CN115583718A - 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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- 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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Abstract
The invention discloses a bioelectrochemical reactor and a wastewater treatment method thereof, 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 board 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 board; electroactive microorganisms grow on the anode plate and the conductive oxidation 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 medium-low concentration wastewater has higher treatment cost and treatment difficulty due to complex water quality components, large concentration change, obviously higher salt content and difficultly-degraded components and the limitation of the traditional treatment process. In addition, the nondegradable wastewater generated in the industries such as landfill leachate, papermaking, pharmacy, petroleum refining and the like has low biodegradability, complex components, toxic and harmful pollutants and large discharge amount, and can seriously damage the ecological environment and harm the human health if the nondegradable wastewater is not effectively treated.
At present, the domestic treatment mode of medium-low concentration wastewater is mainly a biofilm method. The biomembrane process is used as a biological sewage treatment technology, and is used for degrading organic pollutants in sewage with medium and low concentration by utilizing a biomembrane, decomposing the organic pollutants by using microbial flora and removing the organic pollutants in the sewage. However, the refractory organic wastewater has strong biological toxicity and low biochemical oxygen demand, and microorganisms in the biochemical treatment mode are easy to inactivate in the refractory wastewater in the traditional sense, so that the wastewater is difficult to be effectively treated.
The sequencing batch activated sludge process has the disadvantages of too long storage time of sewage in the reactor, low pollutant removal efficiency, sludge bulking and the like. And when the traditional physicochemical method is adopted to treat the difficult-to-degrade wastewater, secondary pollution is easily caused due to excessive addition of chemical reagents.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a bioelectrochemical reactor and a method for treating wastewater by using the same.
In order to achieve the purpose, the 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 arranged alternately in series, wherein,
the anode chamber is provided with a water inlet, an anode plate is vertically arranged in the anode chamber to divide the anode chamber into two parts, and the anode chamber is filled with conductive oxidation filler;
the cathode chamber is vertically provided with a cathode plate, the cathode plate divides the cathode chamber into two parts, and the cathode chamber is filled with conductive reducing filler;
an insulating partition board 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 board;
electroactive microorganisms grow on the anode plate and the conductive oxidation filler.
In a second aspect, the present invention provides a bioelectrochemical wastewater treatment method, comprising the steps of:
sewage flows into the anode chamber from the bottom, flows through the conductive oxidation filler, overflows to the other side through the anode plate and continues to flow through the conductive oxidation filler; in the flowing process of the 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 continues to flow through the conductive reducing filler; in the flowing process of the sewage, organic matter ions obtained by oxidizing the sewage by the anode chamber are reduced into water or gas, and the water or gas is discharged outside to realize the removal of organic pollutants;
in the process that the sewage flows through the cathode chamber, heavy metal ions are reduced to obtain a heavy metal simple substance, and the heavy metal simple substance is attached to the conductive reducing filler to realize the removal of heavy metals.
The beneficial effects achieved by one or more of the embodiments of the invention are as follows:
sufficient microorganism adsorption area is provided by filling a large amount of conductive oxidation fillers in the reaction bin so as to increase the contact area of the biological membrane and the sewage and improve the removal efficiency of the bioreactor to pollutants. An external electric field generates oxidation-reduction reaction at the cathode and the anode 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 the voltage intensity, and the activation of the microbes can strengthen the biological conversion capacity, accelerate the migration and conversion of pollutants and improve the removal efficiency of the bioreactor to the pollutants. In addition, electrolysis can alter the chemical morphology of the contaminants, removing the contaminants through oxidation, reduction, and the like.
The bioelectrochemical system of the invention is the organic combination of an electrochemical reactor and a biomembrane method, and the biodegradation capacity of the reactor is enhanced along with the stimulation of an electric field to the metabolism of microorganisms and the acclimation of a microbial community. The electric field can increase the activity of the microorganism and promote the growth of the microorganism in an optimized range. The addition of the conductive reducing material in the bioelectrochemical reactor increases the area of the biofilm. 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 by applying an electric field to culture a biological membrane to adsorb and degrade the organic matters, removing the organic matters by an anode, reducing heavy metal ions by a cathode and the like. The applied electric field is a key part of the structure and the function of a bioelectrochemical system, can promote the electroactive bacteria to carry out electron transfer, accelerate the degradation of the nondegradable pollutants and improve the biodegradability of the nondegradable pollutants.
The invention integrates the biological membrane and the electrochemical technology, combines the advantages of the two treatment processes and integrates the electrochemical degradation and the biological degradation into a system. The invention aims to solve the problems of low treatment efficiency of medium-low concentration wastewater, low treatment efficiency of degradation-resistant sewage, poor biodegradability, slow mass transfer and low electrocatalytic degradation efficiency caused by low biomembrane amount and poor pollutant removal capability of biological flora in the conventional bioelectrochemical bioreactor. Meanwhile, the synergistic effect of the electrochemical active bacteria and the traditional anaerobic bacteria is promoted, and the high-efficiency removal of the 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 incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is a schematic view of 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 ammonian (b) at different hydraulic retention times according to the example of the present invention.
Wherein, 1, a stack 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 oxidized filler; 13. an insulating spacer; 14. a water permeable barrier film; 15. a cathode plate; 16. conductive reducing filler.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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 arranged alternately in series, wherein,
the anode chamber is provided with a water inlet, an anode plate is vertically arranged in the anode chamber to divide the anode chamber into two parts, and the anode chamber is filled with conductive oxidation filler;
the cathode chamber is vertically provided with a cathode plate, the cathode plate divides the cathode chamber into two parts, and the cathode chamber is filled with conductive reducing filler;
an insulating partition board 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 board;
electroactive microorganisms grow on the anode plate and the conductive oxidation filler.
In some embodiments, the electrically conductive oxidized filler is activated carbon or carbon nanotubes.
In some embodiments, the conductive reducing filler is a carbon-based material modified with a nickel, cobalt, or manganese metal oxide catalyst.
In some embodiments, the electroactive microorganism is selected from at least one of Geobacter (Geobacter), proteophilus (Proteiniphilum), or anammox bacteria (cloacammonas).
In some embodiments, the water permeable separating membrane is a net structure made of an insulating material, such as a non-woven fabric or a plastic net.
And arranging a permeable isolating membrane for intercepting the conductive oxidation filler.
In a second aspect, the present invention provides a bioelectrochemical wastewater treatment method, comprising the steps of:
sewage flows into the anode chamber from the bottom, flows through the conductive oxidation filler, overflows to the other side through the anode plate and continues to flow through the conductive oxidation filler; in the flowing process of the 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 continues to flow through the conductive reducing filler; in the flowing process of the sewage, organic matter ions obtained by oxidizing the sewage by the anode chamber are reduced into water or gas, and the water or gas is discharged outside to realize the removal of organic pollutants;
in the process that the sewage flows through the cathode chamber, heavy metal ions are reduced to obtain a heavy metal simple substance, and the heavy metal simple substance is attached to the conductive reduction filler to realize the removal of the heavy metal.
In some embodiments, the method further comprises pretreating the anode plate and the conductive oxidation filler by: the carbon nano tube is plated on the surfaces of the anode plate and the conductive oxidation filler by an electrophoresis method, the thickness is between 20 and 40 micrometers, 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 oxidation filler, prevents water molecules from contacting with a matrix, plays a role in corrosion prevention, prolongs the service life of the anode plate and the conductive oxidation filler, and increases the conductivity of the anode plate and the conductive oxidation filler.
The biological affinity and oxidation performance of the product are improved by treatment with high temperature, acid washing, disinfection and other methods. The pickling treatment method specifically comprises the following steps: and soaking the electrode and the reduction filler in a 1% sodium dodecyl sulfate solution for 24 hours to improve the hydrophilicity of the electrode.
The voltage can regulate and control the change of the flora, and corresponding dominant strains are cultured by regulating and controlling different voltages to be applied to removing different pollutants. 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 mill 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:
soaking the cathode plate and the conductive reduction 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 specific steps: and soaking the electrode and the reduction filler in a 1% sodium dodecyl sulfate solution for 24 hours to improve the hydrophilicity of the electrode.
Catalyst particles or powder of charged carbon nano tubes, nickel, cobalt, manganese and the like are dispersed in the suspension, the catalyst particles or powder are attracted by the cathode plate and the conductive material under the action of a direct current electric field and are deposited on the surface of the cathode plate, the thickness is between 20 and 40 micrometers, 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 illustrated by the following figures and examples.
Example 1
As shown in FIG. 1, the bioelectrochemical reactor is a stack type reactor 1, which is divided into an anode chamber I3, a cathode chamber I4, an anode chamber II 5, and a cathode chamber II 6, and the anode chamber and the cathode chamber can be increased according to the wastewater treatment amount and the wastewater characteristics.
A direct current power supply 8 is arranged outside the bioelectrochemical reactor, 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 negative electrode and the anode, and meanwhile, sewage treatment strains are placed in the reactor to culture electroactive strains.
Wastewater enters an anode chamber I3 from a 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, conductive oxidation fillers (such as activated carbon particles, carbon nano tubes and the like) 12 are filled in the anode plate, and the wastewater overflows to the right side of the anode chamber I3 after flowing up from the left side of the anode chamber.
The anode plate 11 and the conductive oxide filler 12 need to be treated by one or more methods such as high temperature, acid washing, and sterilization to improve the biocompatibility and oxidation performance.
When sewage flows through the anode chamber I3, the electroactive microorganisms attached to the anode plate 11 and the conductive oxidation filler 12 oxidize organic matters to generate carbon dioxide, hydrogen ions and the like, and then the sewage enters the cathode chamber I4 through the water-permeable isolating membrane 14 below the insulating partition plate 13.
Sewage enters the cathode chamber I4 through a permeable isolating membrane (such as non-woven fabrics, plastic nets 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 chamber is divided into two parts by a cathode plate 15, and a conductive reduction filler 16 is filled in the cathode plate.
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 reduction filler 16, and gases such as generated water, hydrogen or methane are discharged, so that the effect of sewage purification is achieved.
The cathode plate 15 and the reducing filler 16 need to be treated by one or more methods such as acid washing, electrophoresis and the like, and one or more catalytic materials such as nickel, cobalt, manganese and the like are attached to the cathode plate to improve the bioaffinity and the reducing performance.
The wastewater is again introduced into the anode chamber II 5 and the cathode chamber II 6, and the above wastewater treatment process is repeated, and more anode chambers and cathode chambers may be provided when the amount of wastewater is larger or the amount of wastewater contaminated is higher.
FIG. 3 shows the effect of the reactor of this example on the treatment of wastewater at different hydraulic retention times. The volume of the reactor is 7 liters, 4 cathode chambers and 4 anode chambers are respectively arranged, a titanium plate is used as an electrode under the condition that the voltage is 1V, and active carbon is used as a filler. The COD concentration of the treated wastewater is more than 600mg/l, and the ammonia nitrogen concentration is more than 50mg/l. As can be seen from the figure, after the adaptation period, the treatment efficiency of the reactor on COD and ammonia nitrogen in the sewage can reach more than 90 percent on average. The efficiency of the reactor for treating wastewater is slightly reduced as the hydraulic retention time is reduced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A bio-electrochemical reactor, characterized by: comprises at least one group of anode chambers and cathode chambers which are alternately connected in series, wherein,
the anode chamber is provided with a water inlet, an anode plate is vertically arranged in the anode chamber to divide the anode chamber 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 board 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 board;
electroactive microorganisms grow on the anode plate and the conductive oxidation filler.
2. The bioelectrochemical reactor according to claim 1, wherein: the conductive oxidation filler is activated carbon or carbon nanotubes.
3. The bioelectrochemical reactor according to claim 1, characterized in that: the conductive reduction filler is a carbon-based material modified by a nickel, cobalt or manganese metal oxide catalyst.
4. The bioelectrochemical reactor according to claim 1, wherein: the electroactive microorganism is at least one of geobacter, proteophilus or anammox bacteria.
5. The bioelectrochemical reactor according to claim 1, characterized in that: the permeable isolating membrane is of a net structure made of insulating materials.
6. A bioelectrochemical wastewater treatment method is characterized in that: the method comprises the following steps:
sewage flows into the anode chamber from the bottom, flows through the conductive oxidation filler, overflows to the other side through the anode plate and continues to flow through the conductive oxidation filler; in the flowing process of the 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 continues to flow through the conductive reducing filler; in the flowing process of the sewage, organic matter ions obtained by oxidizing the sewage by the anode chamber are reduced into water or gas, and the water or gas is discharged outside to remove organic pollutants;
in the process that the sewage flows through the cathode chamber, heavy metal ions are reduced to obtain a heavy metal simple substance, and the heavy metal simple substance is attached to the conductive reducing filler to realize the removal of heavy metals.
7. The bioelectrochemical wastewater treatment method according to claim 6, characterized in that: the anode plate and the conductive oxidation filler are pretreated, and the pretreatment method comprises the following steps: and plating the carbon nano tube on the electrode plate and the conductive oxidation filler by using an electrophoresis method.
8. The bioelectrochemical wastewater treatment method according to claim 6, characterized in that: the potential difference between the cathode plate and the anode plate is 0.1-10V.
9. The bioelectrochemical wastewater treatment method according to claim 6, characterized in that: the method also comprises a step of modifying the cathode plate and the conductive reducing filler, wherein the modification method comprises the following steps: the cathode plate and the conductive reducing filler are soaked in a sodium dodecyl sulfate solution for a set time.
10. The bioelectrochemical wastewater treatment method according to claim 6, characterized in that: the step of modifying also comprises depositing the carbon nano tube, nickel catalyst, cobalt catalyst or manganese catalyst metal oxide particles on the surface of the cathode plate or the conductive reduction filler by using an electrophoresis method.
Applications Claiming Priority (2)
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