CN108503048B - Method for purifying river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis - Google Patents
Method for purifying river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis Download PDFInfo
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- CN108503048B CN108503048B CN201810424388.6A CN201810424388A CN108503048B CN 108503048 B CN108503048 B CN 108503048B CN 201810424388 A CN201810424388 A CN 201810424388A CN 108503048 B CN108503048 B CN 108503048B
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- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
A method for purifying a river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis comprises the following steps: collecting strains, and domesticating to obtain plant source microorganisms; attaching the domesticated plant source microorganisms to an electrode net rack, and installing the electrode net rack in the river black and odorous water body; and (4) introducing current into the electrode net rack. The invention breaks the bottleneck of treating the river black and odorous water body by only depending on microorganisms, realizes effective biofilm formation on the strains by selecting proper strains, domesticating the strains and selecting proper electrode net racks, thereby improving the removal effect on ammonia nitrogen and nitrate nitrogen in the river black and odorous water body and shortening the treatment period.
Description
Technical Field
The invention relates to the technical field of treatment of a black and odorous water body of a river, in particular to a method for purifying the black and odorous water body of the river by utilizing electrogenesis microorganism biofilm anode bioelectrolysis.
Background
In the industrialized, urbanized and modernized processes, the black and odorous river water is often polluted to different degrees. These water body pollutions come from enterprise drainage, mine drainage, municipal sewage, farmland drainage, etc. The polluted water body deteriorates the water quality and aquatic ecology, reduces the beneficial use value of the water body, and can cause serious damage to human bodies, animals, plants and the environment.
The inventors have conducted long-term and intensive studies on the treatment of black and odorous water bodies before that. For example, the invention patent applied by the inventor before discloses that the fecal coliform group in the river black and odorous water body is effectively adsorbed at the upstream position of the river black and odorous water body by adopting the high adsorption effect of the miscellaneous bacteria killing foam carrier filler in the miscellaneous bacteria killing net on the microorganisms, and then the adsorbed fecal coliform group is killed by utilizing the nano silver powder contained in the miscellaneous bacteria killing foam carrier filler; and (3) carrying out next treatment on the wastewater after killing the fecal coliform group by using a strain carrier with mixed strains so as to further improve the water quality after killing the fecal coliform group.
However, the inventors have found in their studies that the properties of the organic substances of the black and odorous water body, such as odor and color, are determined by the specific atoms or groups of atoms they contain. The difficult degradability of these organic substances is also determined by their corresponding specific atomic groups. According to chemical structure analysis, many organic compounds which are difficult to be biochemically degraded have electrophilic groups on the molecular structure, have strong electronegativity, and are difficult to be continuously oxidized. This also makes the improvement of the treatment effect of the river black and odorous water body and the shortening of the cycle encounter bottlenecks.
Therefore, the development of a new method for treating the river black and odorous water body has urgent research value, and also has good economic benefit and industrial application potential, which is the basis and the place where the invention can be completed.
Disclosure of Invention
The present inventors have conducted intensive studies to overcome the above-identified drawbacks of the prior art, and as a result, have completed the present invention after having made a great deal of creative efforts.
Specifically, the technical problems to be solved by the present invention are: provides a method for purifying a river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis, so as to improve the treatment effect of the river black and odorous water body and shorten the treatment period of the river black and odorous water body.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for purifying a river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis comprises the following steps: collecting strains, and domesticating to obtain plant source microorganisms; attaching the domesticated plant source microorganisms to an electrode net rack, and installing the electrode net rack in the river black and odorous water body; and (4) introducing current into the electrode net rack.
As a preferred technical solution, in the present invention, the strain comprises the following microorganisms: bacillus subtilis, saccharomycetes, bacillus licheniformis, phosphorus-accumulating bacteria, photosynthetic bacteria, EM bacteria, trichoderma viride, streptococcus faecalis, lactic acid bacteria, lactobacillus plantarum, lactobacillus acidophilus, nitrobacteria, denitrifying bacteria, nitrosobacteria, bacillus brevis, bacillus coagulans and bacillus natto (all of which are commercially available microorganisms of animal origin); and the microorganisms contained in the mixed strain are domesticated into plant-derived microorganisms, and the short-chain fatty acid is mixed in the mixed strain.
As a preferred embodiment, in the present invention, the domestication of the microorganism is a method comprising the steps of:
A. acclimatization conditions of plant-derived microorganisms:
1) 100 parts of purified water, wherein the conductivity must be 0;
2) 60-80 parts of plant source culture medium, which is prepared by high-temperature steaming and sterilizing 30 minutes in advance;
3) 6-20 parts of animal-derived microorganisms (commercially available) required for forming the mixed strain, and separating anaerobic microorganisms and aerobic microorganisms;
4) acclimating environment, sealing the container, only needing an ultraviolet lamp capable of generating ozone outside, simple and easy to operate, low in cost and free from complex sterile space;
B. acclimatization of plant source microorganisms:
1) adding 30-40 parts by weight of plant source culture medium into 100 parts of purified water, adding 3-10 parts of anaerobic microorganism (animal source anaerobic microorganism required for forming mixed strains), stirring uniformly, and fermenting at constant temperature of 35 ℃ for 24-48 hours in a sealing manner;
2) adding 30-40 parts of plant source culture medium and 3-10 parts of aerobic microorganism (animal source aerobic microorganism required for forming mixed strains), stirring uniformly, fermenting at constant temperature of 30 ℃ for 12-24 hours, and oxygenating and aerating once every 15-30 minutes;
3) fermenting at constant temperature of 25 deg.C for 8-12 hr, and oxygenating and aerating once every 30-60 min;
4) naturally fermenting for 12-24 hours, oxygenating and aerating once every 120-240 minutes, and then adding short-chain fatty acid to obtain the mixed strain. The domestication of the purchased animal source microorganism strains restores the original wild property (very strong survival activity of rapidly adapting to the environment) of the microorganisms, not only enhances the activity, but also can more rapidly adapt to the nature (particularly to the severe environment in sewage treatment), rapidly survive, adapt and propagate, has low requirement on the environment and is convenient to operate. The inventor finds in practice that the strain domesticated by the method can rapidly survive, adapt and propagate in the environment of the black and odorous water body in the river.
As a preferred embodiment, in the present invention, the mixed culture is required to be electrically acclimated, and includes the steps of: manufacturing a cuboid reaction tank by using insulating plastic, wherein one side of the cuboid reaction tank is provided with carbon cloth as an anode, the other opposite side of the cuboid reaction tank is provided with carbon cloth coated with a platinum-containing catalyst on the surface as a cathode, the anode and the cathode are respectively connected with an external circuit through a platinum wire and a copper wire, adding the product obtained in the step B into the cuboid reaction tank, culturing for 3-5 days at 35-37 ℃, then connecting the platinum wire and the copper wire into a 0.4V direct current power supply for 15-25 days, and finally connecting a 1.2V direct current power supply for 30-35 days; and finally, taking out the substance in the cuboid reaction tank, namely the domesticated plant source microorganism.
The plant source microorganisms after the electric domestication can normally live when being electrically stimulated in the black and odorous water body, even have stronger activity, and various microorganisms can also have synergistic action, for example, bacillus subtilis, bacillus licheniformis and the like can improve the problem that algae in the black and odorous water body are inundated, other strains can also play a role in decomposing phosphorus-containing organic matters in water, the growth of phosphorus-accumulating bacteria is inhibited under the anaerobic condition, polyphosphate in cells of the phosphorus-accumulating bacteria is released for the growth of the phosphorus-accumulating bacteria, and meanwhile, energy required by the growth of the phosphorus-accumulating bacteria is generated; after entering an aerobic environment, the activity of the phosphorus accumulating bacteria is fully recovered, and a large amount of dissolved orthophosphate is taken from the wastewater while the matrix is fully utilized, so that the phosphorus accumulating process is completed, and the total phosphorus content of the black and odorous water body is reduced. Under the action of nitrosation bacteria, ammonia (NH) is generated4+) Converting the nitrite nitrogen into nitrite nitrogen, and further converting the nitrite nitrogen into nitrate nitrogen under the action of nitrobacteria. The nitrite bacteria are selected from the group consisting of the genera Nitrosomonas, Nitrospira and Nitrosococcus. The nitrobacteria include genus Nitrobacter and genus Nitrobacter. The nitrate nitrogen and nitrite nitrogen are reduced into gaseous nitrogen (N) under the action of denitrifying bacteria2). Meanwhile, through enzymatic action, after special enzyme is generated through induction, part of volatile phenol pollutants are degraded, and some strains can directly utilize the volatile phenol pollutants as energy sources and carbon sources; recalcitrant degradation can also be stubborn through co-metabolismComplex volatile phenol pollutants are easy to degrade one of the pollutants by first culturing, so that the degradation effect on other pollutants is promoted; the microorganism can also develop the function of detoxification for protecting self survival through the detoxification metabolism, namely the microorganism does not directly utilize the volatile phenol pollutants as nutrition, but takes other organic matters as nutrition and energy. In addition, the above strains can also cause the dissolution of volatile phenolic pollutants by reducing pH in microbial metabolism through non-enzymatic action or generate certain chemical substances to promote the conversion of the volatile phenolic pollutants; the microbial metabolism causes volatile phenolic pollutants to participate in a series of biochemical reactions: dehalogenation, dealkylation, hydrolysis of amides and lipids, redox, ring cleavage, condensation or conjugation effects, etc., cause the gradual degradation of volatile phenolic pollutants.
As a preferable technical scheme, in the invention, when the electric training treatment is carried out, the electromagnetic, the mobile phone and the radio must be shielded.
As a preferable technical scheme, in the invention, the electrode net rack comprises a galvanized iron wire used as a cathode and an oxygen increasing net used as an anode, wherein the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt and the ammonia nitrogen removing filler are sequentially distributed between the cathode and the anode, and the anode is erected on the bottom layer of the river water body when the electrode net rack is installed and used.
As a preferable technical scheme, the oxygen increasing net is a graphene modified nano titanium dioxide photocatalyst fiber net.
The preparation method comprises the following steps:
(1) the composite photocatalyst with the reduced graphene oxide modified nano titanium dioxide heterostructure is constructed by a hydrothermal-thermal treatment-hydrothermal method, and amorphous carbon is used as a heterostructure interface between a TiO2 nanocrystal and a graphene two-dimensional plane, so that the composite effect of TiO2 and graphene is improved, and the visible light catalytic activity of the composite photocatalyst is improved;
manufacturing a water-resistant and impact-resistant aluminum-based cross-linking agent, preparing the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst obtained in the step (1) and the aluminum-based cross-linking agent into a homogeneous mixture, adding the homogeneous mixture into fiber slurry for producing a high-density polyethylene fiber net, or attaching the homogeneous mixture to the high-density polyethylene fiber net together to prepare the high-density polyethylene fiber net with the nano photocatalytic film coating;
(3) and (3) naturally drying the high-density polyethylene fiber net with the nano photocatalytic film coating obtained in the step (2) in the air, and then placing the net in a drying room for drying to obtain the graphene modified nano titanium dioxide photocatalyst high-density polyethylene fiber net.
As a preferred technical scheme, the detailed process of the step (1) comprises the following steps:
flake graphite is used as raw material, concentrated H is used2SO4And KMnO4Preparing graphite oxide as an oxidant by a two-step method, and preparing graphene oxide by ultrasonic dispersion;
by solvothermal method at 180 ℃ with graphene oxide and Ti (OBu)4As an initial reactant, synthesizing the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst in an ethanol solvent.
As a preferred technical scheme, the detailed process in the step (2) is as follows:
firstly diluting butyl aluminate by absolute ethyl alcohol, then adding a mixed solution of glacial acetic acid, absolute ethyl alcohol and water, wherein the volume ratio of water to absolute ethyl alcohol in the mixed solution is 1: 10, putting the mixture into a mixer, starting stirring, heating to 70-80 ℃, stirring for 10-30 minutes to obtain stable, uniform, clear and transparent light yellow sol, then slowly adding the nano alumina suspension, and keeping the temperature at 40 ℃ to obtain a water-resistant and impact-resistant aluminum-based crosslinking agent;
taking an aluminum-based crosslinking agent, heating the aluminum-based crosslinking agent to 50 ℃, slowly adding the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst suspension, wherein the aluminum-based crosslinking agent accounts for 0.1-2 wt% of the total weight of the mixture, and continuously stirring for 15-20 minutes after the addition is finished to obtain a homogeneous mixture;
and then adding the homogeneous mixture into fiber slurry for producing a high-density polyethylene fiber net or attaching the homogeneous mixture to the high-density polyethylene fiber net to prepare the high-density polyethylene fiber net with the nano photocatalytic film coating.
As a preferred technical solution, in the step (2), the technical requirements of the homogeneous mixture are as follows: shape, liquid 2-5%; crystalline, anatase; content, 97.5%; the grain diameter is less than or equal to 10 nm; surface groups, carboxyl, carbonate; the light response range is 300nm-550 nm; surface properties, hydrophilic; pH (1% aqueous solution), 3-4; specific surface area, 400m2/g。
As a preferred technical scheme, in the step (2), the thickness of the nano photocatalytic film coating is 0.5um-50 um.
As a preferred solution, in step (2), the size of the high density polyethylene fiber web can be selected as required, but the most preferred width is 1 meter, 1.5 meters or 2 meters. The high-density polyethylene fiber net under the width is convenient for subsequent processing and installation, and meanwhile, the photocatalysis efficiency is improved to the maximum extent.
In the step (2), the homogeneous mixture obtained in the step (1) is attached to the surface of the high-density polyethylene fiber net by spraying.
As a preferred technical scheme, a high-pressure spray gun is adopted during spraying, and a mode of small-amount uniform spraying for multiple times is adopted. Here, the plural number means at least three times, and the small number means that the sprayed amount per one time does not exceed one third of the total amount of the spray paint.
As a preferred technical solution, in step (2), the high-density polyethylene fiber web is directly leached multiple times in a special tank filled with the homogeneous mixture.
As a preferred technical scheme, in the step (2), the high-density polyethylene fiber net is directly leached for 3 to 7 times in a special barrel filled with the homogeneous mixture.
As a preferable technical scheme, in the step (3), when drying is carried out in a drying room, the drying temperature is 55-65 ℃, and the drying time is 25-35 hours.
As a preferable technical scheme, in the step (3), when drying is carried out in the drying room, the drying temperature is constant at 60 ℃, and the drying time is 30 hours.
The invention adopts a hydrothermal method to prepare Ti02And the nanocrystalline adjusts the thickness and the surface disorder degree of the carbon film on the surface of the sample through heat treatment. Followed by carbon-coated Ti02And compounding with graphene to obtain a series of heterostructure compound samples. TiO22The amorphous carbon on the surface can be used as an excellent heterostructure composite interface to play a role of bridging TiO under the state of certain thickness and disorder degree2And graphene and the function of inhibiting the recombination of photon-generated carriers. The result of the photocatalytic activity test of the inventor shows that the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst can obtain a carbon film with a thinner thickness and a lower surface disorder degree, and the photocatalytic activity of the heterostructure composite is favorably improved. After 4h of visible light irradiation treatment, the degradation rate of methyl orange is 5.2 times that of titanium dioxide, and the degradation rate of P25 and graphene composite is 1.9 times. In addition, in the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst, TiO2 and graphene can be fully combined, so that the dispersity of TiO2 is improved, the transmission efficiency of a photon-generated carrier is also improved, more photon-generated electrons can be transported from Ti02 to graphene through a high-efficiency interface, the recombination of the photon-generated carrier is inhibited, and high photocatalytic activity is obtained.
The invention prepares the graphene modified nano titanium dioxide photocatalyst solution into a nano photocatalytic film coating by using a water-resistant and impact-resistant aluminum-based cross-linking agent, sprays or soaks the nano photocatalytic film coating according to a certain proportion per square meter, and attaches the film to a high-density polyethylene fiber net to produce a novel graphene modified nano titanium dioxide photocatalyst high-density polyethylene fiber net. With modified nanometer titanium dioxide photocatalyst high density polyethylene fiber net direct mount of graphite alkene in the river department, can carry out the photocatalysis to the black smelly water in the river and handle, need not oxygenation pump aeration oxygenation, reduce the waste of the energy, can not influence resident normal life yet, also need not to carry out the moisturizing and the desilting of upper reaches and handle, the time of continuous action is longer, can not cause secondary pollution to the river. Although the traditional titanium dioxide can effectively absorb ultraviolet rays, the traditional titanium dioxide does not have photocatalysis capability, and the essential reasons are that the photogenerated carrier has short service life and high recombination efficiency, can not provide photogenerated electrons and photogenerated holes for surrounding oxygen molecules and water molecules, and can not generate active hydroxyl radicals for oxidation reduction. The same problem exists in the nanometer titanium dioxide photocatalyst, and the heterostructure nanometer titanium dioxide photocatalyst improves the problem to a certain extent, but often cannot meet the ideal requirement of water treatment. Graphene is a typical two-dimensional layered high-conductivity material, and has very excellent load capacity and charge transport capacity. According to the invention, graphene modified nano titanium dioxide is utilized to convert a three-dimensional mode of heterogeneous crystal synthesis into a two-dimensional mode of a multilayer nano film structure, high-quality graphene is utilized as a key photon-generated carrier conducting layer, the photocatalysis efficiency is improved by a plurality of geometric orders, organic matters and water can be decomposed, oxygen can be generated, and visible light response is achieved. Graphene is a typical two-dimensional layered high-conductivity material, and has very excellent load capacity and charge transport capacity. The graphene is used for modifying the nano titanium dioxide heterostructure photocatalyst, the catalytic capability of the photocatalyst is improved to a new height, the recombination rate of photon-generated carriers is effectively reduced, and the nano coating can be applied to the current water treatment environment in a large scale. The invention adopts a real natural two-dimensional material, has a zero defect structure, is different from oxidized and reduced graphene, can ensure high-efficiency photon-generated carrier transfer, is not influenced by pollutants, and can carry out in-situ treatment on black and odorous water. Can increase the dissolved oxygen DO in the river gushing water. The photocatalyst is nano-scale titanium dioxide, and through the photocatalysis principle technology, toxic substances in water can be decomposed as long as visible light exists, water is decomposed to prepare oxygen, the water body recovers the self-purification capacity again, and black and odorous water is changed into clear water.
As a preferred technical scheme, the ammonia nitrogen removing filler comprises ceramsite and vermiculite in a weight ratio of 3: 1, and the surfaces of the ceramsite and the vermiculite are provided with nanoparticle layers, wherein the nanoparticle layers contain graphene oxide, activated zeolite powder and carbon fiber powder.
As a preferable technical scheme, the thickness of the ammonia nitrogen removing filler is 2.5 cm.
In the invention, as a preferred technical scheme, the weight percentage of the nano particles in the polyurethane biological sponge filler is as follows: 0.01-1 parts of graphene oxide; 2-20 parts of activated zeolite powder; 1-6 of carbon fiber powder.
As a preferable technical scheme, the ammonia nitrogen removal filler is prepared by a preparation method comprising the following steps:
grinding graphene oxide, and drying at 115 ℃ for 6.5h until the graphene oxide is completely dried; weighing activated zeolite powder, adding graphene oxide and the activated zeolite powder into a melamine resin adhesive, heating in a water bath at 50-60 ℃, and stirring and dispersing for 30-40 minutes at the speed of 100-; weighing carbon fiber powder, adding the carbon fiber powder into the solution, heating to 65-75 ℃, and stirring and dispersing at the speed of 120-; and then adding the ceramsite and the vermiculite into the solution, stirring for 20-30 minutes, attaching the liquid on the surface layers of the ceramsite and the vermiculite, taking out the ceramsite and the vermiculite, dispersing and airing to obtain the ammonia nitrogen removal filler. The activated zeolite powder is prepared by high-temperature roasting of molecular sieve raw powder. Because the molecular sieve raw powder loses most of moisture in the high-temperature roasting process, the activated zeolite powder has strong activity and can be directly applied to production as an adsorbent with selective adsorption. The activated zeolite powder can adsorb impurities such as moisture and the like which affect the quality of the product under the condition of not changing the physical and chemical properties of the product. Graphene oxide is a product of chemically oxidizing and stripping graphite powder, and is a single atomic layer and can be expanded to tens of microns in the transverse dimension at any time. Graphene oxide can be considered a non-traditional soft material with properties of polymers, colloids, films, and amphiphilic molecules. Graphene oxide has long been considered as a hydrophilic substance because of its superior dispersibility in water, but related experimental results show that graphene oxide is actually amphiphilic, exhibiting a distribution of hydrophilic to hydrophobic properties from the edge to the center of a graphene sheet. Therefore, the graphene oxide may exist at an interface as a surfactant and reduce energy between interfaces. Its hydrophilicity is widely recognized. The graphene oxide has high specific surface area and rich functional groups on the surface, and plays an important role in the adsorption and activation of strains in the invention. The carbon fiber powder, also called milled carbon fiber, is isometric cylindrical particles obtained by carrying out special technical surface treatment, grinding, micro screening, screening and high-temperature drying on high-strength high-modulus carbon fiber filaments, reserves a plurality of excellent properties of the carbon fiber, has a fine shape, a pure surface and a large specific surface area, is easy to be wetted by resin and dispersed, and is a composite material filler with excellent properties. The invention provides the composition of the ammonia nitrogen removal filler and the nano particles, and improves the chemical stability, the ageing resistance and the like of the ammonia nitrogen removal filler. Meanwhile, the enzyme carrier has a reactive functional group, and an active group can act with amino acid residues of a microbial peptide chain to form ionic bond or covalent bond, so that the microbes and the enzymes are fixed on the carrier. Has the advantages of high porosity, abrasion resistance, good hydrophilicity, high microorganism attachment rate and the like. And the introduction of the 'suspension space' on the carrier aims to reduce space obstacle, provide wide metabolism proliferation space for immobilized microorganisms, ensure that sewage, air and microorganisms are fully contacted and exchanged, and a biological membrane can keep good activity and space variability and cannot be adhered and agglomerated. The method has the characteristics of large specific surface area, high biomass in unit volume, uniform contact, high mass transfer speed, low pressure loss and the like. The biomass can maintain high concentration biomass, so that the method has the advantages of large volume load, small occupied area, low construction cost, large impact load resistance, no sludge expansion, high oxygen utilization rate, low operation cost and the like, and is particularly suitable for treating the black and odorous water body in the river. The three-dimensional porous structure of the ammonia nitrogen removal filler carrier can enable microbial populations with different aerobic degrees to propagate and grow, microbes attached to the outside can quickly consume dissolved oxygen in a water body and transfer metabolites, microbes in the middle of the carrier continue to decompose upper metabolites, the dissolved oxygen is further consumed, when the internal filler structure is reached, an anaerobic microbial population is formed, and therefore the carrier can achieve anaerobic, anoxic and aerobic microbial structures from the inside to the outside.
As a preferred technical solution, in the present invention, the domesticated plant-derived microorganism is attached to an electrode grid, and the specific steps include:
preparing the following raw materials in parts by weight: 100 parts of pure water, 150 parts of ammonia nitrogen removal filler and 200 parts of plant source culture medium, 0.5-5 parts of domesticated plant source microorganism and 0.3-2 parts of domesticated plant source microorganism;
100 parts of purified water is added into a culture fermentation container, one third of the ammonia nitrogen removal filler is paved at the bottom of the culture fermentation container, and the culture fermentation container is stood for 15 to 30 minutes;
adding 0.5-5 parts of the plant source culture medium, and uniformly stirring;
adding 0.3-2 parts of the domesticated plant source microorganism, and uniformly stirring;
fermenting at 35 deg.C for 24-48 hr, and oxygenating and aerating once every 15-30 min;
then adding one third of the filler for removing ammonia nitrogen, fermenting for 8-24 hours at constant temperature of 30 ℃, and oxygenating and aerating once every 30-60 minutes;
finally, adding the rest of the filler for removing ammonia nitrogen, naturally fermenting for 12-16 hours, and carrying out oxygen charging and aeration once every 120-240 minutes;
and connecting the anode and the cathode into a direct current power supply, keeping for 12-15 hours on the basis of 0.5V voltage, and then keeping for 5-8 hours on the basis of 1.8V voltage to realize that the domesticated plant source microorganism is attached to the surface layer of the ammonia nitrogen removal filler.
As a preferable technical scheme, the graphite carbon felt is a polyacrylonitrile-based (PAN-based) graphite felt with the thickness of 0.5 cm.
As a preferred technical scheme, when the electrode net rack is installed, a galvanized iron wire, an oxygen increasing net, an ammonia nitrogen removing filler, a graphite carbon felt, an ammonia nitrogen removing filler and an oxygen increasing net are sequentially arranged from top to bottom.
As a preferred technical scheme, when the electrode net rack is connected with a power supply in normal work, firstly, a copper wire cable is used for connecting an anode, a cathode and a direct current power supply, and an external load is used for adjusting the connected voltage value, wherein the voltage of 0.5V is used for processing for 3-5 days, the voltage of 1V is used for processing for 2-3 days, the voltage of 2V is used for processing for 1-3 days, and the steps are repeated until the water quality is optimized.
As a preferred technical scheme, in the invention, the direct current power supply adopts a solar photovoltaic panel or a storage battery connected with the solar photovoltaic panel.
The inventors found in long-term studies that: the properties of the black and odorous water body organic matter, such as odor and color, are determined by the specific atoms or groups of atoms they contain. The difficult degradability of these organic substances is also determined by their corresponding specific atomic groups. According to chemical structure analysis, a plurality of organic matters which are difficult to be biochemically degraded have electrophilic groups on the molecular structure, have strong electronegativity and are difficult to be continuously oxidized; on the contrary, after the electrophilic substituent is removed or the structural double bond is broken, the biochemical performance is greatly improved.
Aiming at the difficulties, the oxygen increasing net is adopted as an anode material, microorganisms can be attached to the surface of the ammonia nitrogen removing filler, and can also be attached to the surface of the oxygen increasing net, the area of the oxygen increasing net is large, the attachment amount is large, the loading of metal nano particles, carbon nano tubes and other substances on the surface of an electrode is stable, the attachment and direct and rapid electronic transmission of a biological film can be realized by comprehensively and systematically utilizing the characteristics of the nano material such as size effect, surface effect and the like, more and more stable extracellular electrons can be received to improve the performance of the anode, and more vacancies matched with bacteria are provided.
The invention sets specific domestication aiming at the strain by domesticating the purchased animal source microorganism, shortens the domestication time, increases the membrane quantity quickly and reduces the internal resistance, and simultaneously, the optimum ecological niche of various microorganisms in the symbiotic membrane environment of the mixed strain at present is beneficial to the selection and the culture of the strain.
The inventor finds that: the electron transfer rate of the electrogenic microorganisms decreases exponentially with the increase of the electron transfer distance. The outer shell of the enzyme molecule protein can shield the direct electron transfer from the active center to the electrode, and the introduction of the mediator can provide an effective electron transfer channel to a certain extent. However, this increases the distance of electron transfer, and the overall effect is not satisfactory.
Therefore, the inventors have selected an appropriate mixed species and, at the same time, have acclimatized and electrically acclimatized microorganisms by a specific method, and have selected highly active microorganisms, particularly, have searched for microorganisms which themselves produce redox mediators and microorganisms having membrane-bound electron transport compounds. The invention can make the adaptation of microbe to new environment faster, and the invention can develop the microstructure change of electrode surface and bacteria surface under different current.
The invention researches a purpose-made filler for removing ammonia nitrogen, and improves the structure and the performance of the filler by utilizing a microorganism immobilization technology, a nano particle loading technology and the like.
Therefore, the invention generates electrons through the electrolysis of microorganisms, thereby destroying electrophilic groups of refractory organic matters. When microorganisms are electrolyzed, countless micro-battery systems are formed due to the difference in electrode potential between the positive electrode and the negative electrode. Both the anode and cathode of the micro-battery system can contribute to the treatment of electrophilic groups of refractory organics. The capability of the anode to release electrons after the microbial reaction can lead part of the cyclic and long-chain organic matters which are difficult to degrade to be decomposed into small molecular organic matters which are easy to biodegrade, and the small molecular organic matters are also easy to be absorbed by the microbes. The microbial electrolysis reaction generates a large amount of nascent state [ H ] and [ O ], and under the condition of weak acidity, the active components can generate oxidation-reduction reaction with a plurality of components in the wastewater, and can also generate chain scission degradation on organic macromolecules, thereby improving the possibility of the organic macromolecules being degraded by the microbes. The microbial electrolysis process apparently can basically accomplish the task of treating electrophilic groups of refractory organics. However, there are problems in practical use, above all because the reaction speed of the bioelectrolysis combination is not fast. To solve both problems, air must be continuously injected into the water to provide oxygen in the chemical reaction. The oxygen increasing net of the invention solves the problems encountered in the microorganism electrolysis. The photocatalyst of the oxygen increasing net adopts nano-scale titanium dioxide, and can decompose toxic substances in water as long as visible light exists through the technology of the photocatalytic principle, so that oxygen is produced by decomposing water, and the substances obtain electrons at the cathode to generate a reduction reaction. The addition of metals such as copper and the like forms galvanic corrosion, and an infinite number of tiny primary batteries are formed, so that the rate of releasing electrons by iron is enhanced, and the capability of reducing and converting pollutants and the reaction rate are improved. The nascent state iron ions generated by the galvanized iron wires have the function of coagulating sedimentation. Elemental iron (zero valent) produces large amounts of Fe2+ and Fe3+ when used to treat wastewater, and in the presence of oxygen, they form Fe (OH)2 and Fe (OH)3, both of which have strong flocculation properties. Therefore, the original suspended matters in the wastewater and insoluble substances generated by micro-electrolysis can be adsorbed, condensed and then settled, so that the wastewater is purified, and the method can also be realized in an iron-carbon method.
And (3) iron-carbon primary battery reaction:
anode: fe-2e → Fe2+E(Fe/Fe2+)＝0.44V
Cathode: 2H +2e → H2E(H﹢/H2)＝0.00V
In the presence of oxygen, the cathodic reaction is as follows:
O2+4H﹢+4e→2H2O E(O2)＝1.23V
O2+2H2O+4e→4OH﹣+E(O2/OH﹣)＝0.41V
after the technical scheme is adopted, the invention has the beneficial effects that:
the invention breaks the bottleneck of treating the river black and odorous water body by only depending on microorganisms, realizes effective biofilm formation on the strains by selecting proper strains, domesticating the strains and selecting proper electrode net racks, thereby improving the removal effect on ammonia nitrogen and total nitrogen in the river black and odorous water body and shortening the treatment period.
Drawings
Fig. 1 is a live view before river surge treatment in embodiment 1 of the present invention;
fig. 2 is a real view of the river inrush construction of embodiment 1 of the present invention;
fig. 3 is a real view after the river surge treatment in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples. The use and purpose of these exemplary embodiments are to illustrate the present invention, not to limit the actual scope of the present invention in any way, and not to limit the scope of the present invention in any way.
Example 1
A method for purifying a river black and odorous water body (shown in figure 1) by utilizing electrogenesis microorganism biofilm anode bioelectrolysis comprises the following steps:
firstly, collecting strains, and domesticating to obtain plant-derived microorganisms:
wherein, the strain comprises the following microorganisms: bacillus subtilis, saccharomycetes, bacillus licheniformis, phosphorus-accumulating bacteria, photosynthetic bacteria, EM bacteria, trichoderma viride, streptococcus faecalis, lactic acid bacteria, lactobacillus plantarum, lactobacillus acidophilus, nitrobacteria, denitrifying bacteria, nitrosobacteria, bacillus brevis, bacillus coagulans and bacillus natto (all of which are commercially available microorganisms of animal origin); and the microorganisms contained in the mixed strain are domesticated into plant-derived microorganisms, and the short-chain fatty acid is mixed in the mixed strain.
The domestication of the microorganism adopts a method comprising the following steps:
A. acclimatization conditions of plant-derived microorganisms:
1) 100 parts of purified water, wherein the conductivity must be 0;
2) 60 parts of plant source culture medium, which is prepared by high-temperature steaming and sterilizing 30 minutes in advance;
3) 6 parts of animal-derived microorganisms (commercially available) required for forming the mixed strain, and separating anaerobic microorganisms and aerobic microorganisms;
4) acclimating environment, sealing the container, only needing an ultraviolet lamp capable of generating ozone outside, simple and easy to operate, low in cost and free from complex sterile space;
B. acclimatization of plant source microorganisms:
1) adding 30 parts by weight of plant source culture medium into 100 parts by weight of purified water, adding 3 parts by weight of anaerobic microorganism (animal source anaerobic microorganism required for forming mixed strains), stirring uniformly, and fermenting at constant temperature of 35 ℃ for 24 hours in a sealed manner;
2) then adding 30 parts of plant source culture medium and 3 parts of aerobic microorganism (animal source aerobic microorganism required for forming mixed strains), uniformly stirring, fermenting at constant temperature of 30 ℃ for 12 hours, and oxygenating and aerating once every 15 minutes;
3) fermenting at constant temperature of 25 deg.C for 8 hr, and oxygenating and aerating once every 30 min;
4) naturally fermenting for 12 hours, oxygenating and aerating once every 120 minutes, and then adding short-chain fatty acid to obtain the mixed strain.
The mixed strain needs to be subjected to electric domestication treatment, and the method comprises the following steps: b, manufacturing a cuboid reaction tank by using insulating plastics, wherein one side of the cuboid reaction tank is provided with a carbon cloth as an anode, the other opposite side of the cuboid reaction tank is provided with a carbon cloth coated with a platinum-containing catalyst on the surface as a cathode, the anode and the cathode are respectively connected with an external circuit through a platinum wire and a copper wire, adding the product obtained in the step B into the cuboid reaction tank, culturing for 3 days at 35 ℃, then connecting the platinum wire and the copper wire into a 0.4V direct current power supply for 15 days, and finally connecting a 1.2V direct current power supply for 30 days; and finally, taking out the substance in the cuboid reaction tank, namely the domesticated plant source microorganism.
During the domestication process, the electromagnetism, the mobile phone and the radio must be shielded.
As shown in fig. 2, the acclimated plant-derived microorganisms are then attached to an electrode grid, and the electrode grid is installed in the river black and odorous water body:
the electrode net rack comprises a galvanized iron wire used as a cathode and an oxygen increasing net used as an anode, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt and the ammonia nitrogen removing filler are sequentially distributed between the cathode and the anode, and the anode is erected on the bottom layer of the river water body when the electrode net rack is installed and used. When the electrode net rack is installed, the galvanized iron wire, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt, the ammonia nitrogen removing filler and the oxygen increasing net are sequentially arranged from top to bottom
The oxygenation net is a graphene modified nano titanium dioxide photocatalyst fiber net and is prepared by the method comprising the following steps: (1) flake graphite is used as raw material, concentrated H is used2SO4And KMnO4Preparing graphite oxide as an oxidant by a two-step method, and preparing graphene oxide by ultrasonic dispersion; by solvothermal method at 180 ℃ with graphene oxide and Ti (OBu)4As an initial reactant, synthesizing a reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst in an ethanol solvent; (2) firstly, diluting butyl aluminate by absolute ethyl alcohol,and adding a mixed solution of glacial acetic acid, absolute ethyl alcohol and water, wherein the volume ratio of the water to the absolute ethyl alcohol in the mixed solution is 1: 10, putting the mixture into a mixer, starting stirring, heating to 70 ℃, stirring for 10 minutes to obtain stable, uniform, clear and transparent light yellow sol, then slowly adding the nano alumina suspension, and keeping the temperature at 40 ℃ to obtain a water-resistant and impact-resistant aluminum-based crosslinking agent; taking an aluminum-based crosslinking agent, heating the aluminum-based crosslinking agent to 50 ℃, slowly adding the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst suspension, wherein the aluminum-based crosslinking agent accounts for 0.1 wt% of the total weight of the mixture, and continuously stirring for 15 minutes after the aluminum-based crosslinking agent is added to obtain a homogeneous mixture, wherein the technical requirements of the homogeneous mixture are as follows: shape, liquid 2-5%; crystalline, anatase; content, 97.5%; the grain diameter is less than or equal to 10 nm; surface groups, carboxyl, carbonate; the light response range is 300nm-550 nm; surface properties, hydrophilic; pH (1% aqueous solution), 3-4; specific surface area, 400m2(ii)/g; then adding the homogeneous mixture into fiber slurry for producing a high-density polyethylene fiber net or attaching the homogeneous mixture to the high-density polyethylene fiber net, wherein the size of the high-density polyethylene fiber net can be selected according to the requirement, the width of the high-density polyethylene fiber net is 1 m, and the high-density polyethylene fiber net with the nano photocatalytic film coating is manufactured, and the thickness of the nano photocatalytic film coating is 0.5 um; and (3) attaching the homogeneous mixture obtained in the step (1) to the surface of the high-density polyethylene fiber net in a spraying mode, wherein a high-pressure spray gun is adopted during spraying, and a small amount of uniform spraying mode is adopted for multiple times.
(3) And (3) naturally drying the high-density polyethylene fiber net with the nano photocatalytic film coating obtained in the step (2) in the air, and then placing the net in a drying room for drying, wherein the drying temperature is 55 ℃, and the drying time is 25 hours, so that the graphene modified nano titanium dioxide photocatalyst high-density polyethylene fiber net is obtained.
In this embodiment, the thickness of the ammonia nitrogen removing filler is 2.5cm, and the ammonia nitrogen removing filler comprises ceramsite and vermiculite in a weight ratio of 3: 1, and the surfaces of the ceramsite and the vermiculite are provided with nanoparticle layers, wherein the nanoparticle layers contain graphene oxide, activated zeolite powder and carbon fiber powder. The weight percentage of the nano particles in the polyurethane biological sponge filler is as follows: 0.01 parts of graphene oxide; activating zeolite powder 2; carbon fiber powder 1. The ammonia nitrogen removal filler is prepared by a preparation method comprising the following steps: grinding graphene oxide, and drying at 115 ℃ for 6.5h until the graphene oxide is completely dried; weighing activated zeolite powder, adding graphene oxide and the activated zeolite powder into a melamine resin adhesive, heating in a water bath at 50 ℃, and stirring and dispersing for 30 minutes at 100 revolutions per minute to obtain a solution; weighing carbon fiber powder, adding the carbon fiber powder into the solution, heating to 65 ℃, and stirring and dispersing at the speed of 120 revolutions per minute for 40 minutes; and then adding the ceramsite and the vermiculite into the solution, stirring for 20 minutes, attaching the liquid on the surface layers of the ceramsite and the vermiculite, taking out the ceramsite and the vermiculite, dispersing and airing to obtain the ammonia nitrogen removal filler.
Attaching the domesticated plant source microorganism to an electrode net rack, and the specific steps comprise: preparing the following raw materials in parts by weight: 100 parts of pure water, 150 parts of ammonia nitrogen removal filler, 0.5 part of plant source culture medium and 0.3 part of domesticated plant source microorganism; adding 100 parts of purified water into a culture fermentation container, paving one third of the ammonia nitrogen removal filler at the bottom of the culture fermentation container, and standing for 15 minutes; adding 0.5 part of the plant source culture medium, and uniformly stirring; adding 0.3 part of the domesticated plant source microorganism, and uniformly stirring; fermenting at constant temperature of 35 deg.C for 24 hr, and oxygenating and aerating once every 15 min; then adding one third of the filler for removing ammonia nitrogen, fermenting for 8 hours at the constant temperature of 30 ℃, and oxygenating and aerating once every 30 minutes; finally, adding the rest of the filler for removing ammonia nitrogen, naturally fermenting for 12 hours, and oxygenating and aerating once every 120 minutes; and connecting the anode and the cathode into a direct current power supply, keeping for 12 hours on the basis of 0.5V voltage, and then keeping for 5 hours on the basis of 1.8V voltage, so that the domesticated plant source microorganism is attached to the surface layer of the ammonia nitrogen removal filler.
In this embodiment, the graphite carbon felt is a polyacrylonitrile-based (PAN-based) graphite felt, and the thickness is 0.5 cm.
And finally, introducing current into the electrode net frame:
when the electrode net rack is connected with a power supply in normal work, firstly, a copper wire cable is used for connecting an anode, a cathode and a direct current power supply, and an external load is used for adjusting the connected voltage value, wherein 0.5V voltage is used for processing for 3 days, 1V voltage is used for processing for 2 days, and 2V voltage is used for processing for 1 day, and the process is circulated until the water quality is optimized; the direct current power supply adopts a solar photovoltaic panel or a storage battery connected with the solar photovoltaic panel.
The live view after processing is shown in fig. 3.
Example 2
A method for purifying a river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis comprises the following steps:
firstly, collecting strains, and domesticating to obtain plant-derived microorganisms:
wherein, the strain comprises the following microorganisms: bacillus subtilis, saccharomycetes, bacillus licheniformis, phosphorus-accumulating bacteria, photosynthetic bacteria, EM bacteria, trichoderma viride, streptococcus faecalis, lactic acid bacteria, lactobacillus plantarum, lactobacillus acidophilus, nitrobacteria, denitrifying bacteria, nitrosobacteria, bacillus brevis, bacillus coagulans and bacillus natto (all of which are commercially available microorganisms of animal origin); and the microorganisms contained in the mixed strain are domesticated into plant-derived microorganisms, and the short-chain fatty acid is mixed in the mixed strain.
The domestication of the microorganism adopts a method comprising the following steps:
A. acclimatization conditions of plant-derived microorganisms:
1) 100 parts of purified water, wherein the conductivity must be 0;
2) 80 parts of plant source culture medium, and preparing by 30 minutes in advance through high-temperature cooking and disinfection;
3) 20 parts of animal-derived microorganisms (commercially available) required for forming the mixed strain, and separating anaerobic microorganisms and aerobic microorganisms;
4) acclimating environment, sealing the container, only needing an ultraviolet lamp capable of generating ozone outside, simple and easy to operate, low in cost and free from complex sterile space;
B. acclimatization of plant source microorganisms:
1) adding 40 parts by weight of plant source culture medium into 100 parts by weight of purified water, adding 10 parts by weight of anaerobic microorganism (animal source anaerobic microorganism required for forming mixed strains), stirring uniformly, and fermenting at constant temperature of 35 ℃ for 48 hours in a sealed manner;
2) adding 40 parts of plant source culture medium and 10 parts of aerobic microorganism (animal source aerobic microorganism required for forming mixed strains), stirring uniformly, fermenting at constant temperature of 30 ℃ for 24 hours, and oxygenating and aerating once every 30 minutes;
3) fermenting at constant temperature of 25 deg.C for 12 hr, and oxygenating and aerating once every 60 min;
4) naturally fermenting for 24 hr, oxygenating and aerating once every 240 min, and adding short chain fatty acid to obtain mixed strain.
The mixed strain needs to be subjected to electric domestication treatment, and the method comprises the following steps: b, manufacturing a cuboid reaction tank by using insulating plastics, wherein one side of the cuboid reaction tank is provided with carbon cloth as an anode, the other opposite side of the cuboid reaction tank is provided with carbon cloth coated with a platinum-containing catalyst on the surface as a cathode, the anode and the cathode are respectively connected with an external circuit through a platinum wire and a copper wire, adding the product obtained in the step B into the cuboid reaction tank, culturing for 5 days at 37 ℃, then connecting the platinum wire and the copper wire into a 0.4V direct current power supply for 25 days, and finally connecting a 1.2V direct current power supply for 35 days; and finally, taking out the substance in the cuboid reaction tank, namely the domesticated plant source microorganism.
During the domestication process, the electromagnetism, the mobile phone and the radio must be shielded.
Then, attaching the domesticated plant source microorganisms to an electrode net rack, and installing the electrode net rack in the river black and odorous water body:
the electrode net rack comprises a galvanized iron wire used as a cathode and an oxygen increasing net used as an anode, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt and the ammonia nitrogen removing filler are sequentially distributed between the cathode and the anode, and the anode is erected on the bottom layer of the river water body when the electrode net rack is installed and used. When the electrode net rack is installed, the galvanized iron wire, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt, the ammonia nitrogen removing filler and the oxygen increasing net are sequentially arranged from top to bottom
The oxygenation net is a graphene modified nano titanium dioxide photocatalyst fiber net and is prepared by the method comprising the following steps: (1) flake graphite is used as raw material, concentrated H is used2SO4And KMnO4Preparing graphite oxide as an oxidant by a two-step method, and preparing graphene oxide by ultrasonic dispersion; by solvothermal method at 180 ℃ with graphene oxide and Ti (OBu)4As an initial reactant, synthesizing a reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst in an ethanol solvent; (2) firstly diluting butyl aluminate by absolute ethyl alcohol, then adding a mixed solution of glacial acetic acid, absolute ethyl alcohol and water, wherein the volume ratio of water to absolute ethyl alcohol in the mixed solution is 1: 10, putting the mixture into a mixer, starting stirring, heating to 80 ℃, stirring for 30 minutes to obtain stable, uniform, clear and transparent light yellow sol, then slowly adding the nano alumina suspension, and keeping the temperature at 40 ℃ to obtain a water-resistant and impact-resistant aluminum-based crosslinking agent; taking an aluminum-based cross-linking agent, heating the aluminum-based cross-linking agent to 50 ℃, slowly adding the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst suspension, wherein the aluminum-based cross-linking agent accounts for 2 wt% of the total weight of the mixture, and continuously stirring for 20 minutes after the aluminum-based cross-linking agent is added, so as to obtain a homogeneous mixture, wherein the technical requirements of the homogeneous mixture are as follows: shape, liquid 2-5%; crystalline, anatase; content, 97.5%; the grain diameter is less than or equal to 10 nm; surface groups, carboxyl, carbonate; the light response range is 300nm-550 nm; surface properties, hydrophilic; pH (1% aqueous solution), 3-4; specific surface area, 400m2(ii)/g; then adding the homogeneous mixture into fiber slurry for producing a high-density polyethylene fiber net or attaching the homogeneous mixture to the high-density polyethylene fiber net, wherein the size of the high-density polyethylene fiber net can be selected according to the requirement, the width of the high-density polyethylene fiber net is 2 meters, and the high-density polyethylene fiber net with the nano photocatalytic film coating is manufactured, and the thickness of the nano photocatalytic film coating is 50 microns; directly leaching the high-density polyethylene fiber net in a special barrel filled with the homogeneous mixture for multiple times, and directly leaching the high-density polyethylene fiber net in the special barrel filled with the homogeneous mixture for 3 times;
(3) and (3) naturally drying the high-density polyethylene fiber net with the nano photocatalytic film coating obtained in the step (2) in the air, and then placing the net in a drying room for drying, wherein the drying temperature is 65 ℃, and the drying time is 35 hours, so that the graphene modified nano titanium dioxide photocatalyst high-density polyethylene fiber net is obtained.
In this embodiment, the thickness of the ammonia nitrogen removing filler is 2.5cm, and the ammonia nitrogen removing filler comprises ceramsite and vermiculite in a weight ratio of 3: 1, and the surfaces of the ceramsite and the vermiculite are provided with nanoparticle layers, wherein the nanoparticle layers contain graphene oxide, activated zeolite powder and carbon fiber powder. The weight percentage of the nano particles in the polyurethane biological sponge filler is as follows: 1, graphene oxide; activated zeolite powder 20; carbon fiber powder 6. The ammonia nitrogen removal filler is prepared by a preparation method comprising the following steps: grinding graphene oxide, and drying at 115 ℃ for 6.5h until the graphene oxide is completely dried; weighing activated zeolite powder, adding graphene oxide and the activated zeolite powder into a melamine resin adhesive, heating in a water bath at 60 ℃, and stirring and dispersing for 40 minutes at 150 revolutions per minute to obtain a solution; weighing carbon fiber powder, adding the carbon fiber powder into the solution, heating to 75 ℃, and stirring and dispersing at the speed of 160 revolutions per minute for 60 minutes; and then adding the ceramsite and the vermiculite into the solution, stirring for 30 minutes, attaching the liquid on the surface layers of the ceramsite and the vermiculite, taking out the ceramsite and the vermiculite, dispersing and airing to obtain the ammonia nitrogen removal filler.
Attaching the domesticated plant source microorganism to an electrode net rack, and the specific steps comprise: preparing the following raw materials in parts by weight: 100 parts of pure water, 200 parts of ammonia nitrogen removal filler, 5 parts of plant source culture medium and 2 parts of domesticated plant source microorganism; 100 parts of purified water is added into a culture fermentation container, one third of the ammonia nitrogen removal filler is paved at the bottom of the culture fermentation container, and the culture fermentation container is stood for 30 minutes; adding 5 parts of the plant source culture medium, and uniformly stirring; adding 2 parts of the domesticated plant source microorganism, and uniformly stirring; fermenting at constant temperature of 35 deg.C for 48 hr, and oxygenating and aerating once every 30 min; then adding one third of the filler for removing ammonia nitrogen, fermenting for 24 hours at the constant temperature of 30 ℃, and oxygenating and aerating once every 60 minutes; finally, adding the rest filler for removing ammonia nitrogen, naturally fermenting for 16 hours, and oxygenating and aerating once every 240 minutes; and connecting the anode and the cathode into a direct current power supply, keeping for 15 hours on the basis of 0.5V voltage, and then keeping for 8 hours on the basis of 1.8V voltage, so that the domesticated plant source microorganism is attached to the surface layer of the ammonia nitrogen removal filler.
In this embodiment, the graphite carbon felt is a polyacrylonitrile-based (PAN-based) graphite felt, and the thickness is 0.5 cm.
And finally, introducing current into the electrode net frame:
when the electrode net rack is connected with a power supply in normal work, firstly, a copper wire cable is used for connecting an anode, a cathode and a direct current power supply, and an external load is used for adjusting the connected voltage value, wherein 0.5V voltage is used for processing for 5 days, 1V voltage is used for processing for 3 days, 2V voltage is used for processing for 3 days, and the steps are repeated until the water quality is optimized; the direct current power supply adopts a solar photovoltaic panel or a storage battery connected with the solar photovoltaic panel.
Example 3
A method for purifying a river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis comprises the following steps:
firstly, collecting strains, and domesticating to obtain plant-derived microorganisms:
wherein, the strain comprises the following microorganisms: bacillus subtilis, saccharomycetes, bacillus licheniformis, phosphorus-accumulating bacteria, photosynthetic bacteria, EM bacteria, trichoderma viride, streptococcus faecalis, lactic acid bacteria, lactobacillus plantarum, lactobacillus acidophilus, nitrobacteria, denitrifying bacteria, nitrosobacteria, bacillus brevis, bacillus coagulans and bacillus natto (all of which are commercially available microorganisms of animal origin); and the microorganisms contained in the mixed strain are domesticated into plant-derived microorganisms, and the short-chain fatty acid is mixed in the mixed strain.
The domestication of the microorganism adopts a method comprising the following steps:
A. acclimatization conditions of plant-derived microorganisms:
1) 100 parts of purified water, wherein the conductivity must be 0;
2) 70 parts of plant source culture medium, and preparing by 30 minutes in advance through high-temperature cooking and disinfection;
3) 13 parts of animal-derived microorganisms (commercially available) required for forming the mixed strain, and separating anaerobic microorganisms and aerobic microorganisms;
4) acclimating environment, sealing the container, only needing an ultraviolet lamp capable of generating ozone outside, simple and easy to operate, low in cost and free from complex sterile space;
B. acclimatization of plant source microorganisms:
1) adding 30-40 parts by weight of plant source culture medium into 100 parts of purified water, adding 6 parts of anaerobic microorganism (animal source anaerobic microorganism required for forming mixed strains), stirring uniformly, and fermenting at constant temperature of 35 ℃ for 31 hours in a sealing manner;
2) adding 35 parts of plant source culture medium and 6 parts of aerobic microorganism (animal source aerobic microorganism required for forming mixed strains), stirring uniformly, fermenting at constant temperature of 30 ℃ for 18 hours, and oxygenating and aerating once every 25 minutes;
3) fermenting at constant temperature of 25 deg.C for 10 hr, and oxygenating and aerating once every 45 min;
4) naturally fermenting for 18 hours, oxygenating and aerating once every 180 minutes, and then adding short-chain fatty acid to obtain the mixed strain.
The mixed strain needs to be subjected to electric domestication treatment, and the method comprises the following steps: b, manufacturing a cuboid reaction tank by using insulating plastics, wherein one side of the cuboid reaction tank is provided with carbon cloth as an anode, the other opposite side of the cuboid reaction tank is provided with carbon cloth coated with a platinum-containing catalyst on the surface as a cathode, the anode and the cathode are respectively connected with an external circuit through a platinum wire and a copper wire, adding the product obtained in the step B into the cuboid reaction tank, culturing for 4 days at 36 ℃, then connecting the platinum wire and the copper wire into a 0.4V direct current power supply for 20 days, and finally connecting a 1.2V direct current power supply for 32 days; and finally, taking out the substance in the cuboid reaction tank, namely the domesticated plant source microorganism.
During the domestication process, the electromagnetism, the mobile phone and the radio must be shielded.
Then, attaching the domesticated plant source microorganisms to an electrode net rack, and installing the electrode net rack in the river black and odorous water body:
the electrode net rack comprises a galvanized iron wire used as a cathode and an oxygen increasing net used as an anode, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt and the ammonia nitrogen removing filler are sequentially distributed between the cathode and the anode, and the anode is erected on the bottom layer of the river water body when the electrode net rack is installed and used. When the electrode net rack is installed, the galvanized iron wire, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt, the ammonia nitrogen removing filler and the oxygen increasing net are sequentially arranged from top to bottom
The oxygenation net is a graphene modified nano titanium dioxide photocatalyst fiber net and is prepared by the method comprising the following steps: (1) flake graphite is used as raw material, concentrated H is used2SO4And KMnO4Preparing graphite oxide as an oxidant by a two-step method, and preparing graphene oxide by ultrasonic dispersion; by solvothermal method at 180 ℃ with graphene oxide and Ti (OBu)4As an initial reactant, synthesizing a reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst in an ethanol solvent; (2) firstly diluting butyl aluminate by absolute ethyl alcohol, then adding a mixed solution of glacial acetic acid, absolute ethyl alcohol and water, wherein the volume ratio of water to absolute ethyl alcohol in the mixed solution is 1: 10, putting the mixture into a mixer, starting stirring, heating to 75 ℃, stirring for 20 minutes to obtain stable, uniform, clear and transparent light yellow sol, then slowly adding the nano alumina suspension, and keeping the temperature at 40 ℃ to obtain a water-resistant and impact-resistant aluminum-based crosslinking agent; taking an aluminum-based crosslinking agent, heating the aluminum-based crosslinking agent to 50 ℃, slowly adding the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst suspension, wherein the aluminum-based crosslinking agent accounts for 1 wt% of the total weight of the mixture, and continuously stirring for 18 minutes after the aluminum-based crosslinking agent is added to obtain a homogeneous mixture, wherein the technical requirements of the homogeneous mixture are as follows: shape, liquid 2-5%; crystalline, anatase; content, 97.5%; the grain diameter is less than or equal to 10 nm; surface groups, carboxyl, carbonate; the light response range is 300nm-550 nm; surface properties, hydrophilic; pH (1% aqueous solution), 3-4; specific surface area, 400m2(ii)/g; then adding the homogeneous mixture into fiber slurry for producing a high-density polyethylene fiber net or attaching the homogeneous mixture to the high-density polyethylene fiber net, wherein the size of the high-density polyethylene fiber net can be selected according to the requirement, the width of the high-density polyethylene fiber net is 1.5 m, and the high-density polyethylene fiber net with the nano photocatalytic film coating is manufactured, and the thickness of the nano photocatalytic film coating is 24 um;
and (3) attaching the homogeneous mixture obtained in the step (1) to the surface of the high-density polyethylene fiber net in a spraying mode, wherein a high-pressure spray gun is adopted during spraying, and a small amount of uniform spraying mode is adopted for multiple times. Here, the plurality of times means at least three times, and the small amount means that the amount sprayed per time does not exceed one third of the total amount of the spray paint;
(3) and (3) naturally drying the high-density polyethylene fiber net with the nano photocatalytic film coating obtained in the step (2) in the air, and then placing the net in a drying room for drying at the drying temperature of 60 ℃ for 30 hours to obtain the graphene modified nano titanium dioxide photocatalyst high-density polyethylene fiber net.
In this embodiment, the thickness of the ammonia nitrogen removing filler is 2.5cm, and the ammonia nitrogen removing filler comprises ceramsite and vermiculite in a weight ratio of 3: 1, and the surfaces of the ceramsite and the vermiculite are provided with nanoparticle layers, wherein the nanoparticle layers contain graphene oxide, activated zeolite powder and carbon fiber powder. The weight percentage of the nano particles in the polyurethane biological sponge filler is as follows: 0.5 parts of graphene oxide; activating zeolite powder 10; carbon fiber powder 3. The ammonia nitrogen removal filler is prepared by a preparation method comprising the following steps: grinding graphene oxide, and drying at 115 ℃ for 6.5h until the graphene oxide is completely dried; weighing activated zeolite powder, adding graphene oxide and the activated zeolite powder into a melamine resin adhesive, heating in a water bath at 55 ℃, and stirring and dispersing for 30-40 minutes at 120 revolutions per minute to obtain a solution; weighing carbon fiber powder, adding the carbon fiber powder into the solution, heating to 70 ℃, and stirring and dispersing at the speed of 140 revolutions per minute for 40-60 minutes; and then adding the ceramsite and the vermiculite into the solution, stirring for 25 minutes, attaching the liquid on the surface layers of the ceramsite and the vermiculite, taking out the ceramsite and the vermiculite, dispersing and airing to obtain the ammonia nitrogen removal filler.
Attaching the domesticated plant source microorganism to an electrode net rack, and the specific steps comprise: preparing the following raw materials in parts by weight: 100 parts of pure water, 180 parts of ammonia nitrogen removal filler, 2.5 parts of plant source culture medium and 1.5 parts of domesticated plant source microorganism; 100 parts of purified water is added into a culture fermentation container, one third of the ammonia nitrogen removal filler is paved at the bottom of the culture fermentation container, and the culture fermentation container is stood for 20 minutes; adding 2.5 parts of the plant source culture medium, and uniformly stirring; adding 1.5 parts of the domesticated plant source microorganism, and uniformly stirring; fermenting at constant temperature of 35 deg.C for 30 hr, and oxygenating and aerating once every 20 min; then adding one third of the filler for removing ammonia nitrogen, fermenting for 16 hours at the constant temperature of 30 ℃, and oxygenating and aerating once every 45 minutes; finally, adding the rest filler for removing ammonia nitrogen, naturally fermenting for 14 hours, and oxygenating and aerating once every 180 minutes; and connecting the anode and the cathode into a direct current power supply, continuing for 13 hours on the basis of 0.5V voltage, and then maintaining for 6 hours on the basis of 1.8V voltage, so that the domesticated plant source microorganism is attached to the surface layer of the ammonia nitrogen removal filler.
In this embodiment, the graphite carbon felt is a polyacrylonitrile-based (PAN-based) graphite felt, and the thickness is 0.5 cm.
And finally, introducing current into the electrode net frame:
when the electrode net rack is connected with a power supply in normal work, firstly, a copper wire cable is used for connecting an anode, a cathode and a direct current power supply, and an external load is used for adjusting the connected voltage value, wherein 0.5V voltage is used for treating for 4 days, 1V voltage is used for treating for 3 days, 2V voltage is used for treating for 2 days, and the steps are circulated until the water quality is optimized; the direct current power supply adopts a solar photovoltaic panel or a storage battery connected with the solar photovoltaic panel.
Example 4
A method for purifying a river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis comprises the following steps:
firstly, collecting strains, and domesticating to obtain plant-derived microorganisms:
wherein, the strain comprises the following microorganisms: bacillus subtilis, saccharomycetes, bacillus licheniformis, phosphorus-accumulating bacteria, photosynthetic bacteria, EM bacteria, trichoderma viride, streptococcus faecalis, lactic acid bacteria, lactobacillus plantarum, lactobacillus acidophilus, nitrobacteria, denitrifying bacteria, nitrosobacteria, bacillus brevis, bacillus coagulans and bacillus natto (all of which are commercially available microorganisms of animal origin); and the microorganisms contained in the mixed strain are domesticated into plant-derived microorganisms, and the short-chain fatty acid is mixed in the mixed strain.
The domestication of the microorganism adopts a method comprising the following steps:
A. acclimatization conditions of plant-derived microorganisms:
1) 100 parts of purified water, wherein the conductivity must be 0;
2) 60 parts of plant source culture medium, which is prepared by high-temperature steaming and sterilizing 30 minutes in advance;
3) 20 parts of animal-derived microorganisms (commercially available) required for forming the mixed strain, and separating anaerobic microorganisms and aerobic microorganisms;
4) acclimating environment, sealing the container, only needing an ultraviolet lamp capable of generating ozone outside, simple and easy to operate, low in cost and free from complex sterile space;
B. acclimatization of plant source microorganisms:
1) adding 30 parts by weight of plant source culture medium into 100 parts by weight of purified water, adding 10 parts by weight of anaerobic microorganism (animal source anaerobic microorganism required for forming mixed strains), stirring uniformly, and fermenting at constant temperature of 35 ℃ for 24 hours in a sealing manner;
2) adding 40 parts of plant source culture medium and 3 parts of aerobic microorganism (animal source aerobic microorganism required for forming mixed strains), stirring uniformly, fermenting at constant temperature of 30 ℃ for 24 hours, and oxygenating and aerating once every 15 minutes;
3) fermenting at constant temperature of 25 deg.C for 12 hr, and oxygenating and aerating once every 30 min;
4) naturally fermenting for 24 hr, oxygenating and aerating once every 120 min, and adding short chain fatty acid to obtain mixed strain.
The mixed strain needs to be subjected to electric domestication treatment, and the method comprises the following steps: b, manufacturing a cuboid reaction tank by using insulating plastics, wherein one side of the cuboid reaction tank is provided with carbon cloth as an anode, the other opposite side of the cuboid reaction tank is provided with carbon cloth coated with a platinum-containing catalyst on the surface as a cathode, the anode and the cathode are respectively connected with an external circuit through a platinum wire and a copper wire, adding the product obtained in the step B into the cuboid reaction tank, culturing for 3 days at 37 ℃, then connecting the platinum wire and the copper wire into a 0.4V direct current power supply for 25 days, and finally connecting a 1.2V direct current power supply for 30 days; and finally, taking out the substance in the cuboid reaction tank, namely the domesticated plant source microorganism.
During the domestication process, the electromagnetism, the mobile phone and the radio must be shielded.
Then, attaching the domesticated plant source microorganisms to an electrode net rack, and installing the electrode net rack in the river black and odorous water body:
the electrode net rack comprises a galvanized iron wire used as a cathode and an oxygen increasing net used as an anode, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt and the ammonia nitrogen removing filler are sequentially distributed between the cathode and the anode, and the anode is erected on the bottom layer of the river water body when the electrode net rack is installed and used. When the electrode net rack is installed, the galvanized iron wire, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt, the ammonia nitrogen removing filler and the oxygen increasing net are sequentially arranged from top to bottom
The oxygenation net is a graphene modified nano titanium dioxide photocatalyst fiber net and is prepared by the method comprising the following steps: (1) flake graphite is used as raw material, concentrated H is used2SO4And KMnO4Preparing graphite oxide as an oxidant by a two-step method, and preparing graphene oxide by ultrasonic dispersion; by solvothermal method at 180 ℃ with graphene oxide and Ti (OBu)4As an initial reactant, synthesizing a reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst in an ethanol solvent; (2) firstly diluting butyl aluminate by absolute ethyl alcohol, then adding a mixed solution of glacial acetic acid, absolute ethyl alcohol and water, wherein the volume ratio of water to absolute ethyl alcohol in the mixed solution is 1: 10, putting the mixture into a mixer, starting stirring, heating to 80 ℃, stirring for 10 minutes to obtain stable, uniform, clear and transparent light yellow sol, then slowly adding the nano alumina suspension, and keeping the temperature at 40 ℃ to obtain a water-resistant and impact-resistant aluminum-based crosslinking agent; taking an aluminum-based cross-linking agent, heating the aluminum-based cross-linking agent to 50 ℃, slowly adding the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst suspension, wherein the aluminum-based cross-linking agent accounts for 2 wt% of the total weight of the mixture, and continuously stirring for 15 minutes after the aluminum-based cross-linking agent is added, so as to obtain a homogeneous mixture, wherein the technical requirements of the homogeneous mixture are as follows: shape, liquid 2-5%; crystalline, anatase; content, 97.5%; the grain diameter is less than or equal to 10 nm; surface groups, carboxyl, carbonate; the light response range is 300nm-550 nm; surface properties, hydrophilic; pH (1% aqueous solution), 3-4; specific surface area, 400m2(ii)/g; then will beAdding the homogeneous mixture into fiber slurry for producing a high-density polyethylene fiber net or attaching the homogeneous mixture to the high-density polyethylene fiber net, wherein the size of the high-density polyethylene fiber net can be selected according to needs, but the best width is 2 meters, so that the high-density polyethylene fiber net with the nano photocatalytic film coating is manufactured, and the thickness of the nano photocatalytic film coating is 50 microns; directly leaching the high-density polyethylene fiber net in a special barrel filled with the homogeneous mixture for multiple times, and directly leaching the high-density polyethylene fiber net in the special barrel filled with the homogeneous mixture for 7 times;
(3) and (3) naturally drying the high-density polyethylene fiber net with the nano photocatalytic film coating obtained in the step (2) in the air, and then placing the net in a drying room for drying, wherein the drying temperature is 55 ℃, and the drying time is 35 hours, so that the graphene modified nano titanium dioxide photocatalyst high-density polyethylene fiber net is obtained.
In this embodiment, the thickness of the ammonia nitrogen removing filler is 2.5cm, and the ammonia nitrogen removing filler comprises ceramsite and vermiculite in a weight ratio of 3: 1, and the surfaces of the ceramsite and the vermiculite are provided with nanoparticle layers, wherein the nanoparticle layers contain graphene oxide, activated zeolite powder and carbon fiber powder. The weight percentage of the nano particles in the polyurethane biological sponge filler is as follows: 0.01 parts of graphene oxide; activated zeolite powder 20; carbon fiber powder 1. The ammonia nitrogen removal filler is prepared by a preparation method comprising the following steps: grinding graphene oxide, and drying at 115 ℃ for 6.5h until the graphene oxide is completely dried; weighing activated zeolite powder, adding graphene oxide and the activated zeolite powder into a melamine resin adhesive, heating in a water bath at 60 ℃, and stirring and dispersing for 40 minutes at 100 revolutions per minute to obtain a solution; weighing carbon fiber powder, adding the carbon fiber powder into the solution, heating to 65 ℃, and stirring and dispersing at the speed of 160 revolutions per minute for 60 minutes; and then adding the ceramsite and the vermiculite into the solution, stirring for 20 minutes, attaching the liquid on the surface layers of the ceramsite and the vermiculite, taking out the ceramsite and the vermiculite, dispersing and airing to obtain the ammonia nitrogen removal filler.
Attaching the domesticated plant source microorganism to an electrode net rack, and the specific steps comprise: preparing the following raw materials in parts by weight: 100 parts of pure water, 150 parts of ammonia nitrogen removal filler, 5 parts of plant source culture medium and 0.3 part of domesticated plant source microorganism; 100 parts of purified water is added into a culture fermentation container, one third of the ammonia nitrogen removal filler is paved at the bottom of the culture fermentation container, and the culture fermentation container is stood for 30 minutes; adding 0.5 part of the plant source culture medium, and uniformly stirring; adding 2 parts of the domesticated plant source microorganism, and uniformly stirring; fermenting at constant temperature of 35 deg.C for 24 hr, and oxygenating and aerating once every 30 min; then adding one third of the filler for removing ammonia nitrogen, fermenting for 8 hours at the constant temperature of 30 ℃, and oxygenating and aerating once every 60 minutes; finally, adding the rest of the filler for removing ammonia nitrogen, naturally fermenting for 12 hours, and oxygenating and aerating once every 240 minutes; and connecting the anode and the cathode into a direct current power supply, keeping for 12 hours on the basis of 0.5V voltage, and then keeping for 8 hours on the basis of 1.8V voltage, so that the domesticated plant source microorganism is attached to the surface layer of the ammonia nitrogen removal filler.
In this embodiment, the graphite carbon felt is a polyacrylonitrile-based (PAN-based) graphite felt, and the thickness is 0.5 cm.
And finally, introducing current into the electrode net frame:
when the electrode net rack is connected with a power supply in normal work, firstly, a copper wire cable is used for connecting an anode, a cathode and a direct current power supply, and an external load is used for adjusting the connected voltage value, wherein 0.5V voltage is used for treating for 3 days, 1V voltage is used for treating for 3 days, 2V voltage is used for treating for 1 day, and the process is circulated until the water quality is optimized; the direct current power supply adopts a solar photovoltaic panel or a storage battery connected with the solar photovoltaic panel.
Example 5
A method for purifying a river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis comprises the following steps:
firstly, collecting strains, and domesticating to obtain plant-derived microorganisms:
wherein, the strain comprises the following microorganisms: bacillus subtilis, saccharomycetes, bacillus licheniformis, phosphorus-accumulating bacteria, photosynthetic bacteria, EM bacteria, trichoderma viride, streptococcus faecalis, lactic acid bacteria, lactobacillus plantarum, lactobacillus acidophilus, nitrobacteria, denitrifying bacteria, nitrosobacteria, bacillus brevis, bacillus coagulans and bacillus natto (all of which are commercially available microorganisms of animal origin); and the microorganisms contained in the mixed strain are domesticated into plant-derived microorganisms, and the short-chain fatty acid is mixed in the mixed strain.
The domestication of the microorganism adopts a method comprising the following steps:
A. acclimatization conditions of plant-derived microorganisms:
1) 100 parts of purified water, wherein the conductivity must be 0;
2) 75 parts of plant source culture medium, and is prepared by high-temperature steaming and sterilizing 30 minutes in advance;
3) 6 parts of animal-derived microorganisms (commercially available) required for forming the mixed strain, and separating anaerobic microorganisms and aerobic microorganisms;
4) acclimating environment, sealing the container, only needing an ultraviolet lamp capable of generating ozone outside, simple and easy to operate, low in cost and free from complex sterile space;
B. acclimatization of plant source microorganisms:
1) adding 38 parts by weight of plant source culture medium into 100 parts by weight of purified water, adding 9 parts by weight of anaerobic microorganism (animal source anaerobic microorganism required for forming mixed strains), stirring uniformly, and fermenting at constant temperature of 35 ℃ for 45 hours in a sealing manner;
2) then adding 30 parts of plant source culture medium and 8 parts of aerobic microorganism (animal source aerobic microorganism required for forming mixed strains), uniformly stirring, fermenting at constant temperature of 30 ℃ for 13 hours, and oxygenating and aerating once every 28 minutes;
3) fermenting at constant temperature of 25 deg.C for 9 hr, and oxygenating and aerating once every 60 min;
4) naturally fermenting for 13 hours, oxygenating and aerating once every 125 minutes, and then adding short-chain fatty acid to obtain the mixed strain.
The mixed strain needs to be subjected to electric domestication treatment, and the method comprises the following steps: b, manufacturing a cuboid reaction tank by using insulating plastics, wherein one side of the cuboid reaction tank is provided with a carbon cloth as an anode, the other opposite side of the cuboid reaction tank is provided with a carbon cloth coated with a platinum-containing catalyst on the surface as a cathode, the anode and the cathode are respectively connected with an external circuit through a platinum wire and a copper wire, adding the product obtained in the step B into the cuboid reaction tank, culturing for 5 days at 35 ℃, then connecting the platinum wire and the copper wire into a 0.4V direct current power supply for 24 days, and finally connecting a 1.2V direct current power supply for 30 days; and finally, taking out the substance in the cuboid reaction tank, namely the domesticated plant source microorganism.
During the domestication process, the electromagnetism, the mobile phone and the radio must be shielded.
Then, attaching the domesticated plant source microorganisms to an electrode net rack, and installing the electrode net rack in the river black and odorous water body:
the electrode net rack comprises a galvanized iron wire used as a cathode and an oxygen increasing net used as an anode, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt and the ammonia nitrogen removing filler are sequentially distributed between the cathode and the anode, and the anode is erected on the bottom layer of the river water body when the electrode net rack is installed and used. When the electrode net rack is installed, the galvanized iron wire, the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt, the ammonia nitrogen removing filler and the oxygen increasing net are sequentially arranged from top to bottom
The oxygenation net is a graphene modified nano titanium dioxide photocatalyst fiber net and is prepared by the method comprising the following steps: (1) flake graphite is used as raw material, concentrated H is used2SO4And KMnO4Preparing graphite oxide as an oxidant by a two-step method, and preparing graphene oxide by ultrasonic dispersion; by solvothermal method at 180 ℃ with graphene oxide and Ti (OBu)4As an initial reactant, synthesizing a reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst in an ethanol solvent; (2) firstly diluting butyl aluminate by absolute ethyl alcohol, then adding a mixed solution of glacial acetic acid, absolute ethyl alcohol and water, wherein the volume ratio of water to absolute ethyl alcohol in the mixed solution is 1: 10, putting the mixture into a mixer, starting stirring, heating to 70 ℃, stirring for 25 minutes to obtain stable, uniform, clear and transparent light yellow sol, then slowly adding the nano alumina suspension, and keeping the temperature at 40 ℃ to obtain a water-resistant and impact-resistant aluminum-based crosslinking agent; taking an aluminum-based cross-linking agent, heating the aluminum-based cross-linking agent to 50 ℃, slowly adding the reduced graphene oxide modified nano titanium dioxide heterostructure composite photocatalyst suspension, wherein the aluminum-based cross-linking agent accounts for 0.2 wt% of the total weight of the mixture, and continuously stirring for 19 minutes after the addition of the aluminum-based cross-linking agentObtaining a homogeneous mixture, wherein the technical requirements of the homogeneous mixture are as follows: shape, liquid 2-5%; crystalline, anatase; content, 97.5%; the grain diameter is less than or equal to 10 nm; surface groups, carboxyl, carbonate; the light response range is 300nm-550 nm; surface properties, hydrophilic; pH (1% aqueous solution), 3-4; specific surface area, 400m2(ii)/g; then adding the homogeneous mixture into fiber slurry for producing a high-density polyethylene fiber net or attaching the homogeneous mixture to the high-density polyethylene fiber net, wherein the size of the high-density polyethylene fiber net can be selected according to needs, but the best width is 1.5 m, so that the high-density polyethylene fiber net with the nano photocatalytic film coating is manufactured, and the thickness of the nano photocatalytic film coating is 45 um;
and (3) attaching the homogeneous mixture obtained in the step (1) to the surface of the high-density polyethylene fiber net in a spraying mode, wherein a high-pressure spray gun is adopted during spraying, and a small amount of uniform spraying mode is adopted for multiple times. Here, the plural number means at least three times, and the small number means that the sprayed amount per one time does not exceed one third of the total amount of the spray paint.
(3) And (3) naturally drying the high-density polyethylene fiber net with the nano photocatalytic film coating obtained in the step (2) in the air, and then placing the net in a drying room for drying, wherein the drying temperature is 55 ℃, and the drying time is 35 hours, so that the graphene modified nano titanium dioxide photocatalyst high-density polyethylene fiber net is obtained.
In this embodiment, the thickness of the ammonia nitrogen removing filler is 2.5cm, and the ammonia nitrogen removing filler comprises ceramsite and vermiculite in a weight ratio of 3: 1, and the surfaces of the ceramsite and the vermiculite are provided with nanoparticle layers, wherein the nanoparticle layers contain graphene oxide, activated zeolite powder and carbon fiber powder. The weight percentage of the nano particles in the polyurethane biological sponge filler is as follows: 0.02 parts of graphene oxide; activated zeolite powder 18; and (3) carbon fiber powder 2. The ammonia nitrogen removal filler is prepared by a preparation method comprising the following steps: grinding graphene oxide, and drying at 115 ℃ for 6.5h until the graphene oxide is completely dried; weighing activated zeolite powder, adding graphene oxide and the activated zeolite powder into a melamine resin adhesive, heating in a water bath at 55 ℃, stirring and dispersing for 30 minutes at 145 revolutions per minute to obtain a solution; weighing carbon fiber powder, adding the carbon fiber powder into the solution, heating to 66 ℃, and stirring and dispersing at the speed of 160 revolutions per minute for 40 minutes; and then adding the ceramsite and the vermiculite into the solution, stirring for 25 minutes, attaching the liquid on the surface layers of the ceramsite and the vermiculite, taking out the ceramsite and the vermiculite, dispersing and airing to obtain the ammonia nitrogen removal filler.
Attaching the domesticated plant source microorganism to an electrode net rack, and the specific steps comprise: preparing the following raw materials in parts by weight: 100 parts of pure water, 150 parts of ammonia nitrogen removal filler, 4.5 parts of plant source culture medium and 0.4 part of domesticated plant source microorganism; adding 100 parts of purified water into a culture fermentation container, paving one third of the ammonia nitrogen removal filler at the bottom of the culture fermentation container, and standing for 15 minutes; adding 5 parts of the plant source culture medium, and uniformly stirring; adding 0.3 part of the domesticated plant source microorganism, and uniformly stirring; fermenting at constant temperature of 35 deg.C for 24 hr, and oxygenating and aerating once every 28 min; then adding one third of the filler for removing ammonia nitrogen, fermenting for 8 hours at the constant temperature of 30 ℃, and oxygenating and aerating once every 35 minutes; finally, adding the rest filler for removing ammonia nitrogen, naturally fermenting for 15 hours, and oxygenating and aerating once every 120 minutes; and connecting the anode and the cathode into a direct current power supply, continuing for 13 hours on the basis of 0.5V voltage, and then maintaining for 8 hours on the basis of 1.8V voltage, so that the domesticated plant source microorganism is attached to the surface layer of the ammonia nitrogen removal filler.
In this embodiment, the graphite carbon felt is a polyacrylonitrile-based (PAN-based) graphite felt, and the thickness is 0.5 cm.
And finally, introducing current into the electrode net frame:
when the electrode net rack is connected with a power supply in normal work, firstly, a copper wire cable is used for connecting an anode, a cathode and a direct current power supply, and an external load is used for adjusting the connected voltage value, wherein 0.5V voltage is used for processing for 5 days, 1V voltage is used for processing for 2 days, 2V voltage is used for processing for 3 days, and the steps are repeated until the water quality is optimized; the direct current power supply adopts a solar photovoltaic panel or a storage battery connected with the solar photovoltaic panel.
A river with black and odorous water is selected and cut into seven separate areas, randomly labeled ABCDEFG. And the black and odorous water body treatment was carried out by the methods of comparative example 1, comparative example 2 and specific examples 1 to 5 in this order.
Comparative example 1
No measures were taken against the river gush.
Comparative example 2
201711091787.7 the black odorous water body is treated by the method of example 2.
The test river surge section is sampled and detected for six months, and the results are as follows:
as can be seen from the above table, in the examples 1 to 5 of the present invention, when the black and odorous water body of the river is treated, the effect of the previous method for 6 months can be achieved in three months, so that the treatment period is greatly shortened; meanwhile, the effect after six months of treatment is greatly improved. Further, application example 3 is the most effective.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.
Claims (7)
1. A method for purifying a river black and odorous water body by utilizing electrogenesis microorganism biofilm anode bioelectrolysis is characterized by comprising the following steps: the method comprises the following steps: collecting strains, and domesticating to obtain plant source microorganisms; attaching the domesticated plant source microorganisms to an electrode net rack, and installing the electrode net rack in the river black and odorous water body; introducing current into the electrode net rack;
the strain comprises the following microorganisms: bacillus subtilis, saccharomycetes, bacillus licheniformis, phosphorus-accumulating bacteria, photosynthetic bacteria, EM bacteria, trichoderma viride, streptococcus faecalis, lactic acid bacteria, lactobacillus plantarum, lactobacillus acidophilus, nitrobacteria, denitrifying bacteria, nitrosobacteria, bacillus brevis, bacillus coagulans and bacillus natto; the microorganisms contained in the strain are domesticated into plant source microorganisms, and short chain fatty acid is mixed in the strain;
the domestication of the microorganism adopts a method comprising the following steps:
A. acclimatization conditions of plant-derived microorganisms:
1) 100 parts of pure water, and the conductivity must be 0;
2) 60-80 parts of plant source culture medium, which is prepared by high-temperature steaming and sterilizing 30 minutes in advance;
3) 6-20 parts of animal source microorganisms required by the strain, and separating anaerobic microorganisms and aerobic microorganisms;
4) acclimating environment, sealing the container, only needing an ultraviolet lamp capable of generating ozone outside, simple and easy to operate, low in cost and free from complex sterile space;
B. acclimatization of plant source microorganisms:
1) adding 30-40 parts by weight of plant source culture medium into 100 parts of pure water, adding 3-10 parts of anaerobic microorganism, uniformly stirring, and fermenting at constant temperature of 35 ℃ for 24-48 hours in a sealing manner;
2) adding 30-40 parts of plant source culture medium and 3-10 parts of aerobic microorganism, stirring uniformly, fermenting at constant temperature of 30 ℃ for 12-24 hours, and oxygenating and aerating once every 15-30 minutes;
3) fermenting at constant temperature of 25 deg.C for 8-12 hr, and oxygenating and aerating once every 30-60 min;
4) naturally fermenting for 12-24 hours, oxygenating and aerating once every 120-240 minutes, and then adding short-chain fatty acid to obtain a strain;
the strain needs to be subjected to electric domestication treatment, and the method comprises the following steps: manufacturing a cuboid reaction tank by using insulating plastic, wherein one side of the cuboid reaction tank is provided with carbon cloth as an anode, the other opposite side of the cuboid reaction tank is provided with carbon cloth coated with a platinum-containing catalyst on the surface as a cathode, the anode and the cathode are respectively connected with an external circuit through a platinum wire and a copper wire, adding the product obtained in the step B into the cuboid reaction tank, culturing for 3-5 days at 35-37 ℃, then connecting the platinum wire and the copper wire into a 0.4V direct current power supply for 15-25 days, and finally connecting a 1.2V direct current power supply for 30-35 days; and finally, taking out the substance in the cuboid reaction tank, namely the domesticated plant source microorganism.
2. The method for purifying the river black and odorous water body by utilizing the electrogenesis microbial biofilm formation anode bioelectrolysis as claimed in claim 1, wherein: during the domestication process, the electromagnetism, the mobile phone and the radio must be shielded.
3. The method for purifying the river black and odorous water body by utilizing the electrogenesis microbial biofilm formation anode bioelectrolysis as claimed in claim 2, characterized in that: the electrode net rack comprises a galvanized iron wire used as a cathode and an oxygen increasing net used as an anode, wherein the oxygen increasing net, the ammonia nitrogen removing filler, the graphite carbon felt and the ammonia nitrogen removing filler are sequentially arranged between the cathode and the anode, and the anode is erected on the bottom layer of the river water body when the electrode net rack is installed and used.
4. The method for purifying the river black and odorous water body by utilizing the electrogenesis microbial biofilm formation anode bioelectrolysis as claimed in claim 3, wherein: the oxygenation net is a graphene modified nano titanium dioxide photocatalyst fiber net.
5. The method for purifying the river black and odorous water body by utilizing the electrogenesis microbial biofilm formation anode bioelectrolysis as claimed in claim 4, wherein: the ammonia nitrogen removing filler comprises ceramsite and vermiculite in a weight ratio of 3: 1, and the surfaces of the ceramsite and the vermiculite are provided with nanoparticle layers, wherein the nanoparticle layers contain graphene oxide, activated zeolite powder and carbon fiber powder.
6. The method for purifying the river black and odorous water body by utilizing the electrogenesis microbial biofilm formation anode bioelectrolysis as claimed in claim 5, wherein: attaching the domesticated plant source microorganism to an electrode net rack, and the specific steps comprise:
preparing the following raw materials in parts by weight: 100 parts of pure water, 150 parts of ammonia nitrogen removal filler and 200 parts of plant source culture medium, 0.5-5 parts of domesticated plant source microorganism and 0.3-2 parts of domesticated plant source microorganism;
adding 100 parts of pure water into a culture fermentation container, paving one third of the ammonia nitrogen removal filler at the bottom of the culture fermentation container, and standing for 15-30 minutes;
adding 0.5-5 parts of the plant source culture medium, and uniformly stirring;
adding 0.3-2 parts of the domesticated plant source microorganism, and uniformly stirring;
fermenting at 35 deg.C for 24-48 hr, and oxygenating and aerating once every 15-30 min;
then adding one third of the filler for removing ammonia nitrogen, fermenting for 8-24 hours at constant temperature of 30 ℃, and oxygenating and aerating once every 30-60 minutes;
finally, adding the rest of the filler for removing ammonia nitrogen, naturally fermenting for 12-16 hours, and carrying out oxygen charging and aeration once every 120-240 minutes;
and connecting the anode and the cathode into a direct current power supply, keeping for 12-15 hours on the basis of 0.5V voltage, and then keeping for 5-8 hours on the basis of 1.8V voltage to realize that the domesticated plant source microorganism is attached to the surface layer of the ammonia nitrogen removal filler.
7. The method for purifying the river black and odorous water body by utilizing the electrogenesis microbial biofilm formation anode bioelectrolysis as claimed in claim 6, wherein: when the electrode net rack is connected with a power supply in normal work, firstly, a copper wire cable is used for connecting an anode, a cathode and a direct current power supply, and an external load is used for adjusting the connected voltage value, wherein 0.5V voltage is used for processing for 3-5 days, 1V voltage is used for processing for 2-3 days, 2V voltage is used for processing for 1-3 days, and the steps are repeated until the water quality is optimized; the direct current power supply adopts a solar photovoltaic panel or a storage battery connected with the solar photovoltaic panel.
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