on carbon rod electrodes, and an anode chamber is communicated with a cathode chamber through a pipeline provided with a proton transmembrane peristaltic pump; the graphite felt is made of conductive polymer material to prepare an electrode with a three-dimensional structure, and organic matter oxidative degradation is synchronous with CO 2 The methanation method comprises the following steps: electrolyte and anode chamber matrix configuration, proton transmembrane transport and potentiostatic electrochemical degradation. Compared with the prior art, the invention has the functions of enhancing the adhesion growth of electroactive functional bacteria, forming a biological film and conducting electrons, and better solving the problem of proton H caused by PEM pollution in the running process of the reactor + Problems of blocked transmission, avoiding cathode chamber CH 4 Low production efficiency, and improvement of proton H + Transmission flux, facilitate enhancement of CH 4 The production efficiency is high, and the application prospect is wide.
Description
Technical Field
The invention relates to the technical field of microorganism electrochemistry, in particular to a microorganism electrolytic cell and a synchronous CO for strengthening organic oxidative degradation thereof 2 Methanation process.
The background technology is as follows:
microorganismElectrolytic Cell (MEC) technology uses electroactive functional bacteria enriched on the surface of a cathode as a biocatalyst, breaks through the limits of overpotential and internal resistance under the drive of exogenous low potential, uses CO 2 Catalytic synthesis of CH as carbon source 4 Low carbon fuel to realize CO 2 Reducing emission and recycling in value-added mode. Inoculating active microorganism as anode oxidant in the anode of reaction chamber, catalyzing electron donor (water, small molecule organic acid and macromolecular carbohydrate) to generate oxidation reaction, releasing electron and proton H + Wherein electrons are transferred to the cathode via an external circuit, where they are utilized by a reduction reaction; protons H + Enters the cathode through a Proton Exchange Membrane (PEM) between the two reaction chambers to participate in the methane forming reaction.
Currently, in the anode chamber of MEC, water is used as electron/proton H + The theoretical electrode potential required for water molecule cleavage is high (+0.820V vs. SHE), too high a decomposition potential will increase the required exogenous voltage, reduce the overall energy efficiency of the electrodic methane system, and may lead to electrode corrosion, decomposition, even interruption of electrons/protons H + And (5) supplying. In view of this, waste biomass or the like is used as electron/proton H + The donor can improve CH 4 The stability of the synthesis process is realized, and meanwhile, the high-efficiency degradation of organic matters is realized.
Synchronous realization of CO by organic degradation in the prior art 2 In the research of bioelectric methanation, with the extension of the reaction time, the proton exchange membrane may be polluted to different degrees, and the proton H is blocked by the adhesion and deposition of an anode electron donor and electroactive functional bacteria + The passage to the cathode reduces its transfer efficiency, resulting in a blockage of the cathode methane formation process. A better solution to this problem has not been proposed, but short-term batch tests are the main one, to avoid this problem. However, in the case of short-term batch tests, there are some unavoidable imperfections in verifying the timeliness of the expected conclusions. On the one hand, in view of the urgency of the experimental time, high efficiency and high stability activity of the electroactive functional bacteria during short-term experiments are expected, which will increase the demands on the electroactive functional bacteriaThe method comprises the steps of carrying out a first treatment on the surface of the On the other hand, short-term studies have led to results that are sufficient to support conclusions applicable to engineering, and still need to be further explored. Thus, to achieve continuous high efficiency of CO 2 It is necessary to provide a method for effectively enhancing proton transmembrane transport by reducing emission and converting and recycling methane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and designs a microbial electrolytic cell and synchronous CO for organic oxidative degradation 2 Methanation method, adopting composite bioelectrode surface to load electroactive functional bacteria and CO 2 The aeration microbial electrolytic cell structure and proton transmission of proton transmembrane anode chamber and cathode chamber degrade the pre-degradation matrix under the action of external potential to generate proton H + Electrons, protons H + Entry into the cathode through Proton Exchange Membrane (PEM) for bioelectrochemical synthesis of CH 4 In the process, microorganisms receive electrons from the surface of the electrode to be exposed to CO 2 Reduction to CH 4 Thereby realizing carbon emission reduction and value-added recycling and realizing efficient reduction of CO in the cathode chamber 2 Synthesis of CH 4 The proton is provided, the methane recovery efficiency of the cathode chamber is enhanced, the structure is simple, the methane recovery efficiency is high, and the method has good social and economic benefits.
The purpose of the invention is realized in the following way: a microbial electrolytic cell comprises a double-chamber microbial electrolytic cell provided with a potentiostat and a current recorder, a proton exchange membrane is arranged between an anode chamber and a cathode chamber, and is characterized in that an anode composite bioelectrode is arranged in the anode chamber, and a cathode composite bioelectrode and CO are arranged in the cathode chamber 2 The anode chamber is communicated with the cathode chamber through a pipeline provided with a proton transmembrane peristaltic pump; the anode composite bioelectrode and the cathode composite bioelectrode are a plurality of graphite felts axially arranged on the carbon rod electrode; the graphite felt is in a cloth shape and is overlapped and wrapped on the carbon rod electrode, and is wrapped and fixed by the carbon wire; the potentiostat is connected in parallel with the current recorder, the anode of the potentiostat is electrically connected with the anode composite bioelectrode, and the cathode of the potentiostat is electrically connected with the cathode composite bioelectrode and the reference electrode; the cathode chamber is provided with a water outlet pipeline connected with a water outlet peristaltic pump anda methane gas outlet; the anode chamber is provided with a water inlet pipeline connected with a water inlet peristaltic pump.
The graphite felt is made of conductive high polymer material and is made into an electrode with a three-dimensional structure.
Synchronous CO of organic matter oxidative degradation of microbial electrolysis cell 2 The methanation method is characterized by comprising the following steps of:
a. arrangement of electrolyte
Electrolyte according to NaHCO 3 ：KH 2 PO 4 ：K 2 HPO 4 ：NH 4 Cl ：CaCl 2 •2H 2 O ：MgCl 2 •6H 2 O：Na 2 S•9H 2 O: trace 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, the trace solution is according to MnCl 2 •2H 2 O ：NiCl 2 •6H 2 O：CuCl 2 •2H 2 O：H 3 BO 3 ：CoCl 2 •6H 2 O ：FeCl 2 •4H 2 O ：NaMoO 4 •2H 2 O=1.25: 0.01:0.0068:0.015:0.0425: 0.5: 0.0063 configuration.
b. Arrangement of anode chamber substrates
And centrifuging the activated sludge from the sewage plant for six minutes, taking supernatant, adjusting the COD content to 2000-4000 mg/L by using the prepared electrolyte, and taking the supernatant as an anode chamber substrate, wherein the centrifugal rotating speed is 6000 rpm.
c. Electrochemical degradation of organic matter
Controlling the hydraulic retention time of the anode chamber to be four days through a water inlet peristaltic pump and a water outlet peristaltic pump, and circulating organic matter degradation electrolyte of the anode chamber to a cathode chamber through a proton transmembrane peristaltic pump, wherein inoculation liquid of the cathode chamber is taken from activated sludge of a sewage treatment plant; the CO 2 The purity was 99.999%, the aeration flow rate was 0.3L/min, and the aeration time was 30 min/day.
d. Constant potential control
A potential of-0.6V was applied to the cathode composite bioelectrode by potentiostat and amperometric recorder.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) Realizing CO by adopting double-chamber microbial electrolytic cell reactor 2 Compared with a single chamber, the methanation can effectively reduce the cross of microorganisms and final products, improve the purity of the products and avoid short circuits, thereby improving the methane production performance.
(2) The electro-active functional bacteria are attached to the carbon rod-graphite felt material to serve as a bipolar composite bioelectrode, and the three-dimensional structure and excellent conductivity of the graphite felt are fully utilized to strengthen the attachment growth of the electro-active functional bacteria, the formation of a biological film and the conduction of electrons.
(3) CO is processed into 2 The air inlet is tangentially arranged along the PEM membrane surface to supply C source, the arrangement can realize microfluidization of the membrane interface liquid, enhance the shearing and scouring of the membrane surface, reduce the fouling and the membrane resistance of the membrane surface and improve the proton H + Transmission flux, facilitate enhancement of CH 4 Resulting in efficiency.
(4) The proton transmembrane transport pump can pump the matrix degraded by the anode out and pump the matrix into the cathode chamber to realize the enhancement of proton transmembrane transport and avoid proton H caused by PEM pollution in the running process of the reactor + Transmission is blocked, thereby avoiding cathode chamber CH 4 The production efficiency is low.
(5) The device is suitable for different water inlet conditions and treatment requirements, occupies small area, can realize long-term stable operation, and has wider application prospect.
(6) The automatic degree is high, the installation and maintenance are convenient, the operation is stable, and the requirement on operators is low.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
FIG. 2 is a schematic diagram of a composite bioelectrode installation.
Detailed Description
Referring to figure 1, the invention provides a method for enhancing the synchronous CO of the oxidative degradation of organic matters 2 Methanation microbial cell comprising a double-chamber microbial cell (double-chamber MEC reactor) 1 separated by a Proton Exchange Membrane (PEM) 3An anode composite bioelectrode 2 is arranged in the anode chamber, a cathode composite bioelectrode 7, a reference electrode 11 and CO arranged at the bottom are arranged in the cathode chamber 2 An aerator pipe 6, the cathode composite bioelectrode 7 is arranged at the CO 2 The upper part of the aerator pipe 6 is electrically connected with the anode composite bioelectrode 2 through a circuit and the potentiostat 4 and the current recorder 5; the bottom of the anode chamber is provided with a water inlet pipeline connected with a water inlet peristaltic pump 8, and the upper part of the anode chamber is provided with a pipeline connected with a proton transmembrane peristaltic pump 9 and communicated with the bottom of the cathode chamber; the water inlet peristaltic pump 8 sends the pre-degraded matrix into the anode chamber of the double-chamber microbial electrolytic cell 1; the proton transmembrane peristaltic pump 9 pumps out the matrix degraded with the anode and pumps the matrix into the cathode chamber, so that the enhancement of proton transmembrane transmission is realized, the phenomenon that the proton transmission is blocked due to PEM pollution in the operation process of the reactor is avoided, and finally the cathode chamber CH is caused 4 The production efficiency is low.
Referring to fig. 2, the anode composite bioelectrode 2 and the cathode composite bioelectrode 7 include: and two graphite felts 22 arranged in the center of the carbon rod electrode 21, wherein the graphite felts 22 are respectively overlapped and wrapped on the periphery of the carbon rod electrode 21 and are fixedly wrapped by carbon wires 23.
The application method of the invention specifically comprises the following steps: the electrolyte added in the anode chamber and the cathode chamber is prepared as follows (g/L): naHCO (NaHCO) 3 1.25；KH 2 PO 4 0.85；K 2 HPO 4 1.09；NH 4 Cl 0.63；CaCl 2 •2H 2 O 0.19；MgCl 2 •6H 2 O 0.5；Na 2 S•9H 2 O0.5 mL (0.25 g/L), and a trace amount of 0.5 mL. The trace solution was formulated as follows (g/L): mnCl 2 •2H 2 O 0.125；NiCl 2 •6H 2 O 0.01；CuCl 2 •2H 2 O 0.0068；H 3 BO 3 0.015；CoCl 2 •6H 2 O 0.0425；FeCl 2 •4H 2 O0.5 and NaMoO 4 •2H 2 O 0.0063。
The organic matter to be treated in the anode chamber is obtained from sewage plant activated sludge, and after 6 min centrifugation (6000 rpm), the supernatant is diluted with the electrolyteCOD concentration is 2000-4000 mg/L, and the COD concentration is used as the anode chamber substrate. The hydraulic retention time of the anode chamber is controlled to be four days by a water inlet (outlet) peristaltic pump 8 (10) every day, and meanwhile, the continuous transfer of the substrate from the anode chamber to the cathode chamber every day is realized by a proton transmembrane peristaltic pump 9. The inoculation liquid in the cathode chamber is taken from the residual activated sludge of a sewage treatment plant, and the electric potential of-0.6V is applied to the cathode composite bioelectrode 7 through the circuit control of the potentiostat 4. Daily ultra-high purity CO 2 The aeration flow rate (99.999%) was set to 0.3L/min and the aeration time was controlled to 30 min/day. After a long period of operation of the Proton Exchange Membrane (PEM) 3 and the dual chamber MEC, the PEM is subject to the potential for contamination, thus converting CO 2 The air inlet is tangentially arranged along the membrane surface to supply C source, the change realizes microfluidization of the liquid at the membrane interface, enhances shearing and scouring of the membrane surface, reduces fouling and membrane resistance of the membrane surface, and improves proton H + Transmission flux, facilitate enhancement of CH 4 The production efficiency is improved, and the anode water outlet matrix is circularly fed into the cathode chamber to improve the proton H in the cathode chamber + Supplementing and finally improving CO 2 Electric methane synthesis efficiency.
The following describes the CO-oxidation and degradation of organic matter without enhancing proton transport in accordance with embodiments of the present invention 2 The invention will be further illustrated with reference to comparative examples of methanation.
Comparative example 1
The organic matter to be treated in the anode chamber is also obtained from activated sludge in sewage plant, after 6 min centrifugation (8000 r/min), supernatant is diluted with the electrolyte until COD concentration reaches 6383.1 mg/L, the supernatant is taken as anode chamber substrate, the hydraulic retention time of the anode chamber is controlled to be 4 d, and a potential of-0.6V is applied to the cathode through the circuit control of the potentiostat 4. CO 2 Aeration flow rate is set to 0.3L/min, aeration time is controlled to 30 min/d, CH in cathode chamber 4 The yield is 5.80 mL/L/d, and the COD degradation rate in the anode effluent is 79.2%.
Example 1
Referring to FIG. 1, the same method of preparing and using electrolytes, micro-solutions, and the like added to the anode and cathode as in comparative example 1, the culture apparatus used a 520 mL dual chamber MEC reactor 1 in which anode and cathode chambers each 260 mL, were each packedContaining 200 mL reaction volumes and a headspace of 60 mL for biogas collection. The average distance between anode and cathode was 4.0 cm and the two electrodes were connected to a potentiostat 4 via an external circuit to provide the required-0.6V potential, both electrode materials being carbon rod electrodes 21 wrapped with graphite felt 22. The anode chamber substrate is sludge supernatant diluted by electrolyte, and the COD concentration of the sludge supernatant is 3070.2 mg/L, so that the sludge supernatant is taken as the anode chamber substrate. Directly adding electrolyte and 5 mL inoculated sludge into the cathode chamber, and regulating pH of the electrolyte in the cathode chamber and the anode chamber to 7.0 to be suitable for the growth of electroactive functional bacteria, and ultra-high purity CO 2 (99.999%) was blown into the cathode reaction chamber (30 minutes/day) as a functional bacterial carbon source at a flow rate of 0.3L/min. While the continuous daily transfer of matrix from the anode chamber to the cathode chamber is achieved by means of a proton transmembrane peristaltic pump 9. At regular intervals, a volume of biogas (CH) is removed from the head space of the cathode chamber with a syringe 4 ) Analysis was performed by a gas chromatograph equipped with a thermal conductivity detector. COD degradation rate is measured by national standard method, and after the double-chamber MEC reactor 1 is operated for 78 days, the enhanced organic matter oxidative degradation is synchronous with CO 2 Methanation cathode chamber CH 4 The yield is up to 20.80 mL/L/d, which is improved by 258.6% compared with 5.80 mL/L/d in the comparative example 1, and meanwhile, the COD degradation rate in the anode effluent is up to 95.6%, which is improved by 20.7% compared with 79.2% in the comparative example 1. At the same time due to CO 2 The change of the feeding mode reduces the membrane surface fouling and membrane resistance, and the PEM does not generate pollution phenomenon after the reaction is finished.
The invention adopts the double-chamber microbial electrolytic cell 1 to realize CO 2 Compared with a single chamber, the methanation can effectively reduce the cross of microorganisms and final products, improve the purity of the products and avoid short circuits. Meanwhile, the anode composite bioelectrode 2 and the cathode composite bioelectrode 7 are made of carbon rod electrodes 21, graphite felt 22 and loaded microorganisms, and have good three-dimensional structures, so that microorganism adhesion is facilitated. And CO is treated with 2 The air inlet is tangentially arranged along the PEM membrane surface to supply C source, the arrangement can realize microfluidization of the membrane interface liquid, enhance the shearing and scouring of the membrane surface, reduce the fouling and the membrane resistance of the membrane surface and improve the proton H + Transmission flux, facilitate enhancement of CH 4 Resulting in efficiency. At the same timeThe anode effluent matrix is circularly fed into the cathode chamber, and the protons H in the cathode chamber are improved + Supplementing and finally improving CO 2 Electric methane synthesis efficiency.
The invention is further described above without limiting the scope of the claims, which should be construed as being limited to the embodiments disclosed herein.
Claims (3)
1. Synchronous CO for organic oxidative degradation 2 The methanation microbial electrolytic cell comprises a double-chamber microbial electrolytic cell provided with a potentiostat and a current recorder, a proton exchange membrane is arranged between an anode chamber and a cathode chamber, and is characterized in that an anode composite bioelectrode is arranged in the anode chamber, and a cathode composite bioelectrode and CO are arranged in the cathode chamber 2 The anode chamber is communicated with the cathode chamber through a pipeline provided with a proton transmembrane peristaltic pump; the anode composite bioelectrode and the cathode composite bioelectrode are a plurality of graphite felts axially arranged on the carbon rod electrode; the graphite felt is in a cloth shape and is overlapped and wrapped on the carbon rod electrode, and is wrapped and fixed by the carbon wire; the potentiostat is connected in parallel with the current recorder, the anode of the potentiostat is electrically connected with the anode composite bioelectrode, and the cathode of the potentiostat is electrically connected with the cathode composite bioelectrode and the reference electrode; the cathode chamber is provided with a water outlet pipeline and a methane gas outlet which are connected with a water outlet peristaltic pump; the anode chamber is provided with a water inlet pipeline connected with a water inlet peristaltic pump; the organic matter to be treated in the anode chamber is obtained from activated sludge of a sewage plant; CO 2 The air inlet is tangentially arranged along the membrane surface of the proton exchange membrane to supply C source.
2. A microbial electrolysis cell according to claim 1 wherein the graphite felt is an electrically conductive polymer material forming an electrode having a three-dimensional structure.
3. Synchronous CO of organic matter oxidative degradation of a microbial electrolytic cell according to claim 1 2 A process for methanation, characterized in that it comprises in particular the following steps:
a. arrangement of electrolyte
Electrolyte according to NaHCO 3 ：KH 2 PO 4 ：K 2 HPO 4 ：NH 4 Cl ：CaCl 2 •2H 2 O ：MgCl 2 •6H 2 O：Na 2 S•9H 2 O: trace 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, the trace solution is according to MnCl 2 •2H 2 O ：NiCl 2 •6H 2 O：CuCl 2 •2H 2 O：H 3 BO 3 ：CoCl 2 •6H 2 O ：FeCl 2 •4H 2 O ：NaMoO 4 •2H 2 O=1.25: 0.01:0.0068:0.015:0.0425: 0.5: 0.0063 configuration;
b. arrangement of anode chamber substrates
Taking supernatant after centrifugal treatment of activated sludge from a sewage plant for six minutes, and adjusting COD content to 2000-4000 mg/L by using the prepared electrolyte to serve as an anode chamber matrix, wherein the centrifugal rotating speed is 6000 rpm;
c. electrochemical degradation of organic matter
Controlling the hydraulic retention time of an anode chamber to be four days through a water inlet peristaltic pump and a water outlet peristaltic pump, and circulating an organic matter degradation electrolyte of the anode chamber to a cathode chamber through a proton transmembrane peristaltic pump, wherein an inoculation liquid of the cathode chamber is taken from activated sludge of a sewage treatment plant; the CO 2 The purity is 99.999 percent, the aeration flow rate is 0.3L/min, and the aeration time is 30 min/day;
d. constant potential control
A potential of-0.6V was applied to the cathode composite bioelectrode by potentiostat and amperometric recorder.
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| CN113398716B (en) * | 2021-05-14 | 2022-08-23 | 上海电力大学 | Biological methanation system for capturing carbon dioxide in renewable energy hydrogen production coupled power plant |
| 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 |
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