CN109841842A - The solid biologic film MFC promotor preparation facilities and preparation method that charcoal mediates - Google Patents
The solid biologic film MFC promotor preparation facilities and preparation method that charcoal mediates Download PDFInfo
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- CN109841842A CN109841842A CN201711198426.2A CN201711198426A CN109841842A CN 109841842 A CN109841842 A CN 109841842A CN 201711198426 A CN201711198426 A CN 201711198426A CN 109841842 A CN109841842 A CN 109841842A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The solid biologic film MFC promotor preparation facilities and preparation method mediated the present invention relates to a kind of charcoal.A kind of solid biologic film MFC promotor preparation facilities that charcoal mediates, structure mainly includes microbiological fuel cell unit, heating unit and vacuum freeze-drying unit；The anode chamber of the microbiological fuel cell unit includes the area a, anode chamber and the area b, and two sections are separated by by filter plate, and the filter plate is equipped with equidistant sieve pore and with hairbrush scraper plate.The invention also discloses the methods for preparing MFC promotor using described device.The present invention has effectively achieved the preparation of the solid biologic film MFC promotor of charcoal mediation, it ensure that the oxygen free operation of preparation process, the preparation facilities structure of offer is simple, compact, it is easy to operate, start time, fast enriching, stable anode chamber microbiological to MFC is shortened, and effectively improves the efficiency that chemical energy in the adequacy and organic matter of MFC organic matter degradation is converted into electric energy, reduce the internal resistance of cell, raising efficiency of fuel cell generation plays the role of positive.
Description
Technical field
The present invention relates to a kind of microbiological fuel cell promotor preparation facilities and preparation methods, belong to the utilization of resources and ring
Border protection and technical field of microbial fuel battery.The solid biologic film MFC promotor mediated more particularly to a kind of charcoal
Preparation facilities and preparation method.
Background technique
Microbiological fuel cell (Microbial Fuel Cell, MFC) is a kind of using microbial metabolism, will be given birth to
Chemical energy in substance is converted into the Bioelectrochemical device of electric energy.MFC can use agriculture and forestry organic waste material, sludge, city
Organic matter in the discarded ingredients such as rubbish, industrial pollution waste water is changed into electric energy and other energy substances, meet turn waste into wealth, ring
The requirement of border close friend is one very promising technology of pollution control and new energy research field.With the depth of research
Enter the progress with technology, microbiological fuel cell efficiency is continuously improved, but there are still some problems, for example raw material organic matter utilizes
It is not enough, the problems such as coulombic efficiency is lower, and battery is longer from stable period is started to, and the internal resistance of cell is high, efficiency of fuel cell generation is lower,
These problems all restrict the all-round popularization and further development of MFC technology.
To solve the above problems, researchers from the structure of MFC, electrode material, electricity production strain and reaction mechanism etc.
It has carried out a large amount of research work and has proposed the measure of being correspondingly improved.Wherein, anode is microbiological fuel cell performance boost
Restrictive factor, electricity production bacterium organic pollutant is decomposed and is produced electricity in anode of microbial fuel cell room, anode electrode use
More research is obtained in terms of material, such as charcoal cloth anode, carbon paper anode, black lead brush anode etc..Electricity production bacterium is the biology of MFC reaction
Catalyst, therefore finding high electricity production bacterial strain or improving electricity production bacterial strain electricity production effect is to improve another key method of MFC,
Geobactersulfurreducens, Shewanella putrefaciens, Rhodoferaxferrireducens etc. are sent out
Electronics can now be transported from microbial cell to anode without electronics transfer mediator, complete energetic supersession and growth is numerous
It grows.However when MFC is used for organic wastewater, offal treatment, mixed bacteria becomes apparent as electricity production bacterium advantage, such as mixed
Combined bacteria kind has many advantages, such as without considering the growth conditions of strain pure culture, being easy acclimating and being widely used in organic contamination
In improvement.Logan B E and Regan J M has found have more during decomposing organic pollutant produces electricl energy under study for action
Kind strain is participated, and there is synergistic effect (Logan B E, Regan J M. Electricity- between different strain
producing bacterial communities in microbial fuel cells.[J]. Trends in
Microbiology, 2006,14 (12): 512.), all kinds of strain effects are different, and if part bacterium generates electronics, part is thin
Bacterium shifts electronics, metabolite the phenomenon that there is also substrates each other, and Logan B E and Regan J M thinks to produce electricity bacterium
(electrogens) this concept is represented just with a kind of bacterium for generating electronic capability, and practical MFC electricity generation process needs
It to participate in assisting to complete there are many strain, it is more acurrate using mono- word of exoelectrogens, therefore anode mixture strain
Appropriate increase of biomass is an effective way for improving MFC efficiency of fuel cell generation.
Biofilm is a kind of important method of effective enrichment and stabilised microorganism, the small in size, microorganism with biomembrane
It is excellent that amount is high, hydraulic detention time is shorter, biofacies is relatively stable, strong to poisonous substance and impact load repellence, treatment effect is high etc.
Point is widely used in municipal sewage, the biological treatment of industrial wastewater and microbiological fuel cell.The generation of biofilm and
The use for be unableing to do without carrier material is grown, carrier is necessary medium in microorganism fixation procedure, is had in biological film process
Critically important effect affects the growth of microorganism, breeds, falls off and form and space structure.It is applied in biofilm
Carrier should meet following condition: 1. easily fluidizing, but not easily run off；2. easily film forming, but nonhazardous acts on；3. big ratio can be provided
Surface area, to increase biological attachment amount；4. it is cheap, it is easy materials.
Charcoal (biochar) is the ideal material of biofilm carrier in MFC.Charcoal is biomass in anoxic conditions
Under, it is pyrolyzed (usually less than 1000 degrees Celsius) slowly by high temperature and a kind of infusibility, stabilization, the height aromatization and rich in carbon that generate
The solid matter of element, carbon content rate are about 60~80%, mainly by carbon, hydrogen, oxygen etc. elements form, additionally include potassium,
The nutrient metals element such as calcium, iron.In solid waste processing, what is be easily decomposed by the microorganisms can be by anaerobic digestion and micro- life
Object fuel cell technology is turned waste into wealth, and be not easy to be decomposed by the microorganisms can then keep away by way of charcoal is made in pyrolysis
Exempt to realize resource utilization while environmental pollution.Charcoal is with its big specific surface area and porosity, good one's own physical property,
The good physical and chemical performance such as Surface chemical functional group of wood abundant, and material source is extensive, it is cheap, it is environmental-friendly etc. excellent
Gesture has a wide range of applications in fields such as agricultural, environment, the energy.Charcoal is the presoma of active carbon, and active carbon is as MFC
The research of middle biofilm carrier material has longer history.Research of the charcoal as MFC biofilm carrier at present, also obtains
Preferable effect.Especially research in recent years is found, charcoal is added in MFC, can effectively play reduction internal resistance, increases coulomb
Efficiency improves the positive effects such as output voltage and output power.As it can be seen that charcoal is the ideal material of biofilm carrier in MFC.
Although there are many advantages in MFC application using charcoal as the biofilm of carrier, using biofilm
The biofilm time is generally longer, is 7 days to 2 ~ 3 months or so, this is realized to the anode chamber MFC fast enriching, stabilised microorganism
Quick start brings problem.How the advantage of the technology of biological membrane mediated with charcoal is applied to the field MFC, and avoids biology
Embrane method because biofilm time-consuming bring starting overlong time deficiency, be realize MFC shorten starting time and fast enriching, stablize it is micro-
Biology, and improve organic-fuel utilization rate and coulombic efficiency reduces the internal resistance of cell, increases that efficiency of fuel cell generation is to be solved important to ask
Topic, and MFC technical application is promoted to promote the major issue for needing to solve.
Summary of the invention
It is simple, compact that the purpose of the present invention is to overcome the above shortcomings and to provide a kind of structures, and easy to operate charcoal is situated between
The solid biologic film MFC promotor preparation facilities and preparation method led effectively to prepare to have and shorten the MFC starting time, quickly
Enrichment, stable anode chamber microbiological advantage, and effective life, is long, the solid that storage, the convenient charcoal of transportation safety mediate
Biomembrane MFC promotor, to realize that chemical energy is converted into electricity in the adequacy for improving MFC organic matter degradation and raising organic matter
The conversion ratio (i.e. coulombic efficiency) of energy reduces the internal resistance of cell, increases efficiency of fuel cell generation.
Technical solution of the present invention:
A kind of solid biologic film MFC promotor preparation facilities that charcoal mediates, including microbiological fuel cell unit, heating are single
Member and vacuum freeze-drying unit；The microbiological fuel cell unit, including the anode chamber separated by proton exchange membrane and cathode chamber；
The anode chamber includes the area a, anode chamber and the area b, anode chamber, and two sections are separated by by filter plate, and the filter plate is equipped with equidistant sieve
Hole；Positive electrode is housed in the area the anode chamber a, is born equipped with negative electrode with item, the cathode electrode surface is aerated in the cathode chamber
It is loaded with cathod catalyst；The positive electrode and negative electricity interpolar are connected by conducting wire with external resistance and electric switch；The heating is single
Member, including constent temperature heater, collet, heating tube and product heat cal rod；The vacuum freeze-drying unit, including vacuum freeze-drying device；It is described true
Empty lyophilizer is connected with the constent temperature heater；
The area the anode chamber b is provided with scraper plate, and scraper plate is inlaid with hairbrush with what the filter plate contacted on one side；
The scraper plate is connected with movable connecting rod, does the parallel reciprocating movement in left and right along the filter plate；
Feed pipe b is equipped on the upside of the area anode chamber b front face；The feed pipe b is stretched out from anode chamber b area's front face
Afterwards, it passes through outside the collet to jackets outer wall；
The area the anode chamber a, front face are equipped with feed pipe a, and left wall face lower right side is equipped with drainage conduit；The feed pipe a and discharge
Pipe passes through outside the collet to jackets outer wall from after the stretching of anode chamber a area's wall surface；
The heating tube of the constent temperature heater is connected at the top of the jackets outer wall face, and product heat cal rod is connected to the jackets outer wall left side of face
Lower part；
Open up biomembrane gate between the area anode chamber b bottom surface and the collet bottom surface, the biomembrane gate lead to it is described
The connected vacuum freeze-drying device in collet bottom surface, biomembrane knife switch are located at before the collet on the corresponding position of outer wall；
Vacuum freeze-drying device right side sets vacuum freeze-drying discharge port, and the vacuum freeze-drying discharge port is opened when usually closing discharging
It opens；
Water supply pipe is set on the constent temperature heater；
Valve is all provided in the water supply pipe, feed pipe and drainage conduit, valve is opened when usually closing use；
Further, the junction of all valves, the junction of nozzle and collet and proton exchange membrane, seals；
Further, the biomembrane gate, is normally closed gate, and operation is opened when needing；
Preferably, the connecting rod is connected with cylinder；
Preferably, the sieve pore on the filter plate, aperture is 80 ~ 120 mesh；
Preferably, the external resistance, resistance value variable range is 500 ~ 1000 Ω；
Preferably, the jackets outer wall is made of thermal insulation material；
Preferably, the positive electrode and negative electrode, using carbon paper, carbon cloth, carbon fiber brush, carbon felt, vitreous carbon, carbon nanotube,
The production of the materials such as graphite, graphene, stainless (steel) wire, stainless steel plate, titanium plate or titanium net；
Preferably, the cathod catalyst is noble metal catalyst, non-precious metal catalyst or biological-cathode catalyst；Institute
The metallic catalyst stated is one of platinum, palladium, ruthenium and gold or in which several alloys；The non-precious metal catalyst is to live
Property charcoal, carbon dust or acetylene black.
A kind of solid biologic film MFC promotor preparation method that charcoal mediates, based on any one above-mentioned charcoal
The solid biologic film MFC promotor preparation facilities of mediation, includes the following steps:
S1 prepares MFC solid biologic film:
S1.1 culture medium is prepared:
Culture medium: yeast extract 1g, beef extract 3g, peptone 10g, sucrose 10g, NaCl 5g, K2HPO4·3H2O 1g,
MgSO4·7H2O 1g, CaCl20.5g, (NH4)2SO42g, Na2S·9H2O 1g, 10 mL of microelement, vitamin 10
ML(p H 7.0-7.4)；Wherein,
Microelement (g/L): N (CH2COOH) 34.5 (nitrilo acetic acids), FeCl2·4H2O 0.4, MnClH2O
0.1, CoCl2·6H2O 0.12, AlK (SO4 ) 20.01, ZnCl20.1, NaCl 1, CaCl20.02,
Na2MoO40.01, H3BO30.01, NiCl2·6H2O 0.42 ；
Vitamin (g/L): biotin 2.0, thiamine 5.0, puridoxine hydrochloride 10, the general calcium acid 5.0 of D-, lipoic acid 5.0,
Folic acid 2.0, riboflavin 5.0, niacin 5.0, p-aminobenzoic acid 5.0, vitamin B120.1；
S1.2 inoculum enrichment culture:
By inoculum and the culture medium, by volume (1~4): 1 is packed into culture vessel, and closed, in 30~35 DEG C of constant temperature
Under the conditions of stationary culture or 20~120rpm shake culture；Part supernatant is toppled over from the culture vessel every time and is supplemented new
The fresh culture medium, twice a week；
The inoculum, for the total solids content Ts that runs steadily in the long term be 0.8%~12% biogas bottom of pond portion activated sludge, natural pond
Liquid or secondary sedimentation tank of sewage treatment work bottom activated sludge；
The domestication of S1.3 inoculum:
Using organic waste or waste water as raw material, the inoculum of enrichment culture will be completed, by 10%~30% inoculum concentration,
It is added in the area a, anode chamber from feed pipe a；Catholyte is added in the cathodic compartment, and cathode chamber oxygen supply is carried out by air aeration；
Constent temperature heater is opened, under 30~35 DEG C of constant temperature, connection external resistance carries out the domestication of inoculum in the case of being powered；When
When microbiological fuel cell voltage drops to 50mV or less, it is believed that a cycle terminates, and carries out raw material replacement；By constantly replacing
Raw material maintains the operation of fuel cell and the domestication to inoculum；When the maximum output voltage in continuous 3 periods is not further added by
When, it is believed that inoculum domestication is completed；
Further, the area the anode chamber a before raw material and inoculum is added, leads to nitrogen 20min first to remove oxygen, guarantees micro- life
The anaerobic environment of object anode of fuel cell room；
Further, the microbiological fuel cell, which when carrying out raw material replacement, first opens discharge tube valve, is discharged 1/3~1/2 body
The old raw material of product, turns off discharge tube valve while opening the feed pipe a valve, closes institute after supplementing same volume fresh feed
State feed pipe a valve；
The organic waste is one of 40 ~ 100 mesh pig manures, chicken manure, cow dung, kitchen garbage, excess sludge, stalk or mixing；
Preferably, the catholyte is phosphate buffer (phosphate buffered saline, PBS, main component
Are as follows: KCl 100, NaCl 1000, Na2HPO42750, KH2PO44220, unit: mg/L) (pH 7.0)
S1.4 charcoal biofilm:
Complete inoculum domestication after, from feed pipe b add mass fraction be 5%~20% charcoal particle in the area b, anode chamber；
Under 30~35 DEG C of constant temperature, connection external resistance carries out charcoal biofilm in the case of being powered；When the Microbial fuel electricity
When cell voltage drops to 50mV or less, it is believed that a cycle terminates, and carries out raw material replacement；By constantly replacing raw material, combustion is maintained
Expect battery operation；When the maximum output voltage in continuous 3 periods is not further added by, it is believed that charcoal biofilm is completed；
Further, the raw material replacing options, with step S1.3；The raw material is organic waste or waste water；Wherein, described
Organic waste, mesh number are not required, and are one of pig manure, chicken manure, cow dung, kitchen garbage, excess sludge, stalk or mixing；
The charcoal particle, partial size are 1 ~ 5mm；
S1.5 vacuum freeze-drying:
After the completion of biofilm, the discharge tube valve is opened, until closing the discharge pipe valve after feed liquid is all discharged in anode chamber
Door, and opens biomembrane gate, and charcoal and thereon biomembrane are transmitted to vacuum freeze-drying device and carry out vacuum freeze-drying, and freeze-drying is to containing
Water is 8~10%, charcoal and biomembrane, i.e. MFC solid biologic film thereon after being lyophilized；Freeze temperature is -40 DEG C
~-45 DEG C, freeze-drying time is 24~72h；
S2 adds microelement and multi-vitamins:
S2.1 prepares microelement and multi-vitamins mixed powder:
By mass fraction, 1 ~ 2 part of the ferrous sulfate, 0.1 ~ 1 part of cobalt chloride, 0.5 ~ 2 part of chlorination of solid forms are weighed
Nickel, 0.3 ~ 2 part of multi-vitamins, are put into container, add distilled water that saturated solution is made, and are put into the baking that temperature is 60 ~ 90 DEG C
In case, after drying 1 ~ 2h, 100 ~ 130 mesh is ground into pulverizer, obtain microelement and multi-vitamins mixed powder；Its
In, multi-vitamins are by biotin, thiamine, puridoxine hydrochloride, the general calcium acid of D-, lipoic acid, folic acid, riboflavin, niacin, right
Aminobenzoic acid, vitamin B12In three kinds or a variety of compositions；
S2.2 mixing:
MFC solid biologic film obtained in step S1.5 is taken out from the vacuum freeze-drying discharge port of the vacuum freeze-drying device；And it will
The microelement and multi-vitamins mixed powder prepared in step S2.1 is added to prepared by 2% ~ 5% additive amount
In MFC solid biologic film, after mixing to get the solid biologic film MFC promotor of charcoal mediation；
All of above step and corresponding operating carry out under anaerobic environment.
Beneficial effects of the present invention:
(1) the solid biologic film MFC promotor preparation facilities and preparation method that charcoal provided by the invention mediates, ensure that system
The oxygen free operation of standby process, the preparation facilities structure provided is simple, compact, easy to operate, has effectively achieved charcoal mediation
Solid biologic film MFC promotor preparation.The setting of filter plate, makes filtered high-quality MFC especially in the anode chamber MFC
It, effectively will be biological while fuel and electricity-producing microorganism flora successfully penetrate the area b, anode chamber where sieve pore reaches charcoal
Charcoal and thereon biomembrane have been trapped in the area b, anode chamber, make complete biofilm after charcoal and thereon biomembrane realize with very
The seamless interfacing of empty lyophilizer successfully solves biology in the solid biologic film MFC promotor preparation process of charcoal mediation
How charcoal and thereon biomembrane take out, and how to guarantee that anaerobic is transmitted to the problem of vacuum freeze-drying device.
(2) the solid biologic film MFC promotor that charcoal prepared by the present invention mediates, collection technology of biological membrane are enriched with and stablize
The advantages of MFC electricity-producing microorganism flora and charcoal promote the advantages of MFC electricity production efficiency, and are given birth to by microelement and compound dimension
The compound addition of element has shortening MFC starting time, fast enriching, stable anode chamber microbiological, and can effectively improve MFC to have
Chemical energy is converted into the efficiency of electric energy in the adequacy and organic matter of the degradation of machine object, reduces the internal resistance of cell, improves efficiency of fuel cell generation
Beneficial effect.
(3) the solid biologic film MFC promotor preparation facilities and preparation method that charcoal provided by the invention mediates, due to
Using vacuum freeze drying technology, makes charcoal and biomembrane is refrigerated to the below freezing of water in low pressure thereon, make solid content
It is support by the black ice on its seat, in ice distillation, hole can be left in dry surplus materials, ensured that in this way
The biological and chemical structure and its active integrality of charcoal and thereon biomembrane, avoid traditional drying due to material shrinkage
And destroy cell and caused by microbial inactivation phenomenon.
(4) the solid biologic film MFC promotor preparation facilities and preparation method that charcoal provided by the invention mediates, retain
The integrality and diversity of microbial flora, avoid current major part during MFC decomposing organic pollutant produces electricl energy
The single problem of strain present in MFC promotor or electricity production microbial inoculum.It is produced electricl energy because being decomposed from organic matter, is extremely multiple
Miscellaneous process is not that a kind of bacterium or limited several microorganisms can be done, but participate there are many strain, different
There is synergistic effect between strain, all kinds of strain effects are different, and if part bacterium generates electronics, part bacterium shifts electronics,
Metabolite the phenomenon that there is also substrates each other.In addition, single electricity production microbial inoculum has separation, purification difficult, process is complicated, production
Higher cost or even some electricity production microbial inoculums are needed by external import, at high price and there are technology blockages.And prepared by the present invention
MFC promotor, contain complete Bacterial community during entire MFC decomposing organic pollutant produces electricl energy, and by micro-
The addition of secondary element and vitamin can more effectively be suitable for practical MFC engineering.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the solid biologic film MFC promotor preparation facilities that charcoal of the invention mediates.
In figure: 1. cathode chambers, 2. areas b, anode chamber, 3. areas a, anode chamber, 4. scraper plates, 5. collets, 6. positive electrodes, 7. protons are handed over
Change film, 8. negative electrodes, 9. connecting rods, 10. feed pipe b, 11. feed pipe a, 12. sieve pores, 13. filter plates, 14. biomembrane gates,
15. drainage conduit, 16. water supply pipes, 17. product heat cal rods, 18. biomembrane valve switch, 19. heating tubes, 20. aeration items, 21. vacuum
Discharge port, 22. vacuum freeze-drying devices, 23. constent temperature heaters, 24. electric switches, 25. external resistances, 26. conducting wires are lyophilized.
Specific embodiment
Below by embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment one:
A kind of solid biologic film MFC promotor preparation facilities that charcoal mediates, including microbiological fuel cell unit, heating are single
Member and vacuum freeze-drying unit；The microbiological fuel cell unit, including the anode chamber separated by proton exchange membrane 7 and cathode chamber
1；The anode chamber includes the area a, anode chamber 3 and the area b, anode chamber 2, and two sections are separated by by filter plate 13, and the filter plate 13 is equipped with
Equidistant sieve pore 12；Positive electrode 6 is housed in the area the anode chamber a 3, negative electrode 8 and aeration item 20 are housed in the cathode chamber 1,
8 area load of negative electrode has cathod catalyst；The positive electrode 6 and negative electricity interpolar 8, by conducting wire 26 and external resistance 25 and
Electric switch 24 is connected；The heating unit, including constent temperature heater 23, collet 5, heating tube 19 and product heat cal rod 17；The vacuum
Unit, including vacuum freeze-drying device 22 is lyophilized；The vacuum freeze-drying device 22 is connected with the constent temperature heater 23；
The area the anode chamber b 2 is provided with scraper plate 4, and scraper plate 4 is inlaid with hairbrush with what the filter plate 13 contacted on one side；
The scraper plate 4 is connected with movable connecting rod 9, does the parallel reciprocating movement in left and right along the filter plate 13；
Feed pipe b 10 is equipped on the upside of 2 front face of the area the anode chamber b；The feed pipe b 10 is from 2 antetheca of the area the anode chamber b
After face is stretched out, pass through outside the collet 5 to jackets outer wall；
The area the anode chamber a 3, front face are equipped with feed pipe a 11, and left wall face lower right side is equipped with drainage conduit 15；The feed pipe a
11 and drainage conduit 15, from after the stretching of 3 wall surface of the area the anode chamber a, pass through outside the collet 5 to jackets outer wall；
The heating tube 19 of the constent temperature heater 23 is connected at the top of 5 outside wall surface of collet, and product heat cal rod is connected to 5 outer wall of collet
Left side of face lower part；
Biomembrane gate 14 is opened up between 2 bottom surface of the area the anode chamber b and 5 bottom surface of the collet, the biomembrane gate 14 leads to
The vacuum freeze-drying device 22 being connected with 5 bottom surface of collet, biomembrane knife switch 18 are located at the correspondence position of outer wall before the collet 5
It sets；
22 right side of vacuum freeze-drying device sets vacuum freeze-drying discharge port 21, and the vacuum freeze-drying discharge port 21 closes discharging when flat
Shi Kaiqi；
Water supply pipe 16 is set on the constent temperature heater 23；
Valve is all provided in the water supply pipe 16, feed pipe a 11, feed pipe b 10 and drainage conduit 15, when valve usually closes use
It opens；
Further, the junction of all valves, the junction of nozzle and collet and proton exchange membrane, seals；
Further, the biomembrane gate 14, is normally closed gate, and operation is opened when needing；
Preferably, the connecting rod 9 is connected with cylinder；
Preferably, on the filter plate 13 sieve pore 12, aperture be 80 ~ 120 mesh；
Preferably, the external resistance 25, resistance value variable range is 500 ~ 1000 Ω；
Preferably, 5 outer wall of collet is made of thermal insulation material；
Preferably, the positive electrode 6 and negative electrode 8, using carbon paper, carbon cloth, carbon fiber brush, carbon felt, vitreous carbon, carbon nanometer
The production of the materials such as pipe, graphite, graphene, stainless (steel) wire, stainless steel plate, titanium plate or titanium net；
Preferably, the cathod catalyst is noble metal catalyst, non-precious metal catalyst or biological-cathode catalyst；Institute
The metallic catalyst stated is one of platinum, palladium, ruthenium and gold or in which several alloys；The non-precious metal catalyst is to live
Property charcoal, carbon dust or acetylene black.
Embodiment two:
A kind of preparation method for the solid biologic film MFC promotor that charcoal mediates, a kind of charcoal based on embodiment one are situated between
The solid biologic film MFC promotor preparation facilities led, includes the following steps:
S1 prepares MFC solid biologic film:
S1.1 culture medium is prepared:
Culture medium: yeast extract 1g, beef extract 3g, peptone 10g, sucrose 10g, NaCl 5g, K2HPO4·3H2O 1g,
MgSO4·7H2O 1g, CaCl20.5g, (NH4)2SO42g, Na2S·9H2O 1g, 10 mL of microelement, vitamin 10
ML(p H 7.0-7.4)；Wherein,
Microelement (g/L): N (CH2COOH) 34.5 (nitrilo acetic acids), FeCl2·4H2O 0.4, MnClH2O
0.1, CoCl2·6H2O 0.12, AlK (SO4 ) 20.01, ZnCl20.1, NaCl 1, CaCl20.02,
Na2MoO40.01, H3BO30.01, NiCl2·6H2O 0.42 ；
Vitamin (g/L): biotin 2.0, thiamine 5.0, puridoxine hydrochloride 10, the general calcium acid 5.0 of D-, lipoic acid 5.0,
Folic acid 2.0, riboflavin 5.0, niacin 5.0, p-aminobenzoic acid 5.0, vitamin B120.1；
S1.2 inoculum enrichment culture:
Taking the biogas bottom of pond portion activated sludge that the total solids content Ts run steadily in the long term is 7% is inoculum, by itself and the training
1:1 is packed into culture vessel to feeding base by volume, and closed, is shaken and is trained with 100rpm hunting speed under 30 DEG C of constant temperature
It supports；Part supernatant is toppled over from the culture vessel every time and supplements the fresh culture medium, twice a week；
The domestication of S1.3 inoculum:
Lead to nitrogen 20min first to remove oxygen, guarantees the anaerobic environment of anode of microbial fuel cell room in described device；Again with
40 mesh pig manures are raw material, the inoculum of enrichment culture will be completed, by 30% inoculum concentration, are added to from feed pipe a 11
In the area a, anode chamber 3；Phosphate buffer is added in cathode chamber 1 as catholyte, main component are as follows: KCl 100, NaCl
1000, Na2HPO42750, KH2PO44220, unit: mg/L) (pH 7.0)；And cathode chamber 1 is carried out by air aeration and is supplied
Oxygen；Constent temperature heater 23 is opened, under 30 DEG C of constant temperature, 500 Ω external resistances 25 of connection carry out inoculum in the case of being powered
Domestication；When microbiological fuel cell voltage drops to 50mV or less, it is believed that a cycle terminates, and carries out raw material replacement；It is former
When material replacement, first opens 15 valve of drainage conduit and the old raw material of 1/3~1/2 volume is discharged, turn off discharge tube valve 15 while opening
11 valve of feed pipe a closes 11 valve of feed pipe a after supplementing same volume fresh feed；By constantly replacing
Raw material maintains the operation of fuel cell and the domestication to inoculum；When the maximum output voltage in continuous 3 periods is not further added by
When, it is believed that inoculum domestication is completed；
S1.4 charcoal biofilm:
After completing inoculum domestication, charcoal particle that partial size that mass fraction is 10% is 1mm is added in sun from feed pipe b
The area pole room b 2；Under 30 DEG C of constant temperature, connection external resistance 25 carries out charcoal biofilm in the case of being powered；When the microorganism
When fuel battery voltage drops to 50mV or less, it is believed that a cycle terminates, and carries out raw material replacement；The raw material replacing options,
With step S1.3；The raw material is pig manure, and mesh number is not required；By constantly replacing raw material, fuel cell operation is maintained；When even
When maximum output voltage in continuous 3 periods is not further added by, it is believed that charcoal biofilm is completed；
S1.5 vacuum freeze-drying:
After the completion of biofilm, 15 valve of drainage conduit is opened, until closing the drainage conduit after feed liquid is all discharged in anode chamber
15 valves, and biomembrane gate 14 is opened, charcoal and thereon biomembrane are transmitted to vacuum freeze-drying device 22 and carry out vacuum freeze-drying,
Freeze-drying to water content is 8.5%, charcoal and biomembrane, i.e. MFC solid biologic film thereon after being lyophilized；Freeze temperature be-
40 DEG C, freeze-drying time 72h；
S2 adds microelement and multi-vitamins:
S2.1 prepares microelement and multi-vitamins mixed powder:
By mass fraction, 1 part of ferrous sulfate of solid forms, 0.3 part of cobalt chloride, 1 part of nickel chloride, 0.7 part are weighed
Multi-vitamins are put into container, add distilled water that saturated solution is made, and are put into the baking oven that temperature is 60 DEG C, after drying 2h,
100 mesh are ground into pulverizer, obtain microelement and multi-vitamins mixed powder；Wherein, multi-vitamins by biotin,
Thiamine, vitamin B12Composition；
S2.2 mixing:
MFC solid biologic film obtained in step S1.5 is taken out from the vacuum freeze-drying discharge port of the vacuum freeze-drying device；And it will
It is solid to be added to prepared MFC by 3% additive amount for the microelement and multi-vitamins mixed powder prepared in step S2.1
In body biomembrane, after mixing to get the solid biologic film MFC promotor of charcoal mediation；
All of above step and corresponding operating carry out under anaerobic environment.
The solid biologic film MFC that the charcoal according to made from the device and method of embodiment one and embodiment two mediates promotes
Agent by mass fraction is answered by 1 part of ferrous sulfate of solid forms, 0.3 part of cobalt chloride, 1 part of nickel chloride, 0.7 part
Close vitamin, 97 parts of MFC solid biologic film is made；Wherein multi-vitamins are by biotin, thiamine, vitamin B12Composition.
Prepared MFC promotor is added in MFC, compared with the control group for not adding MFC promotor, organic matter drop
Solution rate improves 13.2%, and coulombic efficiency improves 2.1 times, and internal resistance reduces by 24.6%, and output power improves 40.7%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. the solid biologic film MFC promotor preparation facilities that a kind of charcoal mediates, it is characterised in that: including Microbial fuel electricity
Pool unit, heating unit and vacuum freeze-drying unit；The microbiological fuel cell unit, including the sun separated by proton exchange membrane
Pole room and cathode chamber；The anode chamber includes the area a, anode chamber and the area b, anode chamber, and two sections are separated by by filter plate, the filter plate
Equipped with equidistant sieve pore；Positive electrode is housed in the area the anode chamber a, negative electrode and aeration item are housed in the cathode chamber, it is described
Cathode electrode surface load has cathod catalyst；The positive electrode and negative electricity interpolar are connected by conducting wire with external resistance and electric switch；
The heating unit, including constent temperature heater, collet, heating tube and product heat cal rod；The vacuum freeze-drying unit, including vacuum freeze-drying
Device；The vacuum freeze-drying device is connected with the constent temperature heater；The area the anode chamber b is provided with scraper plate, scraper plate and the filtering
Plate contact is inlaid with hairbrush on one side, and scraper plate is connected with movable connecting rod, does the parallel reciprocating movement in left and right along the filter plate；Institute
It states connecting rod and is connected with cylinder；Feed pipe b is equipped on the upside of the area anode chamber b front face；The feed pipe b is from the anode chamber b
After area's front face stretches out, pass through outside the collet to jackets outer wall；The area the anode chamber a, front face are equipped with feed pipe a, left wall
Face lower right side is equipped with drainage conduit；The feed pipe a and drainage conduit pass through the folder from after the stretching of anode chamber a area's wall surface
Outside set to jackets outer wall；The heating tube of the constent temperature heater is connected at the top of the jackets outer wall face, and product heat cal rod is connected to the folder
Outside wall surface left lower is covered, sets water supply pipe on constent temperature heater；；It is opened up between the area anode chamber b bottom surface and the collet bottom surface
Biomembrane gate, the biomembrane gate lead to the vacuum freeze-drying device being connected with the collet bottom surface, biomembrane knife switch position
Before the collet on the corresponding position of outer wall；Vacuum freeze-drying device right side sets vacuum freeze-drying discharge port, and the vacuum is frozen
Do unlatching when material mouth usually closes discharging.
2. the solid biologic film MFC promotor preparation facilities that a kind of charcoal according to claim 1 mediates, feature exist
In: valve is all provided in the water supply pipe, feed pipe and drainage conduit, valve is opened when usually closing use；The biomembrane gate,
For normally closed gate, operation is opened when needing；The connection of all valves, the junction of nozzle and collet and proton exchange membrane
Place, seals.
3. the solid biologic film MFC promotor preparation facilities that a kind of charcoal according to claim 1 mediates, feature exist
In: the sieve pore on the filter plate, aperture are 80 ~ 120 mesh；The external resistance, resistance value variable range are 500 ~ 1000 Ω.
4. the solid biologic film MFC promotor preparation facilities that a kind of charcoal according to claim 1 mediates, feature exist
In: the jackets outer wall is made of thermal insulation material；The positive electrode and negative electrode, using carbon paper, carbon cloth, carbon fiber brush, carbon
The production of the materials such as felt, vitreous carbon, carbon nanotube, graphite, graphene, stainless (steel) wire, stainless steel plate, titanium plate or titanium net；Described
Cathod catalyst is noble metal catalyst, non-precious metal catalyst or biological-cathode catalyst；The metallic catalyst be platinum,
One of palladium, ruthenium and gold or in which several alloys；The non-precious metal catalyst is active carbon, carbon dust or acetylene black.
5. the preparation method for the solid biologic film MFC promotor that a kind of charcoal mediates, based on described in Claims 1 to 4
The solid biologic film MFC promotor preparation facilities that a kind of charcoal of anticipating mediates, includes the following steps:
S1 prepares MFC solid biologic film:
S1.1 culture medium is prepared:
Culture medium: yeast extract 1g, beef extract 3g, peptone 10g, sucrose 10g, NaCl 5g, K2HPO4·3H2O 1g,
MgSO4·7H2O 1g, CaCl20.5g, (NH4)2SO42g, Na2S·9H2O 1g, 10 mL of microelement, vitamin 10
ML(p H 7.0-7.4)；Wherein,
Microelement (g/L): N (CH2COOH) 34.5 (nitrilo acetic acids), FeCl2·4H2O 0.4, MnClH2O 0.1,
CoCl2·6H2O 0.12, AlK (SO4 ) 20.01, ZnCl20.1, NaCl 1, CaCl20.02, Na2MoO4
0.01, H3BO30.01, NiCl2·6H2O 0.42 ；
Vitamin (g/L): biotin 2.0, thiamine 5.0, puridoxine hydrochloride 10, the general calcium acid 5.0 of D-, lipoic acid 5.0,
Folic acid 2.0, riboflavin 5.0, niacin 5.0, p-aminobenzoic acid 5.0, vitamin B120.1；
S1.2 inoculum enrichment culture:
By inoculum and the culture medium, by volume (1~4): 1 is packed into culture vessel, and closed, in 30~35 DEG C of constant temperature
Under the conditions of stationary culture or 20~120rpm shake culture；Part supernatant is toppled over from the culture vessel every time and is supplemented new
The fresh culture medium, twice a week；The inoculum, the total solids content Ts to run steadily in the long term is 0.8%~12%
Biogas bottom of pond portion activated sludge, biogas slurry or secondary sedimentation tank of sewage treatment work bottom activated sludge；
The domestication of S1.3 inoculum:
Using organic waste or waste water as raw material, the inoculum of enrichment culture will be completed, by 10%~30% inoculum concentration,
It is added in the area a, anode chamber from feed pipe a；Phosphate buffer is added in the cathodic compartment as catholyte, main component are as follows:
KCl 100, NaCl 1000, Na2HPO42750, KH2PO44220, unit: mg/L) (pH 7.0), and by air aeration into
The oxygen supply of row cathode chamber；Constent temperature heater is opened, under 30~35 DEG C of constant temperature, connection external resistance is connect in the case of being powered
The domestication of kind object；When microbiological fuel cell voltage drops to 50mV or less, it is believed that a cycle terminates, and carries out raw material more
It changes；By constantly replacing raw material, the operation of fuel cell and the domestication to inoculum are maintained；Highest within continuous 3 periods
When output voltage is not further added by, it is believed that inoculum domestication is completed；The area the anode chamber a first leads to before raw material and inoculum is added
Nitrogen 20min removes oxygen, guarantees the anaerobic environment of anode of microbial fuel cell room；The microbiological fuel cell into
When row raw material is replaced, first opens discharge tube valve and the old raw material of 1/3~1/2 volume is discharged, turn off discharge tube valve while opening
The feed pipe a valve closes the feed pipe a valve after supplementing same volume fresh feed；The organic waste is 40
One of ~ 100 mesh pig manures, chicken manure, cow dung, kitchen garbage, excess sludge, stalk or mixing；
S1.4 charcoal biofilm:
After completing inoculum domestication, the charcoal that partial size that mass fraction is 5%~20% is 1 ~ 5mm is added from feed pipe b
Grain is in the area b, anode chamber；Under 30~35 DEG C of constant temperature, connection external resistance carries out charcoal biofilm in the case of being powered；Work as institute
When stating microbiological fuel cell voltage and dropping to 50mV or less, it is believed that a cycle terminates, and carries out raw material replacement；By constantly more
Raw material is changed, fuel cell operation is maintained；When the maximum output voltage in continuous 3 periods is not further added by, it is believed that charcoal is hung
Film is completed；The raw material replacing options, with step S1.3；The raw material is organic waste or waste water；Wherein, described organic
Waste, mesh number are not required, and are one of pig manure, chicken manure, cow dung, kitchen garbage, excess sludge, stalk or mixing；
S1.5 vacuum freeze-drying:
After the completion of biofilm, the discharge tube valve is opened, until closing the discharge pipe valve after feed liquid is all discharged in anode chamber
Door, and opens biomembrane gate, and charcoal and thereon biomembrane are transmitted to vacuum freeze-drying device and carry out vacuum freeze-drying, and freeze-drying is to containing
Water is 8~10%, charcoal and biomembrane, i.e. MFC solid biologic film thereon after being lyophilized；Freeze temperature is -40 DEG C
~-45 DEG C, freeze-drying time is 24~72h；
S2 adds microelement and multi-vitamins:
S2.1 prepares microelement and multi-vitamins mixed powder:
By mass fraction, 1 ~ 2 part of the ferrous sulfate, 0.1 ~ 1 part of cobalt chloride, 0.5 ~ 2 part of chlorination of solid forms are weighed
Nickel, 0.3 ~ 2 part of multi-vitamins, are put into container, add distilled water that saturated solution is made, and are put into the baking that temperature is 60 ~ 90 DEG C
In case, after drying 1 ~ 2h, 100 ~ 130 mesh is ground into pulverizer, obtain microelement and multi-vitamins mixed powder；Its
In, multi-vitamins are by biotin, thiamine, puridoxine hydrochloride, the general calcium acid of D-, lipoic acid, folic acid, riboflavin, niacin, right
Aminobenzoic acid, vitamin B12In three kinds or a variety of compositions；
S2.2 mixing:
MFC solid biologic film obtained in step S1.5 is taken out from the vacuum freeze-drying discharge port of the vacuum freeze-drying device；And it will
The microelement and multi-vitamins mixed powder prepared in step S2.1 is added to prepared by 2% ~ 5% additive amount
In MFC solid biologic film, after mixing to get the solid biologic film MFC promotor of charcoal mediation.
6. the preparation method for the solid biologic film MFC promotor that a kind of charcoal according to claim 5 mediates, feature
Be: all steps and corresponding operating carry out under anaerobic environment.
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