CN109841842B - Preparation device and preparation method of charcoal-mediated solid biofilm MFC (microbial fuel cell) accelerator - Google Patents
Preparation device and preparation method of charcoal-mediated solid biofilm MFC (microbial fuel cell) accelerator Download PDFInfo
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Abstract
The invention relates to a device and a method for preparing a charcoal-mediated solid biofilm MFC promoter. A biochar-mediated solid biofilm MFC promoter preparation device mainly comprises a microbial fuel cell unit, a heating unit and a vacuum freeze-drying unit; the anode chamber of the microbial fuel cell unit comprises an anode chamber area a and an anode chamber area b, the anode chamber area a and the anode chamber area b are separated by a filter plate, and the filter plate is provided with equidistant sieve pores and a scraper with a hairbrush. The invention also discloses a method for preparing the MFC accelerator by using the device. The invention effectively realizes the preparation of the solid biomembrane MFC accelerant mediated by the biochar, ensures the anaerobic operation of the preparation process, has simple and compact structure and convenient operation, and has positive effects on shortening the starting time of the MFC, quickly enriching and stabilizing the microorganisms in the anode chamber, effectively improving the sufficiency of the degradation of the organic matters of the MFC and the efficiency of converting the chemical energy in the organic matters into electric energy, reducing the internal resistance of the battery and improving the power generation efficiency.
Description
Technical Field
The invention relates to a preparation device and a preparation method of a microbial fuel cell accelerant, and belongs to the technical fields of resource utilization, environmental protection and microbial fuel cells. In particular to a device and a method for preparing a solid biomembrane MFC promoter mediated by biochar.
Background
Microbial Fuel Cells (MFCs) are a bioelectrochemical device that directly converts chemical energy in biomass into electrical energy using a Microbial metabolic process. MFC can utilize organic matters in waste components such as forestry and agricultural residues, sludge, municipal refuse, industrial polluted wastewater and the like to be converted into electric energy and other energy substances, meets the requirements of changing waste into valuables and being environment-friendly, and is a technology with a very wide application prospect in the fields of pollution treatment and new energy research. With the progress of research and technology, the efficiency of microbial fuel cells is continuously improved, but still some problems exist, such as insufficient utilization of raw organic matters, low coulombic efficiency, long period from start-up to stabilization of the cells, high internal resistance of the cells, low electricity generation efficiency and the like, and all the problems restrict the comprehensive popularization and further development of the MFC technology.
In order to solve the above problems, researchers have conducted a lot of research works and proposed corresponding improvement measures in terms of the structure of MFC, electrode materials, species of electrogenic bacteria, reaction mechanism, and the like. The anode is a limiting factor for improving the performance of the microbial fuel cell, the electrogenic bacteria decompose organic pollutants in the anode chamber of the microbial fuel cell and generate electricity, and the anode electrode is researched more in the aspect of materials, such as a carbon cloth anode, a carbon paper anode, a graphite brush anode and the like. The discovery that the electricity-producing bacteria is a biocatalyst for MFC reaction, and thus the search for high-electricity-producing strains or the improvement of the electricity-producing effect of the electricity-producing strains is another key method for improving MFC, geobactrifurrugansens, shewanella pultrefaciens, rhodoferatrireducens and the like have been found to transport electrons from microbial cells to anodes without electron transfer mediators, thereby completing energy metabolism and growth and propagation. However, when MFC is used for organic wastewater and waste treatment, the advantages of the mixed strains as the electrogenic bacteria are more obvious, for example, the mixed strains have the advantages of no need of considering the growth conditions of pure culture of the strains, easy enrichment and domestication, and the like, and are widely used in organic pollution treatment. In the research, logan B E and Regan J M find that in the process of decomposing organic pollutants to generate electric energy, a plurality of strains participate, synergistic action exists among different strains (Logan B E, regan J M, electric-producing bacteria in microbial cells, J. Trends in Microbiology, 2006, 14 (12): 512.), each type of strain has different actions, such as part of bacteria generates electrons, part of bacteria transfers electrons, metabolites of the bacteria also have the phenomenon of mutual substrates, the Logan B E and Regan J M considers that the concept of electrogenic bacteria (electrogens) only represents a type of bacteria with the capability of generating electrons, the actual Electricity generation process of the MFC needs a plurality of strains to participate in assistance to complete, the use of the electrogens is more accurate, and therefore, the proper increase of the anode mixed biomass is an effective way for improving the Electricity generation efficiency of the MFC.
The biomembrane process is an important method for effectively enriching and stabilizing microorganisms, has the advantages of small biomembrane volume, high microorganism content, short hydraulic retention time, relatively stable biological phase, strong resistance to toxicants and impact loads, high treatment effect and the like, and is widely applied to biological treatment of municipal sewage and industrial wastewater and microbial fuel cells. The generation and growth of the biofilm method cannot be separated from the use of a carrier material, and the carrier is a medium necessary in the microorganism fixing process, has very important function in the biofilm treatment and influences the growth, reproduction, shedding, shape and space structure of microorganisms. The carrier applied in the biofilm method should satisfy the following conditions: (1) easy fluidization but not easy loss; (2) easy film formation, but no toxic action; (3) can provide large specific surface area to increase the biological attachment amount; and (4) the price is low, and the materials are easy to obtain.
Biochar (biochar) is an ideal material for biofilm carriers in MFC. The biochar is a refractory, stable, highly aromatic and carbon-rich solid substance produced by slowly pyrolyzing biomass at high temperature (usually less than 1000 ℃) under the condition of oxygen deficiency, the carbon content of the biochar is about 60-80%, the biochar mainly comprises carbon, hydrogen, oxygen and other elements, and the biochar also comprises potassium, calcium, iron and other nutrient metal elements. In the solid waste treatment, the waste which is easy to be decomposed by microorganism can be changed into valuable by anaerobic digestion and microbial fuel cell technology, and the waste which is not easy to be decomposed by microorganism can be prepared into biochar by pyrolysis to avoid environmental pollution and realize resource utilization. The biochar has good physical and chemical properties such as large specific surface area and porosity, good biothilicity, abundant surface chemical functional groups and the like, and has the advantages of wide material source, low manufacturing cost, environmental friendliness and the like, thereby having wide application in the fields of agriculture, environment, energy and the like. Biochar is a precursor of activated carbon, and the research of activated carbon as a biofilm carrier material in MFC has a long history. At present, the research of the biochar as the MFC biomembrane carrier also obtains better effect. In particular, researches in recent years find that the addition of the biochar in the MFC can effectively play positive roles of reducing internal resistance, increasing coulombic efficiency, improving output voltage and output power and the like. It can be seen that biochar is an ideal material for biofilm carriers in MFC.
Although the biofilm method using the biochar as the carrier has many advantages in the application of the MFC, the biofilm time adopting the biofilm method is generally longer, and is about 7 days to 2 to 3 months, which brings problems to the rapid enrichment and the stabilization of microorganisms in the anode chamber of the MFC so as to realize the rapid start. How to apply the advantages of the biological carbon-mediated biological membrane technology to the MFC field and avoid the defect of overlong starting time caused by membrane hanging time of the biological membrane method is an important problem to be solved for shortening the starting time of the MFC, rapidly enriching and stabilizing microorganisms, improving the utilization rate of organic fuel and the coulombic efficiency, reducing the internal resistance of a battery and increasing the electricity generation efficiency, and also an important problem to be solved for promoting the application and popularization of the MFC technology.
Disclosure of Invention
The invention aims to overcome the defects and provide a device and a method for preparing a biochar-mediated solid biomembrane MFC promoter, which have the advantages of simple and compact structure and convenient operation, so as to effectively prepare the biochar-mediated solid biomembrane MFC promoter, which has the advantages of shortening the starting time of MFC, quickly enriching and stabilizing microorganisms in an anode chamber, has long effective service life and is safe and convenient to store and transport, thereby improving the sufficiency of MFC organic matter degradation and the conversion rate (namely coulomb efficiency) of chemical energy in the organic matter into electric energy, reducing the internal resistance of a battery and increasing the electricity generation efficiency.
The technical scheme of the invention is as follows:
a biochar-mediated solid biofilm MFC promoter preparation device comprises a microbial fuel cell unit, a heating unit and a vacuum freeze-drying unit; the microbial fuel cell unit comprises an anode chamber and a cathode chamber which are separated by a proton exchange membrane; the anode chamber comprises an anode chamber a area and an anode chamber b area, the two areas are separated by a filter plate, and the filter plate is provided with equidistant sieve pores; an anode is arranged in the anode chamber a area, a cathode and an aeration strip are arranged in the cathode chamber, and a cathode catalyst is loaded on the surface of the cathode; the anode electrode and the cathode electrode are connected with an external resistor and an electric switch through a lead; the heating unit comprises a constant temperature heater, a jacket, a heating pipe and a heat return pipe; the vacuum freeze-drying unit comprises a vacuum freeze-dryer; the vacuum freeze dryer is connected with the constant temperature heater;
a scraping plate is arranged in the area b of the anode chamber, and a brush is embedded on one surface of the scraping plate, which is in contact with the filter plate;
the scraper is connected with the movable connecting rod and reciprocates horizontally and parallelly along the filter plate;
a feeding pipe b is arranged on the upper side of the front wall surface of the anode chamber b area; the feeding pipe b extends out of the front wall surface of the anode chamber b area and then penetrates through the jacket to the outside of the jacket outer wall;
in the anode chamber a area, the front wall surface is provided with a feeding pipe a, and the right lower side of the left wall surface is provided with a discharging pipe; the feeding pipe a and the discharging pipe both extend out of the wall surface of the anode chamber a area and penetrate through the jacket to the outside of the outer wall of the jacket;
the heating pipe of the constant temperature heater is connected to the top of the outer wall surface of the jacket, and the regenerative pipe is connected to the lower part of the left side of the outer wall surface of the jacket;
a biomembrane gate is arranged between the bottom surface of the area b of the anode chamber and the bottom surface of the jacket, the biomembrane gate leads to a vacuum freeze dryer connected with the bottom surface of the jacket, and a biomembrane gate switch is positioned on the corresponding position of the front outer wall of the jacket;
the right end face of the vacuum freeze dryer is provided with a vacuum freeze-drying discharge port, and the vacuum freeze-drying discharge port is opened when being closed for discharging at ordinary times;
a water replenishing pipe is arranged on the constant temperature heater;
valves are arranged on the water replenishing pipe, the feeding pipe and the discharging pipe, and are opened when the valves are closed for use at ordinary times;
furthermore, the joints of all the valves and the pipe orifices and the joints of the jacket and the proton exchange membrane are sealed;
further, the biomembrane gate is a normally closed gate and is opened when operation is required;
preferably, the connecting rod is connected with a cylinder;
preferably, the aperture of a sieve pore on the filter plate is 80 to 120 meshes;
preferably, the resistance value of the external resistor is in a variable range of 500-1000 omega;
preferably, the outer wall of the jacket is made of a heat-insulating material;
preferably, the positive electrode and the negative electrode are made of carbon paper, carbon cloth, carbon fiber brushes, carbon felts, glassy carbon, carbon nanotubes, graphite, graphene, stainless steel meshes, stainless steel plates, titanium plates or titanium meshes;
preferably, the cathode catalyst is a noble metal catalyst, a non-noble metal catalyst or a biological cathode catalyst; the metal catalyst is one or more of platinum, palladium, ruthenium and gold; the non-noble metal catalyst is active carbon, carbon powder or acetylene black.
A preparation method of a biochar-mediated solid biofilm MFC promoter is based on any biochar-mediated solid biofilm MFC promoter preparation device and comprises the following steps:
s1, preparing an MFC solid biological membrane:
s1.1 culture medium preparation:
culture medium: 1g of yeast extract, 3g of beef extract, 10g of peptone, 10g of cane sugar, 5g of NaCl and K 2 HPO 4 ·3H 2 O 1g， MgSO 4 ·7H 2 O 1g， CaCl 2 0.5g，(NH 4 ) 2 SO 4 2g， Na 2 S·9H 2 O1 g, trace elements 10 mL, vitamins 10 mL (pH 7.0-7.4); wherein the content of the first and second substances,
trace elements (g/L): n (CH 2 COOH) 3 4.5 (Aminoacetic acid), feCl 2 ·4H 2 O 0.4，MnCl·H 2 O 0.1， CoCl 2 ·6H 2 O 0.12， AlK ( SO 4 ) 2 0.01， ZnCl 2 0.1， NaCl 1， CaCl 2 0.02， Na 2 MoO 4 0.01， H 3 BO 3 0.01，NiCl 2 ·6H 2 O 0.42 ；
Vitamins (g/L): 2.0 parts of biotin, 5.0 parts of thiamine, 10 parts of pyridoxine hydrochloride, 5.0 parts of D-pantothenic acid, 5.0 parts of lipoic acid, 2.0 parts of folic acid, 5.0 parts of riboflavin, 5.0 parts of nicotinic acid, 5.0 parts of p-aminobenzoic acid and vitamin B 12 0.1；
S1.2, enrichment culture of inoculum:
inoculating the inoculum and the culture medium according to the volume ratio (1-4): 1, placing the mixture into a culture container, sealing the culture container, and performing static culture or shaking culture at 20-120 rpm under the constant temperature condition of 30-35 ℃; decanting a portion of the supernatant from the culture vessel and replenishing with fresh medium twice a week each time;
the inoculum is activated sludge at the bottom of a methane tank, biogas slurry or activated sludge at the bottom of a secondary sedimentation tank of a sewage treatment plant, wherein the total solid content Ts of the inoculum is 0.8-12% in long-term stable operation;
s1.3 inoculum acclimatization:
taking organic waste or waste water as a raw material, and adding the inoculum which has completed enrichment culture into an anode chamber a area from a feeding pipe a according to the inoculum size of 10-30%; adding catholyte into the cathode chamber, and aerating the cathode chamber by air aeration; starting a constant temperature heater, and carrying out acclimation on the inoculum under the condition of connecting an external resistor and electrifying at the constant temperature of 30-35 ℃; when the voltage of the microbial fuel cell is reduced to below 50mV, considering that one period is finished, and replacing raw materials; maintaining the operation of the fuel cell and the acclimation of the inoculum by continuously replacing the raw materials; when the highest output voltage in 3 consecutive cycles no longer increases, the inoculum acclimation is considered to be complete;
further: before the raw materials and the inoculum are added into the anode chamber a area, nitrogen is introduced for 20min to remove oxygen, so that the anaerobic environment of the anode chamber of the microbial fuel cell is ensured;
further: when the microbial fuel cell is used for replacing raw materials, firstly opening a valve of a discharge pipe to discharge 1/3-1/2 of the volume of old raw materials, then closing the valve of the discharge pipe, simultaneously opening a valve of a feeding pipe a, and closing the valve of the feeding pipe a after supplementing fresh raw materials with the same volume;
the organic waste is one or a mixture of 40-100 meshes of pig manure, chicken manure, cow manure, kitchen waste, excess sludge and straws;
preferably, the catholyte is phosphate buffered saline (PBS, the main components of which are KCl 100, naCl 1000 and Na 2 HPO 4 2750，KH 2 PO 4 4220, unit: mg/L) (pH 7.0)
S1.4 biofilm formation by charcoal:
after the acclimation of the inoculum is finished, adding 5-20% of biochar particles by mass fraction into an anode chamber b from a feeding pipe b; under the constant temperature condition of 30-35 ℃, the membrane is formed by hanging the charcoal under the condition of connecting an external resistor and electrifying; when the voltage of the microbial fuel cell is reduced to be below 50mV, considering that one period is finished, and replacing raw materials; the fuel cell is maintained to operate by continuously replacing the raw materials; when the highest output voltage in 3 continuous periods is not increased any more, the biological carbon film hanging is considered to be completed;
further: the raw material replacing method comprises the steps of S1.3; the raw material is organic waste or waste water; wherein the organic waste is one of or a mixture of pig manure, chicken manure, cow manure, kitchen waste, excess sludge and straws, and the mesh number of the organic waste is not required;
the particle size of the biochar particles is 1 to 5mm;
s1.5, vacuum freeze-drying:
after the membrane is hung, opening a valve of the discharge pipe until all feed liquid in the anode chamber is discharged, closing the valve of the discharge pipe, opening a gate of the biological membrane, transmitting the biochar and the biological membrane on the biochar to a vacuum freeze dryer for vacuum freeze drying until the water content is 8-10%, and obtaining freeze-dried biochar and the biological membrane on the biochar, namely an MFC solid biological membrane; the freeze-drying temperature is-40 ℃ to-45 ℃, and the freeze-drying time is 24-72 hours;
s2, adding trace elements and compound vitamins:
s2.1, preparing mixed powder of trace elements and compound vitamins:
weighing 1 to 2 parts of ferrous sulfate in solid form, 0.1 to 1 part of cobalt chloride, 0.5 to 2 parts of nickel chloride and 0.3 to 2 parts of composite vitamin according to parts by mass, putting the materials into a container, adding distilled water to prepare a saturated solution, putting the saturated solution into an oven at the temperature of 60 to 90 ℃, drying the saturated solution for 1 to 2h, and crushing the saturated solution into 100 to 130 meshes by using a crusher to obtain mixed powder of trace elements and the composite vitamin; wherein the vitamin complex is selected from biotin, thiamine, pyridoxine hydrochloride, D-pantothenic acid, lipoic acid, folic acid,Riboflavin, nicotinic acid, p-aminobenzoic acid, and vitamin B 12 Three or more of (a);
s2.2 mixing:
taking the MFC solid biomembrane prepared in the step S1.5 out of a vacuum freeze-drying discharge port of the vacuum freeze dryer; adding the mixed powder of the trace elements and the compound vitamins prepared in the step S2.1 into the prepared MFC solid biomembrane according to the addition amount of 2-5%, and uniformly mixing to obtain the biochar-mediated solid biomembrane MFC promoter;
all the steps and corresponding operations are carried out in an anaerobic environment.
The invention has the beneficial effects that:
(1) The device and the method for preparing the biochar-mediated solid biomembrane MFC promoter ensure the anaerobic operation in the preparation process, have simple and compact structure and convenient operation, and effectively realize the preparation of the biochar-mediated solid biomembrane MFC promoter. Particularly, the arrangement of the filter plate in the MFC anode chamber enables the filtered high-quality MFC fuel and electrogenesis microbial flora to successfully penetrate through the sieve pores to reach the anode chamber b area where the biochar is located, effectively intercepts the biochar and the biomembrane on the biochar in the anode chamber b area, realizes seamless butt joint of the filmed biochar and the biomembrane on the biochar with the vacuum freeze dryer, and successfully solves the problems that how to take out the biochar and the biomembrane on the biochar in the preparation process of the biochar-mediated solid biomembrane MFC accelerant and how to ensure that the biochar and the biomembrane are transmitted to the vacuum freeze dryer without oxygen.
(2) The biochar-mediated solid biomembrane MFC promoter prepared by the invention integrates the advantages of enriching and stabilizing MFC electrogenesis microbial flora by biomembrane technology and the advantages of promoting MFC electrogenesis efficiency by biochar, and has the beneficial effects of shortening the starting time of MFC, rapidly enriching and stabilizing anode chamber microorganisms, effectively improving the sufficiency of MFC organic matter degradation and the efficiency of converting chemical energy in the organic matter into electric energy, reducing the internal resistance of a battery and improving the electrogenesis efficiency by compositely adding trace elements and composite vitamins.
(3) According to the device and the method for preparing the biochar-mediated solid biofilm MFC promoter, the vacuum freeze-drying technology is adopted, so that the biochar and the biofilm on the biochar are frozen to be below the freezing point of water in low pressure, solid components are supported by the ice on the biochar, and pores are left in dried residual substances when the ice is sublimated, so that the completeness of the biological and chemical structures and the activity of the biochar and the biofilm on the biochar are ensured, and the microbial inactivation phenomenon caused by material shrinkage and cell damage in the traditional drying is avoided.
(4) The device and the method for preparing the solid biomembrane MFC promoter mediated by the biochar provided by the invention keep the integrity and diversity of microbial flora in the process of decomposing organic pollutants by the MFC to generate electric energy, and avoid the problem of single strain in most of the MFC promoters or the electric energy generating microbial agents at present. Because the process from the decomposition of organic matters to the generation of electric energy is extremely complex, the process is not completed by one kind of bacteria or limited microorganisms, but a plurality of species participate, and the synergistic effect exists among different species, so that the effects of various species are different, for example, part of bacteria generate electrons, part of bacteria transfer electrons, and metabolites of the bacteria are mutual substrates. In addition, the single electrogenic bacteria have the defects of difficult separation and purification, complex process and higher manufacturing cost, and even some electrogenic bacteria need to be imported from foreign countries, so the price is high and the technical blockade exists. The MFC accelerator prepared by the invention contains a complete flora structure in the process of decomposing organic pollutants by the whole MFC to generate electric energy, and can be more effectively suitable for actual MFC engineering by adding trace elements and vitamins.
Drawings
Fig. 1 is a schematic structural view of a biochar-mediated solid biofilm MFC promoter preparation apparatus of the present invention.
In the figure: 1. the device comprises a cathode chamber, 2, an anode chamber b area, 3, an anode chamber a area, 4, a scraper plate, 5, a jacket, 6, an anode electrode, 7, a proton exchange membrane, 8, a cathode electrode, 9, a connecting rod, 10, a feeding pipe b,11, a feeding pipe a,12, a sieve mesh, 13, a filter plate, 14, a biomembrane gate, 15, a discharging pipe, 16, a water supplementing pipe, 17, a heat returning pipe, 18, a biomembrane valve switch, 19, a heating pipe, 20, an aeration strip, 21, a vacuum freeze-drying discharging port, 22, a vacuum freeze-dryer, 23, a constant temperature heater, 24, an electric switch, 25, an external resistor and 26 wires.
Detailed Description
The present invention is described in further detail below by way of examples, but the embodiments of the present invention are not limited thereto.
The first embodiment is as follows:
a biochar-mediated solid biofilm MFC promoter preparation device comprises a microbial fuel cell unit, a heating unit and a vacuum freeze-drying unit; the microbial fuel cell unit comprises an anode chamber and a cathode chamber 1 which are separated by a proton exchange membrane 7; the anode chamber comprises an anode chamber a area 3 and an anode chamber b area 2, the two areas are separated by a filter plate 13, and the filter plate 13 is provided with equidistant sieve pores 12; an anode electrode 6 is arranged in the anode chamber a area 3, a cathode electrode 8 and an aeration strip 20 are arranged in the cathode chamber 1, and a cathode catalyst is loaded on the surface of the cathode electrode 8; the anode electrode 6 and the cathode electrode 8 are connected with an external resistor 25 and an electric switch 24 through a lead 26; the heating unit comprises a constant temperature heater 23, a jacket 5, a heating pipe 19 and a regenerative pipe 17; the vacuum freeze-drying unit comprises a vacuum freeze-dryer 22; the vacuum freeze dryer 22 is connected with the constant temperature heater 23;
a scraping plate 4 is arranged in the anode chamber b area 2, and a brush is embedded on one surface of the scraping plate 4, which is in contact with the filter plate 13;
the scraper 4 is connected with the movable connecting rod 9 and reciprocates horizontally and parallelly along the filter plate 13;
a feeding pipe b 10 is arranged on the upper side of the front wall surface of the anode chamber b area 2; the feeding pipe b 10 extends out of the front wall surface of the anode chamber b area 2 and then penetrates through the jacket 5 to the outside of the jacket outer wall;
the front wall of the anode chamber a area 3 is provided with a feeding pipe a 11, and the right lower side of the left wall is provided with a discharging pipe 15; the feeding pipe a 11 and the discharging pipe 15 extend out of the wall surface of the anode chamber a area 3 and then penetrate through the jacket 5 to the outside of the outer wall of the jacket;
a heating pipe 19 of the constant temperature heater 23 is connected to the top of the outer wall surface of the jacket 5, and a regenerative pipe is connected from the lower part of the left side of the outer wall surface of the jacket 5;
a biomembrane gate 14 is arranged between the bottom surface of the anode chamber b area 2 and the bottom surface of the jacket 5, the biomembrane gate 14 is communicated with a vacuum freeze dryer 22 connected with the bottom surface of the jacket 5, and a biomembrane gate switch 18 is positioned on the corresponding position of the front outer wall of the jacket 5;
the right end face of the vacuum freeze dryer 22 is provided with a vacuum freeze-drying discharge port 21, and the vacuum freeze-drying discharge port 21 is opened when the discharge is closed at ordinary times;
a water replenishing pipe 16 is arranged on the constant temperature heater 23;
valves are arranged on the water replenishing pipe 16, the feeding pipe a 11, the feeding pipe b 10 and the discharging pipe 15, and the valves are opened when closed for use at ordinary times;
furthermore, the joints of all the valves and the pipe orifices and the joints of the jacket and the proton exchange membrane are sealed;
further, the biomembrane gate 14 is a normally closed gate and is opened when operation is required;
preferably, the connecting rod 9 is connected with a cylinder;
preferably, the hole diameter of a sieve hole 12 on the filter plate 13 is 80-120 meshes;
preferably, the resistance of the external resistor 25 is 500-1000 Ω;
preferably, the outer wall of the jacket 5 is made of a heat-insulating material;
preferably, the anode electrode 6 and the cathode electrode 8 are made of carbon paper, carbon cloth, carbon fiber brushes, carbon felt, glassy carbon, carbon nanotubes, graphite, graphene, stainless steel mesh, stainless steel plate, titanium plate or titanium mesh;
preferably, the cathode catalyst is a noble metal catalyst, a non-noble metal catalyst or a biological cathode catalyst; the metal catalyst is one or more of platinum, palladium, ruthenium and gold; the non-noble metal catalyst is active carbon, carbon powder or acetylene black.
Example two:
a preparation method of a biochar-mediated solid biofilm MFC promoter is based on a biochar-mediated solid biofilm MFC promoter preparation device of an embodiment I, and comprises the following steps:
s1, preparing an MFC solid biomembrane:
s1.1 culture medium preparation:
culture medium: 1g of yeast extract, 3g of beef extract, 10g of peptone, 10g of cane sugar, 5g of NaCl and K 2 HPO 4 ·3H 2 O 1g， MgSO 4 ·7H 2 O 1g， CaCl 2 0.5g，(NH 4 ) 2 SO 4 2g， Na 2 S·9H 2 1g of O, 10 mL of trace elements and 10 mL of vitamins (p H7.0-7.4); wherein, the first and the second end of the pipe are connected with each other,
trace elements (g/L): n (CH 2 COOH) 3 4.5 (Aminoacetic acid), feCl 2 ·4H 2 O 0.4，MnCl·H 2 O 0.1， CoCl 2 ·6H 2 O 0.12， AlK ( SO 4 ) 2 0.01， ZnCl 2 0.1， NaCl 1， CaCl 2 0.02， Na 2 MoO 4 0.01， H 3 BO 3 0.01，NiCl 2 ·6H 2 O 0.42 ；
Vitamins (g/L): 2.0 parts of biotin, 5.0 parts of thiamine, 10 parts of pyridoxine hydrochloride, 5.0 parts of D-pantothenic acid, 5.0 parts of lipoic acid, 2.0 parts of folic acid, 5.0 parts of riboflavin, 5.0 parts of nicotinic acid, 5.0 parts of p-aminobenzoic acid, and vitamin B 12 0.1；
S1.2, enrichment culture of inoculum:
taking activated sludge at the bottom of the methane tank with the total solid content Ts of 7 percent which runs stably for a long time as an inoculum, and mixing the inoculum with the culture medium according to the volume ratio of 1:1, putting the mixture into a culture container, sealing the culture container, and performing shake culture at a constant temperature of 30 ℃ and an oscillation speed of 100 rpm; decanting a portion of the supernatant from the culture vessel and replenishing with fresh medium twice a week each time;
s1.3 inoculum acclimation:
introducing nitrogen for 20min to remove oxygen and ensure the anaerobic environment of the anode chamber of the microbial fuel cell in the device; then taking 40-mesh pig manure as a raw material, and adding the inoculum which has completed enrichment culture into the anode chamber a area 3 from a feeding pipe a 11 according to the inoculum size of 30%; phosphate buffer is added into the cathode chamber 1The liquid is used as a cathode liquid and comprises the following main components: KCl 100, naCl 1000, na 2 HPO 4 2750，KH 2 PO 4 4220, unit: mg/L) (pH 7.0); oxygen is supplied to the cathode chamber 1 by air aeration; starting a constant temperature heater 23, and performing acclimation of the inoculum under the condition of connecting an external resistor 25 of 500 omega and electrifying at the constant temperature of 30 ℃; when the voltage of the microbial fuel cell is reduced to below 50mV, considering that one period is finished, and replacing raw materials; when the raw materials are replaced, firstly opening a valve of a discharge pipe 15 to discharge 1/3-1/2 of the volume of old raw materials, then closing the valve 15 of the discharge pipe, simultaneously opening a valve of a feed pipe a 11, and closing the valve of the feed pipe a 11 after supplementing the same volume of fresh raw materials; maintaining the operation of the fuel cell and the acclimation of the inoculum by continuously replacing the raw materials; when the highest output voltage in 3 consecutive cycles no longer increases, the inoculum acclimation is considered to be completed;
s1.4 biofilm formation by charcoal:
after the acclimation of the inoculum is finished, adding biochar particles with the mass fraction of 10 percent and the particle size of 1mm into an anode chamber b area 2 from a feeding pipe b; under the constant temperature condition of 30 ℃, the biological carbon film is formed under the condition that an external resistor 25 is connected and electrified; when the voltage of the microbial fuel cell drops below 50mV, considering that one period is finished, and replacing raw materials; the raw material replacing method comprises the steps of S1.3; the raw material is pig manure, and the mesh number is not required; the fuel cell is maintained to operate by continuously replacing the raw materials; when the highest output voltage in 3 continuous periods is not increased any more, the biological carbon film hanging is considered to be completed;
s1.5, vacuum freeze-drying:
after the membrane is formed, opening a valve of the discharge pipe 15 until all feed liquid in the anode chamber is discharged, closing the valve of the discharge pipe 15, opening a biomembrane gate 14, transmitting the biochar and the biomembrane thereon to a vacuum freeze dryer 22 for vacuum freeze-drying until the water content is 8.5%, and obtaining freeze-dried biochar and the biomembrane thereon, namely the MFC solid biomembrane; the freeze-drying temperature is-40 ℃, and the freeze-drying time is 72h;
s2, adding trace elements and compound vitamins:
s2.1, preparing mixed powder of trace elements and compound vitamins:
weighing 1 part of ferrous sulfate in solid form, 0.3 part of cobalt chloride, 1 part of nickel chloride and 0.7 part of composite vitamin according to parts by weight, putting the materials into a container, adding distilled water to prepare a saturated solution, putting the saturated solution into a drying oven at the temperature of 60 ℃, drying the saturated solution for 2 hours, and crushing the saturated solution into 100 meshes by using a crusher to obtain mixed powder of the trace elements and the composite vitamin; wherein the compound vitamin is selected from biotin, thiamine, and vitamin B 12 Composition is carried out;
s2.2 mixing:
taking the MFC solid biomembrane prepared in the step S1.5 out of a vacuum freeze-drying discharge hole of the vacuum freeze dryer; adding the mixed powder of the trace elements and the compound vitamins prepared in the step S2.1 into the prepared MFC solid biomembrane according to the addition of 3 percent, and uniformly mixing to obtain the solid biomembrane MFC promoter mediated by the biochar;
all the steps and corresponding operations are carried out in an anaerobic environment.
The solid biomembrane MFC promoter mediated by the biochar prepared by the device and the method in the first embodiment and the second embodiment is prepared by 1 part of ferrous sulfate, 0.3 part of cobalt chloride, 1 part of nickel chloride, 0.7 part of vitamin complex and 97 parts of MFC solid biomembrane in solid form according to the mass parts; wherein the compound vitamin is selected from biotin, thiamine, and vitamin B 12 And (4) forming.
Compared with a control group without the MFC promoter, the prepared MFC promoter is added into MFC, so that the degradation rate of organic matters is improved by 13.2%, the coulomb efficiency is improved by 2.1 times, the internal resistance is reduced by 24.6%, and the output power is improved by 40.7%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (4)
1. A charcoal-mediated solid biofilm MFC promoter preparation device is characterized in that: comprises a microbial fuel cell unit, a heating unit and a vacuum freeze-drying unit; the microbial fuel cell unit comprises an anode chamber and a cathode chamber which are separated by a proton exchange membrane; the anode chamber comprises an anode chamber a area and an anode chamber b area, the two areas are separated by a filter plate, and the filter plate is provided with equidistant sieve pores; an anode is arranged in the anode chamber a area, a cathode and an aeration strip are arranged in the cathode chamber, and a cathode catalyst is loaded on the surface of the cathode; the anode electrode and the cathode electrode are connected with an external resistor and an electric switch through a lead; the heating unit comprises a constant temperature heater, a jacket, a heating pipe and a regenerative pipe; the vacuum freeze-drying unit comprises a vacuum freeze-dryer; the vacuum freeze dryer is connected with the constant temperature heater; a scraping plate is arranged in the area b of the anode chamber, a brush is embedded on one surface of the scraping plate, which is in contact with the filter plate, and the scraping plate is connected with a movable connecting rod and reciprocates left and right in parallel along the filter plate; the connecting rod is connected with a cylinder; a feeding pipe b is arranged on the upper side of the front wall surface of the anode chamber b area; the feeding pipe b extends out of the front wall surface of the anode chamber b area and then penetrates through the jacket to the outside of the jacket outer wall; in the anode chamber a area, the front wall surface is provided with a feeding pipe a, and the right lower side of the left wall surface is provided with a discharging pipe; the feeding pipe a and the discharging pipe both extend out of the wall surface of the anode chamber a area and penetrate through the jacket to the outside of the outer wall of the jacket; the heating pipe of the constant temperature heater is connected to the top of the outer wall surface of the jacket, the heat return pipe is connected to the lower part of the left side of the outer wall surface of the jacket, and a water replenishing pipe is arranged on the constant temperature heater; a biomembrane gate is arranged between the bottom surface of the area b of the anode chamber and the bottom surface of the jacket, the biomembrane gate is communicated with a vacuum freeze dryer connected with the bottom surface of the jacket, and a biomembrane gate switch is positioned on the corresponding position of the front outer wall of the jacket; the right end face of the vacuum freeze dryer is provided with a vacuum freeze-drying discharge port, and the vacuum freeze-drying discharge port is opened when being closed for discharging at ordinary times.
2. A biochar-mediated solid biofilm MFC promoter preparation apparatus as claimed in claim 1, wherein: valves are arranged on the water replenishing pipe, the feeding pipe and the discharging pipe, and the valves are opened when being closed for use at ordinary times; the biomembrane gate is a normally closed gate and is opened when operation is required; the joints of the valves and the pipe orifices on the water replenishing pipe, the feeding pipe and the discharging pipe, and the joints of the jacket and the proton exchange membrane are sealed.
3. A biochar-mediated solid biofilm MFC promoter preparation apparatus as claimed in claim 1, wherein: the aperture of a sieve pore on the filter plate is 80 to 120 meshes; the variable range of the resistance value of the external resistor is 500-1000 omega.
4. A biochar-mediated solid biofilm MFC promoter preparation apparatus as claimed in claim 1, wherein: the outer wall of the jacket is made of a heat-insulating material; the anode and the cathode are made of carbon paper, carbon cloth, carbon fiber brushes, carbon felts, glassy carbon, carbon nanotubes, graphite, graphene, stainless steel meshes, stainless steel plates, titanium plates or titanium mesh materials; the cathode catalyst is a noble metal catalyst or a non-noble metal catalyst; the noble metal catalyst is one or more of platinum, palladium, ruthenium and gold; the non-noble metal catalyst is active carbon, carbon powder or acetylene black.
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