CN112794553B - Device for treating coal pyrolysis wastewater through micro-electric field coupling sulfur autotrophic denitrification and method for treating coal pyrolysis wastewater by using device - Google Patents
Device for treating coal pyrolysis wastewater through micro-electric field coupling sulfur autotrophic denitrification and method for treating coal pyrolysis wastewater by using device Download PDFInfo
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Abstract
A device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification and a method for treating coal pyrolysis wastewater by utilizing the device relate to a device for treating pyrolysis wastewater and a method for treating coal pyrolysis wastewater. The invention aims to solve the problems that the removal rate of nitrate nitrogen is low and the concentration of total nitrogen is difficult to meet the discharge standard when the existing coal pyrolysis wastewater treatment device is used for treating coal pyrolysis wastewater. A device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification comprises a tank body, a water inlet area, a mixing area, an autotrophic denitrification area, a micro-voltage electrolysis area and a water outlet area. The method comprises the following steps: firstly, domesticating sludge; secondly, water is fed; thirdly, autotrophic denitrification; fourthly, micro-voltage electrolysis; and fifthly, discharging water. The method utilizes the anoxic reactor and the biological electrode coupling system to treat the coal pyrolysis wastewater with high nitrate nitrogen concentration and low COD concentration. The invention is suitable for treating coal pyrolysis wastewater.
Description
Technical Field
The invention relates to a device for treating pyrolysis wastewater and a method for treating coal pyrolysis wastewater.
Background
Coal is one of the main energy sources in China, and accounts for more than 62% of the total energy consumption in nearly five years. With the increasing demand for clean air and the contradiction between air pollution caused by the lagging coal utilization mode, the development of modern coal chemical industry mainly based on clean utilization of coal is important. The low-rank coal pyrolysis co-production technology converts coal resources into gas, liquid and solid three-phase products, can realize the cascade utilization of low-rank coal, and is an important component of modern coal chemical industry. The low-rank coal pyrolysis process in China commonly comprises a solid heat carrier process, a moving bed process and a fluidized bed process. The coal pyrolysis technology has been developed, and the main problems at present are that the yield of pyrolysis is low and the environmental pollution is serious, compared with the common coal chemical industry wastewater, the coal pyrolysis wastewater has higher pollutant concentration in the wastewater due to low coal pyrolysis temperature, the biodegradability is lower, and the hazard is larger.
In recent years, new methods are continuously applied to the treatment of coal pyrolysis wastewater in China, and anaerobic biological treatment can hydrolyze refractory substances in the coal pyrolysis wastewater into easily degradable substances, so that the biodegradability of the wastewater is improved; however, if the wastewater after anaerobic treatment is directly treated aerobically, the high concentration of phenolic substances in the wastewater can inhibit the activity of aerobic bacteria, and the bubbles generated by aeration also increase the cost of sewage treatment. Patent publication No.: CN102515351A publication date: 2012.06.27A biological thickening device for reducing pollutants in coal chemical wastewater, which is tested by practical engineering, can effectively remove COD, phenols and other refractory organics in wastewater, however, the total nitrogen concentration in the effluent of wastewater is still high, and the nitrogen element in the effluent mainly exists in the form of nitrate nitrogen, thus causing difficulty in subsequent treatment. The traditional A/O process is a biological denitrification process which is widely applied at present, the process utilizes an organic carbon source in inlet water to carry out denitrification through the backflow of nitrifying liquid, however, the biodegradability of coal pyrolysis wastewater is low, phenolic substances and nitrogen-containing heterocyclic substances in the wastewater cannot be directly utilized by denitrifying bacteria to carry out biological denitrification, and the removal rate of nitrate nitrogen is not high.
Disclosure of Invention
The invention aims to solve the problems that the removal rate of nitrate nitrogen is low and the concentration of total nitrogen is difficult to meet the discharge standard when the conventional coal pyrolysis wastewater treatment device is used for treating coal pyrolysis wastewater, and provides a device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification and a method for treating coal pyrolysis wastewater by virtue of the device.
A device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification comprises a tank body, a water inlet area, a mixing area, an autotrophic denitrification area, a micro-voltage electrolysis area and a water outlet area;
the water inlet area comprises a water inlet pipe and a water inlet guide plate; the water inlet guide plate comprises a water inlet upper guide plate and a water inlet lower guide plate; the lower end of the water inlet upper guide plate is connected with the upper end of the water inlet lower guide plate; the water inlet pipe is communicated with the upper part of the left wall of the tank body, and the water inlet guide plate is arranged in the tank body; the left wall of the tank body, the water inlet guide plate and the area enclosed by the front wall and the rear wall of the tank body are water inlet areas;
the autotrophic denitrification zone comprises a supporting pore plate and a sulfur granular layer; the supporting pore plate is arranged in the tank body, the side wall of one side of the supporting pore plate is connected with the water inlet upper guide plate, the side wall of the other side of the supporting pore plate is connected with the right wall of the tank body, and the supporting pore plate is provided with a sulfur particle layer; the area formed by the water inlet upper guide plate, the supporting pore plate, the sulfur particle layer and the right wall of the pool body is an autotrophic denitrification area;
the mixing area comprises a submersible stirrer and an emptying pipe; the submersible stirrer is arranged in the tank body and positioned at the bottom of the tank body, and the emptying pipe is communicated with the right wall of the tank body; a mixing area is defined by the water inlet guide plate, the right wall of the tank body, the front wall and the rear wall of the tank body, the support pore plate and the bottom of the tank body;
the micro-voltage electrolysis region comprises a biological cathode, a biological anode, a power supply and a lead; the biological cathode is formed by connecting a plurality of rows of carbon brush cathode electrodes in parallel;
the biological anode is formed by connecting a plurality of rows of carbon brush anode electrodes in parallel;
the biological cathode and the biological anode are arranged in the tank body and are positioned above the sulfur granular layer; the power supply is arranged outside the pool body, the biological cathode is connected with the negative electrode of the power supply through a lead, and the biological anode is connected with the positive electrode of the power supply through a lead;
the water outlet zone comprises a water outlet overflow weir and a water outlet pipe, the front wall and the rear wall above the tank body are provided with the water outlet overflow weir, and the water outlet overflow weir is communicated with the water outlet pipe;
the method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by virtue of the micro-electric field coupling sulfur autotrophic denitrification is completed according to the following steps:
firstly, sludge domestication:
firstly, cleaning activated sludge taken from a coal chemical wastewater treatment plant, then placing the cleaned activated sludge in a device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification, and then adding the coal pyrolysis wastewater to acclimate the activated sludge, wherein the operation condition is 25-30 ℃;
the concentration of the activated sludge in the first step is kept to be 4000-5000 mg/L;
the COD of the coal pyrolysis wastewater in the first step is 200-300 mg/L, the volatile phenol is 50-70 mg/L, the nitrate nitrogen is 90-95 mg/L, the pH value is 7.0-8.0, and the conductivity is 3-4 mu S/cm;
secondly, applying a voltage of 0.7-0.9V to two ends of a biological cathode and a biological anode of the device by using a power supply, and keeping the muddy water mixed liquor uniformly mixed by using a submersible stirrer;
thirdly, domesticating the sludge: the tank body is filled with coal pyrolysis wastewater and activated sludge, the submersible stirrer is closed after the reaction is carried out for 46-48 hours, after the activated sludge is precipitated for 30-40 minutes, the emptying pipe is opened, supernatant liquid flows out of the device, and the emptying pipe is closed, so that sludge domestication is completed;
secondly, water feeding:
coal pyrolysis wastewater enters a water inlet area through a water inlet pipe, enters a mixing area after being guided by a water inlet guide plate, enters an autotrophic denitrification area after being mixed by a submersible stirrer positioned in the mixing area, and is subjected to hydraulic retention time of 12 hours by adjusting the flow rate of the inlet water;
thirdly, autotrophic denitrification:
after the coal pyrolysis wastewater enters the autotrophic denitrification region, the coal pyrolysis wastewater passes through a sulfur particle layer in the region, and sulfur bacteria in the region reduce nitrate nitrogen in the coal pyrolysis wastewater into nitrogen by using elemental sulfur as an electron donor;
fourthly, micro-voltage electrolysis:
the coal pyrolysis wastewater enters a micro-voltage electrolysis region from an autotrophic denitrification region, the direct-current voltage between a biological cathode and a biological anode of the micro-voltage electrolysis region is 0.7-1.2V, the biological anode has an anode potential, electroactive bacteria on the biological anode degrade refractory organic matters in the coal pyrolysis wastewater by taking the biological anode as an electron acceptor, and the electroactive denitrification bacteria on the biological cathode reduce part of nitrate nitrogen into nitrogen by using electrons from the biological anode;
fifthly, water outlet:
and after the reaction is finished, the effluent flows into a water outlet pipe through an effluent overflow weir, and the method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by virtue of the micro-electric field coupling sulfur autotrophic denitrification is finished.
The working principle of the invention is as follows:
the coal pyrolysis wastewater with high nitrate nitrogen concentration and low COD concentration enters a device for treating the coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification, and specific sulfur bacteria can take sulfur simple substances as electron donors and reduce nitrate nitrogen by utilizing electrons obtained by oxidizing the sulfur simple substances, SO that part of nitrate nitrogen in the coal pyrolysis wastewater is removed, and SO obtained by reaction 4 2- And H + On one hand, the conductivity of the wastewater can be increased, the electron transfer efficiency of a subsequent micro-electrolysis region is facilitated, and meanwhile, the pH value of the wastewater can be reduced, and the biological denitrification effect is improved; the electroactive microorganisms enriched in the biological anode in the reactor degrade refractory organic matters such as phenols in the wastewater by taking the anode as an electron acceptor, the electrons obtained by oxidation reach the cathode from the anode through a direct current power supply, and the electroactive denitrifying bacteria on the surface of the biological cathode reduce nitrate nitrogen into nitrogen-containing gas by using the electrons from the anode and remove the nitrogen-containing gas from the water, see formula 2. The method is suitable for the characteristic of low biodegradability of coal pyrolysis wastewater, and removes nitrate nitrogen while degrading refractory organics by using electroactive microorganisms.
C 6 H 6 O+11OH - →6CO 2 +17H + +28e - 1
The invention has the advantages that:
the invention provides a device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification and a method for treating coal pyrolysis wastewater by virtue of the device, wherein an anoxic reactor and a biological electrode coupling system are utilized to treat coal pyrolysis wastewater with high nitrate nitrogen concentration and low COD concentration; the COD of the coal pyrolysis wastewater is 200-300 mg/L, the volatile phenol is 50-70 mg/L, the nitrate nitrogen is 90-95 mg/L, the pH value is 7.0-8.0, and the conductivity is 3-4 mu S/cm, after the treatment by the method, the removal rate of the COD of the coal pyrolysis wastewater is 85-87%, the removal rate of the volatile phenol is 94-96%, the removal rate of the total nitrogen is 88-92%, and the cathode coulombic efficiency of a reactor is 25-28%.
The invention is suitable for treating coal pyrolysis wastewater.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for treating coal pyrolysis wastewater by micro-electric field coupling sulfur autotrophic denitrification according to the first embodiment;
FIG. 2 is a cross-sectional view taken along A-A of FIG. 1;
FIG. 3 is a cross-sectional view taken along line B-B of FIG. 1;
FIG. 4 is a cross-sectional view taken along line C-C of FIG. 1;
fig. 5 is a cross-sectional view taken along line D-D of fig. 1.
Detailed Description
The first embodiment is as follows: the embodiment is a device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification, which comprises a pool body, a water inlet area, a mixing area, an autotrophic denitrification area, a micro-voltage electrolysis area and a water outlet area;
the water inlet area comprises a water inlet pipe 1 and a water inlet guide plate; the water inlet guide plate comprises a water inlet upper guide plate 4-1 and a water inlet lower guide plate 4-2; the lower end of the water inlet upper guide plate 4-1 is connected with the upper end of the water inlet lower guide plate 4-2; the water inlet pipe 1 is communicated with the upper part of the left wall 2-1 of the tank body, and the water inlet guide plate is arranged in the tank body; the left wall 2-1 of the tank body, the water inlet guide plate and the area enclosed by the front wall and the rear wall of the tank body are water inlet areas;
the autotrophic denitrification zone comprises a supporting pore plate 6 and a sulfur granular layer 7; the supporting pore plate 6 is arranged in the tank body, the side wall of one side of the supporting pore plate 6 is connected with the water inlet upper guide plate 4-1, the side wall of the other side of the supporting pore plate 6 is connected with the right wall 2-2 of the tank body, and the supporting pore plate 6 is provided with a sulfur particle layer 7; the area formed by the water inlet upper guide plate 4-1, the supporting pore plate 6, the sulfur particle layer 7 and the right wall 2-2 of the tank body is an autotrophic denitrification area;
the mixing area comprises a submersible stirrer 5 and a vent pipe 14; the submersible stirrer 5 is arranged in the tank body and positioned at the bottom of the tank body, and the emptying pipe 14 is communicated with the right wall 2-2 of the tank body; a mixing area is defined by the water inlet guide plate, the right wall 2-2 of the tank body, the front wall and the rear wall of the tank body, the supporting orifice plate 6 and the bottom of the tank body;
the micro-voltage electrolysis region comprises a biological cathode 8, a biological anode 9, a power supply 15 and a lead; the biological cathode 8 is formed by connecting a plurality of rows of carbon brush cathode electrodes in parallel;
the biological anode 9 is formed by connecting a plurality of rows of carbon brush anode electrodes in parallel;
the biological cathode 8 and the biological anode 9 are arranged in the tank body and are positioned above the sulfur particle layer 7; the power supply 15 is arranged outside the tank body, the biological cathode 8 is connected with the negative electrode of the power supply 15 through a lead, and the biological anode 9 is connected with the positive electrode of the power supply 15 through a lead;
the effluent area comprises an effluent overflow weir 10 and an effluent pipe 13, the front wall and the rear wall above the tank body are provided with the effluent overflow weir 10, and the effluent overflow weir 10 is communicated with the effluent pipe 13.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the distance between the water inlet upper guide plate 4-1 and the left wall 2-1 of the tank body is 40-50 cm, and the included angle between the water inlet lower guide plate 4-2 and the vertical direction is 45-60 degrees. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: each row of carbon brush cathode electrodes consists of a plurality of carbon brushes, and the carbon brushes are formed by twisting carbon fiber wires and titanium wires; and each row of carbon brush anode electrodes consists of a plurality of carbon brushes, and the carbon brushes are formed by twisting carbon fiber wires and titanium wires. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is: the carbon brush cathode electrodes and the carbon brush anode electrodes are alternately arranged, and the distance between every two adjacent rows of carbon brush cathode electrodes and every two adjacent rows of carbon brush anode electrodes is 10-15 cm. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the power supply 15 is a direct current power supply. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: circular holes with the aperture of 0.2-0.5 cm are distributed on the supporting pore plate 6, and the hole distance is 2-3 cm; cobblestones with the grain diameter of 1cm are covered on the supporting hole plate 6, a sulfur particle layer 7 is arranged on the cobblestones, and the height of the sulfur particle layer 7 is one sixth of the height of the pool body. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the embodiment is a method for treating coal pyrolysis wastewater by using a device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification, and the method is completed according to the following steps:
firstly, sludge domestication:
firstly, cleaning activated sludge taken from a coal chemical wastewater treatment plant, then placing the cleaned activated sludge in a device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification, and then adding the coal pyrolysis wastewater to acclimate the activated sludge, wherein the operation condition is 25-30 ℃;
the concentration of the activated sludge in the first step is kept to be 4000-5000 mg/L;
the COD of the coal pyrolysis wastewater in the first step is 200-300 mg/L, the volatile phenol is 50-70 mg/L, the nitrate nitrogen is 90-95 mg/L, the pH value is 7.0-8.0, and the conductivity is 3-4 mu S/cm;
secondly, applying a voltage of 0.7-0.9V to two ends of a biological cathode 8 and a biological anode 9 of the device by using a power supply 15, and keeping the muddy water mixed solution uniformly mixed by using a submersible stirrer 5;
thirdly, domesticating the sludge: filling the tank body with coal pyrolysis wastewater and activated sludge, reacting for 46-48 h, closing the submersible stirrer 5, after the activated sludge is precipitated for 30-40 min, opening the emptying pipe 14, enabling supernatant to flow out of the device, and closing the emptying pipe 14 to finish sludge domestication;
secondly, water feeding:
coal pyrolysis wastewater enters a water inlet area through a water inlet pipe 1, enters a mixing area after being guided by a water inlet guide plate, enters an autotrophic denitrification area after being mixed by a submersible stirrer 5 positioned in the mixing area, and is subjected to hydraulic retention time of 12 hours by adjusting the flow rate of the inlet water;
thirdly, autotrophic denitrification:
after the coal pyrolysis wastewater enters the autotrophic denitrification region, the coal pyrolysis wastewater passes through a sulfur particle layer 7 in the region, and sulfur bacteria in the region reduce nitrate nitrogen in the coal pyrolysis wastewater into nitrogen by using elemental sulfur as an electron donor;
fourthly, micro-voltage electrolysis:
the coal pyrolysis wastewater enters a micro-voltage electrolysis region from an autotrophic denitrification region, the direct-current voltage between a biological cathode 8 and a biological anode 9 of the micro-voltage electrolysis region is 0.7-1.2V, the biological anode 9 has an anode potential, electroactive bacteria positioned on the biological anode 9 degrade refractory organics in the coal pyrolysis wastewater by taking the biological anode 9 as an electron acceptor, and the electroactive denitrification bacteria on the biological cathode 8 reduce part of nitrate nitrogen into nitrogen by using electrons from the biological anode 9;
fifthly, water outlet:
after the reaction is finished, the effluent flows into a water outlet pipe 13 through an effluent overflow weir 10, and the method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by virtue of the micro-electric field coupling sulfur autotrophic denitrification is finished.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the COD of the coal pyrolysis wastewater in the second step is 200-300 mg/L, the volatile phenol is 50-70 mg/L, the nitrate nitrogen is 90-95 mg/L, the pH value is 7.0-8.0, and the conductivity is 3-4 mu S/cm. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and the stirring speed of the submersible stirrer 5 in the step two is 80-100 r/min. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the COD of the effluent in the step five is 30-65 mg/L, the volatile phenol is 2-3 mg/L, the total nitrogen is 4.5-17 mg/L, the pH value is 8.0-8.5, and the conductivity is 3-4 mu S/cm. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the embodiment is described with reference to fig. 1 to 5, and the device for treating coal pyrolysis wastewater by micro-electric field coupling sulfur autotrophic denitrification comprises a tank body, a water inlet area, a mixing area, an autotrophic denitrification area, a micro-voltage electrolysis area and a water outlet area;
the water inlet area comprises a water inlet pipe 1 and a water inlet guide plate; the water inlet guide plate comprises a water inlet upper guide plate 4-1 and a water inlet lower guide plate 4-2; the lower end of the water inlet upper guide plate 4-1 is connected with the upper end of the water inlet lower guide plate 4-2; the water inlet pipe 1 is communicated with the upper part of the left wall 2-1 of the tank body, and the water inlet guide plate is arranged in the tank body; the left wall 2-1 of the tank body, the water inlet guide plate and the area enclosed by the front wall and the rear wall of the tank body are water inlet areas;
the autotrophic denitrification zone comprises a supporting pore plate 6 and a sulfur granular layer 7; the supporting pore plate 6 is arranged in the tank body, the side wall of one side of the supporting pore plate 6 is connected with the water inlet upper guide plate 4-1, the side wall of the other side of the supporting pore plate 6 is connected with the right wall 2-2 of the tank body, and the supporting pore plate 6 is provided with a sulfur particle layer 7; the area formed by the water inlet upper guide plate 4-1, the supporting pore plate 6, the sulfur particle layer 7 and the right wall 2-2 of the tank body is an autotrophic denitrification area;
the mixing area comprises a submersible stirrer 5 and a vent pipe 14; the submersible stirrer 5 is arranged in the tank body and positioned at the bottom of the tank body, and the emptying pipe 14 is communicated with the right wall 2-2 of the tank body; a mixing area is defined by the water inlet guide plate, the right wall 2-2 of the tank body, the front wall and the rear wall of the tank body, the supporting orifice plate 6 and the bottom of the tank body;
the micro-voltage electrolysis region comprises a biological cathode 8, a biological anode 9, a power supply 15 and a lead; the biological cathode 8 is formed by connecting a plurality of rows of carbon brush cathode electrodes in parallel;
the biological anode 9 is formed by connecting a plurality of rows of carbon brush anode electrodes in parallel;
the biological cathode 8 and the biological anode 9 are arranged in the tank body and are positioned above the sulfur particle layer 7; the power supply 15 is arranged outside the tank body, the biological cathode 8 is connected with the negative electrode of the power supply 15 through a lead, and the biological anode 9 is connected with the positive electrode of the power supply 15 through a lead;
the effluent area comprises an effluent overflow weir 10 and an effluent pipe 13, the front wall and the rear wall above the tank body are provided with the effluent overflow weir 10, and the effluent overflow weir 10 is communicated with the effluent pipe 13;
the distance between the water inlet upper guide plate 4-1 and the left wall 2-1 of the tank body is 40-50 cm, and the included angle between the water inlet lower guide plate 4-2 and the vertical direction is 45 degrees;
each row of carbon brush cathode electrodes consists of a plurality of carbon brushes, and the carbon brushes are formed by twisting carbon fiber wires and titanium wires; each row of carbon brush anode electrodes consists of a plurality of carbon brushes, and the carbon brushes are formed by twisting carbon fiber wires and titanium wires;
the carbon brush cathode electrodes and the carbon brush anode electrodes are alternately arranged, and the distance between every two adjacent rows of carbon brush cathode electrodes and every two adjacent rows of carbon brush anode electrodes is 15 cm;
the power supply 15 is a direct current power supply;
circular holes with the aperture of 0.3cm are distributed on the supporting orifice plate 6, and the hole spacing is 3 cm; cobblestones with the grain diameter of 1cm are covered on the supporting hole plate 6, a sulfur particle layer 7 is arranged on the cobblestones, and the height of the sulfur particle layer 7 is one sixth of the height of the pool body;
the method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by virtue of the micro-electric field coupling sulfur autotrophic denitrification is completed according to the following steps:
firstly, sludge domestication:
firstly, cleaning activated sludge taken from a coal chemical wastewater treatment plant, then placing the cleaned activated sludge in a device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification, and then adding synthesized coal pyrolysis wastewater to perform acclimation of the activated sludge, wherein the operation condition is 25 ℃;
the concentration of the activated sludge in the first step is kept to be 4500 mg/L;
the COD of the synthesized coal pyrolysis wastewater in the first step is 500-600 mg/L, wherein 300mg/L of COD is provided by methanol, the rest of COD is provided by coal pyrolysis wastewater, the content of volatile phenol is 50-70 mg/L, the content of nitrate nitrogen is 90-95 mg/L, the pH value is 7.0-8.0, and the conductivity is 3-4 mu S/cm;
secondly, applying 0.7V voltage to two ends of a biological cathode 8 and a biological anode 9 of the device by using a power supply 15, and keeping the muddy water mixed liquor uniformly mixed by using a submersible stirrer 5;
thirdly, domesticating the sludge: the tank body is filled with coal pyrolysis wastewater and activated sludge, the submersible stirrer 5 is closed after the reaction for 46h, the emptying pipe 14 is opened after the activated sludge is precipitated for 40min, the supernatant flows out of the device, and the emptying pipe 14 is closed, so that the sludge domestication is completed;
secondly, water feeding:
coal pyrolysis wastewater enters a water inlet area through a water inlet pipe 1, enters a mixing area after being guided by a water inlet guide plate, enters an autotrophic denitrification area after being mixed by a submersible stirrer 5 positioned in the mixing area, and is subjected to hydraulic retention time of 12 hours by adjusting the flow rate of the inlet water;
the COD of the coal pyrolysis wastewater in the second step is 200-300 mg/L, the volatile phenol is 50-70 mg/L, the nitrate nitrogen is 90-95 mg/L, the pH value is 7.0-8.0, and the conductivity is 3-4 mu S/cm;
the stirring speed of the submersible stirrer 5 in the step two is 100 r/min;
thirdly, autotrophic denitrification:
after the coal pyrolysis wastewater enters the autotrophic denitrification region, the coal pyrolysis wastewater passes through a sulfur particle layer 7 in the region, and sulfur bacteria in the region reduce nitrate nitrogen in the coal pyrolysis wastewater into nitrogen by using elemental sulfur as an electron donor;
fourthly, micro-voltage electrolysis:
the coal pyrolysis wastewater enters a micro-voltage electrolysis region from an autotrophic denitrification region, the direct-current voltage between a biological cathode 8 and a biological anode 9 of the micro-voltage electrolysis region is 0.7-0.9V, the biological anode 9 has an anode potential, electroactive bacteria positioned on the biological anode 9 degrade refractory organic matters in the coal pyrolysis wastewater by taking the biological anode 9 as an electron acceptor, and the electroactive denitrification bacteria on the biological cathode 8 reduce part of nitrate nitrogen into nitrogen by using electrons from the biological anode 9;
fifthly, water outlet:
after the reaction is finished, the effluent flows into a water outlet pipe 13 through an effluent overflow weir 10, and the method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by virtue of the micro-electric field coupling sulfur autotrophic denitrification is finished;
the COD of the effluent in the step five is 43-65 mg/L, the volatile phenol is 5-7 mg/L, the total nitrogen is 15-17 mg/L, the pH value is 8.0-8.5, and the conductivity is 3-4 mu S/cm.
In the first embodiment, the removal rate of COD in the coal pyrolysis wastewater inlet water is 77-79%, the removal rate of volatile phenol is 88-90%, the removal rate of total nitrogen is 82-85%, and the cathode coulombic efficiency of the reactor is 20-21%.
FIG. 1 is a schematic structural diagram of an apparatus for treating coal pyrolysis wastewater by micro-electric field coupling sulfur autotrophic denitrification according to the first embodiment;
FIG. 2 is a cross-sectional view taken along A-A of FIG. 1;
FIG. 3 is a cross-sectional view taken along line B-B of FIG. 1;
FIG. 4 is a cross-sectional view taken along line C-C of FIG. 1;
fig. 5 is a cross-sectional view taken along line D-D of fig. 1.
In fig. 1 to 5, 1 is a water inlet pipe, 2-1 is a left wall of the tank body, 2-2 is a right wall of the tank body, 3 is a water flow indicating arrow, 4-1 is an upper water inlet guide plate, 4-2 is a lower water inlet guide plate, 5 is a submersible stirrer, 6 is a support orifice plate, 7 is a sulfur particle layer, 8 is a biological cathode, 9 is a biological anode, 10 is a water outlet overflow weir, 13 is a water outlet pipe, 14 is an emptying pipe, and 15 is a power supply;
example two: the present embodiment is different from the first embodiment in that: a voltage of 0.9V was applied across the biocathode 8 and the bioanode 9 of the device using a power supply 15. Other steps and parameters are the same as those in the first embodiment.
In the second embodiment, the removal rate of the COD in the coal pyrolysis wastewater inlet water is 85-87%, the removal rate of the volatile phenol is 94-96%, the removal rate of the total nitrogen is 90-92%, and the cathode coulombic efficiency of the reactor is 25-27%.
Example three: the present embodiment is different from the first embodiment in that: a voltage of 1.2V was applied across the biocathode 8 and the bioanode 9 of the device using a power supply 15. Other steps and parameters are the same as those in the first embodiment.
In the third embodiment, the removal rate of the COD in the inlet water of the coal pyrolysis wastewater is 90-92%, the removal rate of the volatile phenol is 98-99%, the removal rate of the total nitrogen is 77-79%, and the cathode coulombic efficiency of the reactor is 36-38%.
Claims (9)
1. The method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by virtue of the micro-electric field coupling sulfur autotrophic denitrification is characterized by comprising the following steps of:
firstly, sludge domestication:
firstly, cleaning activated sludge taken from a coal chemical wastewater treatment plant, then placing the cleaned activated sludge in a device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification, and then adding the coal pyrolysis wastewater to acclimate the activated sludge, wherein the operation condition is 25-30 ℃;
the concentration of the activated sludge in the first step is kept to be 4000-5000 mg/L;
the COD of the coal pyrolysis wastewater in the first step is 200-300 mg/L, the volatile phenol is 50-70 mg/L, the nitrate nitrogen is 90-95 mg/L, the pH value is 7.0-8.0, and the conductivity is 3-4 mu S/cm;
secondly, applying a voltage of 0.7-0.9V to two ends of a biological cathode (8) and a biological anode (9) of the device by using a power supply (15), and keeping the muddy water mixed solution uniformly mixed by using a submersible stirrer (5);
thirdly, domesticating the sludge: the pool body is filled with coal pyrolysis wastewater and activated sludge, the submersible stirrer (5) is closed after the reaction is carried out for 46-48 h, after the activated sludge is precipitated for 30-40 min, the emptying pipe (14) is opened, supernatant liquid flows out of the device, and the emptying pipe (14) is closed, so that sludge domestication is completed;
secondly, water feeding:
coal pyrolysis wastewater enters a water inlet area through a water inlet pipe (1), enters a mixing area after being guided by a water inlet guide plate, enters an autotrophic denitrification area after being mixed by a submersible stirrer (5) positioned in the mixing area, and is subjected to hydraulic retention time of 12 hours by adjusting the flow rate of the inlet water;
thirdly, autotrophic denitrification:
after the coal pyrolysis wastewater enters the autotrophic denitrification region, the coal pyrolysis wastewater passes through a sulfur particle layer (7) in the region, and sulfur bacteria in the region reduce nitrate nitrogen in the coal pyrolysis wastewater into nitrogen by using elemental sulfur as an electron donor;
fourthly, micro-voltage electrolysis:
the coal pyrolysis wastewater enters a micro-voltage electrolysis region from an autotrophic denitrification region, the direct-current voltage between a biological cathode (8) and a biological anode (9) of the micro-voltage electrolysis region is 0.7-1.2V, the biological anode (9) has an anode potential, electroactive bacteria positioned on the biological anode (9) degrade refractory organic matters in the coal pyrolysis wastewater by taking the biological anode (9) as an electron acceptor, and the electroactive denitrification bacteria on the biological cathode (8) reduce part of nitrate nitrogen into nitrogen by using electrons from the biological anode (9);
fifthly, water outlet:
after the reaction is finished, the effluent flows into a water outlet pipe (13) through an effluent overflow weir (10), namely, the method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by virtue of the micro-electric field coupling sulfur autotrophic denitrification is finished;
the device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification comprises a pool body, a water inlet area, a mixing area, an autotrophic denitrification area, a micro-voltage electrolysis area and a water outlet area;
the water inlet area comprises a water inlet pipe (1) and a water inlet guide plate; the water inlet guide plate comprises a water inlet upper guide plate (4-1) and a water inlet lower guide plate (4-2); the lower end of the water inlet upper guide plate (4-1) is connected with the upper end of the water inlet lower guide plate (4-2); the water inlet pipe (1) is communicated with the upper part of the left wall (2-1) of the tank body, and the water inlet guide plate is arranged in the tank body; the left wall (2-1) of the tank body, the water inlet guide plate and the area enclosed by the front wall and the rear wall of the tank body are water inlet areas;
the autotrophic denitrification zone comprises a supporting pore plate (6) and a sulfur granular layer (7); the supporting pore plate (6) is arranged in the tank body, the side wall of one side of the supporting pore plate (6) is connected with the water inlet upper guide plate (4-1), the side wall of the other side of the supporting pore plate is connected with the right wall (2-2) of the tank body, and a sulfur particle layer (7) is arranged on the supporting pore plate (6); the area formed by the water inlet upper guide plate (4-1), the supporting pore plate (6), the sulfur granular layer (7) and the right wall (2-2) of the pool body is an autotrophic denitrification area;
the mixing area comprises a submersible stirrer (5) and a vent pipe (14); the submersible stirrer (5) is arranged in the tank body and positioned at the bottom of the tank body, and the emptying pipe (14) is communicated with the right wall (2-2) of the tank body; a mixing area is defined by the water inlet guide plate, the right wall (2-2) of the tank body, the front wall and the rear wall of the tank body, the support pore plate (6) and the bottom of the tank body;
the micro-voltage electrolysis region comprises a biological cathode (8), a biological anode (9), a power supply (15) and a lead; the biological cathode (8) is formed by connecting a plurality of rows of carbon brush cathode electrodes in parallel;
the biological anode (9) is formed by connecting a plurality of rows of carbon brush anode electrodes in parallel;
the biological cathode (8) and the biological anode (9) are arranged in the pool body and are positioned above the sulfur granular layer (7); the power supply (15) is arranged outside the pool body, the biological cathode (8) is connected with the negative electrode of the power supply (15) through a lead, and the biological anode (9) is connected with the positive electrode of the power supply (15) through a lead;
the water outlet area comprises a water outlet overflow weir (10) and a water outlet pipe (13), the water outlet overflow weir (10) is arranged on the front wall and the rear wall above the pool body, and the water outlet overflow weir (10) is communicated with the water outlet pipe (13).
2. The method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by the micro-electric field coupling sulfur autotrophic denitrification according to claim 1, wherein the distance between the upper water inlet guide plate (4-1) and the left wall (2-1) of the tank body is 40-50 cm, and the included angle between the lower water inlet guide plate (4-2) and the vertical direction is 45-60 degrees.
3. The method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by using the micro-electric field coupled sulfur autotrophic denitrification according to claim 1, wherein the cathode electrode of each row of carbon brushes is composed of a plurality of carbon brushes, and the carbon brushes are formed by twisting carbon fiber wires and titanium wires; and each row of carbon brush anode electrodes consists of a plurality of carbon brushes, and the carbon brushes are formed by twisting carbon fiber wires and titanium wires.
4. The method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by using the micro-electric field coupling sulfur autotrophic denitrification according to claim 1, wherein the carbon brush cathode electrodes and the carbon brush anode electrodes are alternately arranged, and the distance between every two adjacent rows of carbon brush cathode electrodes and carbon brush anode electrodes is 10-15 cm.
5. The method for treating coal pyrolysis wastewater by using the device for treating coal pyrolysis wastewater by using micro-electric field coupled sulfur autotrophic denitrification according to claim 1, wherein the power source (15) is a direct current power source.
6. The method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by using the micro-electric field coupling sulfur autotrophic denitrification according to claim 1, wherein circular holes with the hole diameter of 0.2-0.5 cm are distributed on the supporting hole plate (6), and the hole distance is 2-3 cm; cobblestones with the particle size of 1cm are covered on the supporting hole plate (6), a sulfur particle layer (7) is arranged on the cobblestones, and the height of the sulfur particle layer (7) is one sixth of the height of the pool body.
7. The method for treating coal pyrolysis wastewater by using the device for treating coal pyrolysis wastewater by using micro-electric field coupling sulfur autotrophic denitrification according to claim 1, wherein the COD of the coal pyrolysis wastewater in the second step is 200-300 mg/L, the volatile phenol is 50-70 mg/L, the nitrate nitrogen is 90-95 mg/L, the pH value is 7.0-8.0, and the conductivity is 3-4 μ S/cm.
8. The method for treating the coal pyrolysis wastewater by using the device for treating the coal pyrolysis wastewater by virtue of the micro-electric field coupling sulfur autotrophic denitrification as claimed in claim 1, wherein the stirring speed of the submersible stirrer (5) in the second step is 80-100 r/min.
9. The method for treating coal pyrolysis wastewater by using the device for treating coal pyrolysis wastewater by virtue of micro-electric field coupling sulfur autotrophic denitrification according to claim 1, wherein COD (chemical oxygen demand) of effluent water in the fifth step is 30-65 mg/L, volatile phenol is 2-3 mg/L, total nitrogen is 4.5-17 mg/L, pH value is 8.0-8.5, and conductivity is 3-4 mu S/cm.
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