CN115583718B - Bioelectrochemical reactor and method for treating wastewater by same - Google Patents
Bioelectrochemical reactor and method for treating wastewater by same Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a bioelectrochemical reactor and a method for treating wastewater by the same, wherein the bioelectrochemical reactor comprises at least one group of anode chambers and cathode chambers, the anode chambers and the cathode chambers are alternately connected in series, the anode chambers are provided with water inlets, anode plates are vertically arranged in the anode chambers to divide the anode chambers into two parts, and conductive oxidation fillers are filled in the anode chambers; a cathode plate is vertically arranged in the cathode chamber, the cathode plate divides the cathode chamber into two parts, and the cathode chamber is filled with conductive reducing filler; an insulating partition plate is arranged between the anode chamber and the cathode chamber, and is positioned between the anode chamber and the cathode chamber, and a permeable isolating membrane is arranged below the insulating partition plate; electroactive microorganisms are grown on the anode plate and the conductive oxide filler.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a bioelectrochemical reactor and a wastewater treatment method thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The middle-low concentration wastewater has high treatment cost and treatment difficulty due to complex water quality components, large concentration change, obviously higher salt content and difficult degradation components and the limitations of the traditional treatment process. In addition, the degradation-resistant wastewater from industries such as landfill leachate, papermaking, pharmacy, petroleum refining and the like has low biodegradability, complex components, contains toxic and harmful pollutants, and has large discharge amount, and if the wastewater is not effectively treated, the ecological environment is seriously damaged, and the human health is endangered.
At present, the domestic treatment mode of the medium-low concentration wastewater is mainly a biomembrane method. The biomembrane method is used as sewage biological treatment technology, organic pollutants in low-concentration sewage are degraded by using the biomembrane, and the organic pollutants are decomposed by the microbial community to remove the organic pollutants in the sewage. However, the degradation-resistant organic wastewater has strong biotoxicity and low biochemical oxygen demand, while microorganisms in the traditional biochemical treatment mode are easy to inactivate in the degradation-resistant wastewater, so that the wastewater is difficult to effectively treat.
The sequencing batch activated sludge process has the defects of overlong storage time of sewage in a reactor, low pollutant removal efficiency, sludge expansion and the like. And when the traditional physicochemical method is adopted to treat the waste water difficult to degrade, secondary pollution is easy to be caused due to excessive addition of chemical reagents.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a bioelectrochemical reactor and a method for treating wastewater by using the bioelectrochemical reactor.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the present invention provides a bioelectrochemical reactor comprising at least one set of anode and cathode compartments, the anode and cathode compartments being alternately arranged in series, wherein,
the anode chamber is arranged at the water inlet, an anode plate is vertically arranged in the anode chamber, the anode chamber is divided into two parts, and the anode chamber is filled with conductive oxidation filler;
a cathode plate is vertically arranged in the cathode chamber, the cathode plate divides the cathode chamber into two parts, and the cathode chamber is filled with conductive reducing filler;
an insulating partition plate is arranged between the anode chamber and the cathode chamber, and is positioned between the anode chamber and the cathode chamber, and a permeable isolating membrane is arranged below the insulating partition plate;
electroactive microorganisms are grown on the anode plate and the conductive oxide filler.
In a second aspect, the present invention provides a method of bioelectrochemical wastewater treatment comprising the steps of:
sewage flows into the anode chamber from the bottom, flows through the conductive oxide filler, overflows to the other side through the anode plate, and continuously flows through the conductive oxide filler; in the flowing process of sewage, the electroactive microorganisms oxidize organic matters in the sewage;
the sewage after oxidation treatment flows into the cathode chamber from the lower part, flows through the conductive reducing filler, overflows to the other side through the cathode plate and continuously flows through the conductive reducing filler; in the flowing process of the sewage, organic matter ions obtained by oxidizing the sewage in the anode chamber are reduced into water or gas, and discharged, so that the removal of organic pollutants is realized;
in the process that sewage flows through the cathode chamber, heavy metal ions are reduced to obtain heavy metal simple substances, and the heavy metal simple substances are attached to the conductive reducing filler to remove the heavy metals.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
and a large amount of conductive oxidation filler is filled in the reaction bin to provide sufficient microorganism adsorption area so as to increase the contact area of the biological film and sewage and improve the pollutant removal efficiency of the bioreactor. The external electric field generates oxidation-reduction reaction at the anode and the cathode to promote the removal effect of the system on pollutants. The microbial community structure in the reactor can be changed along with the change of voltage intensity, and the activation of microorganisms can strengthen bioconversion capability, accelerate migration and conversion of pollutants, and improve the removal efficiency of the bioreactor on the pollutants. In addition, the electrolysis can change the chemical form of the pollutant, and the pollutant is removed through oxidation, reduction and the like.
The bioelectrochemical system of the invention is an organic combination of an electrochemical reactor and a biomembrane method, and the biodegradability of the reactor is enhanced along with the stimulation of an electric field to microorganism metabolism and the domestication of microorganism communities. The electric field can improve the microbial activity and promote the growth of the microorganisms in an optimized range. The addition of the conductive reducing material to the bioelectrochemical reactor increases the area of the biofilm. The biological membrane is cultured by applying an electric field to adsorb and degrade organic matters, the organic matters are removed by the anode, and heavy metal ions are reduced by the cathode, so that the purposes of purifying the waste water with medium and low concentration, improving the treatment efficiency of the waste water difficult to degrade, improving the biodegradability of the waste water and recycling the waste water are realized. The applied electric field is a key part of the structure and the function of the bioelectrochemical system, and can promote the electron transfer of electroactive bacteria, accelerate the degradation of nondegradable pollutants and improve the biodegradability of the nondegradable pollutants.
The invention integrates the biological film and the electrochemical technology, combines the advantages of two treatment processes, and integrates the electrochemical degradation and the biological degradation into one system. The invention aims to solve the problems of low treatment efficiency, low degradation-resistant sewage treatment efficiency and poor biodegradability of medium-low concentration wastewater caused by low biological film quantity and poor pollutant removal capability of biological flora in the existing bioelectrochemical bioreactor, and the problems of slow mass transfer and low electrocatalytic degradation efficiency. Meanwhile, the synergistic effect of electrochemical active bacteria and traditional anaerobic bacteria is promoted, and the high-efficiency removal of refractory organic matters is realized. The invention has the advantages of short starting time, strong adaptability to different water qualities, short HRT, high pollutant removal efficiency, low power consumption and small residual sludge yield.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic view showing the overall structure of a bioelectrochemical reactor according to an embodiment of the present invention;
FIG. 2 is a wastewater flow diagram of an embodiment of the present invention;
FIG. 3 is a graph showing the treatment efficiency of the bioelectrochemical reactor for treating COD (a) and ammonia nitrogen (b) at different hydraulic retention times according to the embodiment of the present invention.
Wherein, 1, a stacked reactor; 2. a water inlet; 3. an anode chamber I; 4. a cathode chamber I; 5. an anode chamber II; 6. a cathode chamber II; 7. a water outlet; 8. a direct current power supply; 9. an anode lead; 10. a cathode lead; 11. an anode plate; 12. a conductive oxide filler; 13. an insulating separator; 14. a water permeable barrier membrane; 15. a cathode plate; 16. and (3) conductive reducing filler.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the present invention provides a bioelectrochemical reactor comprising at least one set of anode and cathode compartments, the anode and cathode compartments being alternately arranged in series, wherein,
the anode chamber is arranged at the water inlet, an anode plate is vertically arranged in the anode chamber, the anode chamber is divided into two parts, and the anode chamber is filled with conductive oxidation filler;
a cathode plate is vertically arranged in the cathode chamber, the cathode plate divides the cathode chamber into two parts, and the cathode chamber is filled with conductive reducing filler;
an insulating partition plate is arranged between the anode chamber and the cathode chamber, and is positioned between the anode chamber and the cathode chamber, and a permeable isolating membrane is arranged below the insulating partition plate;
electroactive microorganisms are grown on the anode plate and the conductive oxide filler.
In some embodiments, the conductive oxide filler is activated carbon or carbon nanotubes.
In some embodiments, the electrically conductive reducing filler is a nickel, cobalt, or manganese metal oxide catalyst modified carbon-based material.
In some embodiments, the electroactive microorganism is selected from at least one of geobacillus (geobacillus), proteophilium (proteophilium), or anammox (cloacammonas).
In some embodiments, the water permeable barrier is a mesh structure made of an insulating material, such as a non-woven fabric or a plastic mesh.
And a permeable isolating membrane is arranged for intercepting the conductive oxide filler.
In a second aspect, the present invention provides a method of bioelectrochemical wastewater treatment comprising the steps of:
sewage flows into the anode chamber from the bottom, flows through the conductive oxide filler, overflows to the other side through the anode plate, and continuously flows through the conductive oxide filler; in the flowing process of sewage, the electroactive microorganisms oxidize organic matters in the sewage;
the sewage after oxidation treatment flows into the cathode chamber from the lower part, flows through the conductive reducing filler, overflows to the other side through the cathode plate and continuously flows through the conductive reducing filler; in the flowing process of the sewage, organic matter ions obtained by oxidizing the sewage in the anode chamber are reduced into water or gas, and discharged, so that the removal of organic pollutants is realized;
in the process that sewage flows through the cathode chamber, heavy metal ions are reduced to obtain heavy metal simple substances, and the heavy metal simple substances are attached to the conductive reducing filler to remove the heavy metals.
In some embodiments, the method further comprises pre-treating the anode plate and the conductive oxide filler by: the carbon nano tube is plated on the surfaces of the anode plate and the conductive oxidized filler by adopting an electrophoresis method, the thickness is between 20 and 40 microns, and the proper thickness is selected according to different electrode materials and fillers. The plating layer forms a physical isolation layer on the surfaces of the anode plate and the conductive oxide filler, prevents water molecules from contacting with the matrix, plays a role in corrosion prevention, prolongs the service life of the anode plate and the conductive oxide filler, and increases the conductivity of the anode plate and the conductive oxide filler.
The biological affinity and oxidation performance of the material are improved by treatment of high temperature, acid washing, disinfection and other methods. The pickling treatment method specifically comprises the following steps: the electrode and the reducing filler are soaked in 1% sodium dodecyl sulfate solution for 24 hours, so that the hydrophilicity of the electrode is improved.
The voltage can regulate and control the change of flora, and the corresponding dominant strain is cultured by regulating and controlling different voltages to be applied to different pollutant removal. For example: the dominant bacterial community in the wastewater treatment of the paper mill is Geobacter, the dominant bacterial community in the wastewater of the yogurt factory is Geoailkalibacter, and the dominant bacterial community in the wastewater of the brewery is Desulfovibrio.
In some embodiments, the potential difference between the cathode plate and the anode plate is 0.1-10V.
In some embodiments, the method further comprises the step of modifying the cathode plate and the conductive reducing filler by:
immersing the cathode plate and the conductive reducing filler in a sodium dodecyl sulfate solution for a set time;
or/and, depositing metal oxide particles such as carbon nano tubes, nickel catalysts, cobalt catalysts or manganese catalysts on the surface of the cathode plate or the conductive reduction filler by adopting an electrophoresis method.
The method comprises the following steps: the electrode and the reducing filler are soaked in 1% sodium dodecyl sulfate solution for 24 hours, so that the hydrophilicity of the electrode is improved.
Catalyst particles or powder such as charged carbon nano tubes, nickel, cobalt, manganese and the like are dispersed in suspension, and are attracted by a cathode plate and conductive materials and deposited on the surface of the cathode plate and conductive materials under the action of a direct current electric field, wherein the thickness is between 20 and 40 microns, and the proper thickness is selected according to different electrode materials and fillers.
The biological affinity and the reduction performance of the cathode plate and the conductive reduction filler are improved by modifying the cathode plate and the conductive reduction filler.
The invention is further described below with reference to the drawings and examples.
Example 1
As shown in fig. 1, the bioelectrochemical reactor is a stacked reactor 1, and is divided into an anode chamber I3, a cathode chamber I4, an anode chamber II 5 and a cathode chamber II 6, which can be increased according to the wastewater treatment amount and the wastewater characteristics.
The bioelectrochemical reactor is externally provided with a direct current power supply 8, an anode plate 11 is connected to a positive electrode through an anode lead 9, a cathode plate 15 is connected to a negative electrode through a cathode lead 10, a potential difference of 0.1-10V is provided between the positive electrode and the negative electrode, and meanwhile, sewage treatment strains are placed in the reactor to cultivate electroactive strains.
The wastewater enters the anode chamber I3 from the water inlet 2, a corrosion-resistant metal plate (such as a titanium plate, a stainless steel plate and the like) is arranged in the anode chamber I3 to serve as an anode plate 11, the anode plate 11 divides the anode chamber I3 into two parts and is filled with conductive oxide filler (such as activated carbon particles, carbon nano tubes and the like) 12, and the wastewater overflows to the right side of the anode chamber I3 after flowing upwards from the left side of the anode chamber.
The anode plate 11 and the conductive oxide filler 12 are subjected to one or more of high temperature, acid washing, sterilization, etc. to enhance their biocompatibility and oxidation properties.
When sewage flows through the anode chamber I3, electroactive microorganisms attached and grown on the anode plate 11 and the conductive oxidation filler 12 oxidize organic matters to generate carbon dioxide, hydrogen ions and the like, and then enter the cathode chamber I4 through the permeable separation membrane 14 below the insulating separator 13.
The sewage enters the cathode chamber I4 through a water permeable isolating membrane (such as non-woven fabric, plastic net and other insulating materials) 14, an insulating partition plate (such as a plastic plate and an organic glass plate) 13 is arranged between the anode chamber and the cathode chamber, the cathode plate 15 divides the cathode chamber into two parts, and the cathode chamber is filled with conductive reducing filler 16.
When sewage flows through the cathode chamber I4, organic matter ions oxidized in the anode chamber I3 are attached to the cathode plate 15 and the reducing filler 16, and generated water, hydrogen or methane and other gases are discharged, so that the sewage purifying effect is achieved.
The cathode plate 15 and the reducing filler 16 are subjected to one or more methods such as acid washing, electrophoresis, etc., and one or more catalytic materials such as nickel, cobalt, manganese, etc. are attached thereto to improve the biocompatibility and the reduction performance thereof.
The sewage again enters the anode chamber II 5 and the cathode chamber II 6, and the above-mentioned sewage treatment process is repeated, and when the amount of sewage is larger or the pollution is higher, more anode chambers and cathode chambers can be provided.
FIG. 3 shows the effect of the reactor of this example on wastewater treatment at different hydraulic retention times. The reactor volume was 7 liters, 4 each in the cathode and anode compartments, and titanium plates were used as electrodes and activated carbon as filler at a voltage of 1V. The COD concentration of the treated wastewater is more than 600mg/l, and the ammonia nitrogen concentration is more than 50mg/l. From the graph, the treatment efficiency of the reactor on COD and ammonia nitrogen in sewage after the adaptation period can reach more than 90% on average. With the decrease of the hydraulic retention time, the treatment efficiency of the reactor on the wastewater can be reduced to a small extent.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A bioelectrochemical reactor, characterized in that: comprises at least one group of anode chambers and cathode chambers which are alternately connected in series, wherein,
the anode chamber is arranged at the water inlet, an anode plate is vertically arranged in the anode chamber, the anode chamber is divided into two parts, and the anode chamber is filled with conductive oxidation filler;
a cathode plate is vertically arranged in the cathode chamber, the cathode plate divides the cathode chamber into two parts, and the cathode chamber is filled with conductive reducing filler;
an insulating partition plate is arranged between the anode chamber and the cathode chamber, and is positioned between the anode chamber and the cathode chamber, and a permeable isolating membrane is arranged below the insulating partition plate;
electroactive microorganisms grow on the anode plate and the conductive oxide filler;
the conductive oxidation filler is activated carbon or carbon nano tube;
the conductive reducing filler is a carbon-based material modified by a nickel, cobalt or manganese metal oxide catalyst.
2. The bioelectrochemical reactor according to claim 1, characterized in that: the electroactive microorganism is selected from at least one of Geobacillus, protophilus or anammox.
3. The bioelectrochemical reactor according to claim 1, characterized in that: the water permeable isolating membrane is a net structure made of insulating materials.
4. A method for treating bioelectrochemical wastewater, which adopts the bioelectrochemical reactor as claimed in claim 1, and is characterized in that: the method comprises the following steps:
sewage flows into the anode chamber from the bottom, flows through the conductive oxide filler, overflows to the other side through the anode plate, and continuously flows through the conductive oxide filler; in the flowing process of sewage, the electroactive microorganisms oxidize organic matters in the sewage;
the sewage after oxidation treatment flows into the cathode chamber from the lower part, flows through the conductive reducing filler, overflows to the other side through the cathode plate and continuously flows through the conductive reducing filler; in the flowing process of the sewage, organic matter ions obtained by oxidizing the sewage in the anode chamber are reduced into water or gas, and discharged, so that the removal of organic pollutants is realized;
in the process that sewage flows through the cathode chamber, heavy metal ions are reduced to obtain heavy metal simple substances, and the heavy metal simple substances are attached to the conductive reducing filler to remove the heavy metals.
5. The method for treating bioelectrochemical wastewater according to claim 4, wherein: the anode plate and the conductive oxide filler are pretreated by the following steps: and plating the carbon nano tube on the anode plate and the conductive oxide filler by adopting an electrophoresis method.
6. The method for treating bioelectrochemical wastewater according to claim 4, wherein: the potential difference between the cathode plate and the anode plate is 0.1-10V.
7. The method for treating bioelectrochemical wastewater according to claim 4, wherein: the method also comprises the step of modifying the cathode plate and the conductive reducing filler, wherein the modifying method comprises the following steps: the cathode plate and the conductive reducing filler are soaked in the sodium dodecyl sulfate solution for a set time.
8. The method for treating bioelectrochemical wastewater according to claim 7, wherein: the modifying step further comprises the step of depositing carbon nano tubes, nickel catalysts, cobalt catalysts or manganese catalyst metal oxide particles on the surface of the cathode plate or the conductive reducing filler by adopting an electrophoresis method.
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