CN113735337A - Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device - Google Patents

Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device Download PDF

Info

Publication number
CN113735337A
CN113735337A CN202111012676.9A CN202111012676A CN113735337A CN 113735337 A CN113735337 A CN 113735337A CN 202111012676 A CN202111012676 A CN 202111012676A CN 113735337 A CN113735337 A CN 113735337A
Authority
CN
China
Prior art keywords
conductive filter
membrane
advanced
filter membrane
conductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111012676.9A
Other languages
Chinese (zh)
Inventor
王燕
王敏
倪晓雨
高宝玉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to CN202111012676.9A priority Critical patent/CN113735337A/en
Publication of CN113735337A publication Critical patent/CN113735337A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/36Organic compounds containing halogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/023Reactive oxygen species, singlet oxygen, OH radical

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

本发明涉及利用导电滤膜‑非均相类芬顿水处理装置对难降解污染物进行深度处理的方法,本发明的深度处理方法将导电滤膜和非均相类芬顿氧化方法相结合,以电极板作为阳极,导电滤膜作为阴极,并在导电滤膜之间填充具有催化性能的碳材料,该反应器可同步完成类芬顿反应和膜过滤作用,极大缩短水处理流程,提高水处理效果。本发明的处理方法兼具抑制污染物在膜上的沉积和富集、减少高级氧化工艺催化药剂的使用以及铁、锰等金属离子的排放、提高类芬顿处理效率、缩短水处理流程、提高难降解污染物水处理效果。The invention relates to a method for advanced treatment of refractory pollutants by using a conductive filter membrane-heterogeneous Fenton-like water treatment device. The advanced treatment method of the present invention combines the conductive filter membrane and the heterogeneous Fenton-like oxidation method, With the electrode plate as the anode, the conductive filter membrane as the cathode, and the carbon material with catalytic properties is filled between the conductive filter membranes, the reactor can simultaneously complete the Fenton-like reaction and membrane filtration, greatly shortening the water treatment process and improving water treatment effect. The treatment method of the invention has the functions of inhibiting the deposition and enrichment of pollutants on the membrane, reducing the use of advanced oxidation process catalytic agents and the discharge of metal ions such as iron and manganese, improving the efficiency of Fenton-like treatment, shortening the water treatment process, and improving Refractory pollutant water treatment effect.

Description

Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device
Technical Field
The invention relates to a method for deeply treating difficultly degraded pollutants by using a conductive filter membrane-heterogeneous Fenton-like water treatment device, belonging to the technical field of wastewater treatment.
Background
The advanced treatment of pollutants difficult to degrade in wastewater has been a difficult problem in the environmental protection industry. In order to improve the treatment effect of the pollutants difficult to degrade, the development of novel water treatment equipment, materials and processes becomes a hotspot of the environmental protection industry.
In the existing industrial wastewater treatment process, a biochemical process is an important stage for removing organic pollutants in wastewater, but the removal effect of the stage on the organic pollutants difficult to biodegrade is very little, so that the key point for improving the effluent quality of the industrial wastewater lies in the removal of the organic pollutants difficult to degrade. The existing removal process of the pollutants difficult to degrade has various types, such as coagulating sedimentation, activated carbon adsorption, membrane separation and the like, although the processes can remove the organic pollutants difficult to degrade in the industrial wastewater to a certain degree, secondary pollution can be generated, such as sludge and inactivated activated carbon formed by using a large amount of medicaments; or high construction and operation costs, such as membrane module replacement and maintenance, etc.
The advanced oxidation technology is a novel advanced wastewater treatment technology, and utilizes free radicals (such as hydroxyl free radical. OH) which have strong oxidizing property and no selectivity and are generated under different conditions to oxidize and degrade refractory organic matters in wastewater to easily biodegradable micromolecule organic matters or CO2And water. Common advanced oxidation treatment technologies include fenton oxidation, ozone catalytic oxidation, ultraviolet light catalytic process, and the like. However, the treatment efficiency of the existing process is limited and the cost is high, for example, Fenton oxidation consumes a large amount of medicaments and generates iron-containing sludge, ozone catalytic oxidation has the problems of tail gas treatment, safety, catalyst inactivation and the like, and the conventional ultraviolet light catalytic process has low light energy utilization rate and the like. Therefore, how to make best use of the advantages and avoid the disadvantages and how to construct an efficient advanced oxidation system is the key point of research on the advanced treatment of industrial wastewater.
The membrane separation technology is a typical advanced treatment technology, and has been widely applied in the field of advanced wastewater treatment due to the advantages of good water treatment effect, stable effluent quality, simple and convenient operation, easy equipment integration and the like. However, membrane fouling due to rejection, the tradeoff between membrane permeability and selectivity, and subsequent handling of the concentrate, limit further application of membrane separation techniques. In recent years, the conductive film technology becomes an emerging research direction in the field of water treatment, the conductive film can simultaneously realize the size interception and electrochemical degradation of pollutants, and the existence of an external voltage can inhibit the deposition and enrichment of the pollutants on the film by regulating the interaction force between the pollutants and a film working electrode.
Therefore, the method has the advantages of inhibiting the deposition and enrichment of pollutants on the membrane, reducing the use of catalytic agents of the advanced oxidation process and the discharge of metal ions such as iron, manganese and the like, improving the Fenton-like treatment efficiency, shortening the water treatment process and improving the water treatment effect of the difficultly-degraded pollutants, and has important significance for the advanced treatment of wastewater and good application prospect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for deeply treating refractory pollutants by using a conductive filter membrane-heterogeneous Fenton-like water treatment device.
The treatment method of the invention can inhibit the deposition and enrichment of pollutants on the membrane, reduce the use of catalytic agents of advanced oxidation process and the discharge of metal ions such as iron, manganese and the like, improve the Fenton-like treatment efficiency, shorten the water treatment flow and improve the water treatment effect of the pollutants difficult to degrade.
In order to realize the purpose, the invention is realized by the following technical scheme:
a method for carrying out advanced treatment on difficultly-degraded pollutants by utilizing a conductive filter membrane-heterogeneous Fenton-like water treatment device,
the device for treating the heterogeneous Fenton-like water by the conductive filter membrane is coupled with the conductive filter membrane and the heterogeneous Fenton-like water into a whole and comprises a reactor body, wherein a water inlet is formed in one side of the reactor body, a water outlet is formed in the side wall of the reactor body, the water outlet is connected with a water outlet pipe, the conductive filter membranes which are longitudinally and equally arranged are arranged in the reactor body, high-grade oxidation catalytic fillers are filled among the conductive filter membranes, a plate electrode is longitudinally arranged between the conductive filter membrane close to the water inlet and the water inlet, the plate electrode is an anode, the plate electrode is externally connected with a direct-current power supply anode through a lead, the conductive filter membrane is a cathode, and the plate electrode is externally connected with a direct-current power supply cathode through a lead;
the deep processing method comprises the following steps:
1) the electrode plate and the conductive filter membrane are externally connected with low-voltage direct current, the voltage of an external electric field is 0.5-10V, and the wastewater is mixed with a high-grade oxidation agent and then is injected into the conductive filter membrane-heterogeneous Fenton-like water treatment device through a water inlet by a constant flow pump;
2) pollutants in the advanced oxidation agent and the wastewater are rapidly diffused to the surfaces and inner holes of the filler and the conductive filter membrane, and are rapidly catalyzed and decomposed into strong oxidant OH free radicals under the action of an external electric field, so that an electric field enhanced heterogeneous Fenton-like reaction is formed, and the refractory organic pollutants on the surface of the wastewater neutralization membrane are oxidized and degraded;
3) the organic pollutants which are difficult to degrade in the wastewater are removed through membrane interception and filtration and heterogeneous Fenton-like oxidation degradation, and the treated water is discharged from a water outlet.
According to the invention, the material of the reactor body is preferably organic glass, stainless steel or carbon steel, the cross section is square or round, and the hydraulic retention time is 2-120 minutes.
According to the invention, the conductive filter membrane is preferably a conductive nanofiltration membrane, a conductive microfiltration membrane or a conductive ceramic membrane loaded with carbon nanotubes, graphene or carbon black materials, and the interception aperture of the conductive filter membrane is 1nm-1 μm.
Preferably, according to the invention, the distance between the conducting filter membranes is 5-50 cm.
Most preferably, the distance between the conducting filter membranes is 10 cm.
According to the invention, the electrode plate is preferably a titanium plate, a titanium mesh, a stainless steel plate, a stainless steel mesh, Ti/Sb-SnO2Electrode plate or Ti/PbO2And an electrode plate.
According to the invention, the bottom of the reactor body is preferably provided with aeration heads, the distance between the aeration heads is 5-50cm, the aeration gas is air or oxygen, and the aeration intensity is 5-25m3/m2·h。
According to the invention, the advanced oxidation catalytic filler is a matrix material loaded with metal or metal oxide, the metal is iron, manganese, nickel, copper, cobalt, platinum, silver or palladium, and the matrix material is activated carbon, biochar, nanocarbon or three-dimensional graphene.
According to the invention, the preferred higher oxidizing agent is hydrogen peroxide, persulfate or hypochlorite, and the dosage of the higher oxidizing agent enables the concentration to reach 1-100 mM; further preferably, the higher oxidizing agent is used in an amount to achieve a concentration of 10-30 mM.
The supporting method of the matrix material loaded with the metal or the metal oxide is prepared according to the prior art.
The advanced treatment method of the invention takes a conductive filter membrane and a heterogeneous Fenton-like water treatment device as a core, utilizes an electrode plate as an anode and a conductive filter membrane as a cathode, and fills carbon materials with catalytic performance between the conductive filter membranes to form a coupling system of the conductive filter membrane and the heterogeneous Fenton. The water inlet of the water treatment device is arranged on one side of the anode plate, and the water outlet of the water treatment device is arranged on one side of the cathode filter membrane. The high-grade oxidation agent is quickly catalytically decomposed on the catalytic filler and the conductive filter membrane into a strong oxidant OH free radical to oxidize and degrade the organic pollutants which are difficult to degrade on the surface of the membrane and in the inlet water. The pollutants in the inlet water are removed through heterogeneous Fenton oxidation and membrane interception and filtration, and are discharged from the water outlet. In particular, if no higher oxidizing agent is added, the oxygen provided by aeration can be reduced to H in situ on the catalytic filler and the conductive filter membrane2O2And the function of removing pollutants through oxidation is achieved.
The invention has the technical characteristics and advantages that:
the advanced treatment method combines the conductive filter membrane with the heterogeneous Fenton-like oxidation method, takes the electrode plate as the anode and the conductive filter membrane as the cathode, and fills carbon materials with catalytic performance between the conductive filter membranes, and the reactor can synchronously complete the Fenton-like reaction and the membrane filtration, greatly shortens the water treatment process and improves the water treatment effect.
2. The treatment method is carried out by utilizing the conductive filter membrane-heterogeneous Fenton-like water treatment device, the high-grade oxidation medicament is rapidly catalyzed and decomposed into strong oxidant OH free radicals on the catalytic filler and the conductive filter membrane to form an electric field to strengthen the heterogeneous Fenton-like reaction, and the wastewater can be oxidized and degradedOf (a). In addition, the oxygenation aeration can be reduced into H in situ on the catalytic filler and the conductive filter membrane2O2The catalyst also has the functions of homogenizing and mixing, so that the catalytic filler is uniformly distributed in the reactor, and the mass transfer rate and the treatment efficiency of the device are obviously improved.
3. The method of the invention realizes two functions of membrane filtration and Fenton-like oxidation simultaneously in one water treatment unit. The principle of the device is that a conductive film is used as an electrode of the device, a carbon material with catalytic efficiency and conductivity is loaded on the conductive film, the catalytic generation of free radicals such as hydroxyl free radicals, oxygen free radicals, chlorine free radicals, sulfate free radicals and the like is realized on the surface of the film through electrochemical reaction, the contact reaction efficiency of pollutants and the hydroxyl free radicals in the wastewater is improved by utilizing the process that the wastewater passes through film holes, and the purposes of quickly degrading the pollutants and improving the water treatment efficiency are achieved by combining the physical interception of the film. In addition, in order to improve the efficiency of the Fenton-like treatment, the equipment can be filled with advanced oxidation catalytic filler.
Drawings
FIG. 1 is a schematic view of a conducting membrane-heterogeneous Fenton-like water treatment device;
in the figure, the device comprises a reactor body 1, a reactor body 2, a water inlet 3, an electrode plate 4, a water outlet pipe 5, a conductive filter membrane 6, a lead 7, a high-grade oxidation catalytic filler 8, an aeration head 9, a lead 10, a water outlet pump 11 and a mixing device.
FIG. 2 is a graph showing the removal rate of rhodamine B in application example 1.
FIG. 3 is a graph showing the decolorization effect of rhodamine B in application example 1.
FIG. 4 is a graph of the removal rate of tetracycline by application example 2.
FIG. 5 is a plot of HPLC peak areas before (a) and after (b) tetracycline removal using example 2.
Detailed Description
The invention will be further explained with reference to the drawings and examples.
Example 1
A method for carrying out advanced treatment on difficultly-degraded pollutants by utilizing a conductive filter membrane-heterogeneous Fenton-like water treatment device,
the conductive filter membrane-heterogeneous Fenton-like water treatment device is coupled with a conductive filter membrane and heterogeneous Fenton-like water into a whole, and has a structure shown in figure 1, and comprises a reactor body 1, wherein the reactor body 1 is a cuboid with the size of 50cm multiplied by 30cm multiplied by 10cm, a water inlet 2 is arranged on one side of the reactor body, a water outlet is arranged on the side wall of the reactor body, conductive filter membranes 5 which are longitudinally and equally arranged are arranged inside the reactor body, the size of each conductive filter membrane 5 is 25cm multiplied by 8cm, the membrane aperture is 0.8um, the distance between every two conductive filter membranes 5 is 3cm, each conductive filter membrane is a conductive nanofiltration membrane loaded with carbon nanotubes, advanced oxidation catalytic fillers 7 are filled between every two conductive filter membranes, the advanced oxidation catalytic fillers 7 are biological carbon loaded with ferromanganese, an electrode plate 3 is longitudinally arranged between the conductive filter membrane close to the water inlet 2 and the water inlet 2, and the electrode plate 3 is an anode, the electrode plate 3 is a titanium mesh and is externally connected with a direct current power supply anode through a lead, the conductive filter membrane 5 is a cathode, and is externally connected with a direct current power supply cathode through a lead; the bottom of the reactor body 1 is provided with an oxygen aeration head 8 with aeration quantity of 10m3/m2H, the distance between the aeration heads is 25cm, and the aeration gas is air. The water outlet is connected with a water outlet pipe 4 in a converging manner, and a water outlet pump 10 is arranged on the water outlet pipe 4.
The deep processing method comprises the following steps:
1) the electrode plate and the conductive filter membrane are externally connected with low-voltage direct current, the voltage of an external electric field is 3V, and the wastewater is mixed with 10% potassium persulfate solution and then is injected into the conductive filter membrane-heterogeneous Fenton-like water treatment device through a water inlet 2 by a constant flow pump; the flow rate is 20L/h, the concentration of the potassium persulfate after mixing is 10mg/L,
2) potassium persulfate and pollutants in the wastewater rapidly diffuse into the surfaces and internal holes of the filler and the conductive filter membrane, and under the action of an external electric field, the potassium persulfate catalyzes the surfaces of the iron-manganese-loaded biochar advanced oxidation catalytic filler 7 and the conductive ultrafiltration membrane 5 to generate sulfate radicals and hydroxyl radicals so as to form an electric field reinforced heterogeneous Fenton-like reaction and oxidize and degrade refractory organic pollutants on the surface of the wastewater neutralization membrane;
3) the organic pollutants which are difficult to degrade in the wastewater are removed through membrane interception and filtration and heterogeneous Fenton-like oxidation degradation, and the treated water is discharged from a water outlet.
Application Experimental example 1
The method of example 1 is adopted to treat the simulated rhodamine B dye wastewater,
when the device operates, the voltage applied by low-voltage direct current is 3V, 10% potassium persulfate solution is added into rhodamine B dye wastewater through a mixing device 11, the concentration of the mixed potassium persulfate is 10mg/L, then the rhodamine B wastewater mixed with the potassium persulfate is injected from a bottom water inlet 2 of a reactor 1 by using a constant flow pump, the flow rate is 20L/h, and the potassium persulfate generates sulfate radicals and hydroxyl radicals in the surface catalysis of a biological carbon advanced oxidation catalysis filler 7 loaded with iron and manganese and a conductive ultrafiltration membrane 5 so as to oxidize and decompose organic pollutants in the wastewater. Then, filtering by a membrane, and completely decoloring the rhodamine B dye simulated wastewater; the removal rate and the decoloring effect of rhodamine B are shown in FIGS. 2 and 3.
The specific water inlet and outlet indexes are as follows, the COD of inlet water is 10.2mg/L, the absorbance at 554nm is 0.403, the absorbance of outlet water can be reduced to 0.033 after the device runs for 5min, and the COD can be reduced to 7.8 mg/L.
Example 2
A method for carrying out advanced treatment on refractory pollutants by utilizing a conductive filter membrane-heterogeneous Fenton-like water treatment device, wherein the water treatment device is the same as that in the embodiment 1; the difference lies in that:
the deep processing method comprises the following steps:
1) the electrode plate and the conductive filter membrane are externally connected with low-voltage direct current, the voltage of an external electric field is 5V, and the wastewater is mixed with 10% potassium persulfate solution and then is injected into the conductive filter membrane-heterogeneous Fenton-like water treatment device through a water inlet 2 by a constant flow pump; the flow rate is 15L/h, the concentration of the potassium persulfate after mixing is 20mg/L,
2) potassium persulfate and pollutants in the wastewater rapidly diffuse into the surfaces and internal holes of the filler and the conductive filter membrane, and under the action of an external electric field, the potassium persulfate catalyzes the surfaces of the iron-manganese-loaded biochar advanced oxidation catalytic filler 7 and the conductive ultrafiltration membrane 5 to generate sulfate radicals and hydroxyl radicals so as to form an electric field reinforced heterogeneous Fenton-like reaction and oxidize and degrade refractory organic pollutants on the surface of the wastewater neutralization membrane;
3) the organic pollutants which are difficult to degrade in the wastewater are removed through membrane interception and filtration and heterogeneous Fenton-like oxidation degradation, and the treated water is discharged from a water outlet.
Application Experimental example 2
The method of example 2 was used to treat the simulated tetracycline wastewater,
when the device operates, the low-voltage direct current applied voltage is 5V, 10% potassium persulfate solution is added into the tetracycline wastewater through the mixing device 11, the concentration of the mixed potassium persulfate is 20mg/L, then the tetracycline wastewater mixed with the potassium persulfate is injected from the bottom water inlet 2 of the reactor by using a constant flow pump, and the flow rate is 15L/h. The potassium persulfate is catalyzed on the surfaces of the biological carbon advanced oxidation catalytic filler loaded with iron and manganese and the conductive ultrafiltration membrane to generate sulfate radicals and hydroxyl radicals so as to oxidize and decompose tetracycline in the wastewater. Then, the removal efficiency of tetracycline in the wastewater can reach 99.3 percent through membrane filtration. The tetracycline removal effect is shown in fig. 4 and 5.
The specific water inlet and outlet indexes are as follows, the COD of inlet water is 230.4mg/L, the tetracycline concentration is 200mg/L, and after the device runs for 5min, the COD of outlet water can be reduced to 196.2mg/L, and the tetracycline concentration can be reduced to 13.02 mg/L.
Example 3
The method for performing advanced treatment on refractory pollutants by using the conductive filter membrane-heterogeneous Fenton-like water treatment device is the same as that in the embodiment 1, and is different from the method in that:
the conductive filter membrane is a conductive microfiltration membrane loaded with carbon black materials, the interception aperture is 1nm, and the distance between the conductive filter membranes is 10 cm.
The electrode plate is a titanium plate.
The distance between the aeration heads is 30cm, the aeration gas is air, and the aeration intensity is 20m3/m2·h。
The other was carried out as in example 1.
Example 4
The method for carrying out advanced treatment on the pollutants difficult to degrade by utilizing the conductive filter membrane-heterogeneous Fenton-like water treatment device is the same as that in the embodiment 1,
the difference lies in that:
the deep processing method comprises the following steps:
1) the electrode plate and the conductive filter membrane are externally connected with low-voltage direct current, the voltage of an external electric field is 8V, and the wastewater is mixed with 10% potassium persulfate solution and then is injected into the conductive filter membrane-heterogeneous Fenton-like water treatment device through a water inlet 2 by a constant flow pump; the flow rate is 20L/h, the hydraulic retention time is 60 minutes, the concentration of the potassium persulfate after mixing is 20mg/L,
2) potassium persulfate and pollutants in the wastewater rapidly diffuse into the surfaces and internal holes of the filler and the conductive filter membrane, and under the action of an external electric field, the potassium persulfate catalyzes the surfaces of the iron-manganese-loaded biochar advanced oxidation catalytic filler 7 and the conductive ultrafiltration membrane 5 to generate sulfate radicals and hydroxyl radicals so as to form an electric field reinforced heterogeneous Fenton-like reaction and oxidize and degrade refractory organic pollutants on the surface of the wastewater neutralization membrane;
3) the organic pollutants which are difficult to degrade in the wastewater are removed through membrane interception and filtration and heterogeneous Fenton-like oxidation degradation, and the treated water is discharged from a water outlet.

Claims (9)

1.利用导电滤膜-非均相类芬顿水处理装置对难降解污染物进行深度处理的方法,1. A method for advanced treatment of refractory pollutants using a conductive filter membrane-heterogeneous Fenton-like water treatment device, 所述的导电滤膜-非均相类芬顿水处理装置耦合导电滤膜和非均相类芬顿于一体,包括反应器本体,反应器本体一侧设置有进水口,反应器本体侧壁上设置有出水口,出水口连接出水管,在反应器本体内部设置有纵向均等排列的导电滤膜,导电滤膜之间填充有高级氧化催化填料,在与进水口临近的导电滤膜与进水口之间纵向设置有电极板,电极板为阳极,经导线外接直流电源正极,导电滤膜为阴极,经导线外接直流电源负极;The conductive filter membrane-heterogeneous Fenton-like water treatment device is coupled with the conductive filter membrane and the heterogeneous Fenton-like water treatment device, and includes a reactor body, one side of the reactor body is provided with a water inlet, and a side wall of the reactor body is provided. A water outlet is provided on the upper part, and the water outlet is connected to the water outlet pipe. The inside of the reactor body is provided with conductive filter membranes that are evenly arranged in the longitudinal direction. The conductive filter membranes are filled with advanced oxidation catalyst fillers. An electrode plate is arranged longitudinally between the nozzles, the electrode plate is the anode, the positive electrode of the DC power supply is externally connected through the wire, the conductive filter membrane is the cathode, and the negative electrode of the DC power supply is externally connected through the wire; 所述的深度处理方法,包括步骤如下:The deep processing method includes the following steps: 1)电极板和导电滤膜外接低压直流电,外加电场电压为0.5-10V,废水混合高级氧化药剂后,用恒流泵由进水口注入导电滤膜-非均相类芬顿水处理装置中;1) The electrode plate and the conductive filter membrane are connected with low-voltage direct current, and the applied electric field voltage is 0.5-10V. After the wastewater is mixed with the advanced oxidizing agent, it is injected into the conductive filter membrane-heterogeneous Fenton-like water treatment device from the water inlet with a constant current pump; 2)高级氧化药剂和废水中的污染物迅速扩散到填料和导电滤膜的表面及内部孔洞中,在外加电场作用下,迅速催化分解为强氧化剂·OH自由基,形成电场强化非均相类芬顿反应,氧化降解废水中和膜表面的难降解有机污染物;2) Advanced oxidizing agents and pollutants in wastewater quickly diffuse to the surface and internal pores of fillers and conductive filter membranes, and under the action of an external electric field, they are rapidly catalytically decomposed into strong oxidant OH radicals, forming electric field-enhanced heterogeneous types. Fenton reaction, oxidative degradation of wastewater and refractory organic pollutants on the membrane surface; 3)废水中的难降解有机污染物经膜截留过滤和非均相类芬顿氧化降解而去除,处理完成的水由出水口排出。3) The refractory organic pollutants in the wastewater are removed by membrane retention filtration and heterogeneous Fenton-like oxidation degradation, and the treated water is discharged from the water outlet. 2.根据权利要求1所述的深度处理的方法,其特征在于,反应器本体的材质为有机玻璃、不锈钢或碳钢,横截面为方形或圆形,水力停留时间为2-120分钟。2 . The method for advanced treatment according to claim 1 , wherein the material of the reactor body is plexiglass, stainless steel or carbon steel, the cross section is square or circular, and the hydraulic retention time is 2-120 minutes. 3 . 3.根据权利要求1所述的深度处理的方法,其特征在于,导电滤膜为负载了碳纳米管、石墨烯或炭黑材料的导电纳滤膜、导电微滤膜或导电陶瓷膜,其截留孔径为1nm-1μm。3. The method for advanced treatment according to claim 1, wherein the conductive filter membrane is a conductive nanofiltration membrane, a conductive microfiltration membrane or a conductive ceramic membrane loaded with carbon nanotubes, graphene or carbon black materials, which The cut-off pore size is 1 nm-1 μm. 4.根据权利要求1所述的深度处理的方法,其特征在于,导电滤膜之间的间距为5-50cm。4 . The method for advanced treatment according to claim 1 , wherein the distance between the conductive filters is 5-50 cm. 5 . 5.根据权利要求4所述的深度处理的方法,其特征在于,导电滤膜之间的间距为10cm。5 . The method for advanced treatment according to claim 4 , wherein the distance between the conductive filters is 10 cm. 6 . 6.根据权利要求1所述的深度处理的方法,其特征在于,电极板为钛板、钛网、不锈钢板、不锈钢网、Ti/Sb-SnO2电极板或Ti/PbO2电极板。6 . The method for advanced treatment according to claim 1 , wherein the electrode plate is a titanium plate, a titanium mesh, a stainless steel plate, a stainless steel mesh, a Ti/Sb-SnO 2 electrode plate or a Ti/PbO 2 electrode plate. 7 . 7.根据权利要求1所述的深度处理的方法,其特征在于,反应器本体的底部设置有曝气头,曝气头的间距为5-50cm,曝气气体采用的是空气或者氧气,曝气强度为5-25m3/m2·h。7. The method for advanced treatment according to claim 1, wherein the bottom of the reactor body is provided with an aeration head, the spacing of the aeration head is 5-50cm, and the aeration gas adopts air or oxygen, and the aeration head is The gas intensity is 5-25 m 3 /m 2 ·h. 8.根据权利要求1所述的深度处理的方法,其特征在于,高级氧化催化填料为负载金属或金属氧化物的基质材料,金属为铁、锰、镍、铜、钴、铂、银或钯,基质材料为活性炭、生物炭、纳米碳材或三维石墨烯。8. The method for advanced treatment according to claim 1, wherein the advanced oxidation catalytic filler is a matrix material supporting metal or metal oxide, and the metal is iron, manganese, nickel, copper, cobalt, platinum, silver or palladium , the matrix material is activated carbon, biochar, nano-carbon material or three-dimensional graphene. 9.根据权利要求1所述的深度处理的方法,其特征在于,高级氧化药剂为双氧水、过硫酸盐或次氯酸盐,高级氧化药剂的用量使其浓度达到10-30mM。9 . The method for advanced treatment according to claim 1 , wherein the advanced oxidizing agent is hydrogen peroxide, persulfate or hypochlorite, and the dosage of the advanced oxidizing agent makes its concentration reach 10-30 mM. 10 .
CN202111012676.9A 2021-08-31 2021-08-31 Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device Pending CN113735337A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111012676.9A CN113735337A (en) 2021-08-31 2021-08-31 Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111012676.9A CN113735337A (en) 2021-08-31 2021-08-31 Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device

Publications (1)

Publication Number Publication Date
CN113735337A true CN113735337A (en) 2021-12-03

Family

ID=78734232

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111012676.9A Pending CN113735337A (en) 2021-08-31 2021-08-31 Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device

Country Status (1)

Country Link
CN (1) CN113735337A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114538572A (en) * 2022-04-11 2022-05-27 青岛科技大学 Method for treating reverse osmosis concentrated water by using electrochemical water treatment device
CN114772688A (en) * 2022-05-25 2022-07-22 合肥工业大学 Micro-current Fenton fluidized bed membrane reactor for treating refractory wastewater
CN115155332A (en) * 2022-07-07 2022-10-11 南京大学 In-situ membrane pollution resisting method for low-voltage electric field coupling conductive ultrafiltration membrane
WO2024146144A1 (en) * 2023-01-06 2024-07-11 哈尔滨工业大学 Membrane-mediated electrooxidation-reduction advanced water treatment device and operation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109607746A (en) * 2019-01-17 2019-04-12 天津工业大学 A new type of electro-Fenton device, method and application based on carbon membrane
CN212581573U (en) * 2020-07-02 2021-02-23 广州市金龙峰环保设备工程股份有限公司 electro-Fenton organic wastewater advanced treatment device
US20210230030A1 (en) * 2020-01-23 2021-07-29 The Board Of Trustees Of The Leland Stanford Junior University Organic wastewater treatment by a single-atom catalytic fenton filter and electrolytically-generated h2o2

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109607746A (en) * 2019-01-17 2019-04-12 天津工业大学 A new type of electro-Fenton device, method and application based on carbon membrane
US20210230030A1 (en) * 2020-01-23 2021-07-29 The Board Of Trustees Of The Leland Stanford Junior University Organic wastewater treatment by a single-atom catalytic fenton filter and electrolytically-generated h2o2
CN212581573U (en) * 2020-07-02 2021-02-23 广州市金龙峰环保设备工程股份有限公司 electro-Fenton organic wastewater advanced treatment device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
姚方元等: "《石墨烯与轨道交通》", 31 August 2016, 湖南教育出版社, pages: 79 - 83 *
李银峰等, 中国原子能出版社, pages: 129 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114538572A (en) * 2022-04-11 2022-05-27 青岛科技大学 Method for treating reverse osmosis concentrated water by using electrochemical water treatment device
CN114538572B (en) * 2022-04-11 2023-11-03 青岛科技大学 Method for treating reverse osmosis concentrated water by using electrochemical water treatment device
CN114772688A (en) * 2022-05-25 2022-07-22 合肥工业大学 Micro-current Fenton fluidized bed membrane reactor for treating refractory wastewater
CN115155332A (en) * 2022-07-07 2022-10-11 南京大学 In-situ membrane pollution resisting method for low-voltage electric field coupling conductive ultrafiltration membrane
CN115155332B (en) * 2022-07-07 2023-12-19 南京大学 A method for in-situ anti-membrane fouling resistance of low-voltage electric field coupled conductive ultrafiltration membranes
WO2024146144A1 (en) * 2023-01-06 2024-07-11 哈尔滨工业大学 Membrane-mediated electrooxidation-reduction advanced water treatment device and operation method thereof

Similar Documents

Publication Publication Date Title
CN113735337A (en) Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device
CN108358362B (en) Advanced treatment method of high-concentration organic wastewater
US10662095B2 (en) Ozone-photocatalysis reactor and water treatment method
CN206720796U (en) A kind of photoelectrocatalysioxidization oxidization rolling membrane reactor device for water process
CN112159011A (en) Advanced oxidation system of ultraviolet/ozone coupling catalyst and sewage treatment process
CN1562795A (en) Photoelectrocatalysis and oxidation device for treating organic substance in water
CN110921980B (en) A kind of electrochemically enhanced ozone-biological activated carbon water treatment equipment and method for using the same to treat water
CN114538572B (en) Method for treating reverse osmosis concentrated water by using electrochemical water treatment device
CN112321034A (en) Device and method for synchronously electrolyzing/membrane separating/advanced oxidizing and cooperatively treating ammonium sulfate-containing wastewater and organic wastewater
CN111470676A (en) System and method for treating industrial wastewater by ozone ceramic membrane coupling oxidation technology
CN101913693A (en) Device and method for treating refractory organic wastewater by using electrocatalysis to activate molecular oxygen
CN116874043A (en) Electrochemical double-membrane reactor and wastewater treatment method based on electrochemical double-membrane reactor
CN103030244B (en) Combined pretreatment method for industrial wastewater
CN113716756B (en) Non-load type ozone catalytic oxidation sewage treatment system and method
CN107840441A (en) Intelligent suitching type ozone/electric filter collaboration water treatment facilities and the method using its progress water process
CN211471172U (en) Organic wastewater treatment system
CN210438469U (en) Catalytic oxidation reaction system for advanced wastewater treatment
CN103214133B (en) Graphene sewage purification combined device and sewage purification method thereof
CN113003877B (en) Treatment device and method for refractory organic wastewater
CN111170567A (en) Integrated electrochemical coupling membrane aeration biofilm reactor and its application
CN202116407U (en) A device for treating catering wastewater
CN214270532U (en) Membrane filtration concentrate system is handled to electrooxidation method
CN108751573B (en) A kind of printing and dyeing wastewater BAME treatment and reuse method
CN209098291U (en) A kind of device of ozone and the processing of electrochemistry concerted catalysis oxidized waste water
CN112919700A (en) Reactor for advanced treatment of high-salinity organic wastewater by using multistage photoelectric tubes

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20211203

RJ01 Rejection of invention patent application after publication