CN107082485B - Method for removing azo dye mixed polluted wastewater by using bioelectrochemical reactor system - Google Patents
Method for removing azo dye mixed polluted wastewater by using bioelectrochemical reactor system Download PDFInfo
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Images
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- Chemical & Material Sciences (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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- Water Supply & Treatment (AREA)
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- Biodiversity & Conservation Biology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for removing azo dye mixed polluted wastewater by using a bioelectrochemical reactor system, and relates to a treatment method of azo dye mixed polluted wastewater. The invention aims to solve the technical problems of low treatment speed and low efficiency of azo dye wastewater and high cost of a physical chemical method in the existing anaerobic biological method. The method comprises the following steps: firstly, building a bioelectrochemical reactor system; secondly, culturing and domesticating sludge of the bioelectrochemical reactor system; and thirdly, operating the bioelectrochemical reactor system. The removal rates of COD, inorganic nitrogen and azo dyes in the effluent of the reactor can respectively reach 89%, 75% and 92%, mixed polluted wastewater containing the azo dyes can be effectively removed, and the method can be used in sewage treatment engineering.
Description
Technical Field
The invention relates to a method for treating azo dye mixed polluted wastewater.
Technical Field
The printing and dyeing wastewater, especially the wastewater containing azo dyes, has the characteristics of large discharge, high organic matter content, large biological toxicity and high chromaticity, and the treatment of the wastewater is always the key and difficult point in the field of water treatment. The reduction of the chromaticity of the wastewater containing the azo dyes is a key link for treating the wastewater containing the azo dyes, the chromophoric and color-assisting groups of the dyes can be damaged in a targeted manner by utilizing biological and chemical methods, so that the dyes are decolorized, meanwhile, the biotoxicity of the decolorized products of the dyes is also greatly reduced, and the aims of decolorizing and detoxifying the wastewater containing the dyes are fulfilled. Wherein, anaerobic biological method is the main technique for treating wastewater containing azo dyes, and in the process that anaerobic microorganisms use organic substrates in water as carbon sources, electrons are provided for azo groups (-N ═ N-) to break and reduce azo bonds. The anaerobic biological process has the characteristics of low cost and environmental friendliness, but also has the defects of low reaction speed, low efficiency and large occupied area. While the physical and chemical method can decolorize the dye wastewater quickly and efficiently, the high cost also makes the physical and chemical method difficult to be applied in large scale.
Disclosure of Invention
The invention aims to solve the technical problems of low treatment speed, low efficiency and high cost of a physical and chemical method of azo dye wastewater in the existing anaerobic biological method, and provides a method for removing azo dye mixed polluted wastewater by utilizing an electrically-stimulated anaerobic-aerobic continuous flow reaction device.
The method for removing azo dye mixed polluted wastewater by utilizing the electric stimulation anaerobic-aerobic continuous flow reaction device comprises the following steps:
firstly, building a bioelectrochemical reactor system: the bioelectrochemical reactor system consists of a reactor shell, a clapboard, a secondary sedimentation tank, a first reflux pump, a second reflux pump and an adjustable direct current power supply;
the shell is divided into an anaerobic tank and an aerobic tank by the partition board; the lower part of the clapboard is provided with a water through hole;
a stirrer and a pair of electrodes are arranged in the anaerobic tank; the electrode is connected with an adjustable direct current power supply; the lower end of the side wall of one side of the anaerobic tank is provided with a water inlet and a nitrifying liquid return port, and the upper end is provided with a sludge return port;
an aeration device is arranged in the aerobic tank; a nitrifying liquid outlet is formed in the lower end of the side wall of one side of the aerobic tank, and a water outlet is formed in the upper end of the side wall of one side of the aerobic tank;
the upper end of the secondary sedimentation tank is provided with a water inlet and an overflow port, and the lower end of the secondary sedimentation tank is connected with a sludge discharge pipe;
the first reflux pump is arranged on a pipeline between the nitrifying liquid outlet of the aerobic tank and the nitrifying liquid reflux outlet of the anaerobic tank;
the second reflux pump is arranged on a pipeline between the sludge discharge pipe of the secondary sedimentation tank and the sludge reflux port of the anaerobic tank;
secondly, sludge culture and domestication of the bioelectrochemical reactor system:
a. according to the concentration of 1.0g/L of glucose and the concentration of 0.04g/L, NH of alizarin yellow R4The Cl concentration was 0.04g/L, KNO3The concentration of the vitamin solution is 0.07g/L, the concentration of the vitamin solution is 0.5ml/L and the concentration of the mineral element solution is 0.1ml/L, and then domesticated water is prepared according to the volume ratio of the domesticated water to the activated sludge of 1: 10 adding acclimatized water and activated sludge to the reactionIn the shell, the anaerobic tank is sealed by a cover plate, the stirrer is started, and aeration is carried out for 24-26 hours in the aerobic tank through the aeration device;
b. introducing domesticated water into an anaerobic tank through a water inlet, then introducing the domesticated water into an aerobic tank through a water passing hole, and refluxing liquid at the bottom of the aerobic tank into the anaerobic tank through a nitrifying liquid outlet and a first reflux pump; the water flowing out of the water outlet of the aerobic tank enters a secondary sedimentation tank, clear water flows out of the overflow port after sedimentation, partial sludge flows back to the anaerobic tank through a second reflux pump, and residual sludge is discharged from a sludge discharge pipe; the running time is 7-10 days; during operation, the reflux volume ratio of the nitrifying liquid is gradually reduced from 400-500% to 300%, the reflux volume ratio of the sludge is gradually reduced from 100-120% to 50%, and the hydraulic retention time is gradually reduced from 20-24 h to 9 h;
c. keeping the reflux ratio of nitrifying liquid at 300%, the reflux ratio of sludge at 50% and the hydraulic retention time at 9h, and gradually increasing the concentration of alizarin yellow R in the acclimation water at a speed of increasing 0.005-0.01 g/L every day until the concentration of alizarin yellow R reaches 0.1 g/L;
d. keeping the reflux ratio of nitrifying liquid of a bioelectrochemical reactor system at 300%, the reflux ratio of sludge at 50%, the hydraulic retention time at 9h and the concentration of alizarin yellow R at 0.1g/L unchanged, continuously measuring the COD (chemical oxygen demand) and the concentration of alizarin yellow R of effluent, and finishing the starting of the reactor when the concentrations of the COD and the alizarin yellow R of the effluent are stable;
thirdly, operating the bioelectrochemical reactor system:
replacing domesticated water distribution in the started bioelectrochemical reactor system with the azo dye mixed polluted wastewater to be treated, connecting the electrodes with an adjustable direct current power supply, and using the adjustable direct current power supply to change the voltage from V1Starting at 0.1V, increasing gradually to V with an increase of 0.1V per day20.5-1.5V; then, while keeping the voltage at V2, controlling the reflux ratio of the nitrifying liquid at 300%, the reflux ratio of the sludge at 50% and the hydraulic retention time at 9h, and operating the bioelectrochemical reactor system to complete the treatment of the azo dye mixed polluted wastewater.
The reaction device and the wastewater treatment method of the invention promote the reduction of microorganisms by applying voltage stimulation to the anaerobic section of the traditional anaerobic-aerobic process, so that COD, inorganic nitrogen and azo dyes in the wastewater containing azo dye mixed pollution are synchronously removed. On the basis of the biological reduction method, a small external electric field is input to provide extra reducing force for microorganisms and stimulate the extracellular electron transfer efficiency of the microorganisms, so that the aims of strengthening the reduction of the azo dye by the microorganisms and realizing the rapid reduction and mineralization of the azo dye are fulfilled. The invention adopts the coupling of the traditional anaerobic-aerobic process and the bioelectrochemical system to promote the treatment effect of the azo dye-containing mixed polluted wastewater, and needs two processes: (1) culturing and domesticating microorganisms; (2) and (5) applying an electric field for stimulation. And carrying out quantitative and qualitative analysis on the degradation efficiency of the anaerobic-aerobic process under the stimulation of an external electric field to synchronously remove COD, inorganic nitrogen and azo dyes. The method adopted by the invention has the removal rates of 90%, 88% and 87% for effluent COD, inorganic nitrogen and azo dyes respectively, and has the characteristics of high efficiency, low energy consumption and large-scale production compared with the traditional physical, chemical and biological treatment methods. Provides a method for solving the problem of treating the mixed polluted wastewater containing azo dyes in the sewage treatment.
Drawings
FIG. 1 is a schematic diagram of a bioelectrochemical reactor system of the present invention, in which 1 is a reactor housing, 2 is a partition, 3 is a secondary sedimentation tank, 4 is a first reflux pump, 5 is a second reflux pump, and 6 is an adjustable DC power supply; 1-1 is an anaerobic tank, 1-1-1 is a stirrer, and 1-1-2 is an electrode; 1-1-3 is a water inlet, 1-1-4 is a nitrifying liquid return port, and 1-1-5 is a sludge return port; 1-2 is an aerobic tank, 1-2-1 is an aeration device, 1-2-2 is a nitrified liquid outlet, and 1-2-3 is a water outlet; 2-1 is a water through hole; 3-1 is a water inlet, 3-2 is an overflow port, and 3-3 is a sludge discharge pipe;
FIG. 2 shows the change of the removal rate of the wastewater index in test 1 when a voltage of 1.5V is applied;
FIG. 3 shows the change of the removal rate of the index of wastewater when the power supply was not turned on in comparative test 1.
FIG. 4 is a graph comparing the removal effects of COD, inorganic nitrogen and azo dyes after treatment of test 1 and comparative test 1;
Detailed Description
The first embodiment is as follows: the method for removing azo dye mixed polluted wastewater by utilizing the electrically-stimulated anaerobic-aerobic continuous flow reaction device comprises the following steps:
firstly, building a bioelectrochemical reactor system: the bioelectrochemical reactor system consists of a reactor shell 1, a clapboard 2, a secondary sedimentation tank 3, a first reflux pump 4, a second reflux pump 5 and an adjustable direct current power supply 6; the shell 1 is divided into an anaerobic tank 1-1 and an aerobic tank 1-2 by the clapboard 2; the lower part of the clapboard 2 is provided with a water through hole 2-1; a stirrer 1-1-1 and a pair of electrodes 1-1-2 are arranged in the anaerobic tank 1-1; the electrode 1-1-2 is connected with an adjustable direct current power supply 6; the lower end of the side wall of one side of the anaerobic tank 1-1 is provided with a water inlet 1-1-3 and a nitrifying liquid return port 1-1-4, and the upper end is provided with a sludge return port 1-1-5; an aeration device 1-2-1 is arranged in the aerobic tank 1-2; a nitrifying liquid outlet 1-2-2 is arranged at the lower end of the side wall of one side of the aerobic tank 1-2, and a water outlet 1-2-3 is arranged at the upper end; the upper end of the secondary sedimentation tank 3 is provided with a water inlet 3-1 and an overflow port 3-2, and the lower end is connected with a sludge discharge pipe 3-3; the first reflux pump 4 is arranged on a pipeline between the nitrifying liquid outlet 1-2-2 of the aerobic tank 1-2 and the nitrifying liquid reflux opening 1-1-4 of the anaerobic tank 1-1; the second reflux pump 5 is arranged on a pipeline between the sludge discharge pipe 3-3 of the secondary sedimentation tank 3 and the sludge reflux port 1-1-5 of the anaerobic tank 1-1;
secondly, sludge culture and domestication of the bioelectrochemical reactor system:
a. according to the concentration of 1.0g/L of glucose and the concentration of 0.04g/L, NH of alizarin yellow R4The Cl concentration was 0.04g/L, KNO3The concentration of the vitamin solution is 0.07g/L, the concentration of the vitamin solution is 0.5ml/L and the concentration of the mineral element solution is 0.1ml/L, and then domesticated water is prepared according to the volume ratio of the domesticated water to the activated sludge of 1: (9-10) adding the domesticated water and activated sludge into the reactor shell 1, sealing the anaerobic tank 1-1 with a cover plate, starting the stirrer 1-1-1, and aerating the aerobic tank 1-2 for 24-26 hours through the aeration device 1-2-1;
b. domesticated water is introduced into an anaerobic tank 1-1 through a water inlet 1-1-3, then enters an aerobic tank 1-2 through a water through hole 2-1, and liquid at the bottom of the aerobic tank 1-2 flows back to the anaerobic tank 1-1 through a nitrified liquid outlet 1-2-2 and a first reflux pump 4; the water flowing out of the water outlet 1-2-3 of the aerobic tank 1-2 enters a secondary sedimentation tank 3, clear water flows out of an overflow port 3-2 after sedimentation, partial sludge flows back to the anaerobic tank 1 through a second reflux pump 5, and residual sludge is discharged from a sludge discharge pipe 3-3; the running time is 7-10 days; during operation, the reflux volume ratio of the nitrifying liquid is gradually reduced from 400-500% to 300%, the reflux volume ratio of the sludge is gradually reduced from 100-120% to 50%, and the hydraulic retention time is gradually reduced from 20-24 h to 9 h;
c. keeping the reflux ratio of nitrifying liquid at 300%, the reflux ratio of sludge at 50% and the hydraulic retention time at 9h, and gradually increasing the concentration of alizarin yellow R in the acclimation water at a speed of increasing 0.005-0.01 g/L every day until the concentration of alizarin yellow R reaches 0.1 g/L;
d. keeping the reflux ratio of nitrifying liquid of a bioelectrochemical reactor system at 300%, the reflux ratio of sludge at 50%, the hydraulic retention time at 9h and the concentration of alizarin yellow R at 0.1g/L unchanged, continuously measuring the COD (chemical oxygen demand) and the concentration of alizarin yellow R of effluent, and finishing the starting of the reactor when the concentrations of the COD and the alizarin yellow R of the effluent are stable;
thirdly, operating the bioelectrochemical reactor system:
replacing domesticated water distribution in the started bioelectrochemical reactor system with the azo dye mixed polluted wastewater to be treated, connecting the electrodes 1-1-2 with a direct current power supply 6, and using an adjustable direct current power supply to change the voltage from V1Starting at 0.1V, increasing gradually to V with an increase of 0.1V per day20.5-1.5V; then at a holding voltage of V2Meanwhile, the reflux ratio of the nitrifying liquid is controlled to be 300 percent, the reflux ratio of the sludge is controlled to be 50 percent, and the hydraulic retention time is 9 hours, and the bio-electrochemical reactor system is operated to finish the treatment of the azo dye mixed polluted wastewater.
The second embodiment is as follows: the difference between the embodiment and the first embodiment is that in the second embodiment, the vitamin solution is a solution prepared by mixing 2.0mg of vitamin H, 2.0mg of folic acid, 10.0mg of pyridoxine hydrochloride, 5.0mg of thiamine, 5.0mg of riboflavin, 5.0mg of nicotinic acid, 5.0mg of D-calcium pantothenate, 120.1mg of vitamin B, 5.0mg of p-aminobenzoic acid, 5.0mg of lipoic acid and 1L of distilled water; the rest is the same as the first embodiment.
The third concrete implementation mode: the embodiment differs from the first or second embodiment in that the mineral element liquid in the second step a is composed of 1.5g of nitrilotriacetic acid and MgSO4·7H2O 3.0g、MnSO4·H2O 0.5g、NaCl 1.0g、FeSO4·7H2O0.1g、CoCl2·6H2O 0.1g、CaCl2 0.1g、ZnSO4·7H2O 0.1g、CuSO4·5H2O 0.01g、AlK(SO4)2·12H2O 0.01g、H3BO30.01g、Na2MoO4·2H2A solution obtained by mixing 0.01g of O and 1L of distilled water; the other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between the embodiment and one of the first to third embodiments is that the reduction rate of the reflux volume ratio of the nitrified liquid in the step two b is reduced by 10 to 29 percent per day; the others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between the embodiment and one of the first to the fourth embodiments is that the reduction speed of the sludge reflux volume ratio in the step two b is reduced by 5 to 10 percent per day; the other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between the embodiment and one of the first to the fifth embodiments is that the reduction speed of the hydraulic retention time in the second step is reduced by 1.1 to 2.2 hours per day; the other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between the embodiment and the first to sixth embodiments is that the stabilization of the concentration of the COD in the second step means that the change rate of the removal rate of the COD is less than 2% within three consecutive days; the other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is that the concentration of alizarin yellow R in step two d is stable, which means that the change rate of the removal rate of alizarin yellow R within three consecutive days is less than 2%; the other is the same as one of the first to seventh embodiments.
The following tests were used to verify the beneficial effects of the present invention:
test 1: the method for removing azo dye mixed polluted wastewater by utilizing the electrically-stimulated anaerobic-aerobic continuous flow reaction device comprises the following steps:
firstly, building a bioelectrochemical reactor system: the bioelectrochemical reactor system consists of a reactor shell 1, a clapboard 2, a secondary sedimentation tank 3, a first reflux pump 4, a second reflux pump 5 and an adjustable direct current power supply 6; the reactor shell 1 is of a cuboid structure, has an effective volume of 24L and is made of organic glass materials; the shell 1 is divided into an anaerobic tank 1-1 and an aerobic tank 1-2 by the clapboard 2; the lower part of the clapboard 2 is provided with a water through hole 2-1; a stirrer 1-1-1 and a pair of electrodes 1-1-2 are arranged in the anaerobic tank 1-1; the electrode 1-1-2 is connected with a direct current power supply 6 by a titanium wire; the electrode is made of titanium wires and carbon brushes, wherein the diameter of the brush part is phi 10cm, and the length of the brush part is 12 cm; the voltage of the adjustable direct current power supply is adjustable from 1v to 30 v; the lower end of the side wall of one side of the anaerobic tank 1-1 is provided with a water inlet 1-1-3 and a nitrifying liquid return port 1-1-4, and the upper end is provided with a sludge return port 1-1-5; an aeration head 1-2-1 is arranged in the aerobic tank 1-2, and the aeration head 1-2-1 is connected with an aeration pump; a nitrifying liquid outlet 1-2-2 is arranged at the lower end of the side wall of one side of the aerobic tank 1-2, and a water outlet 1-2-3 is arranged at the upper end; the upper end of the secondary sedimentation tank 3 is provided with a water inlet 3-1 and an overflow port 3-2, and the lower end is connected with a sludge discharge pipe 3-3; the first reflux pump 4 is arranged on a pipeline between the nitrifying liquid outlet 1-2-2 of the aerobic tank 1-2 and the nitrifying liquid reflux opening 1-1-4 of the anaerobic tank 1-1; the second reflux pump 5 is arranged on a pipeline between the sludge discharge pipe 3-3 of the secondary sedimentation tank 3 and the sludge reflux port 1-1-5 of the anaerobic tank 1-1;
secondly, sludge culture and domestication of the bioelectrochemical reactor system:
a. according to the concentration of 1.0g/L of glucose and the concentration of 0.04g/L, NH of alizarin yellow R4The Cl concentration was 0.04g/L, KNO3The concentration of the vitamin solution is 0.07g/L, the concentration of the vitamin solution is 0.5ml/L and the concentration of the mineral element solution is 0.1ml/L, and then domesticated water is prepared according to the volume ratio of the domesticated water to the activated sludge of 1: 10 adding domesticated water and activated sludge into a reactor shell 1, sealing an anaerobic tank 1-1 with a cover plate, starting a stirrer 1-1-1, and aerating the aerobic tank 1-2 for 24 hours through an aeration device 1-2-1; wherein the vitamin solution is composed of vitamin H2A solution obtained by mixing 0mg, 2.0mg of folic acid, 10.0mg of pyridoxine hydrochloride, 5.0mg of thiamine, 5.0mg of riboflavin, 5.0mg of nicotinic acid, 5.0mg of D-calcium pantothenate, 5.0mg of vitamin B120.1 mg, 5.0mg of p-aminobenzoic acid, 5.0mg of lipoic acid, and 1L of distilled water; the mineral element liquid is composed of nitrilotriacetic acid 1.5g and MgSO4·7H2O3.0g、MnSO4·H2O 0.5g、NaCl 1.0g、FeSO4·7H2O0.1g、CoCl2·6H2O 0.1g、CaCl20.1g、ZnSO4·7H2O 0.1g、CuSO4·5H2O 0.01g、AlK(SO4)2·12H2O 0.01g、H3BO30.01g、Na2MoO4·2H20.01g of O and 1L of distilled water.
b. Domesticated water is introduced into an anaerobic tank 1-1 through a water inlet 1-1-3, then enters an aerobic tank 1-2 through a water through hole 2-1, and liquid at the bottom of the aerobic tank 1-2 flows back to the anaerobic tank 1-1 through a nitrified liquid outlet 1-2-2 and a first reflux pump 4; the water flowing out of the water outlet 1-2-3 of the aerobic tank 1-2 enters a secondary sedimentation tank 3, clear water flows out of an overflow port 3-2 after sedimentation, partial sludge flows back to the anaerobic tank 1 through a second reflux pump 5, and residual sludge is discharged from a sludge discharge pipe 3-3; the running time is 7 days; during the operation, the reflux volume ratio of the nitrifying liquid is reduced to 300 percent from 500 percent at a speed of reducing 28.6 percent per day, the reflux volume ratio of the sludge is reduced to 50 percent from 100 percent at a speed of reducing 7.1 percent per day, and the hydraulic retention time is reduced to 9 hours from 20 hours at a speed of reducing 1.6 hours per day;
c. keeping the reflux ratio of nitrifying liquid at 300%, the reflux ratio of sludge at 50% and the hydraulic retention time at 9h, and gradually increasing the concentration of alizarin yellow R in the acclimation water at a speed of increasing 0.01g/L every day until the concentration of alizarin yellow R reaches 0.1 g/L;
d. keeping the reflux ratio of nitrifying liquid of a bioelectrochemical reactor system at 300%, the reflux ratio of sludge at 50%, the hydraulic retention time at 9h and the concentration of alizarin yellow R at 0.1g/L unchanged, continuously measuring the COD (chemical oxygen demand) and the concentration of alizarin yellow R of the effluent, and when the change of the COD and the concentration of alizarin yellow R of the effluent in three consecutive days is less than 1%, considering that the electrochemical reactor system is stable, and finishing the starting of the reactor;
thirdly, operating the bioelectrochemical reactor system:
replacing domesticated water distribution in the started bioelectrochemical reactor system with the azo dye mixed polluted wastewater to be treated, connecting the electrodes 1-1-2 with a direct current power supply 6, and switching the voltage from V to V by using an adjustable direct current power supply on a loop1Starting at 0.1V, increasing gradually to V with an increase of 0.1V per day20.5, 1.0 or 1.5V; then at a holding voltage of V2Meanwhile, the reflux ratio of nitrifying liquid is controlled to be 300%, the reflux ratio of sludge is controlled to be 50%, and the hydraulic retention time is controlled to be 9, and the bioelectrochemical reactor system is operated to finish the treatment of the azo dye mixed polluted wastewater. Wherein the COD concentration of the azo dye mixed polluted wastewater to be treated is 1050-1100mg/L, the concentration of nitrate nitrogen is 24.6-25.3mg/L, the concentration of ammonia nitrogen is 25.5-26.5mg/L, and the concentration of alizarin yellow R is 39.9-40.7 mg/L.
V in step three of test 12The removal rates of the COD, nitrate nitrogen, ammonia nitrogen and azo dyes of the azo dye mixed polluted wastewater treated under the condition of 1.5V are shown in fig. 2, and it can be seen from fig. 2 that the treatment effect of the reactor in the early stage fluctuates greatly, and the treatment effect reaches a stable state around the seventh day of starting detection, and the removal rates of the COD, nitrate nitrogen, ammonia nitrogen and azo dyes by the reactor reach 89%, 71%, 80% and 90% respectively.
Comparative experiment 1: the difference between the comparative experiment and experiment 1 is that the procedure of step three is as follows:
thirdly, operating the bioelectrochemical reactor system:
and replacing domesticated water distribution in the started bioelectrochemical reactor system with the azo dye mixed polluted wastewater to be treated, and operating the bioelectrochemical reactor system to finish the treatment of the azo dye mixed polluted wastewater when the nitrification liquid reflux ratio is kept at 300%, the sludge reflux ratio is kept at 50% and the hydraulic retention time is kept at 9. Wherein the COD concentration of the azo dye mixed polluted wastewater to be treated is 1050-1100mg/L, the concentration of nitrate nitrogen is 24.6-25.3mg/L, the concentration of ammonia nitrogen is 25.5-26.5mg/L, and the concentration of alizarin yellow R is 39.9-40.7 mg/L.
The removal rates of COD, nitrate nitrogen, ammoniacal nitrogen and azo dyes in the azo dye mixed polluted wastewater treated by the comparative test 1 are shown in figure 3, and as can be seen from figure 3, the pretreatment effect fluctuates greatly in the early stage, the treatment effect reaches a stable state around the ninth day of continuous monitoring, and the removal rates of COD, nitrate nitrogen, ammoniacal nitrogen and azo dyes by the reactor reach 85%, 65%, 55% and 41% respectively.
Applied voltage V in step three of experiment 12The removal rates of the reactor for COD, nitrate nitrogen, ammoniacal nitrogen and AYR reaching the steady state when the voltage is not applied are 0.5V, 1.0V and 1.5V and the comparison test 1 are combined as shown in figure 4, and it can be seen from figure 4 that all indexes of effluent water of the test 1 are improved compared with the removal rate of the comparison test 1 when the voltage is not applied, wherein the improvement effect of the removal rate of AYR is most obvious. By inputting a small external electric field, extra reducing power is provided for the microorganisms, and the extracellular electron transfer efficiency of the microorganisms is stimulated, so that the reduction of the azo dye by the microorganisms is enhanced, and the azo dye is rapidly reduced and mineralized.
Claims (8)
1. The method for removing azo dye mixed polluted wastewater by using the electrical stimulation anaerobic-aerobic continuous flow reaction device is characterized by comprising the following steps of:
firstly, building a bioelectrochemical reactor system: the bioelectrochemical reactor system consists of a reactor shell (1), a clapboard (2), a secondary sedimentation tank (3), a first reflux pump (4), a second reflux pump (5) and an adjustable direct current power supply (6); the shell (1) is divided into an anaerobic tank (1-1) and an aerobic tank (1-2) by the partition plate (2); the lower part of the clapboard (2) is provided with a water through hole (2-1); a stirrer (1-1-1) and a pair of electrodes (1-1-2) are arranged in the anaerobic tank (1-1); the electrode (1-1-2) is connected with an adjustable direct current power supply (6); the lower end of the side wall of one side of the anaerobic tank (1-1) is provided with a water inlet (1-1-3) and a nitrifying liquid return port (1-1-4), and the upper end is provided with a sludge return port (1-1-5); an aeration device (1-2-1) is arranged in the aerobic tank (1-2); a nitrifying liquid outlet (1-2-2) is arranged at the lower end of the side wall of one side of the aerobic tank (1-2), and a water outlet (1-2-3) is arranged at the upper end; the upper end of the secondary sedimentation tank (3) is provided with a water inlet (3-1) and an overflow port (3-2), and the lower end is connected with a sludge discharge pipe (3-3); the first reflux pump (4) is arranged on a pipeline between the nitrifying liquid outlet (1-2-2) of the aerobic tank (1-2) and the nitrifying liquid reflux outlet (1-1-4) of the anaerobic tank (1-1); the second reflux pump (5) is arranged on a pipeline between the sludge discharge pipe (3-3) of the secondary sedimentation tank (3) and the sludge reflux port (1-1-5) of the anaerobic tank (1-1);
secondly, sludge culture and domestication of the bioelectrochemical reactor system:
a. according to the concentration of 1.0g/L of glucose and the concentration of 0.04g/L, NH of alizarin yellow R4The Cl concentration was 0.04g/L, KNO3The concentration of the vitamin solution is 0.07g/L, the concentration of the vitamin solution is 0.5ml/L and the concentration of the mineral element solution is 0.1ml/L, and then domesticated water is prepared according to the volume ratio of the domesticated water to the activated sludge of 1: (9-10) adding the domesticated water and activated sludge into the reactor shell (1), sealing the anaerobic tank (1-1) by a cover plate, starting the stirrer (1-1-1), and aerating the aerobic tank (1-2) for 24-26 hours by the aeration device (1-2-1);
b. domesticated water is introduced into an anaerobic tank (1-1) through a water inlet (1-1-3), then enters an aerobic tank (1-2) through a water passing hole (2-1), and liquid at the bottom of the aerobic tank (1-2) flows back into the anaerobic tank (1-1) through a nitrifying liquid outlet (1-2-2) and a first backflow pump (4); water flowing out of a water outlet (1-2-3) of the aerobic tank (1-2) enters a secondary sedimentation tank (3), clear water flows out of an overflow port (3-2) after sedimentation, part of sludge flows back to the anaerobic tank (1-1) through a second return pump (5), and residual sludge is discharged from a sludge discharge pipe (3-3); the running time is 7-10 days; during operation, the reflux volume ratio of the nitrifying liquid is gradually reduced from 400-500% to 300%, the reflux volume ratio of the sludge is gradually reduced from 100-120% to 50%, and the hydraulic retention time is gradually reduced from 20-24 h to 9 h;
c. keeping the reflux ratio of nitrifying liquid at 300%, the reflux ratio of sludge at 50% and the hydraulic retention time at 9h, and gradually increasing the concentration of alizarin yellow R in the acclimation water at a speed of increasing 0.005-0.01 g/L every day until the concentration of alizarin yellow R reaches 0.1 g/L;
d. keeping the reflux ratio of nitrifying liquid of a bioelectrochemical reactor system at 300%, the reflux ratio of sludge at 50%, the hydraulic retention time at 9h and the concentration of alizarin yellow R at 0.1g/L unchanged, continuously measuring the COD (chemical oxygen demand) and the concentration of alizarin yellow R of effluent, and finishing the starting of the reactor when the concentrations of the COD and the alizarin yellow R of the effluent are stable;
thirdly, operating the bioelectrochemical reactor system:
replacing domesticated water distribution in the started bioelectrochemical reactor system with the azo dye mixed polluted wastewater to be treated, connecting the electrodes (1-1-2) with a direct current power supply (6), and switching the voltage from V to V by using an adjustable direct current power supply1Starting at 0.1V, increasing gradually to V with an increase of 0.1V per day20.5-1.5V; then at a holding voltage of V2Meanwhile, the reflux ratio of the nitrifying liquid is controlled to be 300 percent, the reflux ratio of the sludge is controlled to be 50 percent, and the hydraulic retention time is 9 hours, and the bio-electrochemical reactor system is operated to finish the treatment of the azo dye mixed polluted wastewater.
2. The method for removing azo dye mixed polluted wastewater using an electro-stimulation anaerobic-aerobic continuous flow reaction device according to claim 1, wherein in the step two a, the vitamin solution is a solution prepared by mixing vitamin H2.0 mg, folic acid 2.0mg, pyridoxine hydrochloride 10.0mg, thiamine 5.0mg, riboflavin 5.0mg, nicotinic acid 5.0mg, calcium D-pantothenate 5.0mg, vitamin B120.1mg, p-aminobenzoic acid 5.0mg, lipoic acid 5.0mg and 1L of distilled water.
3. The method for removing azo dye mixed polluted wastewater by using the electrically-stimulated anaerobic-aerobic continuous flow reaction device as claimed in claim 1 or 2, wherein the mineral element liquid in the step two a is composed of nitrilotriacetic acid 1.5g, MgSO4·7H2O3.0g、MnSO4·H2O 0.5g、NaCl 1.0g、FeSO4·7H2O 0.1g、CoCl2·6H2O 0.1g、CaCl20.1g、ZnSO4·7H2O 0.1g、CuSO4·5H2O 0.01g、AlK(SO4)2·12H2O 0.01g、H3BO30.01g、Na2MoO4·2H20.01g of O and 1L of distilled water.
4. The method for removing azo dye mixed polluted wastewater by using an electrically stimulated anaerobic-aerobic continuous flow reaction device according to claim 1 or 2, wherein the reduction rate of the reflux volume ratio of the nitrifying liquid in the step two b is 10 to 29 percent per day.
5. The method for removing azo dye mixed polluted wastewater using the electrically stimulated anaerobic-aerobic continuous flow reaction device according to claim 1 or 2, wherein the reduction rate of the sludge reflux volume ratio in the step two b is 5% to 10% per day.
6. The method for removing azo dye mixed polluted wastewater by using the electrically-stimulated anaerobic-aerobic continuous flow reaction device according to claim 1 or 2, wherein the reduction rate of the hydraulic retention time in the step two b is 1.1 to 2.2 hours per day.
7. The method for removing azo dye mixed polluted wastewater using an electro-stimulation anaerobic-aerobic continuous flow reaction device according to claim 1 or 2, wherein the stabilization of the COD concentration in the step two d means that the change rate of the removal rate of COD is less than 2% within three consecutive days.
8. The method for removing azo dye mixed polluted wastewater by using the electrically-stimulated anaerobic-aerobic continuous flow reaction device according to claim 1 or 2, wherein the stabilization of the concentration of alizarin yellow R in the step two d means that the change rate of the removal rate of alizarin yellow R within three consecutive days is less than 2%.
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