CN113845217A - Method and device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry enhancement - Google Patents

Method and device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry enhancement Download PDF

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CN113845217A
CN113845217A CN202111288012.5A CN202111288012A CN113845217A CN 113845217 A CN113845217 A CN 113845217A CN 202111288012 A CN202111288012 A CN 202111288012A CN 113845217 A CN113845217 A CN 113845217A
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sulfur
refractory organic
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organic pollutants
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吕慧
权昊婷
张会群
孙连鹏
贾妍艳
梁慧宇
周思宁
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Sun Yat Sen University
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Abstract

The invention belongs to the technical field of biological sewage treatment, and particularly relates to a method and a device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry reinforcement, wherein the device adopts an up-flow sulfate reduction anaerobic sludge bed reactor and an external power supply, main functional bacteria in the reactor are sulfate reduction bacteria, electrodes are placed in an up-and-down manner, the reaction process is an anaerobic condition, and the process is simple to operate and convenient to operate; the device is adopted to carry out sulfur-mediated bioelectrochemical sewage treatment, so that the typical refractory organic pollutants in the sewage can be effectively removed; the method has the advantages of high treatment efficiency, low material consumption and energy consumption, low sludge yield, no need of subsequent treatment of excess sludge, capability of recovering biological elemental sulfur generated in a reaction system, economic value generation, effective removal of refractory organic pollutants in sewage and good popularization and application values.

Description

Method and device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry enhancement
Technical Field
The invention belongs to the technical field of sewage biological treatment, and particularly relates to a method and a device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry reinforcement.
Background
With the sustainable development of socioeconomic in China, the protection and improvement of water environment become the major strategic needs of China. Industrial wastewater discharge is one of the important causes of water environmental pollution. Currently, industrial wastewater in China mainly comes from basic pillar industries such as fine chemical engineering (such as pharmacy, pesticides, printing and dyeing, explosives and powders and the like), petrifaction, electronics, papermaking and the like. Wherein, the industrial wastewater represented by fine chemical wastewater and pharmaceutical wastewater has high pollutant concentration, complex components, contains a large amount of organic pollutants (such as antibiotics, medicaments and the like) which are difficult to degrade and inorganic pollutants such as nitrogen, sulfur and the like, has poor biodegradability, large treatment difficulty and high cost.
At present, the treatment method of industrial wastewater mainly comprises a physical and chemical method (adsorption, filtration, precipitation, chemical oxidation, etc.) and a biological treatment method. Among them, the biological treatment method has been an important research direction of water treatment technology due to the advantages of economy, environmental friendliness, ecological safety and the like. In recent years, the sulfur-recycling-based biological treatment process of sewage is widely applied to treatment of saline domestic sewage and industrial wastewater due to the advantages of high efficiency, low consumption and low sludge yield. In addition, researches show that the sulfur synergistic sewage biological treatment process has better tolerance and degradation potential on nondegradable drug pollutants (such as ciprofloxacin, sulfamethoxazole, ibuprofen and the like). However, the high-concentration refractory organic pollutants in the industrial wastewater have complicated structures, large inhibition effect on biological systems, difficult release of pollutant electrons, and low electron transfer and electron utilization rate, which result in slow biological conversion rate and low efficiency of the composite pollutants, and is a common problem faced by the current biological treatment of industrial wastewater.
The bioelectrochemical method has a high-efficiency catalytic conversion effect on refractory and toxic pollutants in wastewater, and has excellent electronic regulation and control capability and electronic transfer rate, so that the bioelectrochemical method becomes a research hotspot and frontier in the technical field of international environments. In a bioelectrochemical system, an electrode can be used as an electron donor and participate in a pollutant oxidation-reduction process, and under the action of proper external voltage, macromolecular refractory organic matters can be directly converted into micromolecular refractory organic matters, so that effective endogenous electron donors are released; meanwhile, under the stimulation of an external electric field, a biological film can be formed around the electrode, so that various electroactive microorganisms are enriched to promote electron transfer; in addition, the water-microorganism-electrode multiphase micro-interface function can also improve the electron transfer efficiency and the mass transfer efficiency of pollutants. However, the practical application of the bioelectrochemical system as an independent sewage treatment unit is limited due to the limited biomass retention rate in the bioelectrochemical system, poor quality of effluent and low treatment efficiency. The bioelectrochemical system and the sewage biological treatment process are coupled, so that the disadvantages of the bioelectrochemical system and the sewage biological treatment process can be effectively avoided, the metabolism of microorganisms is regulated and controlled by an exogenous electric field, and the electron transfer is promoted, so that the biotransformation effect of the organic pollutants difficult to degrade is enhanced. At present, although the technology for enhancing the removal of the refractory pollutants by adopting an electrochemical coupling sewage biological treatment process, particularly the traditional anaerobic process, has been reported, the key effect of the thionin substance as an electron transfer mediator in the carbon and nitrogen pollutant removal process is ignored, so that the technology for enhancing the removal of the refractory organic pollutants by adopting an exogenous electric field coupling sulfur and a sewage biological treatment process has not been reported.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a sulfur-mediated bioelectrochemistry-enhanced device for removing refractory organic pollutants, which is an improved upflow anaerobic sludge blanket and is externally connected with a power supply, the main functional bacteria in a reaction device are sulfate reducing bacteria, the device can be used for removing typical refractory organic pollutants in sewage, the treatment efficiency is high, and the device is a process method for effectively removing the refractory organic pollutants in the sewage and has better popularization and application values.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a sulfur-mediated bioelectrochemistry-enhanced refractory organic pollutant removal device, which comprises a device main body, wherein the interior of the device main body is divided into a reaction zone at the lower part and an overflow zone at the upper part, an overflow weir is arranged between the reaction zone and the overflow zone, a heat-insulating layer is arranged on the outer wall of the device corresponding to the reaction zone, the reaction zone is used for inoculating activated sludge taking sulfate reducing bacteria as dominant flora, an anode is arranged at the upper part of the reaction zone, a cathode is arranged at the upper part of the reaction zone, the anode is connected with the anode of an external power supply, the cathode is connected with the cathode of the external power supply, a resistor is arranged between the anode and the external power supply, a water inlet is arranged at the bottom of the reaction zone, the water inlet is connected with a water inlet barrel through a water inlet pipe, a water inlet pump is arranged on the water inlet pipe, and a circulation port is arranged at the lower end of the overflow zone, the circulating port is connected with the water inlet pipe through a circulating pipe, the circulating pipe is provided with a circulating pump, the middle part of the overflow area is provided with a water outlet, the water outlet is connected with the water outlet barrel through a water outlet pipe, and the water outlet pipe is provided with a water outlet pump.
Preferably, the cathode is made of carbon brush materials, and the anode is made of carbon felt materials. Further, the carbon brush is soaked in acetone for 24 hours before use, then is washed by deionized water, and then is subjected to heat treatment by a muffle furnace at 400-500 ℃ to remove surface impurities.
Preferably, the concentration of the inoculated activated sludge is 16gMLSS/L, MLVSS/MLSS is 0.81, and COD S is 1.8.
Preferably, a base is provided at the bottom of the device body.
Preferably, the number of the cathodes is two, and the two cathodes are connected in parallel.
Preferably, the water inlet pump, the circulating pump and the water outlet pump are all peristaltic pumps.
Preferably, the external power supply is a direct current constant voltage power supply.
The invention also provides a method for removing the refractory organic pollutants through sulfur-mediated bioelectrochemistry reinforcement, which comprises the following steps: the sulfur-mediated bioelectrochemistry reinforced refractory organic pollutant removal device is used for degrading refractory organic pollutants in wastewater to be treated.
When the sulfur-mediated bioelectrochemistry reinforced refractory organic pollutant removal device is used for treating wastewater, Sulfate Reducing Bacteria (SRB) are used as functional bacteria in a reactor, sulfate and other oxidation state sulfur compounds can be used as electron acceptors in metabolic activity of the SRB, and various organic matters including alkane, long-chain fatty acid and aromatic compounds are used as electron donors to complete sulfate reduction reaction, so that the aim of removing organic pollutants is fulfilled. However, in the process, due to the complex structure of the pollutants, the problems of difficult electron release and low electron transfer efficiency exist, and under the stimulation of an external electric field, the electrode can be used as an electron donor and can form a biological film rich in electroactive microorganisms around the electrode, so that the electron release and the electron transfer efficiency of the pollutants are promoted, and the biological film participates in the redox reaction process of the pollutants, and the removal of the difficultly-degradable organic pollutants by the SRB activated sludge system is enhanced. The adsorption and biodegradation of the SRB activated sludge on the organic pollutants difficult to degrade are strengthened through electrochemistry, so that the organic pollutants difficult to degrade can be effectively removed.
Preferably, the operating process conditions of the degradation treatment are as follows: the applied voltage is 1V, the external resistance is 50 omega, the system current is 10mA, and the hydraulic retention time is 6 h.
Preferably, the pH of the wastewater to be treated is 7.0 and COD: N: P: 100:5: 1.
Preferably, before the degradation treatment is carried out, a stable process environment needs to be established for the sulfur-mediated bioelectrochemistry reinforced refractory organic pollutant removal device.
When the reaction device is started, firstly domestication of SRB sludge reduction sulfate is carried out in stages, then on the basis of sulfur reduction, the electrode is placed into the reactor and voltage is applied, on one hand, membrane formation of the electrode is carried out, on the other hand, domestication of applied electric stimulation is carried out on activated sludge, and the domestication process ensures the stability of a reaction system for removing refractory organic pollutants by sulfur reduction under the stimulation of the applied voltage in the later stage.
Further, establishing a stable process environment includes the steps of:
s1, starting a first stage: inoculating activated sludge taking sulfate reducing bacteria as dominant flora into a reaction zone 1 of the sulfur-mediated bioelectrochemistry-enhanced refractory organic pollutant removing device, controlling a system to be in an anaerobic environment, introducing artificial synthetic wastewater containing a carbon source, a sulfur source, a nitrogen source, a phosphorus source, calcium chloride, magnesium chloride, ammonium chloride and trace elements, and acclimating the sludge to enable microorganisms in the system to gradually adapt to the existence of the sulfur source until the sulfur reduction effect is stable and the sulfur reduction efficiency is more than 60%;
in the stage, the addition of the refractory organic pollutants is avoided, and the main purpose is to ensure that the sludge is stably adapted to the environment of the reactor and improve the removal rate of the organic pollutants (COD) and the conversion efficiency of sulfur. The operating state of the reactor was monitored by periodically measuring the COD and sulfur concentrations in and out of the water during the operation of the reactor. In order to ensure that the quality of inlet water does not change too much (COD: N: P: 100:5: 1;), inlet water is replaced every day.
S2, starting a second stage: after the first stage, the voltage of the external power supply is applied in a gradient manner, the resistance is adjusted to 50 omega, each period is 0.5 month, and the resistance voltage, the cathode and anode potentials and current, and SO are measured every day4 2-Reducing efficiency, biological elemental sulfur generation amount and COD removal condition until SO4 2-The reduction efficiency reaches more than 60 percent, the COD removal efficiency reaches more than 80 percent, and the generation amount of biological simple substances is stable;
the main purpose of this stage is to form a biological membrane (i.e. the hanging membrane of the electrode) on the electrode and enrich multiple electroactive microorganisms to promote the electron transfer process under the stimulation of an external electric field. At the same time, by adjusting the applied voltage, the SO component is obtained4 2-The reduction and S2-oxidation process is favorable oxidation-reduction potential, thereby improving the efficiency of sulfur reduction and organic matter removal of the reactor, and simultaneously recovering the biological elemental sulfur, thereby generating economic value.
S3, establishment of stable operation environment: after the reactor runs stably, adding refractory organic matters into the artificially synthesized wastewater, ensuring that the COD (chemical oxygen demand) of the wastewater is 100:5:1, and then strengthening the synergistic degradation removal effect of the refractory organic matters under the conditions that the voltage of an external power supply is 1V, the resistance is 50 omega and the system current is 10mA until the SO is removed4 2-The reduction efficiency reaches more than 60 percent, the COD removal efficiency reaches more than 80 percent, and the generation amount of the biological simple substance is stable.
Preferably, the process operating conditions of steps S1 and S2 are both: the inflow Q is 22.5L/d, the muddy water is uniformly mixed by a circulating pump, the circulating setting is 5Q, the reaction temperature is 25 +/-1 ℃, the inflow pH is 7.0 +/-0.1, and the hydraulic retention time is 6 h; the acclimation time in the first stage was 1 month, and the operation time in the second stage was 2.5 months.
Preferably, in step S3, the concentration of the refractory organics is 100 μ g/L; the refractory organics include Ciprofloxacin (CIP), Sulfamethoxazole (SMX), and Chloramphenicol (CAP).
Preferably, the synthetic wastewater of step S1 is aerated with nitrogen before being introduced, and the pH is adjusted to 7.0 + -0.1.
Preferably, in step S2, the external voltage is applied in a gradient of 0.2, 0.4, 0.6, 0.8, 1.0V.
Preferably, in step S1, the sulfur source of the synthetic wastewater is anhydrous Na2SO4The carbon source is sodium acetate CH3COONa and NH as nitrogen source4Cl and a phosphorus source is provided by K2HPO4·3H2O and KH2PO4Providing K2HPO4·3H2O and KH2PO4Used to buffer the reactor pH, magnesium chloride and calcium chloride are required for microbial growth; the microelements comprise microelements such as Fe, Cu, Mn, Zn, Co, K, I, etc. Further, the pH value of the artificial synthetic wastewater is 7.0 +/-0.1, the COD is about 500mg/L, the initial concentration of the sulfur source is about 275mg/L, and the KH concentration is2PO4Has an initial concentration of about 10.58mg/L, KH2PO4Is about 5.13mg/L, MgCl2Has an initial concentration of 37.95mg/L of CaCl2The initial concentration of (3) is 26 mg/L; trace elementsAnd its content is FeCl3·6H2O 6mg/L、ZnSO4·7H2O 0.45mg/L、MnSO4·H2O 0.75mg/L、H3BO3 0.6mg/L、CuSO40.15 mg/L、KI 0.24mg/L、CoCl2·6H2O 0.6mg/L。
Preferably, in step S1, the anaerobic environment is N2The aeration is carried out to remove the air in the reaction system, the system is controlled to be in an anaerobic environment, and the time of N2 aeration is based on the removal of the air in the reaction system, and is preferably 25-30 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a sulfur-mediated bioelectrochemistry reinforced device for removing refractory organic pollutants, which adopts an up-flow sulfate reduction anaerobic sludge bed reactor and an external power supply, wherein the main functional bacteria in the reactor are sulfate reduction bacteria, electrodes are placed in an up-and-down manner, the reaction process is an anaerobic condition, and the process operation is simple and convenient to operate. Meanwhile, a method for removing the refractory organic pollutants through sulfur-mediated bioelectrochemistry reinforcement is provided on the basis of the device, a sulfur-mediated bioelectrochemistry sewage treatment process is adopted, typical refractory organic pollutants (ciprofloxacin, sulfamethoxazole, chloramphenicol and the like) in sewage can be effectively removed, SRB sludge has better degradation capability on the refractory organic pollutants (ciprofloxacin, sulfamethoxazole and chloramphenicol) under the stimulation of external voltage, and the removal rates of the ciprofloxacin, sulfamethoxazole and chloramphenicol with the concentration of 100 mug/L respectively reach more than 90%, 40% and 98% within 6h of hydraulic retention time; the method has the advantages of high treatment efficiency, low material consumption and energy consumption, low sludge yield, no need of subsequent treatment of excess sludge, capability of recovering biological elemental sulfur generated in a reaction system, economic value generation, effective removal of refractory organic pollutants in sewage and good popularization and application values.
Drawings
FIG. 1 is a schematic structural diagram of a sulfur-mediated bioelectrochemically enhanced refractory organic pollutant removal device;
in fig. 1: 1-reaction zone, 2-overflow zone, 3-overflow weir, 4-external power supply, 5-resistor, 6-water inlet bucket, 7-water inlet pump, 8-circulating pump, 9-water outlet bucket, 10-water outlet pump, 11-heat insulation layer, 12-anode, 13-cathode, 14-water inlet, 21-circulating port and 22-water outlet.
FIG. 2 is a graph of COD removal efficiency in a sulfur-mediated bioelectrochemically enhanced refractory organic pollutant removal device;
FIG. 3 is a graph of the effect of sulfur reduction in a sulfur-mediated bioelectrochemically enhanced refractory organic pollutant removal device;
FIG. 4 is a diagram of the amount of elemental sulfur produced in a sulfur-mediated bioelectrochemical enhanced refractory organic pollutant removal device;
FIG. 5 is a graph showing the SRB sludge-based removal effect of CIP with a concentration of 100 μ g/L in a sulfur-mediated bioelectrochemical enhanced refractory organic pollutant removal device;
FIG. 6 is a graph showing the SRB sludge-based removal effect of SMX at a concentration of 100 μ g/L in a sulfur-mediated bioelectrochemically enhanced refractory organic pollutant removal device;
FIG. 7 is a graph showing the SRB sludge-based removal effect of CAP with a concentration of 100 μ g/L in a sulfur-mediated bioelectrochemical enhanced refractory organic pollutant removal device.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
The SRB activated sludge in the embodiment of the invention is activated sludge taking Sulfate Reducing Bacteria (SRB) as a dominant flora and is taken from a secondary sedimentation tank of a certain sewage treatment plant in hong Kong. As the hong Kong utilizes seawater to flush toilets, the concentration of sulfate in domestic sewage is higher, and the sludge contains rich SRB. The sludge at the initial stage of inoculation is yellow brown, and is in loose cotton floccule shape, and MLVSS/MLSS is 0.42. After two weeks of SRB enrichment culture, the color of the sludge is changed into black flocculent, MLVSS/MLSS is 0.81, and the sludge at the stage is used as the inoculation sludge of the SRUSB reactor.
The wastewater in the embodiment of the invention is artificially synthesized wastewater, and the components mainly comprise Ciprofloxacin (CIP), Sulfamethoxazole (SMX), Chloramphenicol (CAP), sodium sulfate, various nutrient elements (Stock solution, shown in table 1) and Trace elements (Trace Stock solution, shown in table 2);
TABLE 1 nutrient Stock solution (Stock) component Table
Figure BDA0003333605800000061
TABLE 2 Trace element stock solution (Trace) component Table
Figure BDA0003333605800000062
After the sludge is inoculated, the acclimation of the sludge is carried out, and the water quality of the reactor inlet is shown in the following table 3: adopting artificially synthesized wastewater, taking sodium acetate as a carbon source, and ensuring that COD is about 500 mg/L; using anhydrous sodium sulfate as sulfur source, SO4 2--S concentration of about 275 mg/L; with K2HPO4·3H2O and KH2PO4As a phosphorus source, NH4Cl as a nitrogen source, N, P is 100:5: 1; meanwhile, in order to meet the requirement of the growth process of microorganisms, trace elements such as Fe, Cu, Mn, Zn and the like are added into the synthetic wastewater. The pH was maintained at about 7 and the temperature at about 25 ℃.
TABLE 3 Water quality meter
Figure BDA0003333605800000063
Figure BDA0003333605800000071
Example 1 sulphur mediation biological electrochemistry strengthens refractory organic pollutant remove device
As shown in fig. 1, the device comprises a device body, a base is arranged at the bottom of the device body, the interior of the device body is divided into a reaction zone 1 at the lower part and an overflow zone 2 at the upper part, an overflow weir 3 is arranged between the reaction zone 1 and the overflow zone 2, a heat-insulating layer 11 made of organic glass is arranged on the outer wall of the device corresponding to the reaction zone 1, the reaction zone 1 is used for inoculating activated sludge taking sulfate reducing bacteria as dominant flora, an anode 12 is arranged at the upper part of the reaction zone 1, a cathode 13 is arranged at the lower part of the reaction zone 1, the cathode 13 is made of carbon brush material, the anode 12 is made of carbon felt material, the anode 12 is connected with the anode of an external power supply 4, the cathode 13 is connected with the cathode of the external power supply 4, a resistor 5 is arranged between the anode 12 and the external power supply 4, and two cathodes 13 are arranged, two negative poles 13 adopt parallelly connected mode to connect, water inlet 14 has been seted up to the bottom in reaction zone 1, water inlet 14 links to each other with bucket 6 of intaking through the inlet tube, be provided with intake pump 7 on the inlet tube, circulation mouth 21 has been seted up to the lower extreme in overflow district 2, circulation mouth 21 passes through the circulating pipe and links to each other with the inlet tube, be provided with circulating pump 8 on the circulating pipe, delivery port 22 has been seted up at the middle part in overflow district 2, delivery port 22 passes through the outlet pipe and links to each other with bucket 9 of going out, be provided with out water pump 10 on the outlet pipe.
When the sulfur-mediated bioelectrochemistry reinforced refractory organic pollutant removal device is used for treating wastewater, Sulfate Reducing Bacteria (SRB) are used as functional bacteria in a reactor, sulfate and other oxidation state sulfur compounds can be used as electron acceptors in metabolic activity of the SRB, and various organic matters including alkane, long-chain fatty acid and aromatic compounds are used as electron donors to complete sulfate reduction reaction, so that the aim of removing organic pollutants is fulfilled. However, in the process, due to the complex structure of the pollutants, the problems of difficult electron release and low electron transfer efficiency exist, and under the stimulation of an external electric field, the electrode can be used as an electron donor and can form a biological film rich in electroactive microorganisms around the electrode, so that the electron release and the electron transfer efficiency of the pollutants are promoted, and the biological film participates in the redox reaction process of the pollutants, and the removal of the difficultly-degradable organic pollutants by the SRB activated sludge system is enhanced. The adsorption and biodegradation of the SRB activated sludge on the organic pollutants difficult to degrade are strengthened through electrochemistry, so that the organic pollutants difficult to degrade can be effectively removed.
Example 2 establishment of Sulfur-mediated bioelectrochemical enhanced method for removing refractory organic pollutants
The method is based on the sulfur-mediated bioelectrochemistry reinforced refractory organic pollutant removal device in the embodiment 1, and specifically comprises the following steps:
(1) establishment of stable process environment for removing refractory organic pollutants based on sulfur-mediated bioelectrochemical sewage treatment process
1) Starting the reactor:
the first stage is started: adding activated sludge with Sulfate Reducing Bacteria (SRB) as dominant flora into the reactor, and allowing the reactor to be in anaerobic environment (with N) by using a closed control system2Aerating for 28min) to facilitate the growth of SRB sludge until the sludge color is changed into black floccule, wherein the concentration of SRB activated sludge is 16gMLSS/L, MLVSS/MLSS is 0.81, and COD is 1.8. Adopting N as artificial synthetic wastewater containing carbon source, sulfur source, nitrogen source, phosphorus source, calcium chloride, magnesium chloride, ammonium chloride and trace elements (Fe, Zn, Mn, Co, Cu and the like)2Aerating to remove air, introducing into a reactor for acclimatization of sludge for 1 month until the sulfur reduction effect is stable and the sludge activity is high (the sulfur reduction efficiency is more than 60%), so that microorganisms in the system gradually adapt to the existence of a sulfur source; the pH of the synthetic wastewater is 7.0 (adjusted by hydrochloric acid or sodium hydroxide solution), the COD is about 500mg/L, the initial concentration of the sulfur source is about 275mg/L, and KH2PO4Has an initial concentration of about 10.58mg/L, KH2PO4Is about 5.13mg/L, MgCl2Has an initial concentration of 37.95mg/L of CaCl2The initial concentration of (3) is 26 mg/L; trace elements and FeCl content3·6H2O 6mg/L、ZnSO4·7H2O 0.45mg/L、MnSO4·H2O 0.75mg/L、H3BO30.6 mg/L、CuSO40.15 mg/L、KI 0.24mg/L、CoCl2·6H2O0.6 mg/L. At the initial stage of starting the reactor, no refractory organic pollutants are added in the whole process, and the method mainly aims to ensure that the sludge is stably adapted to the environment of the reactor and improve the removal rate of organic pollutants (COD) and the conversion efficiency of sulfur. The operating state of the reactor was monitored by periodically measuring the COD and sulfur concentrations in and out of the water during the operation of the reactor. The COD of the inlet water is N, P is 100, 5 and 1; in order to ensure that the quality of the inlet water does not change too much, the inlet water is replaced every day. The inlet and outlet water is controlled by a peristaltic pump, the inlet water flow Q is 22.5L/d, simultaneously, the muddy water is uniformly mixed by circulation, the circulation is set to be 5Q, the reaction temperature is 25 +/-1 ℃, the inlet water pH is 7.0, the hydraulic retention time is 6h, the domestication time of the first stage is 1 month, and when the COD removal rate and the SO removal rate are reached, the water is treated4 2-And (5) after the conversion rate is stable, the reactor runs stably, and the first stage is started.
And starting a second stage: after the reactor is operated stably, the pretreated electrodes (cathode carbon brushes, anode carbon felts) are placed in the reactor with the cathode on the lower anode, and are externally connected with a power supply and a resistor. The external voltage is applied according to the gradient of 0.2, 0.4, 0.6, 0.8 and 1.0V, the external resistance is 50 omega, and each period is 0.5 month. The main purpose is to form a biological film (namely, a hanging film of the electrode) on the electrode and generate a plurality of electroactive microorganisms to promote an electron transfer process under the stimulation of an external electric field. At the same time, the applied voltage is adjusted to obtain beneficial SO4 2-Reduction and S2-The oxidation-reduction potential of the oxidation process into elemental sulfur improves the efficiency of sulfur reduction and organic matter removal in the reactor, and simultaneously recovers the biological elemental sulfur, thereby generating economic value. The resistance voltage, cathode and anode potential and current and SO were measured every day during the whole process4 2-Reduction efficiency, biological elemental sulfur generation amount and COD removal condition. The inlet and outlet water is controlled by a peristaltic pump, the inlet water flow Q is 22.5L/d, simultaneously, the muddy water is uniformly mixed by circulation, the circulation is set to be 5Q, the reaction temperature is 25 +/-1 ℃, and the pH value of the inlet water7.0, hydraulic retention time 6h, run time for the second stage 2.5 months. When SO4 2-The reactor can be determined to be started up after the reduction efficiency reaches more than 60 percent, the COD removal efficiency reaches more than 80 percent and the generation amount of the biological simple substance is stable, and then the next stage of removing the organic pollution which is difficult to degrade is started. FIGS. 2, 3 and 4 are a COD removal effect diagram, a sulfur reduction effect diagram and a production amount diagram of biological elemental sulfur of the reaction system after the steady state is reached in the start-up stage respectively. It can be seen that after the stable operation state is achieved, the removal rate of the reaction system to COD reaches more than 90%, which shows that the sulfur-mediated bioelectrochemical sewage treatment process has a good effect on removal of COD. System SO4 2-The reduction efficiency reaches 60 percent, and meanwhile, biological elemental sulfur is generated and can be recovered to generate economic value.
(2) Establishing a stable operation environment of the wastewater treatment system:
and after the reactor is started, entering the establishment process of a stable operation stage. The quality of the inlet water is consistent with that of the inlet water in the starting stage, and simultaneously three antibiotics emerging refractory organic matters of Ciprofloxacin (CIP), Sulfamethoxazole (SMX) and Chloramphenicol (CAP) are added, so that the concentrations of the three medicines in the inlet water are respectively 100 mug/L. And (3) keeping COD (chemical oxygen demand) N: P (100: 5: 1), gradually strengthening the synergistic degradation removal effect of the SRB sludge on carbon, nitrogen, sulfur and refractory organic matters under the conditions that the applied voltage is 1V, the external resistance is 50 omega and the system current is 10mA until the removal effect of the refractory organic matters is stable, namely establishing a stable process environment for treating the composite pollutants by the sulfur-mediated bioelectrochemical sewage treatment process, wherein the running time is 40 d.
After a stable process environment is established, the degradation treatment of the organic pollutants which are difficult to degrade in the wastewater to be treated can be carried out.
Example 3 Sulfur-mediated bioelectrochemically enhanced method for removing refractory organic pollutants from Ciprofloxacin (CIP)
Ciprofloxacin (CIP) was removed by the sulfur-mediated bioelectrochemical wastewater treatment process established in example 2.
When the sulfur-mediated bioelectrochemistry-enhanced refractory organic pollutant removal device in the embodiment 1 establishes a stable process environment, the operation is continued for 40d, the quality of inlet water in the stage is consistent with that in the starting stage, Ciprofloxacin (CIP) serving as a refractory organic pollutant is added, the concentration of CIP in the inlet water is 100 mug/L, the COD (chemical oxygen demand) of the inlet water is maintained, and the N is 100:5:1, and then the synergistic degradation removal effect of the SRB sludge on carbon, nitrogen, sulfur and the refractory organic pollutant is gradually enhanced under the conditions that the applied voltage is 1V, the external resistance is 50 omega, and the system current is 10 mA.
In a hydraulic retention time (6h), 1mL of inlet water in a water barrel is taken out when the water inlet is started, 1mL of supernatant above a reactor is taken as outlet water when the water inlet is ended, a PTFE filter head of 0.22um is used for filtering the mixture into a 2mL brown sample bottle, the sample bottle is stored in a refrigerator at the temperature of 4 ℃, and the change of the CIP content is detected and analyzed by UPLC-DAD on the same day.
FIG. 5 is a graph showing the effect of CIP concentration of 100. mu.g/L on SRB-rich activated sludge removal in a sulfur-mediated bioelectrochemical wastewater treatment process. As can be seen from the figure, under the anaerobic condition, the sulfur-mediated bioelectrochemistry sewage treatment process has a good CIP removing effect which reaches more than 90%.
Example 4 Sulfur-mediated bioelectrochemically enhanced Sulfamethoxazole (SMX) removal Effect of refractory organic contaminant removal method
Sulfamethoxazole (SMX) is removed by the sulfur-mediated bioelectrochemical sewage treatment process established in example 2 to remove the refractory organic pollutants.
The sulfur-mediated bioelectrochemistry-enhanced refractory organic pollutant removal device in example 1 was operated for 40 days after establishing a stable process environment. The quality of inlet water at the stage is consistent with that at the starting stage, Sulfamethoxazole (SMX) which is a difficultly degraded organic pollutant is added at the same time, the concentration of SMX in the inlet water is 100 mu g/L, the COD (chemical oxygen demand): N: P: 100:5:1 is kept, and then the synergistic degradation removal effect of SRB sludge on carbon, nitrogen, sulfur and a difficultly degraded organic matter SMX is gradually enhanced under the conditions that the applied voltage is 1V, the external resistance is 50 omega and the system current is 10 mA.
In a hydraulic retention time (6h), 1mL of inlet water in a water barrel is taken out when the water inlet is started, 1mL of supernatant above a reactor is taken as outlet water when the water inlet is ended, a PTFE filter head of 0.22um is used for filtering the mixture into a 2mL brown sample bottle, the sample bottle is stored in a refrigerator at the temperature of 4 ℃, and the change of the SMX content is detected and analyzed by UPLC-DAD on the same day.
FIG. 6 is a graph showing the effect of SMX concentration of 100. mu.g/L on SRB-rich activated sludge removal in a sulfur-mediated bioelectrochemical wastewater treatment process. As can be seen from the figure, under the anaerobic condition, the sulfur-mediated bioelectrochemistry sewage treatment process has a good removal effect on SMX, and the removal effect reaches more than 40%.
Example 5 Sulfur-mediated bioelectrochemically enhanced removal of refractory organic contaminants from Chloramphenicol (CAP)
The method for removing the refractory organic pollutants by adopting the sulfur-mediated bioelectrochemical sewage treatment process established in the example 2 is adopted to remove the Chloramphenicol (CAP).
The sulfur-mediated bioelectrochemistry-enhanced refractory organic pollutant removal device in example 1 was operated for 40 days after establishing a stable process environment. The quality of inlet water at the stage is consistent with that at the starting stage, meanwhile, Chloramphenicol (CAP) which is a difficultly-degradable organic pollutant is added, the concentration of the CAP in the inlet water is 100 mug/L, the COD (chemical oxygen demand) of the inlet water is maintained, N: P: 100:5:1, and then the synergistic degradation and removal effect of the SRB sludge on carbon, nitrogen, sulfur and CAP which are difficultly-degradable organic matters is gradually enhanced under the conditions that the applied voltage is 1V, the external resistance is 50 omega and the system current is 10 mA.
In a hydraulic retention time (6h), 1mL of inlet water in a water barrel is taken out when the water inlet is started, 1mL of supernatant above a reactor is taken as outlet water when the water inlet is ended, a PTFE filter head of 0.22um is used for filtering the mixture into a 2mL brown sample bottle, the sample bottle is stored in a refrigerator at the temperature of 4 ℃, and the change of CAP content is detected and analyzed by UPLC-DAD on the same day.
FIG. 7 is a graph showing the effect of CAP at a concentration of 100. mu.g/L on SRB-rich activated sludge removal in a sulfur-mediated bioelectrochemical wastewater treatment process. As can be seen from the figure, under the anaerobic condition, the sulfur-mediated bioelectrochemistry sewage treatment process has a good CAP removal effect, and the CAP removal effect reaches more than 98%.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.

Claims (10)

1. The sulfur-mediated bioelectrochemistry reinforced refractory organic pollutant removal device is characterized by comprising a device main body, wherein the inside of the device main body is divided into a reaction zone (1) at the lower part and an overflow zone (2) at the upper part, an overflow weir (3) is arranged between the reaction zone (1) and the overflow zone (2), a heat preservation layer (11) is arranged on the outer wall of the device corresponding to the reaction zone (1), the reaction zone (1) is used for inoculating activated sludge taking sulfate reducing bacteria as dominant flora, an anode (12) is arranged at the upper part of the reaction zone (1), a cathode (13) is arranged at the lower part of the reaction zone (1), the anode (12) is connected with the positive pole of an external power supply (4), the cathode (13) is connected with the negative pole of the external power supply (4), and a resistor (5) is arranged between the anode (12) and the external power supply (4), water inlet (14) have been seted up to the bottom in reaction zone (1), water inlet (14) link to each other with into cask (6) through the inlet tube, be provided with intake pump (7) on the inlet tube, circulation mouth (21) have been seted up to the lower extreme in overflow district (2), circulation mouth (21) link to each other with the inlet tube through the circulating pipe, be provided with circulating pump (8) on the circulating pipe, delivery port (22) have been seted up at the middle part in overflow district (2), delivery port (22) link to each other with play cask (9) through the outlet pipe, be provided with out water pump (10) on the outlet pipe.
2. The sulfur-mediated bioelectrochemically enhanced device for removing refractory organic pollutants according to claim 1, wherein a carbon brush material is adopted for the cathode (13), and a carbon felt material is adopted for the anode (12).
3. The device for removing the refractory organic pollutants through sulfur-mediated bioelectrochemistry reinforcement according to claim 1, wherein the concentration of the inoculated activated sludge is 16gMLSS/L, MLVSS/MLSS is 0.81, and COD S is 1.8.
4. A method for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry reinforcement, which is characterized in that the refractory organic pollutants in wastewater to be treated are degraded by using the device for removing the refractory organic pollutants through sulfur-mediated bioelectrochemistry reinforcement according to any one of claims 1 to 3.
5. The method for sulfur-mediated bioelectrochemically enhanced removal of refractory organic pollutants according to claim 4, wherein the degradation treatment is performed under the following operating conditions: the applied voltage is 1V, the external resistance is 50 omega, the system current is 10mA, and the hydraulic retention time is 6 h.
6. The method of claim 4, wherein the wastewater to be treated has a pH of 7.0 and a COD N P of 100:5: 1.
7. The method of claim 4, wherein the sulfur-mediated bioelectrochemically enhanced refractory organic pollutant removal device is required to establish a stable process environment before degradation treatment.
8. The method of claim 4, wherein establishing a stable process environment comprises the steps of:
s1, starting a first stage: inoculating activated sludge taking sulfate reducing bacteria as dominant flora into a reaction zone (1) of the sulfur-mediated bioelectrochemistry reinforced refractory organic pollutant removing device according to any one of claims 1 to 3, controlling a system to be in an anaerobic environment, then introducing artificial synthetic wastewater containing a carbon source, a sulfur source, a nitrogen source, a phosphorus source, calcium chloride, magnesium chloride, ammonium chloride and trace elements, wherein COD (chemical oxygen demand) is N: P (100: 5: 1), and domesticating the sludge to enable microorganisms in the system to gradually adapt to the existence of the sulfur source until the sulfur reduction effect is stable and the sulfur reduction efficiency is more than 60%;
s2, starting a second stage: after the first stage, the voltage of the external power supply is applied in a gradient manner, the resistance is adjusted to 50 omega, each period is 0.5 month, and the resistance voltage, the cathode and anode potentials and current, and SO are measured every day4 2-Reducing efficiency, biological elemental sulfur generation amount and COD removal condition until SO4 2-The reduction efficiency reaches more than 60 percent, the COD removal efficiency reaches more than 80 percent, and the generation amount of biological simple substances is stable;
s3, establishing a stable operation environment: after the reactor operates stably, refractory organic matters are added into the synthetic wastewater, the COD (chemical oxygen demand) of the wastewater is ensured to be 100:5:1, and then the synergistic degradation removal effect of the refractory organic matters is enhanced under the conditions that the voltage of an external power supply is 1V, the resistance is 50 omega and the system current is 10mA until the removal effect of the refractory organic matters is stable.
9. The method of claim 8, wherein the process conditions of steps S1 and S2 are as follows: the inflow Q is 22.5L/d, the muddy water is uniformly mixed by a circulating pump, the circulating setting is 5Q, the reaction temperature is 25 +/-1 ℃, the inflow pH is 7.0 +/-0.1, and the hydraulic retention time is 6 h; the acclimation time in the first stage was 1 month, and the operation time in the second stage was 2.5 months.
10. The method of claim 8, wherein in step S3, the concentration of the refractory organic substance is 100 μ g/L.
CN202111288012.5A 2021-11-02 2021-11-02 Method and device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry enhancement Pending CN113845217A (en)

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