CN111170598A - Method for modifying carbon felt anode by manganese dioxide and application - Google Patents

Method for modifying carbon felt anode by manganese dioxide and application Download PDF

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Publication number
CN111170598A
CN111170598A CN202010068531.XA CN202010068531A CN111170598A CN 111170598 A CN111170598 A CN 111170598A CN 202010068531 A CN202010068531 A CN 202010068531A CN 111170598 A CN111170598 A CN 111170598A
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anode
carbon felt
sludge
anaerobic
sol
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李超
贺含悦
操家顺
努尔
周康
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Hohai University HHU
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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
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/02—Biological treatment
    • C02F11/04—Anaerobic treatment; Production of methane by such processes
    • 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 invention discloses a method for modifying a carbon felt anode by manganese dioxide, which prepares MnO by adopting a sol-gel method2And then modifying the carbon felt anode by a sol impregnation method, and further applying the modified carbon felt anode to an MFC-anaerobic digestion coupled system anode. The system is a new method for sludge treatment and disposal, not only can improve the sludge reduction effect, but also strengthens the electricity generation performance and anaerobic digestion performance of the sludge MFC-anaerobic digestion coupled system. The invention adopts a sol-gel method to prepare MnO2And then the carbon felt anode electrode is modified by a sol impregnation method, so that the recovery and utilization of energy substances (including electric energy, methane, VFA and the like) are further improved, and the recovery of system electric energy is particularly promoted. The method has simple operation and obvious effect, and realizes the directional control and the recycling of energy.

Description

Method for modifying carbon felt anode by manganese dioxide and application
Technical Field
The invention discloses MnO2A method for modifying an anode of a sludge MFC-anaerobic digestion coupling system and an application thereof belong to the technical field of new energy and environmental engineering.
Background
MFC (microbial fuel cell) is a device that degrades organic substances in wastewater by the catalytic action of microorganisms to directly convert chemical energy of the organic substances into electrical energy. In the anode compartment, for example a conventional MFC, microorganisms (in particular microorganisms attached to the surface of the electrode) anaerobically oxidize and degrade organic material to produce H+Electron and CO2(ii) a Electrons in microbial cells are transferred to certain proteins outside the cells (such as C-type extracellular cytochrome) through a series of respiratory enzymes, and are transferred to the surface of an anode through different extracellular electron transfer modes; the electrons are transferred from an external circuit to the cathode, H+Across the proton exchange membrane to the cathode; on the cathode surface, electrons, H+And O2A reduction reaction occurs to complete the entire redox process.
It is reported that cytochrome species have the ability to store electrons and thus act as a supercapacitor in the anodic biofilm, rendering it electrochemically active. For example, Mn in the molecular structure of cytochrome C can be reduced by Mn in the reduced state3+Mn in oxidized state4+The reversible change between the anode and the cathode realizes the storage of electrons and the transmission of the electrons to the surface of the anode. Li Weixin (Liweixin, Yin Yao, Dimengjie, et al. Mn3O4 modifies electrogenesis performance of anode microbial fuel cell [ J]A report of university of eastern Engineers 2016,42(2): 194-199), et al, teach the use of Mn prepared by sol-gel impregnation3O4As an anode, the maximum power density of the MFC can reach 0.431W/m2Compared with the control group, the increase is 93 percent; the MFC has 67% reduced internal resistance for charge transfer and has pseudocapacitance characteristics. Roche et al (Roche I, Katuri K, Scott K.A microbial fuel cell using a mangannese oxide reduction catalysts [ J)]Journal of applied electrochemistry.2010,40(1):13-21.) points out the MnO loading of the carbon in MFC2The power density of the particle electrode can reach 161mW/m2While the power density of the reference Pt/C is only 19mW/m2. Further investigation revealed that in neutral pH solution, MnO was present2The activity of catalyzing ORR reaction through 4-electron transfer pathway is shown as follows:
2MnOx+2H++2e-→2MnOx-1OH
2MnOx-1OH+O2→|(MnOx-1OH)Oads|2
|(MnOx-1OH)Oads|2+H++e-→(MnOx-1OH)Oads+H2O+MnOx
(MnOx-1OH)Oads+H++e-→MnOx+H2O
the manganese can also enhance the atmosphere of anaerobic environment, thereby improving the performance of anaerobic fermentation. Research shows that manganese reduction of microorganisms is a special form of anaerobic respiration and terminal electron acceptor transfer process, and has certain competition with iron reduction, sulfate reduction and other processes in anaerobic fermentation. The researchers have pointed out (Tian T, Qiao S, Yu C, et al, Distinguist and biochemical reactivity in response to MnO2nanoparticles in biochemical two tablet slurry [ J]Water research.2017,123: 206), adding nanoparticles MnO2A significant increase in the abundance of methanosarcina was later observed, probably because the VFA degradation products could serve as substrates for hydrogenotrophic methanogens. The intensive research finds that the mechanism of promoting anaerobic digestion to produce methane by manganese is basically similar to that of iron, namely, methanogens can utilize Mn2+Electrons and CO liberated during oxidation to manganese oxide2Combine to form CH4。
Chinese patent with publication number CN 106207239A provides a synthesis method of nitrogen-doped porous carbon and application thereof in the aspect of microbial fuel cell anodes. The method has the advantages of complex material preparation process, high requirement on equipment, certain toxicity of chemical agents such as melamine and the like, and negative influence on sludge microorganisms. Chinese patent publication No. CN 106920982A provides a method for in-situ modification of a three-dimensional carbonaceous microbial fuel cell anode by nano-porous platinum carbide, which uses a carbon felt electrode as a substrate, phosphomolybdic acid as a molybdenum source, and allows nano-molybdenum carbide with a porous structure to grow in situ and uniformly on carbon felt fibers through two processes of static self-assembly mediated by poly diallyldimethylammonium chloride and high-temperature carbonization in a reducing atmosphere. The process of the prepared three-dimensional composite electrode is extremely complex, the requirement on the device condition is high, the realizability is not strong, time and material consumption are realized, and the cost is high.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention provides MnO2The method for modifying the carbon felt anode is applied to the sludge MFC-anaerobic digestion coupled system, so that the sludge reduction effect is improved, and the electricity generation performance and the anaerobic digestion performance of the sludge MFC-anaerobic digestion coupled system are enhanced.
The technical scheme is as follows: in order to realize the technical scheme, the invention provides a method for modifying an anode of a sludge MFC-anaerobic digestion coupled system by manganese dioxide, wherein a reactor of the sludge MFC-anaerobic digestion coupled system comprises a closed anaerobic anode chamber and an aerated cathode chamber, the anode chamber and the cathode chamber are connected through a communicating pipeline, a proton exchange membrane is arranged in the communicating pipeline, a carbon felt anode of the anode chamber and a carbon felt cathode in the cathode chamber are connected through an alligator clamp lead, an external resistor is arranged between the anode and the cathode, a circular hole is arranged on the cover surface of the anode and connected with an air collecting bag for collecting methane gas generated by anode anaerobic sludge fermentation, and MnO is prepared by adopting a sol-gel method2And then modifying the carbon felt anode by a sol dipping method.
Specifically, the carbon felt anode is modified by the following steps:
(1) sol preparation: weighing 2-5g of citric acid and 5-10g of manganese acetate, dissolving in 100-150mL of deionized water, stirring by using a magnetic stirrer until the citric acid and the manganese acetate are completely dissolved, adjusting the pH value to be neutral by using ammonia water at the temperature of 60-70 ℃, standing, and naturally aging to convert the solution into sol;
(2) preparing a carbon felt by a sol impregnation method: and (3) placing the anode carbon felt into the sol, soaking for 1-2h, dehydrating in a drying oven at 100-120 ℃, and calcining in a muffle furnace at 300-400 ℃ for 12-15h to obtain the modified carbon felt anode.
Further, after the carbon felt anode is modified and placed in an anaerobic anode chamber of a reactor of the sludge MFC-anaerobic digestion coupled system, nitrogen is blown into the reactor for 30-60 seconds by using a nitrogen blowing device, so that all air in the reactor is discharged, and then an organic glass cover is quickly covered tightly, so that the test device is kept under a closed anaerobic condition.
Wherein the size of the sludge MFC-anaerobic digestion coupled system reactor configuration is 12cm multiplied by 18 cm; the sizes of the cathode carbon felt and the anode carbon felt are 4cm multiplied by 5cm multiplied by 0.3 cm; the size of the proton exchange membrane is 10cm2(ii) a The external resistance is 1000 omega; the diameter of the circular hole on the cover surface of the anode is 1 cm.
Specifically, nutrient solution is added to the anode to culture and domesticate electrogenesis bacteria and anaerobic digestion bacteria, wherein the nutrient solution comprises the following components in per liter of deionized water: 3.13g NaHCO3、0.13g KCl、4.22gNaH2PO4、2.75g Na2HPO4、0.56g(NH4)2SO4、0.2g MgSO4·7H2O、2mg H3BO3、2mg FeCl2·4H2O、2mg EDTA、0.4mg ZnCl2·4H2O、0.8mg MnCl2·4H2O、0.2mgCuCl2·2H2O、1.1mg(NH4)6MO7·4H2O、1mg NiCl2·6H2O。
Before use, the proton exchange membrane is firstly placed in an absolute ethyl alcohol solution with the mass percentage concentration of 0.5-1% at the temperature of 20-30 ℃ for soaking for 1-2h, is washed and then is placed in a hydrogen peroxide solution with the mass percentage concentration of 5-10% at the temperature of 70-80 ℃ for soaking for 2-3h, and is finally washed by ultrapure water for 3-5 times for later use.
In one embodiment, the anode sludge substrate is a sewage treatment plant A2Taking the residual sludge of the/O process and the mixture of the residual sludge and anaerobic sludge at the bottom of a river channel, standing and precipitating for 20-30 hours after the sludge is taken back, scraping the upper part of floating slag and unknown impurities, and storing at 10-20 ℃ for later useBefore feeding, the test sludge is screened to remove impurities, deposited and concentrated. Preferably, the screen mesh size is 0.18 mm.
Preferably, the bottom of the anaerobic anode chamber of the reactor of the sludge MFC-anaerobic digestion coupling system is provided with a magnetic stirring device, and the device is always stirred at a medium speed of 500-800rpm during operation; aerating air in cathode chamber of reactor to provide O for cathode reaction2As an electron acceptor.
The invention further provides application of the anode prepared by the method in preparation of a microbial fuel cell.
Wherein the reactor is operated at the room temperature of 20-30 ℃, the voltage change of the reactor, the VFAs and the methane yield are monitored, and a reaction period is 40-70 days according to the actual operation condition.
Advantageous effects
The invention innovatively adopts a sol-gel method to prepare MnO2And then the carbon felt anode electrode is modified by a sol dipping method, and a set of sludge MFC-anaerobic digestion coupled system is further constructed by utilizing the carbon felt anode electrode, and the system is a new method for sludge treatment and disposal, so that the sludge reduction effect is improved, the electricity generation performance and the anaerobic digestion performance of the sludge MFC-anaerobic digestion coupled system are enhanced, the recovery and utilization of energy substances (including electric energy, methane, VFA and the like) are further improved, and the recovery of the electric energy of the system is particularly promoted.
Drawings
FIG. 1(a) is a graph passing through MnO2SEM images of modified sludge MFC-anaerobic digestion coupled system anodes, (b) is unmodified sludge MFC-anaerobic digestion coupled system anodes.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The embodiment provides a sludge MFC-anaerobic digestion coupled system reactor which adopts an MFC double-chamber configuration (12cm multiplied by 18cm), and comprises a closed anaerobic anode chamber and an aerated cathode chamber, wherein the anode chamber and the cathode chamber are connected through a communication pipeline, and a proton exchange membrane (with the membrane area of 10 cm) is arranged in the communication pipeline2) Carbon felt cathodes (4cm x 5cm x 0.3cm) in the anode chamber and carbon felt cathodes (4cm x 5cm x 0) in the cathode chamber.3cm) is connected through a crocodile clip lead, an external resistor (1000 omega) is arranged between the anode and the cathode, and a round hole connected with an air collecting bag is arranged on the cover surface of the anode. Wherein:
(1) the nutrient solution of the sludge MFC-anaerobic digestion coupled system reactor anode comprises (per liter of deionized water): NaHCO 23(3.13g)、KCl(0.13g)、NaH2PO4(4.22g)、Na2HPO4(2.75g)、(NH4)2SO4(0.56g)、MgSO4·7H2O (0.2 g). In addition, in order to maintain the metabolism and growth of the microorganisms, trace elements are added to the solution, including (per liter of deionized water): h3BO3(2mg)、FeCl2·4H2O(2mg)、EDTA(2mg)、ZnCl2·4H2O(0.4mg)、MnCl2·4H2O(0.8mg)、CuCl2·2H2O(0.2mg)、(NH4)6MO7·4H2O(1.1mg)、NiCl2·6H2O(1mg)；
(2) Before use, the proton exchange membrane is firstly placed in an absolute ethyl alcohol solution with the mass percentage concentration of 1% at 25 ℃ for soaking for 1.5h, then is washed and then is placed in a hydrogen peroxide solution with the mass percentage concentration of 10% at 75 ℃ for soaking for 2h, and finally is washed by ultrapure water for 3 times for later use;
(3) taking back the sludge, standing for precipitation for 25 hours, scraping off upper part of scum and unknown impurities, storing at 15 ℃ for later use, removing impurities from the test sludge through a screen with the mesh size of 0.18mm before feeding, precipitating and concentrating;
(4) the method for modifying the carbon felt anode electrode comprises the following steps:
a) sol preparation: 3g of citric acid and 5g of manganese acetate are weighed and dissolved in 100mL of deionized water, stirred by a magnetic stirrer until the citric acid and the manganese acetate are completely dissolved, then ammonia water is used for adjusting the pH value to be neutral under the condition of 65 ℃, and the mixture is kept stand and naturally aged to be converted into sol.
b) Preparing a carbon felt by a sol impregnation method: and (3) placing the carbon felt into the sol and soaking for 1 h. Then dehydrated in an oven at 100 ℃ and calcined in a muffle furnace at 300 ℃ for 12h to prepare the carbon felt electrode.
(5) After the modified electrode is placed at the anode of the system reactor, nitrogen is blown into the reactor for 60 seconds by using a nitrogen blowing device, so that the air in the reactor is completely discharged, and then an organic glass cover is quickly covered tightly, so that the test device is kept under the closed anaerobic condition. The bottom of the anode chamber is provided with a magnetic stirring device, the device is always stirred at a medium speed of 500rpm during the operation, the reactor is operated at a normal temperature of 20 ℃, the voltage change of the reactor, the VFAs and the methane yield are monitored, and 60 days is selected as an operation period.
Passing through MnO2The performance of each parameter of the modified sludge MFC-anaerobic digestion coupled system is shown in table 1. As shown in Table 1, the maximum peak voltage of the coupled system after anode modification is 311.5mV, which is significantly increased compared to the unmodified test group. The electric power density of the coupled system subjected to anode modification is 34.93mW/m2The resistance value obtained by fitting is 359.03 omega, and the electric power density is improved by 22.93mW/m compared with that of an unmodified test group2The resistance value is reduced by 94.99 omega, and the electrochemical performance is obviously improved. The coupled system after anode modification shows a weak oxidation peak near-0.6V, while the unmodified test group has no obvious oxidation reduction peak. In addition, the peak area of the cyclic voltammetry can reflect the amount of electricity exchanged by the oxidation and reduction reactions of the electroactive substance, and therefore, the size of the envelope area of the oxidation peak and the reduction peak actually reflects the polarization state inside the electrode and the utilization rate of the active substance. And through analysis of test results, the electric quantity of electroactive substance exchange of the coupling system modified by the anode is large, and the electricity generation efficiency is improved. The acetic acid content of the coupled system subjected to anodic modification is 499.5mg/L, which is improved by 50% compared with that of an unmodified test group. The cumulative yield of methane in the coupled system subjected to anodic modification is 43.2mL/gVS, and compared with that in an unmodified test group, the cumulative yield of methane is improved by 0.4 times. FIG. 1(a) is a graph passing through MnO2SEM image of modified sludge MFC-anaerobic digestion coupled system anode, which is known to pass through MnO2The modified carbon felt electrode has dense biological film and forms a net structure with large specific surface area, which shows that the electrode is enriched with certain electrogenesis bacteria and anaerobic digestion bacteria and strengthens the synthesis of a coupling systemAnd (4) performance.
Comparative example
A set of sludge MFC-anaerobic digestion coupled system is constructed as a control test group, namely, the system does not pass through MnO2A modified sludge MFC-anaerobic digestion coupling system, wherein a reactor adopts an MFC double-chamber configuration (12cm multiplied by 18cm), comprises a closed anaerobic anode chamber and an aerated cathode chamber, the anode chamber and the cathode chamber are connected through a communicating pipeline, and a proton exchange membrane (with the membrane area of 10 cm) is arranged in the communicating pipeline2) The carbon felt cathode (4cm multiplied by 5cm multiplied by 0.3cm) in the anode chamber is connected with the carbon felt cathode (4cm multiplied by 5cm multiplied by 0.3cm) in the cathode chamber through an alligator clip lead, an external resistor (1000 omega) is arranged between the anode and the cathode, and a circular hole is arranged on the cover surface of the anode to be connected with a gas collecting bag. Wherein:
(1) the nutrient solution of the sludge MFC-anaerobic digestion coupled system reactor anode comprises (per liter of deionized water): NaHCO 23(3.13g)、KCl(0.13g)、NaH2PO4(4.22g)、Na2HPO4(2.75g)、(NH4)2SO4(0.56g)、MgSO4·7H2O (0.2 g). In addition, in order to maintain the metabolism and growth of the microorganisms, trace elements are added to the solution, including (per liter of deionized water): h3BO3(2mg)、FeCl2·4H2O(2mg)、EDTA(2mg)、ZnCl2·4H2O(0.4mg)、MnCl2·4H2O(0.8mg)、CuCl2·2H2O(0.2mg)、(NH4)6MO7·4H2O(1.1mg)、NiCl2·6H2O(1mg)。
(2) Before use, the proton exchange membrane is firstly placed in an absolute ethyl alcohol solution with the mass percentage concentration of 1% at 25 ℃ for soaking for 1.5h, then is washed and then is placed in a hydrogen peroxide solution with the mass percentage concentration of 10% at 75 ℃ for soaking for 2h, and finally is washed by ultrapure water for 3 times for later use.
(3) Taking the sludge back, standing for precipitation for 25 hours, scraping the upper part of scum and unknown impurities, storing at 15 ℃ for later use, removing the impurities from the test sludge through a screen with the mesh size of 0.18mm before feeding, and precipitating and concentrating.
(4) Will not be MnO2DecorationAfter the electrode is arranged at the anode of the system reactor, nitrogen is blown into the reactor for 60 seconds by using a nitrogen blowing device, so that the air in the reactor is completely exhausted, and then an organic glass cover is quickly covered tightly, so that the test device is kept under the closed anaerobic condition. The bottom of the anode chamber is provided with a magnetic stirring device, the device is always stirred at a medium speed of 500rpm during the operation, the reactor is operated at a normal temperature of 20 ℃, the voltage change of the reactor, the VFAs and the methane yield are monitored, and 60 days is selected as an operation period.
Not requiring MnO2The performance of each parameter of the modified sludge MFC-anaerobic digestion coupled system is shown in table 1.
TABLE 1
Figure BDA0002376669580000071
As can be seen from Table 1, the maximum peak voltage of the unmodified coupled system was 209.1mV, and the electric power density was 12.00mW/m2The resistance value obtained by fitting was 454.02 Ω, and the unmodified test group did not have a distinct redox peak. In addition, the acetic acid content in the unmodified coupled system was 332.5mg/L, and the cumulative methane yield was 30.5 mL/gVS. FIG. 1(b) is a non-MnO2SEM image of modified sludge MFC-anaerobic digestion coupled system anode, which is clear without MnO2The biological film on the surface of the modified carbon felt electrode is very loose and presents a sparse point-shaped form, which shows that the electrode has less electrogenesis bacteria and anaerobic digestion bacteria and the coupling system has lower comprehensive performance.

Claims (10)

1. A method for modifying a carbon felt anode by manganese dioxide is characterized in that MnO is prepared by adopting a sol-gel method2And then modifying the carbon felt anode by a sol dipping method.
2. The method of claim 1, wherein the carbon felt anode is modified by:
(1) sol preparation: weighing 2-5g of citric acid and 5-10g of manganese acetate, dissolving in 100-150mL of deionized water, stirring by using a magnetic stirrer until the citric acid and the manganese acetate are completely dissolved, adjusting the pH value to be neutral by using ammonia water at the temperature of 60-70 ℃, standing, and naturally aging to convert the solution into sol;
(2) preparing a carbon felt by a sol impregnation method: and (3) placing the anode carbon felt into the sol, soaking for 1-2h, dehydrating in a drying oven at 100-120 ℃, and calcining in a muffle furnace at 300-400 ℃ for 12-15h to obtain the modified carbon felt anode.
3. The application of the carbon felt anode prepared by the method in the claims 1-2 in constructing a sludge MFC-anaerobic digestion coupled system.
4. The application of claim 3, wherein the reactor of the sludge MFC-anaerobic digestion coupling system comprises a closed anaerobic anode chamber and an aerated cathode chamber, the anode chamber and the cathode chamber are connected through a communication pipeline, a proton exchange membrane is arranged in the communication pipeline, a carbon felt anode in the anode chamber and a carbon felt cathode in the cathode chamber are connected through an alligator clamp lead, an external resistor is arranged between the anode and the cathode, and a circular hole is arranged on the cover surface of the anode and connected with a gas collecting bag for collecting methane gas generated by the fermentation of the anode anaerobic sludge; the carbon felt anode is the carbon felt anode modified by manganese dioxide prepared by the method in claim 1 or 2.
5. The application of claim 3, wherein after the carbon felt anode modified by manganese dioxide is placed in the anaerobic anode chamber of the sludge MFC-anaerobic digestion coupling system, nitrogen is blown into the reactor for 30-60 seconds by using a nitrogen blowing device to ensure that all air in the reactor is exhausted, and then the organic glass cover is quickly closed to keep the test device under a closed anaerobic condition.
6. The use according to claim 3, characterized in that the sludge MFC-anaerobic digestion coupled system configuration has a size of 12cm by 18 cm; the sizes of the cathode carbon felt and the anode carbon felt are 4cm multiplied by 5cm multiplied by 0.3 cm; the size of the proton exchange membrane is 10cm2(ii) a The external resistorThe size is 1000 omega; the diameter of the circular hole on the cover surface of the anode is 1 cm.
7. The use of claim 3, wherein a nutrient solution is added to the anode to culture the domesticated electrogenic bacteria and anaerobic digesters, wherein the nutrient solution comprises the following components per liter of deionized water: 3.13g NaHCO3、0.13g KCl、4.22g NaH2PO4、2.75g Na2HPO4、0.56g(NH4)2SO4、0.2g MgSO4·7H2O、2mg H3BO3、2mg FeCl2·4H2O、2mg EDTA、0.4mg ZnCl2·4H2O、0.8mg MnCl2·4H2O、0.2mg CuCl2·2H2O、1.1mg(NH4)6MO7·4H2O、1mg NiCl2·6H2O。
8. The use of claim 3, wherein the proton exchange membrane is soaked in 20-30 ℃ absolute ethanol solution with the mass percentage concentration of 0.5-1% for 1-2h before use, soaked in 70-80 ℃ hydrogen peroxide solution with the mass percentage concentration of 5-10% for 2-3h after being washed, and finally washed with ultrapure water for 3-5 times for later use.
9. Use according to claim 3, characterized in that the anode sludge substrate is a sewage treatment plant A2Taking the residual sludge of the/O process and the mixture of anaerobic sludge at the bottom of a river channel, standing and precipitating for 20-30 hours after the sludge is taken back, scraping the upper part of scum and unknown impurities, storing at 10-20 ℃ for later use, removing the impurities from the test sludge through a screen before feeding, precipitating and concentrating.
10. The use according to claim 1, characterized in that the bottom of the anaerobic anode chamber of the reactor of the sludge MFC-anaerobic digestion coupled system is equipped with a magnetic stirring device, which keeps a medium speed stirring of 500-800rpm during the operation; the cathode chamber of the reactor is aerated toCathodic reaction to provide O2As an electron acceptor.
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CN111682225A (en) * 2020-07-03 2020-09-18 朱义奎 Titanium doping modification method for graphite felt electrode material of vanadium battery
CN111682226A (en) * 2020-07-03 2020-09-18 朱义奎 Nickel doping modification method for graphite felt electrode material of vanadium battery

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111682225A (en) * 2020-07-03 2020-09-18 朱义奎 Titanium doping modification method for graphite felt electrode material of vanadium battery
CN111682226A (en) * 2020-07-03 2020-09-18 朱义奎 Nickel doping modification method for graphite felt electrode material of vanadium battery

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