Modularized device for treating phenol-ammonia wastewater by using photoelectric enhanced bacteria-algae electrochemical system and method for treating phenol-ammonia wastewater by using modularized device

Abstract

The invention discloses a modular device for treating phenol-ammonia wastewater by using a photoelectric enhanced bacteria-algae electrochemical system and a method for treating phenol-ammonia wastewater by using the modular device, and relates to the technical field of sewage treatment. Microorganism and electrochemical technologies are combined, phenols and ammonia nitrogen in the wastewater are efficiently removed through the algal-bacterial symbiotic system, the synergistic effect is achieved, and the treatment effect is improved. Compared with traditional anaerobic treatment of coal chemical industry wastewater, ammonia nitrogen in effluent is usually increased, while ammonia nitrogen is greatly reduced on the premise of guaranteeing the phenol removal rate after treatment by the device, the limitation of traditional anaerobic treatment of phenol and ammonia combined inhibition is broken through, and synergistic and efficient removal of phenol and ammonia is realized. According to the invention, the modularized device for treating the phenol-ammonia wastewater by the photoelectric enhanced bacteria-algae electrochemical system and the method for treating the phenol-ammonia wastewater by using the modularized device can be obtained.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, and in particular to a modular device for treating phenol-ammonia wastewater by a photoelectrically enhanced bacteria-algae electrochemical system and a method for treating phenol-ammonia wastewater by using the modular device. Background Art

[0003] The traditional coal chemical wastewater treatment process is based on biotechnology and mainly relies on the redox reaction of bacteria to degrade phenol and ammonia pollutants. It has the inherent defect of "using energy to consume energy and transferring pollution", that is, it needs to consume a lot of energy to convert pollutants such as phenol and ammonia into CO2 and N2, etc. Phenol and ammonia in the wastewater are not fully utilized as important carbon and nitrogen resources. At the same time, the sludge produced becomes toxic and harmful hazardous waste, which still needs further high-cost treatment. How to turn these energy-containing carbon and nitrogen pollutants into resources and energy has become an increasingly urgent practical need.

[0004] The bacteria-algae symbiotic technology has the unique advantages of simultaneously removing organic matter and ammonia nitrogen, strengthening the treatment of phenol-ammonia wastewater, and recovering organisms. However, the single bacteria-algae system has poor shock resistance and is inhibited by the combined toxicity of phenol and ammonia. Toxic organic matter such as phenols will inhibit the growth of microalgae and limit the recovery of microalgae biomass. High concentrations of ammonia nitrogen will also inhibit bacterial metabolic performance. In recent years, bacteria-algae biofuel cells have achieved the metabolic advantages of bacteria and algae by relieving the combined inhibition of phenol and ammonia, providing a new idea for the efficient treatment and resource utilization of coal chemical wastewater. Summary of the invention

[0005] The purpose of the present invention is to solve the following technical problems and to provide a modular device for treating phenol-ammonia wastewater by a photoelectrically enhanced bacteria-algae electrochemical system and a method for treating phenol-ammonia wastewater by using the modular device.

[0006] (1) The current coal chemical wastewater treatment process usually treats phenol-ammonia wastewater in the manner of "energy consumption and pollution transfer";

[0007] (2) The current problem of high concentrations of phenol and ammonia pollutants coexisting, antagonizing, and being difficult to remove simultaneously in coal chemical wastewater.

[0008] A modular device for treating phenol-ammonia wastewater by a photoelectrically enhanced bacteria-algae electrochemical system, comprising a bacteria-algae electrochemical device and a solar-assisted photoelectric compensation device, wherein the bacteria-algae electrochemical device comprises a bacteria-algae primary battery device, a physical adsorption device and an internal reflux control device; and the solar-assisted photoelectric compensation device comprises an electrolytic cell device and a light compensation device.

[0009] The bacteria-algae primary battery device comprises an anode pool 3, a buffer pool 6, a cathode pool 8, an anode carbon brush 12 and a cathode carbon brush 14; an anode pool water inlet 2 is provided on one side of the anode pool 3, a plurality of anode carbon brushes 12 are provided in the anode pool 3, and anaerobic sludge 11 is attached to the anode carbon brush 12; the anode pool 3 is connected to the buffer pool 6 through the buffer pool water inlet 5, the buffer pool 6 is connected to the cathode pool 8 through the cathode pool water inlet 7, and an overflow pipe 10 is provided on one side of the cathode pool 8; a plurality of cathode carbon brushes 14 are provided in the cathode pool 8, and Synechocystis 13 is attached to the cathode carbon brush 14;

[0010] The physical adsorption device comprises an activated carbon adsorption layer 4 and a zeolite adsorption layer 9; the activated carbon adsorption layer 4 is arranged at the bottom of the anode pool 3 and the buffer pool 6, and the zeolite adsorption layer 9 is arranged at the bottom of the cathode pool 8;

[0011] The internal reflux control device comprises a reflux pipe 15, a phenol concentration sensor a21, a phenol concentration sensor b22 and a motor drive device 30; the water inlet of the reflux pipe 15 is arranged in the buffer tank 6, the water outlet of the reflux pipe 15 is arranged on the water inlet pipe 1 at the anode tank water inlet 2, the water inlet pipe 1 is provided with a water inlet pump 31, and the reflux pipe 15 is provided with a reflux pump 32; the phenol concentration sensor a21 is arranged at the anode tank water inlet 2, and the phenol concentration sensor b22 is arranged at the buffer tank water inlet 5; the motor drive device 30 is electrically connected to the water inlet pump 31 and the reflux pump 32 respectively;

[0012] The electrolytic cell device includes a photovoltaic panel 16, a solar charging management device 17 and a relay a18. The photovoltaic panel 16 and the solar charging management device 17 are both arranged above the anode pool 3 and the buffer pool 6. The photovoltaic panel 16 is electrically connected to the solar charging management device 17. The voltage output end of the solar charging management device 17 is electrically connected to the relay a18. The common end of the relay a18 is electrically connected to the anode carbon brush 12. The normally closed end of the relay a18 is electrically connected to the cathode carbon brush 14 to form a primary battery circuit. The normally open end of the relay a18 is electrically connected to the cathode carbon brush 14 to form an electrolytic cell circuit.

[0013] The light compensation device includes a relay b19 and an LED lamp tube 20, and the voltage output end of the solar charging management device 17 is electrically connected to the LED lamp tube 20 through the relay b19.

[0014] The method for treating phenol-ammonia wastewater by using a modular device for treating phenol-ammonia wastewater by using a photoelectric enhanced bacteria-algae electrochemical system is carried out in the following steps:

[0015] Step S1: injecting the phenol-ammonia wastewater into the anode pool 3 through the anode pool water inlet 2 by the water inlet pump 31, and then passing through the buffer pool 6 and the cathode pool 8 in sequence, and finally flowing out from the overflow pipe 10 of the cathode pool 8, and the hydraulic retention time is 48 to 72 hours;

[0016] Step S2: The phenol concentration sensor a21 arranged at the anode cell water inlet 2 monitors the phenol concentration of the phenol-ammonia wastewater in real time. The main control microcontroller 25 reads the monitoring result of the phenol concentration sensor a21 once per second and controls the working circuit of the relay a18 switching device according to the average phenol concentration of the phenol-ammonia wastewater within 1 minute: when the average phenol concentration is within 900 mg / L, the primary battery circuit, i.e., the normally closed end of the relay a18 is electrically connected to the cathode carbon brush 14; when the average phenol concentration is higher than 1100 mg / L, the electrolytic cell circuit, i.e., the normally open end of the relay a18 is electrically connected to the cathode carbon brush 14.

[0017] Beneficial effects of the present invention:

[0018] (1) Strong resistance to water quality and environmental changes: The present invention demonstrates the convenience of modularization of the device and its adaptability to water quality and natural environment, and is mainly due to its advanced monitoring and feedback mechanism. By setting phenol concentration sensor a and phenol concentration sensor b at the total water inlet and the buffer zone outlet, the concentration of phenol in the water can be monitored in real time. When the phenol concentration of the effluent from the buffer tank exceeds 150 mg / L or 300 mg / L, the system will automatically adjust to return the high-concentration water to the total water inlet, and adjust the inlet flow rate accordingly at 1:0.5 (inlet pump outlet: reflux pump outlet) and 1:1, respectively, so as to ensure that the effluent phenol concentration is less than 50 mg / L, so that the water quality of the treatment process is always within a controllable range. The system can automatically switch the working mode as needed, and adopt solar-assisted photoelectric compensation to achieve auxiliary light growth of Synechocystis on rainy days and free switching circuits of primary cells / electrolytic cells to adapt to different environmental conditions. This highly automated and self-regulating mechanism enables the device to respond quickly to changes in water quality and maintain treatment efficiency while reducing energy and resource waste, demonstrating its efficient water quality and environmental adaptability.

[0019] (2) Breaking through the bottleneck of synergistic inhibition of phenol and ammonia, and turning inhibition into promotion: In the process of coal chemical wastewater treatment, high concentrations of phenols and ammonia nitrogen will produce joint inhibition on microorganisms. Phenols in wastewater have significant toxic effects on microalgae. If the ammonia nitrogen concentration in the wastewater is too high, it will seriously inhibit the metabolic activities of anaerobic bacteria, thereby affecting their ability to degrade phenols. In the modular device of the present invention, the cathode uses microalgae and zeolite to effectively absorb ammonia nitrogen, and the anode area uses anaerobic sludge and activated carbon to degrade phenolic compounds. The present invention utilizes the metabolic advantages of bacteria and algae respectively, and removes the joint inhibition of phenol and ammonia by separating phenol and ammonia pollutants, thereby achieving the synergistic removal of phenol and ammonia pollutants in coal chemical wastewater.

[0020] (3) Utilizing electrochemical symbiosis of bacteria and algae to achieve efficient and coordinated removal of phenol and ammonia: The present invention combines microorganisms and electrochemical technology to efficiently remove phenols and ammonia nitrogen in wastewater through a bacteria-algae symbiotic system, achieving a synergistic effect and improving the treatment effect. Compared with traditional anaerobic treatment of coal chemical wastewater, the effluent ammonia nitrogen usually increases, while after treatment by the device of the present invention, the ammonia nitrogen is greatly reduced while ensuring the phenol removal rate, breaking through the limitations of the traditional anaerobic treatment of phenol and ammonia combined inhibition, and achieving efficient and coordinated removal of phenol and ammonia.

[0021] (4) Energy and resource utilization of carbon and nitrogen pollutants: The present invention combines the metabolic carbon and nitrogen advantages of bacteria and algae, and phenol and ammonia pollutants are no longer restricted to traditional treatment and ultimately converted into CO2 and N2 for direct emission. The mineralization of phenol pollutants into CO2 can promote the photosynthetic reaction of Synechocystis, and ammonia nitrogen can also be assimilated by Synechocystis to increase algae biomass. While breaking through the combined inhibition of phenol and ammonia to achieve "reverse inhibition to promotion", the present invention provides a new direction for collecting algae biomass and converting it into bioenergy.

[0022] The invention can obtain a modular device for treating phenol-ammonia wastewater by a photoelectrically enhanced bacteria-algae electrochemical system and a method for treating phenol-ammonia wastewater by using the modular device. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A front view of a modular device for treating phenol-ammonia wastewater by a photoelectrically enhanced bacteria-algae electrochemical system of the present invention is shown, wherein 1 represents a water inlet pipe, 2 represents a water inlet of an anode cell, 3 represents an anode cell, 4 represents an activated carbon adsorption layer, 5 represents a water inlet of a buffer cell, 6 represents a buffer cell, 7 represents a water inlet of a cathode cell, 8 represents a cathode cell, 9 represents a zeolite adsorption layer, 10 represents an overflow pipe, 11 represents anaerobic sludge, 12 represents an anode carbon brush, 13 represents Synechocystis, 14 represents a cathode carbon brush, 15 represents a reflux pipe, 16 represents a photovoltaic panel, 20 represents an LED lamp tube, 21 represents a phenol concentration sensor a, 22 represents a phenol concentration sensor b, and 33 represents a steel frame;

[0024] Figure 2 A left view of a modular device for treating phenol-ammonia wastewater using a photoelectrically enhanced bacteria-algae electrochemical system according to the present invention is shown, 1 represents a water inlet pipe, 3 represents an anode cell, 4 represents an activated carbon adsorption layer, 11 represents anaerobic sludge, 12 represents an anode carbon brush, 15 represents a reflux pipe, 16 represents a photovoltaic panel, 17 represents a solar charging management device, and 33 represents a steel frame;

[0025] Figure 3A top view of a modular device for treating phenol-ammonia wastewater using a photoelectrically enhanced bacteria-algae electrochemical system according to the present invention is shown, wherein 1 represents a water inlet pipe, 3 represents an anode tank, 6 represents a buffer tank, 8 represents a cathode tank, 10 represents an overflow pipe, 12 represents an anode carbon brush, 14 represents a cathode carbon brush, 15 represents a reflux pipe, 16 represents a photovoltaic panel, 20 represents an LED lamp tube, and 33 represents a steel frame;

[0026] Figure 4 A connection diagram showing a modular device for treating phenol-ammonia wastewater using a photoelectrically enhanced bacteria-algae electrochemical system according to the present invention, 17 represents a solar charging management device, 18 represents a relay a, 19 represents a relay b, 20 represents an LED lamp tube, 21 represents a phenol concentration sensor a, 22 represents a phenol concentration sensor b, 23 represents a light sensor, 24 represents a Bluetooth device, 25 represents a main control microcontroller, 30 represents a motor drive device, 31 represents a water inlet pump, and 32 represents a reflux pump;

[0027] Figure 5 A schematic diagram showing the present invention using a modular device to treat phenol-ammonia wastewater. DETAILED DESCRIPTION

[0028] Specific implementation method 1: The modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacteria-algae electrochemical system in this implementation method includes a bacteria-algae electrochemical device and a solar-assisted photoelectric compensation device. The bacteria-algae electrochemical device includes a bacteria-algae primary battery device, a physical adsorption device and an internal reflux control device; the solar-assisted photoelectric compensation device includes an electrolytic cell device and a light compensation device;

[0029] The bacteria-algae primary battery device comprises an anode pool 3, a buffer pool 6, a cathode pool 8, an anode carbon brush 12 and a cathode carbon brush 14; an anode pool water inlet 2 is provided on one side of the anode pool 3, a plurality of anode carbon brushes 12 are provided in the anode pool 3, and anaerobic sludge 11 is attached to the anode carbon brush 12; the anode pool 3 is connected to the buffer pool 6 through the buffer pool water inlet 5, the buffer pool 6 is connected to the cathode pool 8 through the cathode pool water inlet 7, and an overflow pipe 10 is provided on one side of the cathode pool 8; a plurality of cathode carbon brushes 14 are provided in the cathode pool 8, and Synechocystis 13 is attached to the cathode carbon brush 14;

[0030] The physical adsorption device comprises an activated carbon adsorption layer 4 and a zeolite adsorption layer 9; the activated carbon adsorption layer 4 is arranged at the bottom of the anode pool 3 and the buffer pool 6, and the zeolite adsorption layer 9 is arranged at the bottom of the cathode pool 8;

[0031] The internal reflux control device comprises a reflux pipe 15, a phenol concentration sensor a21, a phenol concentration sensor b22 and a motor drive device 30; the water inlet of the reflux pipe 15 is arranged in the buffer tank 6, the water outlet of the reflux pipe 15 is arranged on the water inlet pipe 1 at the anode tank water inlet 2, the water inlet pipe 1 is provided with a water inlet pump 31, and the reflux pipe 15 is provided with a reflux pump 32; the phenol concentration sensor a21 is arranged at the anode tank water inlet 2, and the phenol concentration sensor b22 is arranged at the buffer tank water inlet 5; the motor drive device 30 is electrically connected to the water inlet pump 31 and the reflux pump 32 respectively;

[0032] The electrolytic cell device includes a photovoltaic panel 16, a solar charging management device 17 and a relay a18. The photovoltaic panel 16 and the solar charging management device 17 are both arranged above the anode pool 3 and the buffer pool 6. The photovoltaic panel 16 is electrically connected to the solar charging management device 17. The voltage output end of the solar charging management device 17 is electrically connected to the relay a18. The common end of the relay a18 is electrically connected to the anode carbon brush 12. The normally closed end of the relay a18 is electrically connected to the cathode carbon brush 14 to form a primary battery circuit. The normally open end of the relay a18 is electrically connected to the cathode carbon brush 14 to form an electrolytic cell circuit.

[0033] The light compensation device includes a relay b19 and an LED lamp tube 20, and the voltage output end of the solar charging management device 17 is electrically connected to the LED lamp tube 20 through the relay b19.

[0034] Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that the volume ratio of the anode pool 3, buffer pool 6 and cathode pool 8 is (1-1.5): (0.5-0.7): (0.8-1), and the inner wall of the buffer pool 6 uses a cation exchange membrane made of sulfonated polystyrene as the filling material.

[0035] The other steps are the same as those in the first specific implementation.

[0036] Specific embodiment three: The difference between this embodiment and specific embodiment one or two is that: the anode pool water inlet 2 is arranged on the upper side wall of the anode pool 3, the buffer pool water inlet 5 is arranged on the lower side wall of the buffer pool 6, the cathode pool water inlet 7 is arranged on the upper side wall of the cathode pool 8, and the overflow pipe 10 is arranged on the upper side wall.

[0037] The other steps are the same as those in the first or second embodiment.

[0038] Specific implementation method four: The difference between this implementation method and specific implementation methods one to three is that the anode carbon brush 12, cathode carbon brush 14, photovoltaic panel 16, LED lamp tube 20 are all arranged on the steel frame 33 above the anode pool 3 and the buffer pool 6.

[0039] The other steps are the same as those in Specific Embodiments 1 to 3.

[0040] Specific embodiment 5: The difference between this embodiment and specific embodiments 1 to 4 is that the number of the anode carbon brushes 12 and the cathode carbon brushes 14 are both 4 to 8.

[0041] The other steps are the same as those in Specific Embodiments 1 to 4.

[0042] Specific embodiment 6: This embodiment differs from specific embodiments 1 to 5 in that: the electrolytic cell device further includes a Bluetooth device 24 and a main control microcontroller 25;

[0043] The main control microcontroller 25 reads the world time through the Bluetooth device 24; the main control microcontroller 25 is electrically connected to the solar charging management device 17, the relay a18, the phenol concentration sensor a21, the phenol concentration sensor b22 and the motor drive device 30.

[0044] The other steps are the same as those in Specific Embodiments 1 to 5.

[0045] Specific embodiment seven: The difference between this embodiment and any one of specific embodiments one to six is ​​that the light compensation device further includes a light sensor 23, and the main control microcontroller 25 is electrically connected to the light sensor 23 and the relay b19 respectively.

[0046] The other steps are the same as those in Specific Embodiments 1 to 6.

[0047] Specific embodiment eight: The difference between this embodiment and specific embodiments one to seven is that the solar charging management device 17 , the Bluetooth device 24 and the main control microcontroller 25 are all arranged on the back side of the photovoltaic panel 16 .

[0048] The other steps are the same as those in Specific Embodiments 1 to 7.

[0049] Specific embodiment 9: In this embodiment, a method for treating phenol-ammonia wastewater by using a modular device for treating phenol-ammonia wastewater using a photoelectrically enhanced bacterial-algal electrochemical system is carried out in the following steps:

[0050] Step S1: injecting the phenol-ammonia wastewater into the anode pool 3 through the anode pool water inlet 2 by the water inlet pump 31, and then passing through the buffer pool 6 and the cathode pool 8 in sequence, and finally flowing out from the overflow pipe 10 of the cathode pool 8, and the hydraulic retention time is 48 to 72 hours;

[0051] Step S2: The phenol concentration sensor a21 arranged at the anode cell water inlet 2 monitors the phenol concentration of the phenol-ammonia wastewater in real time. The main control microcontroller 25 reads the monitoring result of the phenol concentration sensor a21 once per second and controls the working circuit of the relay a18 switching device according to the average phenol concentration of the phenol-ammonia wastewater within 1 minute: when the average phenol concentration is within 900 mg / L, the primary battery circuit, i.e., the normally closed end of the relay a18 is electrically connected to the cathode carbon brush 14; when the average phenol concentration is higher than 1100 mg / L, the electrolytic cell circuit, i.e., the normally open end of the relay a18 is electrically connected to the cathode carbon brush 14.

[0052] Specific embodiment ten: The difference between this embodiment and specific embodiment nine is that: when the phenol concentration sensor b22 detects that the phenol concentration in the buffer tank 6 is 150-300 mg / L, an electronic signal is fed back to the main control microcontroller 25, and the main control microcontroller 25 controls the reflux pump 32 to start, and the waste water in the buffer tank 6 is refluxed to the anode tank 3 through the water inlet pipe 1, and at the same time, the rotation speed of the water inlet pump 31 is reduced to ensure that the flow ratio of the outlet water of the water inlet pump 31 to the inlet water of the reflux pump 32 is adjusted to (2-2.5):1 when the total water inlet flow rate remains unchanged;

[0053] When the phenol concentration of the effluent from the buffer tank 6 exceeds 300 mg / L, the rotation speed of the inlet pump 31 is further reduced to ensure that the flow rate ratio of the effluent from the inlet pump 31 to the inlet from the reflux pump 32 is adjusted to (1-1.5):1 while the total inlet flow rate remains unchanged;

[0054] The main control microcontroller 25 connects to the PC device to read the time via the Bluetooth device 24; when the time is between 6:00 and 18:00, the main control microcontroller 25 receives the light signal returned by the light sensor 23: if the natural light intensity is ≥5100Lx, the relay b19 is disconnected, and natural light is used as the growth light source for the Synechocystis 13 in the cathode pool 8; if the natural light intensity is lower than 4900Lx, the main control microcontroller 25 issues a light compensation instruction, controls the relay b19 to close, and the solar charging management device 17 provides a stable voltage to the LED lamp tube 20.

[0055] The other steps are the same as those in the ninth embodiment.

[0056] The following examples are used to verify the beneficial effects of the present invention:

[0057] Embodiment 1: A modular device for treating phenol-ammonia wastewater by a photoelectrically enhanced bacteria-algae electrochemical system is a vertical flow baffled, semi-buried electrochemical biological retention tank, comprising a bacteria-algae electrochemical device and a solar-assisted photoelectric compensation device, wherein the bacteria-algae electrochemical device comprises a bacteria-algae primary battery device, a physical adsorption device, and an internal reflux control device; the solar-assisted photoelectric compensation device comprises an electrolytic cell device and a light compensation device;

[0058] The bacteria-algae primary battery device comprises an anode pool 3, a buffer pool 6, a cathode pool 8, an anode carbon brush 12 and a cathode carbon brush 14; an anode pool water inlet 2 is provided on one side of the anode pool 3, a plurality of anode carbon brushes 12 are provided in the anode pool 3, and anaerobic sludge 11 is attached to the anode carbon brush 12 to form a biofilm; the anode pool 3 is connected to the buffer pool 6 through the buffer pool water inlet 5, and the buffer pool 6 is connected to the cathode pool 8 through the cathode pool water inlet 7, and an overflow pipe 10 (DN=100mm) is provided on one side of the cathode pool 8; a plurality of cathode carbon brushes 14 are provided in the cathode pool 8, and Synechocystis 13 is attached to the cathode carbon brush 14 to form a biofilm; the Synechocystis 13 is a common commercially available product;

[0059] The physical adsorption device comprises an activated carbon adsorption layer 4 and a zeolite adsorption layer 9; the activated carbon adsorption layer 4 is laid on the bottom of the anode pool 3 and the buffer pool 6, with a laying thickness of 0.30m; the zeolite adsorption layer 9 is laid on the bottom of the cathode pool 8, with a laying thickness of 0.30m;

[0060] The internal reflux control device comprises a reflux pipe 15 (DN=50mm), a phenol concentration sensor a21, a phenol concentration sensor b22 and a motor drive device 30; the water inlet of the reflux pipe 15 is arranged in the buffer tank 6, the water outlet of the reflux pipe 15 is arranged on the water inlet pipe 1 (DN=100mm) at the water inlet 2 of the anode tank, the water inlet pipe 1 is provided with a water inlet pump 31, and the reflux pipe 15 is provided with a reflux pump 32; the phenol concentration sensor a21 is arranged at the water inlet 2 of the anode tank, and the phenol concentration sensor b22 is arranged at the water inlet 5 of the buffer tank; the motor drive device 30 is electrically connected to the water inlet pump 31 and the reflux pump 32 respectively;

[0061] The electrolytic cell device includes a photovoltaic panel 16, a solar charging management device 17 and a relay a18. The photovoltaic panel 16 and the solar charging management device 17 are both arranged above the anode pool 3 and the buffer pool 6. The photovoltaic panel 16 is electrically connected to the solar charging management device 17. The voltage output end of the solar charging management device 17 is electrically connected to the relay a18. The common end of the relay a18 is electrically connected to the anode carbon brush 12. The normally closed end of the relay a18 is electrically connected to the cathode carbon brush 14 to form a primary battery circuit. The normally open end of the relay a18 is electrically connected to the cathode carbon brush 14 to form an electrolytic cell circuit.

[0062] The light compensation device includes a relay b19 and an LED lamp tube 20 (the number of lamp tubes is selected as needed), and the voltage output end of the solar charging management device 17 is electrically connected to the LED lamp tube 20 through the relay b19.

[0063] The volume ratio of the anode pool 3, the buffer pool 6 and the cathode pool 8 is 1:0.7:0.8. The inner wall of the buffer pool 6 uses a cation exchange membrane made of sulfonated polystyrene as a filling material. When the reflux system is started and the anode pool 3 and the cathode pool 8 are hydraulically disconnected, ammonia ions can migrate through the cation exchange membrane of the buffer pool 6.

[0064] The anode pool water inlet 2 is arranged on the upper side wall of the anode pool 3, the buffer pool water inlet 5 is arranged on the lower side wall of the buffer pool 6, the cathode pool water inlet 7 is arranged on the upper side wall of the cathode pool 8, and the overflow pipe 10 is arranged on the upper side wall.

[0065] The anode carbon brush 12 , cathode carbon brush 14 , photovoltaic panel 16 , and LED lamp tube 20 are all arranged on a steel frame 33 above the anode tank 3 and the buffer tank 6 .

[0066] The number of the anode carbon brush 12 and the number of the cathode carbon brush 14 are both four.

[0067] The electrolytic cell device further includes a Bluetooth device 24 and a main control microcontroller (MCU) 25;

[0068] The main control microcontroller 25 reads the world time through the Bluetooth device 24; the main control microcontroller 25 is electrically connected to the solar charging management device 17, the relay a18, the phenol concentration sensor a21, the phenol concentration sensor b22 and the motor drive device 30.

[0069] The main control microcontroller 25 is purchased from Guangzhou Xingyi Electronic Technology Co., Ltd. (Zhengdian Atom), and its model is STM32F407ZGT6.

[0070] The light compensation device further comprises a light sensor 23, and the main control microcontroller 25 is electrically connected to the light sensor 23 and the relay b19 respectively.

[0071] The solar charging management device 17 , the Bluetooth device 24 and the main control microcontroller 25 are all arranged on the back side of the photovoltaic panel 16 .

[0072] Example 2: A method for treating phenol-ammonia wastewater using a modular device for treating phenol-ammonia wastewater using a photoelectrically enhanced bacteria-algae electrochemical system as described in Example 1, according to the following steps:

[0073] Step S1: injecting the phenol-ammonia wastewater into the anode pool 3 through the anode pool water inlet 2 by the water inlet pump 31, and then passing through the buffer pool 6 and the cathode pool 8 in sequence, and finally flowing out from the overflow pipe 10 of the cathode pool 8, and the hydraulic retention time is 48h;

[0074] Step S2: The phenol concentration sensor a21 arranged at the anode cell water inlet 2 monitors the phenol concentration of the phenol-ammonia wastewater in real time. The main control microcontroller 25 reads the monitoring result of the phenol concentration sensor a21 once per second and controls the working circuit of the relay a18 switching device according to the average phenol concentration of the phenol-ammonia wastewater within 1 minute: when the average phenol concentration is within 900 mg / L, the primary battery circuit, i.e., the normally closed end of the relay a18 is electrically connected to the cathode carbon brush 14; when the average phenol concentration is higher than 1100 mg / L, the electrolytic cell circuit, i.e., the normally open end of the relay a18 is electrically connected to the cathode carbon brush 14.

[0075] When the primary cell circuit is used, the phenol pollutants in the influent are degraded by the anaerobic sludge biofilm attached to the anode carbon brush 12 in the anode pool 3 as electron donors; after the wastewater flows into the buffer pool 6, the concentration of the phenol pollutants gradually decreases under the continuous adsorption of the activated carbon adsorption layer 4; when it flows into the cathode pool 8, the Synechocystis 13 can also further degrade the phenol pollutants; the electrons generated by the phenol pollutants on the anode carbon brush 12 are transmitted to the cathode carbon brush 14 via the primary cell circuit, driving the ammonium ions to migrate to the cathode through the cation exchange membrane made of sulfonated polystyrene, and the ammonium ions enriched in the cathode pool 8 are assimilated and absorbed by the Synechocystis 13 attached to the cathode carbon brush 14, the ion exchange capacity of the cation exchange membrane is 0.9-1.1 meq / g, and the thickness is 50-200 μm; when the ammonium ion concentration is high, the zeolite adsorption layer 9 can continuously adsorb ammonium ions to reduce the nitrogen load, while ensuring the cathode nitrogen removal rate, maintaining a sustainable nitrogen source supply for the cathode microalgae through adsorption-slow release.

[0076] When the electrolytic cell circuit is used, the lithium battery is used as a working power source to output a stable voltage to electrolyze the phenol-ammonia wastewater. The anode carbon brush 12 is connected to the positive electrode of the lithium battery to accelerate the oxidation and removal of phenol pollutants; the cathode carbon brush 14 is connected to the negative electrode of the lithium battery, and electrons flow from the negative electrode of the lithium battery to the cathode carbon brush 14, and the ammonium ions in the wastewater move to the cathode cell 8 for enrichment, which can promote the assimilation and absorption of ammonium ions by the Synechocystis 13.

[0077] When the phenol concentration sensor b22 detects that the phenol concentration in the buffer tank 6 is 150-300 mg / L, an electronic signal is fed back to the main control microcontroller 25, and the main control microcontroller 25 controls the reflux pump 32 to start, and the waste water in the buffer tank 6 is refluxed to the anode tank 3 through the water inlet pipe 1, and at the same time, the rotation speed of the water inlet pump 31 is reduced to ensure that the flow rate ratio of the outlet water of the water inlet pump 31 to the inlet water of the reflux pump 32 is adjusted to (2-2.5):1 when the total water inlet flow rate remains unchanged;

[0078] When the phenol concentration of the effluent from the buffer tank 6 exceeds 300 mg / L, the rotation speed of the inlet pump 31 is further reduced to ensure that the flow rate ratio of the effluent from the inlet pump 31 to the inlet from the reflux pump 32 is adjusted to (1-1.5):1 while the total inlet flow rate remains unchanged;

[0079] The photovoltaic panel 16 converts solar energy into electrical energy and stores it in the lithium battery of the solar charging management device 17. Under the control of the main control microcontroller 25, the solar charging management device 17 provides adaptive voltage to each electronic component and external circuit (the water pump is powered separately). The main control microcontroller 25 connects to the PC device to read the time through the Bluetooth device 24; when the time is between 6:00 and 18:00, the main control microcontroller 25 receives the light signal returned by the light sensor 23: if the natural light intensity is ≥5100Lx, the relay b19 is disconnected, and natural light is used as the growth light source for the Synechocystis 13 in the cathode pool 8; if the natural light intensity is lower than 4900Lx, the main control microcontroller 25 issues a light compensation instruction to control the relay b19 to close, and the solar charging management device 17 provides a stable voltage to the LED lamp 20.

[0080] The main control microcontroller 25 in the electrolytic cell device can regularly collect and process signals from various electronic devices, determine the operating status of the device, realize communication between various systems, and make adaptive feedback instructions in time according to the operating status of the device to optimize the operation of the device.

[0081] The photovoltaic panel 16 is a single crystal 50W, 12V solar panel with a size of 670mm×450mm. Under sunlight, the photovoltaic panel produces a photoelectric effect, stimulates electron flow, and outputs a DC voltage (0.9V) to the solar charging management device 17. Studies have shown that low-intensity external voltage (0.5-2V) can promote the removal of organic matter and nitrogen in wastewater, and the removal effect is best at 0.9V, with a COD removal rate of 95.30±2.25%, so the working voltage of 0.9V is used in this embodiment; the solar charging management device 17 is composed of a CN3791 chip and a lithium battery, and the solar charging management circuit of the system is constructed inside; the relay a18 is a single-pole double-throw switch; the relay b19 is a single-pole single-throw switch;

[0082] Optimal selection of environmental conditions and optimal treatment effects:

[0083] The performance of the photoelectric enhanced bacteria-algae electrochemical system for treating phenol-ammonia wastewater was verified by a small modular device and the conditions were further optimized. Two glass bottles were processed into an anode chamber and a cathode chamber. The effective volume of the electrode chamber was 400mL, separated by a cation exchange membrane in the middle. Brushes were used as cathode and cathode electrode materials, and connected by a titanium wire with an external load of 1000Ω. Anaerobic sludge and Synechocystis were added to the anode and cathode, respectively, with a sludge concentration of 5000mg / L and an algae concentration of 500mg / L, and stirred with a magnetic stirrer.

[0084] A three-factor three-level orthogonal experiment was designed (see Table 1), and the light intensity, illumination time and temperature were adjusted to explore the effect of the photoelectric enhanced bacteria-algae electrochemical system on the degradation performance of phenol-ammonia pollutants under different environmental factors. The experiment was run in batch mode, and phenol-ammonia wastewater was prepared with phenol and ammonium chloride. The influent COD concentration was 800 mg / L, and the ammonia nitrogen concentration was 100 mg / L. The wastewater entered the anode chamber from the light-shielded anode, and the hydraulic retention time was 48 hours. The experimental results are shown in Table 2.

[0085] Table 1 is the level table of orthogonal experimental factors;

[0086] Table 1

[0087]

[0088] Table 2 shows the orthogonal experimental design and experimental results;

[0089] Table 2

[0090]

[0091] Based on the data calculated by DPS, COD and NH4 were obtained in the equation + The simplified regression equation of -N removal efficiency is shown in equations (1) and (2).

[0092] Y1=-4.22+68.92+17.72 -15.58 (1);

[0093] Y2=-30.8+48.1+19.5-24.0-11.9-4.4+6.2 (2);

[0094] Combined with Table 2, the environmental factors on NH4 + -N and COD removal efficiency are affected in the following order: light intensity (A) > light duration (C) > temperature (B). In addition, equations (1) and (2) show that these three factors have a significant effect on NH4 + -There was no significant interaction between the effects of N and COD removal efficiency. Light intensity, as the most influential factor, can be attributed to its effect on open circuit potential (OCP). According to the Nernst equation, OCP can be changed by any redox reaction in a chemical process. When the light intensity reached 5000Lx, the algae in the cathode seemed to produce more dissolved oxygen, resulting in an increase in OCP. This demonstrates the positive correlation between light intensity and OCP within a specific range, and OCP reaches a maximum value at 5000Lx, and the optimal OCP promotes the transfer of electrons and the migration of substances in the anode chamber.

[0095] Therefore, the optimal environmental conditions are light intensity of 5000Lx, illumination time of 16h / d, and temperature of 25℃. Under this operating condition, the photoelectrically enhanced bacteria-algae electrochemical system has the strongest adaptability to the environment, the ability to break through the combined inhibition of phenol and ammonia and ultimately achieve reverse inhibition and promotion, and the resource utilization of phenol and ammonia pollutants. This is reflected in the COD removal rate of 96.7% and the ammonia nitrogen assimilation removal rate of more than 20%, which can be used to synthesize algae biomass resources.

Claims

1. A modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacterial-algal electrochemical system, characterized in that The modular device includes a bacteria-algae electrochemical device and a solar-assisted photoelectric compensation device, wherein the bacteria-algae electrochemical device includes a bacteria-algae primary battery device, a physical adsorption device and an internal reflux control device; the solar-assisted photoelectric compensation device includes an electrolytic cell device and a light compensation device; The bacteria-algae primary battery device comprises an anode pool (3), a buffer pool (6), a cathode pool (8), an anode carbon brush (12) and a cathode carbon brush (14); an anode pool water inlet (2) is provided on one side of the anode pool (3), a plurality of anode carbon brushes (12) are provided in the anode pool (3), and anaerobic sludge (11) is attached to the anode carbon brush (12); the anode pool (3) is connected to the buffer pool (6) through the buffer pool water inlet (5), the buffer pool (6) is connected to the cathode pool (8) through the cathode pool water inlet (7), and an overflow pipe (10) is provided on one side of the cathode pool (8); a plurality of cathode carbon brushes (14) are provided in the cathode pool (8), and Synechocystis (13) is attached to the cathode carbon brush (14); The physical adsorption device comprises an activated carbon adsorption layer (4) and a zeolite adsorption layer (9); the activated carbon adsorption layer (4) is arranged at the bottom of the anode pool (3) and the buffer pool (6), and the zeolite adsorption layer (9) is arranged at the bottom of the cathode pool (8); The internal reflux control device comprises a reflux pipe (15), a phenol concentration sensor a (21), a phenol concentration sensor b (22) and a motor drive device (30); the water inlet of the reflux pipe (15) is arranged in the buffer tank (6), the water outlet of the reflux pipe (15) is arranged on the water inlet pipe (1) at the anode tank water inlet (2), the water inlet pipe (1) is provided with a water inlet pump (31), and the reflux pipe (15) is provided with a reflux pump (32); the phenol concentration sensor a (21) is arranged at the anode tank water inlet (2), and the phenol concentration sensor b (22) is arranged at the buffer tank water inlet (5); the motor drive device (30) is electrically connected to the water inlet pump (31) and the reflux pump (32) respectively; The electrolytic cell device comprises a photovoltaic panel (16), a solar charging management device (17) and a relay a (18), wherein the photovoltaic panel (16) and the solar charging management device (17) are both arranged above the anode cell (3) and the buffer cell (6), the photovoltaic panel (16) is electrically connected to the solar charging management device (17), the voltage output end of the solar charging management device (17) is electrically connected to the relay a (18), the common end of the relay a (18) is electrically connected to the anode carbon brush (12), the normally closed end of the relay a (18) is electrically connected to the cathode carbon brush (14) to form a primary battery circuit, and the normally open end of the relay a (18) is electrically connected to the cathode carbon brush (14) to form an electrolytic cell circuit; The light compensation device comprises a relay b (19) and an LED lamp tube (20), and the voltage output end of the solar charging management device (17) is electrically connected to the LED lamp tube (20) via the relay b (19).

2. The modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacteria-algae electrochemical system according to claim 1 is characterized in that The volume ratio of the anode pool (3), the buffer pool (6) and the cathode pool (8) is (1-1.5): (0.5-0.7): (0.8-1), and the inner wall of the buffer pool (6) is filled with a cation exchange membrane made of sulfonated polystyrene.

3. The modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacteria-algae electrochemical system according to claim 1 is characterized in that The anode pool water inlet (2) is arranged on the upper side wall of the anode pool (3), the buffer pool water inlet (5) is arranged on the lower side wall of the buffer pool (6), the cathode pool water inlet (7) is arranged on the upper side wall of the cathode pool (8), and the overflow pipe (10) is arranged on the upper side wall.

4. The modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacteria-algae electrochemical system according to claim 1 is characterized in that The anode carbon brush (12), cathode carbon brush (14), photovoltaic panel (16), and LED lamp tube (20) are all arranged on a steel frame (33) above the anode tank (3) and the buffer tank (6).

5. The modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacteria-algae electrochemical system according to claim 1 is characterized in that The number of the anode carbon brush (12) and the cathode carbon brush (14) is 4 to 8.

6. The modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacteria-algae electrochemical system according to claim 1 is characterized in that The electrolytic cell device further comprises a Bluetooth device (24) and a main control microcontroller (25); The main control microcontroller (25) reads the world time through the Bluetooth device (24); the main control microcontroller (25) is electrically connected to the solar charging management device (17), the relay a (18), the phenol concentration sensor a (21), the phenol concentration sensor b (22) and the motor drive device (30).

7. The modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacteria-algae electrochemical system according to claim 1 is characterized in that The light compensation device further comprises a light sensor (23), and the main control microcontroller (25) is electrically connected to the light sensor (23) and the relay b (19) respectively.

8. The modular device for treating phenol-ammonia wastewater by photoelectrically enhanced bacteria-algae electrochemical system according to claim 1 is characterized in that The solar charging management device (17), the Bluetooth device (24) and the main control microcontroller (25) are all arranged on the back of the photovoltaic panel (16).

9. A method for treating phenol-ammonia wastewater using a modular device for treating phenol-ammonia wastewater using a photoelectrically enhanced bacteria-algae electrochemical system as described in any one of claims 1 to 8, characterized in that The method proceeds as follows: Step S1: injecting the phenol-ammonia wastewater into the anode pool (3) through the anode pool water inlet (2) by means of a water inlet pump (31), then passing through the buffer pool (6) and the cathode pool (8) in sequence, and finally flowing out from the overflow pipe (10) of the cathode pool (8), with a hydraulic retention time of 48 to 72 hours; Step S2: The phenol concentration sensor a (21) arranged at the anode cell water inlet (2) monitors the phenol concentration of the phenol-ammonia wastewater in real time. The main control microcontroller (25) reads the monitoring result of the phenol concentration sensor a (21) once per second and controls the working circuit of the relay a (18) switching device according to the average value of the phenol concentration of the phenol-ammonia wastewater within 1 minute: when the average value of the phenol concentration is within 900 mg / L, the normally closed end of the primary battery circuit, i.e. the relay a (18), is electrically connected to the cathode carbon brush (14); when the average value of the phenol concentration is higher than 1100 mg / L, the normally open end of the electrolytic cell circuit, i.e. the relay a (18), is electrically connected to the cathode carbon brush (14).

10. The method for treating phenol-ammonia wastewater by using a modular device for treating phenol-ammonia wastewater by using a photoelectrically enhanced bacteria-algae electrochemical system according to claim 9, characterized in that When the phenol concentration sensor b (22) detects that the phenol concentration in the buffer tank (6) is 150-300 mg / L, an electronic signal is fed back to the main control microcontroller (25), and the main control microcontroller (25) controls the reflux pump (32) to start, so that the waste water in the buffer tank (6) flows back to the anode tank (3) through the water inlet pipe (1), and at the same time reduces the rotation speed of the water inlet pump (31) to ensure that the flow rate ratio of the outlet water of the water inlet pump (31) to the inlet water of the reflux pump (32) is adjusted to (2-2.5):1 when the total water inlet flow rate remains unchanged; When the phenol concentration of the effluent from the buffer tank (6) exceeds 300 mg / L, the rotation speed of the water inlet pump (31) is further reduced to ensure that the flow rate ratio of the effluent from the water inlet pump (31) to the influent from the reflux pump (32) is adjusted to (1-1.5):1 while the total influent flow rate remains unchanged; The main control microcontroller (25) is connected to a PC device via a Bluetooth device (24) to read the time; when the time is between 6:00 and 18:00, the main control microcontroller (25) receives a light signal returned by a light sensor (23); if the natural light intensity is ≥5000 Lx, the relay b (19) is disconnected, and natural light is used as a growth light source for the Synechocystis (13) in the cathode pool (8); if the natural light intensity is lower than 5000 Lx, the main control microcontroller (25) issues a light compensation instruction, controls the relay b (19) to close, and the solar charging management device (17) provides a stable voltage to the LED lamp tube (20).

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