CN112390374A - Method for improving power generation, nitrogen and phosphorus removal performance of microalgae cathode microbial fuel cell - Google Patents
Method for improving power generation, nitrogen and phosphorus removal performance of microalgae cathode microbial fuel cell Download PDFInfo
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- C02F3/00—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a method for improving the power generation and nitrogen and phosphorus removal performance of a microalgae cathode microbial fuel cell, which comprises the following steps: preparing a biochar-sodium alginate combined immobilized microalgae colloidal sphere; step two: constructing a double-chamber microbial fuel cell: the device consists of a cathode chamber and an anode chamber, wherein the middle part is separated by a proton exchange membrane, the anode is inoculated with activated sludge, anolyte is artificial wastewater, and the cathode is inoculated with biochar-sodium alginate combined immobilized microalgae colloidal spheres. The invention improves the specific surface area and mass transfer performance of the rubber ball, promotes the absorption of nitrogen, phosphorus and other substances by the microalgae, improves the electrogenesis performance of the immobilized microalgae, and further improves the electrogenesis performance of the immobilized microalgae biological cathode microbial fuel cell. The method has the advantages of good denitrification and dephosphorization and electrogenesis performances, strong impact load resistance, low treatment cost and the like.
Description
Technical Field
The invention relates to the technical field of sewage control, in particular to a method for improving the power generation and nitrogen and phosphorus removal performance of a microalgae cathode microbial fuel cell.
Background
Along with the rapid development of industry and agriculture, the number of pollution sources and the total discharge amount of ammonia nitrogen wastewater show an increasing trend, the water eutrophication and the water body black and odor caused by the pollution sources seriously threaten the water body ecological balance and the normal production and life of human beings, and the treatment of ammonia nitrogen in the water body is not slow at all. Research and development of economic and efficient nitrogen removal treatment technology has become one of the key fields of research in the field of water pollution control engineering.
The conversion from chemical energy to electric energy is further realized by utilizing the self metabolism of the electrogenesis microorganisms in the bioelectrochemical system, wherein the microbial fuel cell technology converts the chemical energy contained in pollutants into electric energy by the metabolism of the electrogenesis microorganisms, and the microbial fuel cell technology is more and more widely concerned in the field of environmental remediation. The microalgae treatment method is a novel sewage treatment mode at present, rich nutrient substances such as nitrogen, phosphorus and the like contained in the livestock and poultry breeding sewage can provide nutrition for the microalgae, and the microalgae treatment sewage can be coupled with the large-scale production of the microalgae at the same time, so that the cyclic utilization of resources is realized. The microalgae is applied to a microbial cathode, oxygen generated through photosynthesis can provide sufficient electron acceptors, and the microalgae type microbial fuel cell can be divided into a microalgae biological cathode, a microalgae biological anode and a microalgae anode substrate according to the action of the microalgae in a microbial fuel cell system.
Algae, as an important primary producer of water ecological environment, is applied to a cathode of a microbial fuel cell, absorbs nitrogen and phosphorus in water to maintain the growth and reproduction of the water, fixes carbon dioxide through photosynthesis, and generates oxygen which can serve as an electron acceptor to improve the resource degree of pollutants.
The microalgae immobilization technology realizes high-density culture of algae cells, enhances the stress resistance of the algae cells, and improves the power generation and wastewater treatment capacity of the microalgae microbial fuel cell. However, microalgae gel spheres prepared from immobilized materials represented by sodium alginate, chitosan and the like have poor mass transfer performance, and the growth of microalgae in the gel spheres and the removal of pollutants in water are limited.
Therefore, the inventor further researches the problems and develops a method for improving the power generation performance and the nitrogen and phosphorus removal performance of the microalgae cathode microbial fuel cell, and the method is generated by the method.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for improving the power generation and nitrogen and phosphorus removal performance of a microbial fuel cell of a microalgae cathode, which can efficiently remove nitrogen and phosphorus in wastewater, can obtain more microalgae for preparing biological oil and fat, and can improve the power generation of the microbial fuel cell.
In order to solve the technical problems, the technical solution of the invention is as follows:
a method for improving the power generation and nitrogen and phosphorus removal performance of a microalgae cathode microbial fuel cell comprises the following steps:
the method comprises the following steps: preparing a biochar-sodium alginate combined immobilized microalgae colloidal sphere: 1) centrifuging the algae solution in a centrifuge tube, discarding part of supernatant, and centrifuging to concentrate the algae solution; 2) weighing sodium alginate powder, adding water, heating and dissolving in a magnetic stirring heating furnace, adding appropriate amount of biochar after completely dissolving, stirring uniformly, adding algae liquid when the temperature of the solution is reduced to room temperature, and mixing uniformly; 3) dropwise adding 0.5-3% of CaCl into the mixed solution2Standing in the solution, and washing with deionized water to obtain biochar-sodium alginate combined immobilized microalgae gel balls;
step two: constructing a double-chamber microbial fuel cell: consists of a cathode chamber and an anode chamber, the middle part is separated by a proton exchange membrane, the anode chamber of the microalgae biocathode double-chamber microbial fuel cell is inoculated with activated sludge, anolyte is artificial wastewater, microbes in the anode chamber decompose organic matters in the wastewater and generate H after catabolism+、e-And CO2In the cathode chamber of the double-chamber microbial fuel cell, the cathode is inoculated with biochar-sodium alginate combined immobilized microalgae colloidal spheres to generate O through photosynthesis2Directly as electron acceptor, H+Transferred to the cathode through the proton exchange membrane e-Oxygen is transmitted to the cathode electron acceptor through the external lead to form a closed loop.
Further, in the first step, the centrifugation conditions are as follows: centrifuging at 3500r/min for 3 min.
Further, the biochar is obtained by grinding after carbonization preparation of waste biomass.
Further, the waste biomass is specifically straw or shaddock peel.
Further, in the first step, the microalgae in the algae solution is one or more of chlorella, nannochloropsis, scenedesmus, chrysophyceae, porphyridium, phaeomorpha tricornutum, haematococcus pluvialis, anabaena, synechocystis and synechococcus.
Further, in the second step, the electrode materials of the cathode and the anode are both carbon felts.
After the scheme is adopted, due to the characteristics of developed pore structure, large specific surface area, good biocompatibility and the like of the biochar, the biochar mediates sodium alginate immobilized chlorella to prepare the rubber ball, the mass transfer performance of the immobilized rubber ball is improved, the synergistic effect of biochar adsorption and microbial degradation is fully exerted, an adsorption-degradation-adsorption synergistic process is established, high-concentration nitrogen and phosphorus removal of high-density microalgae in a cathode of the microbial fuel cell is realized, the growth of the microalgae is promoted to obtain more microalgae biomass, and the nitrogen and phosphorus removal and electricity production performance of the immobilized microalgae cathode microbial fuel cell are improved. The method has the advantages of good denitrification and dephosphorization and electrogenesis performances, strong impact load resistance, low treatment cost and the like.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is the output voltage variation curve of three kinds of microalgae biocathode double-chamber microbial fuel cells under the light and dark conditions;
FIG. 3 is a graph showing growth influence variation of immobilized chlorella versus time;
FIG. 4 is a graph comparing the removal variation of total phosphorus in immobilized microalgae cathode microbial fuel cell;
FIG. 5 is a comparison curve of ammonia nitrogen removal variation of the immobilized microalgae cathode microbial fuel cell.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. The invention discloses a method for improving the performance of microalgae cathode microbial fuel cell in power generation and nitrogen and phosphorus removal, as shown in figure 1, which is a preferred embodiment of the invention and comprises the following steps:
the method comprises the following steps: charcoal-sodium alginate combinationPreparing immobilized microalgae gel balls: 1) centrifuging the algae solution in a centrifuge tube at 3500r/min for 3min, discarding part of supernatant, and centrifuging to concentrate the algae solution; 2) weighing sodium alginate powder, adding water, heating and dissolving in a magnetic stirring heating furnace, adding appropriate amount of biochar after completely dissolving, stirring uniformly, adding algae liquid when the temperature of the solution is reduced to room temperature, and mixing uniformly; 3) the mixture was added dropwise to 0.5 to 3% (preferably 1% in this example) of CaCl using a syringe2Standing the solution for 30min, washing the solution for 3 times with water, and putting the solution into a culture medium to obtain biochar-sodium alginate combined immobilized microalgae gel balls;
step two: constructing a double-chamber microbial fuel cell: comprises a cathode chamber and an anode chamber, the middle part is separated by a proton exchange membrane, the anode of the microbial fuel cell with microalgae biological cathode is inoculated with active sewage sludge, the anolyte is artificial wastewater, the microbes in the anode chamber decompose the organic matters in the wastewater, and the H is generated after catabolism+、e-And CO2In the cathode chamber of the microbial fuel cell, the cathode is inoculated with biochar-sodium alginate combined immobilized microalgae colloidal spheres, and the algae can generate O through photosynthesis2Directly as electron acceptor, H+Transferred to the cathode through the proton exchange membrane e-Then the oxygen is transmitted to the cathode electron acceptor through an external lead to form a closed loop, and the reaction is continuously carried out.
The reaction process can be represented by the following formula:
and (3) anode reaction: (CH)2O)n+nH2O→nCO2+4ne-+4nH+
And (3) cathode reaction: o is2+4H++4e-→2H2O
Further, the biochar is obtained by grinding after carbonization preparation of waste biomass.
Further, the straw or the shaddock peel is concretely.
Further, in the first step, the microalgae in the algae solution is one or more of chlorella, nannochloropsis, scenedesmus, chrysophyceae, porphyridium, phaeomorpha tricornutum, haematococcus pluvialis, anabaena, synechocystis and synechococcus.
Further, in the second step, the electrode materials of the cathode and the anode are both carbon felts.
A double-chamber microbial fuel cell constructed by adopting a transparent acrylic plate is inoculated with activated sludge at the anode, artificial wastewater is used as anolyte, free algae, sodium alginate immobilized algae and biochar-sodium alginate combined immobilized algae are respectively inoculated at the cathode, the voltage output of the cell is inspected under the operation conditions of the same illumination and the like, FIG. 2 shows the output voltage change curves of three different forms of chlorella cathode microbial fuel cells (respectively sodium alginate immobilization, biochar-sodium alginate co-immobilization and suspended algae) under dark conditions and under the illumination condition (1500lux light intensity), and the external resistance is 1000 omega. As can be seen from FIG. 2, the cell output voltage of the biochar-added cell in the dark is below 40mV, while the cell output voltages of the free algae group and the immobilized cell are only about 4 mV. After illumination, the output voltages of the three batteries are obviously improved, and finally, stable output is kept. Under the illumination condition, the output voltage of the battery added with the biochar is stabilized at 0.181V, the output voltage of the battery of the immobilized group is stabilized at 0.114V, and the output voltage of the battery of the free algae group is stabilized at 0.075V. The illumination obviously reduces the resistance of the microalgae cathode, and improves the performance of the microalgae type microbial fuel cell; the immobilized microalgae further improves the electricity generation of the microalgae type microbial fuel cell, the addition of the biochar further improves the electricity generation of the microalgae type microbial fuel cell, and the promotion effect is obvious.
In this embodiment, the chlorella is used as the chlorella liquid, 3 biochar-sodium alginate combined immobilized chlorella cathode microbial fuel cells are arranged, the catholyte is artificial wastewater with ammonia nitrogen concentration of 120mg/L, and the concentration of the measured chlorella cells every two days is used to draw a chlorella growth curve as shown in fig. 3. As can be seen from FIG. 3, the difference between the density of Chlorella in the two kinds of rubber balls gradually increased with the increase of the culture time, and the cell density of Chlorella in the biochar-sodium alginate combined immobilized Chlorella rubber balls reached 2.45X 10 after the culture for the 8 th day6cells/mL, while in sodium alginate alone immobilized gel beads there is only 1.72X 106Cellsand/mL. Therefore, the growth of the immobilized chlorella in the sodium alginate gel balls is promoted by the charcoal, and the growth is promoted probably because the addition of the charcoal increases the specific surface area of the gel balls and the adsorption effect of organisms, so that the chlorella in the gel balls can obtain nutrients more easily.
The removal performance of total phosphorus is determined by taking a sample once a day to determine the concentration of total phosphorus in a culture medium and calculating the removal rate of the total phosphorus, wherein the catholyte is artificial wastewater containing 40mg/L of total phosphorus, and the determination period is five days. As can be seen from FIG. 4, the removal rate of total phosphorus from non-immobilized free algae inoculated is relatively slow, the removal efficiency of total phosphorus after five days is only 32.55%, and the removal rate of total phosphorus from free algae is far lower than 62.21% of that of the sodium alginate immobilized chlorella group and 91.23% of that of biochar sodium alginate combined immobilized chlorella group. The total phosphorus removal rate of the sodium alginate immobilized chlorella group and the biochar sodium alginate combined immobilized chlorella group is basically the same in the first two days, but after the second day, the total phosphorus removal efficiency of the combined and immobilized chlorella group is higher than that of the sodium alginate immobilized group, and the difference is more obvious along with the prolonging of the treatment time.
As can be seen from fig. 5, the ammonia nitrogen content of the three treatment groups, namely, the biochar-combined immobilized algae, the biochar-free immobilized algae (the chlorella fixed by sodium alginate) and the biochar empty rubber ball (the chlorella is not added), rapidly decreases on day 1, and is possibly related to strong adsorption of the rubber ball to the ammonia nitrogen. Through metabolism of the suspended microalgae, the ammonia nitrogen concentration in the water to be treated is continuously reduced, but the ammonia nitrogen removal rate is slow, and the ammonia nitrogen concentration in the solution after 4 days of treatment is slightly lower than that in the empty micelle treatment group.
The cheap biochar has a large specific surface area, can improve the mass transfer performance of the traditional immobilized rubber ball, promotes nitrogen and phosphorus and other nutrient elements to enter the rubber ball to contact with high-density microalgae, promotes the growth, nitrogen and phosphorus removal of the microalgae, provides enough oxygen for the microalgae microbial fuel cell as an electron acceptor by more oxygen generated by photosynthesis, and finally improves the nitrogen and phosphorus removal and electricity generation performance of the immobilized microalgae microbial fuel cell.
The invention can obtain more microalgae for preparing biological oil while efficiently removing nitrogen and phosphorus in the wastewater, and can improve the electricity generation of the microbial fuel cell; the addition of the biochar improves the mass transfer performance of the rubber ball, promotes the microalgae to better obtain nutrient substances and grow faster, the photosynthesis of the microalgae with high density generates enough oxygen, and the common mechanical aeration (the mechanical aeration refers to a method for fully mixing wastewater and sludge in an activated sludge method aeration tank by mechanical equipment such as blades, impellers and the like and enabling the liquid level of the mixed liquid to be continuously updated and contacted with air so as to increase dissolved oxygen in water) is cancelled.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the technical scope of the present invention, so that the changes and modifications made by the claims and the specification of the present invention should fall within the scope of the present invention.
Claims (6)
1. A method for improving the power generation and nitrogen and phosphorus removal performance of a microalgae cathode microbial fuel cell is characterized by comprising the following steps: the method comprises the following steps: preparing a biochar-sodium alginate combined immobilized microalgae colloidal sphere: 1) centrifuging the algae solution in a centrifuge tube, discarding part of supernatant, and centrifuging to concentrate the algae solution; 2) weighing sodium alginate powder, adding water, heating and dissolving in a magnetic stirring heating furnace, adding appropriate amount of biochar after completely dissolving, stirring uniformly, adding algae liquid when the temperature of the solution is reduced to room temperature, and mixing uniformly; 3) dropwise adding 0.5-3% of CaCl into the mixed solution2Standing in the solution, and washing with deionized water to obtain biochar-sodium alginate combined immobilized microalgae gel balls; step two: constructing a double-chamber microbial fuel cell: consists of a cathode chamber and an anode chamber, the middle part is separated by a proton exchange membrane, the anode of the microalgae biocathode double-chamber microbial fuel cell is inoculated with active sewage sludge, anolyte is artificial wastewater, microbes in the anode chamber decompose organic matters in the wastewater, and H is generated after decomposition and metabolism+、e-And CO2In the cathode chamber of the double-chamber microbial fuel cell, the cathode is inoculated with biochar-sodium alginate combined immobilized microalgae colloidal spheres to generate O through photosynthesis2Directly as electron acceptor, H+Transferred to the cathode through the proton exchange membrane e-Oxygen is transmitted to the cathode electron acceptor through the external lead to form a closed loop.
2. The method for improving the power generation and nitrogen and phosphorus removal performance of the microalgae cathode microbial fuel cell according to claim 1, characterized in that: in the first step, the centrifugation conditions are as follows: centrifuging at 3500r/min for 3 min.
3. The method for improving the power generation and nitrogen and phosphorus removal performance of the microalgae cathode microbial fuel cell according to claim 1, characterized in that: the biochar is obtained by grinding after carbonization preparation of waste biomass.
4. The method for improving the power generation and nitrogen and phosphorus removal performance of the microalgae cathode microbial fuel cell according to claim 3, characterized in that: the waste biomass is straw or shaddock peel.
5. The method for improving the power generation and nitrogen and phosphorus removal performance of the microalgae cathode microbial fuel cell according to claim 1, characterized in that: in the first step, the microalgae in the algae solution is one or more of chlorella, nannochloropsis, scenedesmus, chrysophyceae, porphyridium, phaeosphaera trigonorum, haematococcus pluvialis, anabaena, synechocystis and synechococcus.
6. The method for improving the power generation and nitrogen and phosphorus removal performance of the microalgae cathode microbial fuel cell according to claim 1, characterized in that: in the second step, the electrode materials of the cathode and the anode are both carbon felts.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113061914A (en) * | 2021-03-19 | 2021-07-02 | 江苏大学 | Light-induced biosynthesis H based on microbial fuel cell2O2Method (2) |
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| JP2018142541A (en) * | 2017-02-28 | 2018-09-13 | 公立大学法人大阪府立大学 | Electrochemical device and manufacturing method thereof |
| CN108821439A (en) * | 2018-06-20 | 2018-11-16 | 哈尔滨工业大学 | Immersion microalgae-microorganism electrochemical the system and restorative procedure that nutritive salt pollutes in in-situ immobilization surface water body |
| CN111254137A (en) * | 2020-01-19 | 2020-06-09 | 深圳大学 | Immobilized carbon algae material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103086520A (en) * | 2013-01-23 | 2013-05-08 | 中国科学院城市环境研究所 | Device and a method for producing biodiesel in a coupling way by treating livestock and poultry breeding wastewater |
| CN106898803A (en) * | 2015-12-18 | 2017-06-27 | 王冰 | A kind of multiple-effect photosynthesis microorganism fuel cell and implementation method |
| JP2018142541A (en) * | 2017-02-28 | 2018-09-13 | 公立大学法人大阪府立大学 | Electrochemical device and manufacturing method thereof |
| CN108821439A (en) * | 2018-06-20 | 2018-11-16 | 哈尔滨工业大学 | Immersion microalgae-microorganism electrochemical the system and restorative procedure that nutritive salt pollutes in in-situ immobilization surface water body |
| CN111254137A (en) * | 2020-01-19 | 2020-06-09 | 深圳大学 | Immobilized carbon algae material and preparation method and application thereof |
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| CN113061914A (en) * | 2021-03-19 | 2021-07-02 | 江苏大学 | Light-induced biosynthesis H based on microbial fuel cell2O2Method (2) |
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