CN113683234A - Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method - Google Patents

Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method Download PDF

Info

Publication number
CN113683234A
CN113683234A CN202111072954.XA CN202111072954A CN113683234A CN 113683234 A CN113683234 A CN 113683234A CN 202111072954 A CN202111072954 A CN 202111072954A CN 113683234 A CN113683234 A CN 113683234A
Authority
CN
China
Prior art keywords
tubular membrane
ozone
membrane electrode
anode
degradation
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
CN202111072954.XA
Other languages
Chinese (zh)
Inventor
魏卡佳
王陆
韩卫清
刘启擎
顾连凯
刘思琪
刘润
戴君诚
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.)
Nanjing University of Science and Technology
Original Assignee
Nanjing University of Science and Technology
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 Nanjing University of Science and Technology filed Critical Nanjing University of Science and Technology
Priority to CN202111072954.XA priority Critical patent/CN113683234A/en
Publication of CN113683234A publication Critical patent/CN113683234A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F7/00—Aeration of stretches of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/062—Tubular membrane modules with membranes on a surface of a support tube
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46128—Bipolar electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • C02F2001/46166—Gas diffusion electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46171—Cylindrical or tubular shaped
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4616—Power supply
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4619—Supplying gas to the electrolyte
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/78—Details relating to ozone treatment devices
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/20—Total organic carbon [TOC]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/44—Time
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/14—Maintenance of water treatment installations

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Manufacturing & Machinery (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and a degradation method, and belongs to the technical field of wastewater treatment. The device comprises a tubular membrane electrode, a heterogeneous ozone catalyst and an ozone aeration unit; the tubular membrane electrode comprises a tubular membrane cathode and a tubular membrane anode, wherein the tubular membrane cathode is sleeved outside the tubular membrane anode, and the tubular membrane anode comprises a titanium-based tubular membrane anode; the ozone aeration unit is arranged at the bottom of the tubular membrane electrode, and the aeration direction of the ozone aeration unit is upward; the heterogeneous ozone catalyst includes a carbon-based material supporting a transition metal or a transition metal oxide, which is disposed in wastewater. The invention can effectively treat high-concentration and high-COD wastewater, effectively reduce the degradation-resistant organic matters such as nitrogen-containing heterocycles or benzene rings and the like, and improve the water treatment efficiency.

Description

Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and a degradation method.
Background
Nitrogen-containing heterocyclic compounds (NHCs), such as cycloumile compounds, pyrimidine compounds, and the like, belong to typical chemical industry compositions, and are widely used in the industries of medicine, cosmetics, disinfectants, dyes, pesticides, and the like. NHCs have been reported to exhibit toxicity, mutagenicity, and carcinogenicity even at low concentrations. NHCs have complete resistance to conventional biochemical systems, cannot be removed efficiently by conventional biochemical methods, have a long half-life in the environment, and can be continuously accumulated in natural media such as water, soil and the like, and then food chains enter organisms and are gradually enriched, thereby posing a serious threat to the health of organisms, microorganisms and human beings. Therefore, the development of more efficient and economic means for removing NHCs from chemical wastewater is the focus of current research.
In recent years, advanced oxidation water treatment technology has gained wide attention of researchers all over the world due to its excellent mineralization effect on organic pollutants, and such as ozone oxidation technology, electrochemical oxidation technology, fenton oxidation technology and the like are developed rapidly, and are considered to be technologies with great application prospects in the process of controlling refractory organic pollutants in water. The advanced oxidation water treatment technology mainly utilizes strong oxidants such as hydroxyl radicals, ozone and the like generated in the system to oxidize organic pollutants into harmless substances or thoroughly mineralize the organic pollutants into water and carbon dioxide, thereby efficiently removing the organic pollutants which are difficult to degrade in the wastewater and realizing the harmlessness of the wastewater. The advanced oxidation water treatment technology can be used independently or combined with other treatment technologies. In practical application, the advanced oxidation water treatment technology can be used as a pretreatment technology or an advanced treatment technology in a biochemical treatment process, so that the treatment cost is reduced, the treatment efficiency is improved, and the advanced oxidation water treatment technology is a flexible and efficient water treatment technology.
The electrochemical-ozone combined technology is used as a new advanced oxidation technology, not only can rapidly degrade common biological refractory organic pollutants (such as NHCs) in water, but also can degrade refractory organic pollutants which are difficult to degrade by other chemical methods. The electrochemical-ozone combined technology has two main mechanisms, namely, ozone is subjected to reduction reaction at a cathode to generate hydroxyl radicals, and hydrogen peroxide generated by electricity is reacted with ozone to generate the hydroxyl radicals. Under the condition of normal temperature and pressure, the combined use of the electrochemical technology and the ozone makes the degradation efficiency of the organic pollutants in water far larger than the sum of the two independent functions. Depending on the reaction conditions, the combination effect is that through the combination of the electrochemical technology and the ozone technology, hydroxyl radicals which are far larger than those generated when the two technologies are used for treating water pollution independently are generated in water, so that the aim of purifying the water is achieved. In addition, the combination effect is also expressed as the synergistic effect of the electrochemical reaction and the degradation of the organic pollutants, so that the time required by the thorough mineralization of the organic pollutants is obviously shortened, and the water treatment efficiency is improved.
However, the problems that membrane blockage is easy to occur to a membrane electrode and the mass transfer performance of an ozone catalyst is poor in practical application still exist in the combined technology, the ozone catalytic oxidation technology is commonly used for deep treatment of low-concentration and low-COD wastewater, the ozone catalytic oxidation technology does not have obvious superiority to high-concentration and high-COD heterocyclic substances, the treatment effect of the high-COD refractory chemical wastewater is far lower than that of electrochemical oxidation, and due to the fact that the cost of the ozone related technology is high, the ozone related technology has the problem that the cost is high all the time. Meanwhile, the electrochemical oxidation has a remarkable treatment effect when treating high-concentration chemical wastewater, such as COD (chemical oxygen demand) of over tens of thousands, and can treat the wastewater with COD of about 1000 within a certain time; however, in the advanced treatment of wastewater, the electrochemical oxidation effect is poor, and the substances which have completed ring opening and chain formation and the target substances which have been subjected to the low molecular acid step cannot be further treated.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the membrane electrode is easy to block, the mass transfer performance of an ozone catalyst is poor and the device cannot treat heterocyclic organic substances with high concentration and high COD in practical application of the coupling technology in the prior art, the invention provides a tubular membrane electrode and heterogeneous ozone catalyst coupling degradation device and a degradation method; through reasonable arrangement of the tubular membrane electrode, the heterogeneous ozone catalyst and the ozone aeration unit, the problems that in the prior art, the membrane electrode is easy to block, the mass transfer performance of the ozone catalyst is poor, and heterocyclic substances with high concentration and high COD (chemical oxygen demand) cannot be treated are effectively solved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device, which is used for degrading organic matters in wastewater and comprises a tubular membrane electrode, a heterogeneous ozone catalyst and an ozone aeration unit; the tubular membrane electrode comprises a tubular membrane cathode and a tubular membrane anode, wherein the tubular membrane cathode is sleeved outside the tubular membrane anode, and the tubular membrane anode comprises a titanium-based tubular membrane anode; the ozone aeration unit is arranged at the bottom of the tubular membrane electrode, and the aeration direction of the ozone aeration unit is upward; the heterogeneous ozone catalyst includes a carbon-based material supporting a transition metal or a transition metal oxide, which is disposed in wastewater. The degradation device has remarkable treatment effect on high-concentration and high-COD wastewater, and particularly has excellent treatment effect on benzene ring or heterocyclic organic matters containing 30000 mg/L-100000 mg/L of COD; the benzene ring or heterocyclic organic compound comprises p-chlorobenzoic acid, pentafluorouracil, rhodamine B, tricyclazole, ibuprofen, and the like, and the above is only examples of several typical benzene ring or heterocyclic pollutants, and does not limit the types of the benzene ring or heterocyclic organic compound.
The wastewater in the invention comprises water systems of pollutants such as various printing and dyeing wastewater, pesticide wastewater, medical wastewater, pharmaceutical wastewater and the like. The tubular membrane electrode has good mass transfer performance and extremely high electrochemical oxidation treatment efficiency, and simultaneously has the functions of membrane separation and membrane filtration, and the diffusion effect of the membrane separation greatly improves the contact probability of pollutants and the electrode, so that the electrochemical oxidation efficiency can be further improved.
Preferably, the ozone aeration unit is arranged at the bottom between the tubular membrane cathode and the tubular membrane anode and is used for driving the wastewater between the tubular membrane cathode and the tubular membrane anode to flow upwards; the concentration of ozone in the aeration of the ozone aeration unit is 2 mg/L-50 mg/L, and the aeration flow is 0.5L/min-5L/min. Set up the aeration unit through the bottom between tubular membrane cathode and tubular membrane anode to let the aeration unit upwards aerate, can drive the waste water upflow between tubular membrane cathode and the tubular membrane anode, the waste water downflow outside tubular membrane cathode, thereby form the circulation, set up like this and effectively avoided the membrane of tubular membrane anode to block up the problem, in addition, ozone can effectively strengthen the mass transfer effect at tubular membrane anode surface aeration.
Preferably, a plating layer is arranged on the surface of the titanium-based tubular membrane anode, and the plating layer comprises lead dioxide or ruthenium dioxide; the titanium-based tubular membrane anode has the length of 80-800 mm, the outer diameter of 30-300 mm and the inner diameter of 26-260 mm; the tubular membrane cathode comprises a metal tubular membrane electrode or a carbon-based tubular membrane electrode, and the diameter of the tubular membrane cathode is 80-800 mm; the tubular membrane cathode and the tubular membrane anode are coaxially arranged. The titanium-based tubular membrane anode is a tubular membrane electrode which is obtained by taking a porous titanium tube as a substrate and plating a catalytic oxidation layer on the surface of the porous titanium tube, wherein the catalytic oxidation layer is a plating layer, and lead dioxide is preferably adopted; the material of the metal tubular membrane electrode is preferably platinum, titanium, stainless steel, etc., and the carbon-based tubular membrane electrode includes graphite tubular membrane electrode, etc., which are further explained for the electrode material used in the present invention, and are not limited to cathode and anode materials, and other types of cathode and anode electrode materials are within the protection scope of the present invention.
Preferably, the tubular membrane anode is Ti/PbO2The tubular membrane electrode of the invention is applied to well solve the problem of mass transfer of pollutants in the system, and Ti/PbO2The anode material has high activity, can degrade pollutants adsorbed on the surface of the anode material in situ, and relieves the membrane pollution problem to a certain extent; the tubular membrane cathode is a stainless steel tubular membrane electrode; the heterogeneous ozone catalyst is Fe3O4The MWCNTs are multi-wall carbon nano tubes.
Preferably, a fluidized bed reactor is also included; the heterogeneous ozone catalyst is filled in a fluidized bed reactor, the fluidized bed reactor is arranged in the degradation device, the length of the fluidized bed reactor is 100 mm-1000 mm, and the outer diameter of the fluidized bed reactor is 200 mm-2000 mm. The catalytic material in the fluidized bed reactor is loaded with magnetic Fe3O4And the separation and recovery are easy.
The degradation method is based on the tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device, the tubular membrane anode and the heterogeneous ozone catalyst are prepared firstly, and then the heterogeneous ozone catalyst, the tubular membrane cathode, the tubular membrane anode and the ozone aeration unit are assembled into a tubular membrane electrode and heterogeneous ozone catalyst coupled reaction system; introducing wastewater into a reaction system, electrifying a tubular membrane cathode and a tubular membrane anode for electrochemical oxidation in the first stage, and simultaneously starting an ozone aeration unit to carry out ozone catalysis on the aeration of the reaction system, wherein the reaction time in the first stage is T1; then stopping electrochemical oxidation in the second stage, and independently carrying out ozone catalysis, wherein the reaction time in the second stage is T2; and (T1+ T2) T1 is 1-20.
Preferably, the preparation steps of the tubular membrane anode are as follows:
(1) preparing PbO2Coating liquid: firstly, 0.1 mol/L-1.5 mol/L Pb2+Dissolving salt in distilled water until Pb2+After the salt is completely dissolved, 0.01 mol/L-1.5 mol/L NaF is dissolved in distilled water;
(2) preparation of Ti/PbO2Tubular membrane electrode: immersing the porous titanium tube in the PbO by an inflatable electrodeposition method2Taking the film coating liquid as an anode and a stainless steel ring as a cathode; one end of the porous titanium tube is sealed by silica gel, the other end of the porous titanium tube is continuously introduced with air, the air flow is 0.1L/min-5L/min until the electrodeposition is finished to prepare Ti/PbO2Tubular membrane electrode.
Preferably, the heterogeneous ozone catalyst is prepared by the steps of:
(1) preparing modified MWCNTs: preparing a mixed solution of nitric acid and sulfuric acid, soaking the MWCNTs in the mixed solution for reaction, and drying the MWCNTs after the reaction is finished to obtain modified MWCNTs;
(2) preparation of Fe3O4MWCNTs composite ozone catalyst: uniformly dispersing the modified MWCNTs in deionized water to obtain a modified MWCNTs dispersion liquid, transferring the dispersion liquid to a heat collection type constant-temperature magnetic stirrer at the temperature of 30-120 ℃, stirring for 20-120 min, adding ferric ion salt and ferrous ion salt into the dispersion liquid, and simultaneously introducing argon to stir for 20-120 min; slowly adding 2-20 wt% of ammonia water, and placing the flask at the constant temperature of 30-200 ℃ for reacting for 1-10 h; cooling to room temperature after the reaction is finished, separating supernatant through magnetic separation, washing the supernatant for multiple times through deionized water and ethanol, and drying the washed material in a drying oven for 4-24 h to finally obtain Fe3O4the/MWCNTs composite ozone catalyst.
Preferably, in the step (1), the ratio of deionized water, concentrated sulfuric acid and concentrated nitric acid in the mixed solution of nitric acid and sulfuric acid is 1: (1-20): 1, the reaction conditions are as follows: and (2) soaking the MWCNTs in the mixed solution, stirring for 2-h 20h, heating to 50-250 ℃, performing reflux reaction for 2-12 h, centrifuging to remove the mixed solution after the reflux reaction is finished, washing the precipitate with deionized water to be neutral, washing the precipitate with absolute ethyl alcohol for 1-8 times, and drying in a vacuum oven at 30-150 ℃ for 4-24 h to finally obtain the modified MWCNTs.
Preferably, in the step (2), the concentration of the modified MWCNTs dispersion liquid is 1 g/L-20 g/L, and the concentrations of the ferric ion salt and the ferrous ion salt after being added into the dispersion liquid are 0.01 mol/L-0.35 mol/L and 0.01 mol/L-0.3 mol/L respectively.
Preferably, in the Ti/PbO2Tubular membrane electrode and Fe3O4After the preparation of the/MWCNTs composite ozone catalyst is finished, the specific operation steps are as follows:
(1) mixing Ti/PbO2The tubular membrane electrode is used as a tubular membrane anode and embedded in a tubular membrane cathode made of stainless steel materials, and the tubular membrane electrode is placed in an electrolytic bath and externally connected with a stabilized voltage power supply;
(2) adding Fe to an electrolytic cell3O4The MWCNTs composite ozone catalyst is arranged at the bottom of the catalyst, and an ozone aeration unit with an upward aeration direction is arranged at the bottom of the catalyst;
(3) preparing a solution to be degraded, pouring the solution to be degraded into an electrolytic bath, starting a stabilized voltage power supply and aerating ozone for reaction; the solution to be degraded comprises an organic matter to be degraded and an electrolyte, wherein the electrolyte comprises anhydrous sodium sulfate with the concentration of 1 g/L-20 g/L; the current density of the stabilized voltage supply is 2mA/cm2～100mA/cm2。
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device, which is used for degrading organic matters in wastewater and comprises a tubular membrane electrode, a heterogeneous ozone catalyst and an ozone aeration unit; the tubular membrane electrode comprises a tubular membrane cathode and a tubular membrane anode, wherein the tubular membrane cathode is sleeved outside the tubular membrane anode, and the tubular membrane anode comprises a titanium-based tubular membrane anode; the ozone aeration unit is arranged at the bottom of the tubular membrane electrode, and the aeration direction of the ozone aeration unit is upward; the heterogeneous ozone catalyst comprises a carbon-based material loaded with a transition metal or a transition metal oxide, which is disposed in the wastewater; through the arrangement, most of organic matters which are difficult to degrade in the wastewater can be treated by electrochemical oxidation carried out by the tubular membrane electrode in the coupling degradation device, if nitrogen-containing heterocyclic substances are removed, part of benzene ring pollutants are subjected to ring opening and decomposed to low molecular organic acids or the mineralization process is finished, most of COD in the wastewater is removed when the treatment is finished, then the pollutants in the wastewater are contacted with a heterogeneous ozone catalyst, the circulating wastewater is subjected to advanced treatment of ozone catalytic oxidation under the aeration action of ozone, and the organic matters subjected to ring opening are further oxidized until most of the pollutants in the wastewater are subjected to the mineralization process. According to the invention, the tubular membrane electrode and the heterogeneous ozone catalyst are combined to generate hydroxyl radicals in wastewater which are far larger than those generated when the tubular membrane electrode and the heterogeneous ozone catalyst are used for treating water pollution independently, so that the water quality is effectively evolved, and the water treatment efficiency is improved while the mineralization efficiency and the mineralization degree of pollutants difficult to degrade are ensured.
(2) The degradation method is based on the tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device, the tubular membrane anode and the heterogeneous ozone catalyst are prepared firstly, and then the heterogeneous ozone catalyst, the tubular membrane cathode, the tubular membrane anode and the ozone aeration unit are assembled into a tubular membrane electrode and heterogeneous ozone catalyst coupled reaction system; introducing wastewater into a reaction system, electrifying a tubular membrane cathode and a tubular membrane anode for electrochemical oxidation in the first stage, and simultaneously starting an ozone aeration unit to carry out ozone catalysis on the aeration of the reaction system, wherein the reaction time in the first stage is T1; then stopping electrochemical oxidation in the second stage, and independently carrying out ozone catalysis, wherein the reaction time in the second stage is T2; in the step (T1+ T2), T1 is 1-20; by the method, most of organic matters containing nitrogen heterocycles or benzene rings are subjected to ring opening or removal by combining an electrochemical catalytic oxidation technology and an ozone catalytic oxidation technology in the former stage, and the rest organic matters are further effectively removed under the action of single ozone catalytic oxidation in the latter stage, so that the mineralization efficiency and the mineralization degree of pollutants difficult to degrade are greatly improved, and the energy consumption of a coupled degradation device is reduced.
Drawings
FIG. 1 is a schematic diagram showing the effect of the embodiment of example 1 on p-chlorobenzoic acid treatment compared with comparative examples 1 and 2;
FIG. 2 is a graph showing the effect of example 1 in comparison to comparative examples 1 and 2 on the treatment of pentafluorouracil;
FIG. 3 is a graph showing the effect of treating COD in wastewater from a certain pharmaceutical factory according to example 1 of the present invention;
FIG. 4 is a graph showing the effect of treating TOC in wastewater from a pharmaceutical factory according to example 1 of the present invention;
FIG. 5 is a graph showing the effect of the example 2 on the TOC treatment of p-chlorobenzoic acid compared to the comparative examples 3, 4 and 5;
FIG. 6 is a graph showing the effect of example 2 in comparison with comparative examples 3, 4 and 5 on TOC treatment in Pentafluorouracil;
FIG. 7 is a graph showing the effect of the embodiment of example 3 on TOC treatment in p-chlorobenzoic acid and pentafluorouracil;
FIG. 8 is a graph showing the effect of the embodiment of example 4 on TOC treatment in p-chlorobenzoic acid and pentafluorouracil;
FIG. 9 is a graph showing the effect of the embodiment of example 5 on TOC treatment in p-chlorobenzoic acid and pentafluorouracil;
FIG. 10 is a schematic diagram of a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device according to the present invention.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration exemplary embodiments in which the invention may be practiced, and in which features of the invention are identified by reference numerals. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It will be understood that when an element is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present; when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present; the terms "top," "bottom," "upper," "lower," and the like are used herein for descriptive purposes only.
The invention is further described with reference to specific examples.
Example 1
The embodiment provides a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device for degrading organic matters in wastewater, which comprises a tubular membrane electrode, a heterogeneous ozone catalyst and an ozone aeration unit, as shown in fig. 10. The tubular membrane electrode comprises a tubular membrane cathode and a tubular membrane anode, wherein the tubular membrane cathode is sleeved outside the tubular membrane anode. The ozone aeration unit is arranged at the bottom between the tubular membrane cathode and the tubular membrane anode, the aeration direction of the ozone aeration unit is upward and is used for driving the wastewater between the tubular membrane cathode and the tubular membrane anode to flow upward, namely an up-flow region shown in fig. 10, the upward aeration water flow can fully contact and react with the catalytic oxidation membrane on the surface of the tubular membrane anode as shown by black arrows in fig. 10, so that the synergistic effect of electrochemical oxidation and ozone catalytic oxidation is effectively promoted, in addition, the water flow flowing out of the top of the tubular membrane electrode can flow downward outside the tubular membrane cathode to form a down-flow region shown in fig. 10, so that circulating water flow can be formed inside and outside the tubular membrane cathode, and organic matters in the wastewater are continuously degraded; the ozone aeration unit comprises an ozone generator, an ozone concentration detector, an oxygen source and an aeration head in the embodiment, wherein the ozone concentration in aeration is 5mg/L, and the aeration flow is 0.5L/min. The heterogeneous ozone catalyst is disposed in the wastewater.
In this embodiment, the titanium-based tubular membrane anode is Ti/PbO2A tubular membrane electrode coated with PbO2The length of the porous titanium tube for catalyzing the oxidation layer is 80mm, the outer diameter is 30mm, and the inner diameter is 26 mm; the tubular membrane cathode is a stainless steel tubular membrane electrode, and the diameter of the tubular membrane cathode is 80 mm; the tubular membrane cathode and the tubular membrane anode are coaxially arranged. The heterogeneous ozone catalyst is Fe3O4The MWCNTs composite ozone catalyst is characterized in that the heterogeneous ozone catalyst is filled in a fluidized bed reactor, the fluidized bed reactor is arranged in a degradation device, the length of the fluidized bed reactor is 1000mm, and the outer diameter of the fluidized bed reactor is 2000 mm.
The invention also provides a degradation method, based on the coupled degradation device, Ti/PbO is prepared firstly2Tubular membrane electrode and Fe3O4the/MWCNTs composite ozone catalyst is added with Fe3O4MWCNTs composite ozone catalyst, stainless steel tube type membrane electrode and Ti/PbO2The tubular membrane electrode and the ozone aeration unit are assembled into the tubular membrane electrode and Fe3O4The MWCNTs composite ozone catalyst coupling reaction system is characterized in that wastewater is introduced into the reaction system, and a stainless steel tube type membrane electrode and Ti/PbO are treated2And electrifying the tubular membrane electrode and starting the ozone aeration unit to carry out aeration reaction on the reaction system. The method comprises the following specific steps:
Ⅰ)Ti/PbO2preparing a tubular membrane electrode;
(1) pretreatment of the porous titanium tube: boiling the porous titanium tube in a 10% NaOH solution and a 10% oxalic acid solution for 40min in sequence, etching to form a gray pitted titanium substrate, taking out, cleaning, washing with acetone by ultrasonic oscillation for 30min, and storing in absolute ethyl alcohol for later use.
(2) Preparing a lead dioxide coating liquid: 150 g of Pb (NO) are weighed out3)2Dissolving the mixture in 500mL of distilled water, magnetically stirring the mixture until the mixture is completely dissolved, adding 0.25 g of NaF, stirring the mixture for dissolving at the temperature of 90 ℃, dropwise adding 0.005moL of concentrated nitric acid after the mixture is dissolved, fully stirring the mixture, standing the mixture, and sealing the mixture by using a preservative film.
(3) Preparing a lead dioxide coating on the porous titanium tube by adopting an inflatable electrodeposition method: selecting a stainless steel ring with the diameter of 80mm as a cathode, placing a porous titanium tube as an anode in the stainless steel ring, sealing one end of the titanium tube by using silicic acid, connecting the other end of the titanium tube with an air pump for ventilation, wherein the air flow is 500mL/min, and placing the whole body in lead dioxide coating liquid for electrodeposition for 80 minutes. The constant temperature of the coating liquid is controlled at 40 ℃ to obtain Ti/PbO2Tubular membrane electrode.
II) preparing a heterogeneous ozone catalyst;
(1) preparing modified MWCNTs: accurately weighing 1g of unmodified MWCNTs according to the weight ratio of 1: 3: 1, preparing 300mL of mixed solution of deionized water, concentrated sulfuric acid and concentrated nitric acid, placing the mixed solution into a 1L three-neck flask, soaking MWCNTs in the mixed solution, stirring for 12 hours, heating to 100 ℃, performing reflux reaction for 4 hours, centrifuging after the reaction is finished, discarding the mixed solution, washing the mixed solution to be neutral by using deionized water, washing the mixed solution for 3 times by using absolute ethyl alcohol, and drying the washed solution in a vacuum oven at 80 ℃ for 12 hours to finally obtain the modified MWCNTs.
(2) Preparation of Fe3O4MWCNTs composite ozone catalyst: weighing 0.2g of the modified MWCNTs, putting the modified MWCNTs into 100mL of deionized water, adding the mixture into a three-neck flask, performing ultrasonic treatment for 30min to uniformly disperse the modified MWCNTs to obtain modified MWCNTs dispersion liquid, transferring the dispersion liquid into a heat collection type constant-temperature magnetic stirrer at 90 ℃, stirring for 30min, weighing 0.015mol of ferric chloride hexahydrate and 0.01mol of ferrous chloride tetrahydrate, adding the mixture into the dispersion liquid, introducing argon gas, and stirring for 30 min; slowly adding 6 wt% ammonia water, and keeping the flask at the constant temperature of 80 ℃ for 4 hours; cooling to room temperature after the reaction is finished, separating supernatant through magnetic separation, and passing deionized waterWashing with ethanol for multiple times, and drying the washed material in an oven for 12h to obtain Fe3O4the/MWCNTs composite ozone catalyst.
III) degradation experiment of the heterogeneous ozone catalyst-tubular membrane electrode coupling system;
(1) mixing Ti/PbO2The tubular membrane electrode is embedded in the tubular membrane cathode made of stainless steel material as the tubular membrane anode, and is placed in the electrolytic bath and externally connected with a stabilized voltage power supply.
(2) Adding Fe to an electrolytic cell3O4The MWCNTs composite ozone catalyst is arranged at the bottom of the catalyst, and an ozone aeration unit with an upward aeration direction is arranged at the bottom of the catalyst.
(3) Preparing a solution to be degraded, pouring the solution to be degraded into an electrolytic bath, starting a stabilized voltage power supply and aerating ozone for reaction, wherein the simultaneous reaction time of the first stage is 15min, the single ozone reaction time of the second stage is 0min, the total reaction time is 15min, and the current density of the stabilized voltage power supply is 5mA/cm2. The solution to be degraded comprises organic matters to be degraded and electrolyte, in the embodiment, the parachlorobenzoic acid with the concentration of 40mg/L and the volume of 500mL and the pentafluorouracil with the concentration of 50mg/L and the volume of 200mL are respectively subjected to independent degradation experiments, and the electrolyte is anhydrous sodium sulfate with the concentration of 2 g/L.
In order to understand the degradation conditions of the chlorobenzoic acid and the pentafluorouracil in the experimental process, a degradation experiment is carried out for sampling within 15min of running time, the sampling time is 0, 1min, 2min, 3min, 5min, 7.5min, 10min and 15min respectively, target pollutants in a water sample are detected to evaluate the degradation performance of the coupling degradation device on organic matters, wherein the organic matter removal rate at 15min is recorded in table 1.
In addition, the embodiment of the invention also uses the coupled degradation device of the invention to treat the wastewater of a certain pharmaceutical factory, the COD of the wastewater is about 30000mg/L, and the treatment effect in practical application is simulated to evaluate the performance of the degradation method of the invention for degrading TOC and COD. After the coupling degradation device is arranged, the ozone is electrified and aerated at the same time, the reaction time of the first stage is 240min, the reaction time of the second stage of the single ozone is 480min, and the total reaction time isThe time is 480min, and the volume of the solution is 4L. Electrified current density is 20mA/cm2The electrolyte is 2g/L of anhydrous sodium sulfate solution, the ozone concentration is 10mg/L, and the flow rate is 0.8L/min. In order to know the degradation conditions of TOC and COD in the experimental process, the running time of the degradation process is 480min, sampling is carried out, the sampling time is 0min, 30min, 90min, 150min, 240min, 330min and 480min, and the TOC and the COD in the water sample are detected to evaluate the degradation performance of the degradation process. As shown in fig. 3, when the coupled degradation device and the degradation method in the embodiment are used for treating wastewater of a certain pesticide factory, the removal rate of COD of the wastewater reaches more than 60% within 480min of reaction time; as can be seen from FIG. 4, the TOC removal rate of the wastewater in 480min reaction time is all over 70%. Therefore, the invention has excellent treatment effect on the wastewater of the pesticide factory.
TABLE 1, EXAMPLES AND COMPARATIVE EXAMPLES the effectiveness of the treatment of p-chlorobenzoic acid and pentafluorouracil
Figure BDA0003261073390000081
Figure BDA0003261073390000091
Example 2
The embodiment provides a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and a degradation method, and the specific implementation manner is basically the same as that of embodiment 1, and the main differences are as follows: the reaction time of the first stage is 50min, the reaction time of the second stage with single ozone is 40min, the total reaction time is 90min, and the sampling time is 0, 15, 30, 60 and 90 min.
In the embodiment, separate degradation experiments are respectively carried out on p-chlorobenzoic acid with the concentration of 40mg/L and the volume of 500mL and pentafluorouracil with the concentration of 50mg/L and the volume of 200mL, and the electrolyte is anhydrous sodium sulfate with the concentration of 2 g/L. In order to understand the removal condition of the TOC in the experimental process, the degradation experiment was performed with sampling within 90min of operation time, and the target pollutants in the water sample were detected to evaluate the removal performance of the coupling degradation device of the present invention on the TOC, wherein the TOC removal rate at 90min is recorded in table 1.
Example 3
The embodiment provides a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and a degradation method, and the specific implementation manner is basically the same as that of embodiment 2, and the main differences are as follows: the tubular membrane anode is made of Ti/RuO2The preparation method mainly comprises the following steps:
Ⅰ)Ti/PbO2preparing a tubular membrane electrode;
(1) pretreatment of the porous titanium tube: the method comprises the steps of firstly washing a titanium matrix with distilled water, removing oil stains attached to the surface of the titanium matrix, heating the titanium matrix in 18% hydrochloric acid solution for 20min to remove an oxide layer on the surface of the titanium matrix, then washing the titanium matrix with distilled water for several times, then boiling the titanium matrix in 20% oxalic acid solution for 120min, then washing the titanium matrix with distilled water, and finally putting the titanium matrix in the distilled water for later use.
(2) Preparing a lead dioxide precursor: weighing 4g of RuO2·3H2O was mixed with 250mL of analytically pure isopropanol and 4mL of 37% pure hydrochloric acid. Then the mixture is placed in a magnetic stirrer to be stirred for 24 hours to obtain RuO2A precursor of the electrode.
(3) The Ti/PbO is prepared by adopting a sol-gel method, a vacuum induction method and a thermal decomposition method2An electrode: and drying the pretreated titanium matrix by an oven, putting the dried titanium matrix into a vacuum induction device, and pumping the device to a vacuum state. Flowing the brush-coated precursor into a three-neck flask until the liquid level of the brush-coated precursor is submerged in the titanium substrate; opening the three-neck flask to release pressure, wherein the brush-coated precursor enters micropores of the titanium substrate, and taking out the titanium substrate to prepare for the next step; besides the micropores, the surface of the titanium matrix needs to be coated with the precursor by brush coating. In order to ensure that the precursor can be uniformly dispersed on the surface of the titanium substrate, the coating must be slowly and repeatedly coated. After the brush coating is finished, drying the mixture in a drying oven at 105 ℃ for 10min to volatilize the solvent; and (3) putting the dried titanium substrate into a box-type resistance furnace at 450 ℃ to sinter for 15min in the air, wherein the heating rate is 5 ℃/min. Repeating the above 3 steps 21 times, and sintering in a box-type resistance furnace at 550 ℃ for 1h to obtain Ti/RuO2Electrode for electrochemical cell。
In the embodiment, separate degradation experiments are respectively carried out on p-chlorobenzoic acid with the concentration of 40mg/L and the volume of 500mL and pentafluorouracil with the concentration of 50mg/L and the volume of 200mL, and the electrolyte is anhydrous sodium sulfate with the concentration of 2 g/L. In order to understand the removal condition of the TOC in the experimental process, the degradation experiment was performed with sampling within 90min of operation time, and the target pollutants in the water sample were detected to evaluate the removal performance of the coupling degradation device of the present invention on the TOC, wherein the TOC removal rate at 90min is recorded in table 1.
Example 4
The embodiment provides a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and a degradation method, and the specific implementation manner is basically the same as that of embodiment 2, and the main differences are as follows: the tubular membrane cathode is made of lead electrodes.
In the embodiment, separate degradation experiments are respectively carried out on p-chlorobenzoic acid with the concentration of 40mg/L and the volume of 500mL and pentafluorouracil with the concentration of 50mg/L and the volume of 200mL, and the electrolyte is anhydrous sodium sulfate with the concentration of 2 g/L. In order to understand the removal condition of the TOC in the experimental process, the degradation experiment was performed with sampling within 90min of operation time, and the target pollutants in the water sample were detected to evaluate the removal performance of the coupling degradation device of the present invention on the TOC, wherein the TOC removal rate at 90min is recorded in table 1.
Example 5
The embodiment provides a tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and a degradation method, and the specific implementation manner is basically the same as that of embodiment 2, and the main differences are as follows: the heterogeneous ozone catalyst is made of Fe3O4The main preparation method of the/AC comprises the following steps:
1) pretreating powdered activated carbon: accurately weighing 1g of AC (activated carbon), and carrying out the following steps of 1: 3: 1, preparing 300mL of mixed solution of deionized water, concentrated sulfuric acid and concentrated nitric acid, placing the mixed solution in a 1L three-neck flask, soaking AC in the mixed solution, stirring for 12 hours, then heating to 100 ℃, carrying out reflux reaction for 4 hours, centrifuging after the reflux reaction is finished, discarding the mixed solution, washing the mixed solution to be neutral by using deionized water, and placing the mixed solution in a 100 ℃ vacuum oven to dry for 8 hours.
2) Preparation of Fe3O4The catalyst is prepared from the following components in percentage by weight: 0.2g of pretreated powdered activated carbon is weighed and placed in 100mL of deionized water, 0.015mol of ferric chloride hexahydrate and 0.01mol of ferrous chloride tetrahydrate are weighed and added into the mixed solution, and the solution is mixed uniformly by ultrasonic treatment for 30 min. Then, the temperature of the mixed solution was controlled to 70 ℃ using a constant temperature water bath and stirred while 40mL of 2mol sodium hydroxide solution was rapidly dropped dropwise into the mixed solution for a reaction time of 1 hour. And after the reaction is finished, cleaning the composite material by ultrapure water until the supernatant is neutral, and drying the obtained precipitate in an oven at 60 ℃ to obtain the magnetic activated carbon catalyst.
In the embodiment, separate degradation experiments are respectively carried out on p-chlorobenzoic acid with the concentration of 40mg/L and the volume of 500mL and pentafluorouracil with the concentration of 50mg/L and the volume of 200mL, and the electrolyte is anhydrous sodium sulfate with the concentration of 2 g/L. In order to understand the removal condition of the TOC in the experimental process, the degradation experiment was performed with sampling within 90min of operation time, and the target pollutants in the water sample were detected to evaluate the removal performance of the coupling degradation device of the present invention on the TOC, wherein the TOC removal rate at 90min is recorded in table 1.
Comparative example 1
The present comparative example provides a degradation device and a degradation method for a tubular membrane electrode, and the specific implementation manner is basically the same as that of example 1, and the main differences are as follows: and the electrochemical oxidation of the tubular membrane electrode is independently carried out without adding a heterogeneous ozone catalyst and an ozone aeration unit.
In this comparative example, separate degradation experiments were carried out for p-chlorobenzoic acid at a concentration of 40mg/L and a volume of 500mL and for pentafluorouracil at a concentration of 50mg/L and a volume of 200mL, respectively, and the electrolyte was anhydrous sodium sulfate at a concentration of 2 g/L. In order to understand the degradation conditions of the chlorobenzoic acid and the pentafluorouracil in the experimental process, a sample is taken in the running time of 15min in the degradation experiment, and a target pollutant in a water sample is detected to evaluate the degradation performance of the degradation device of the comparative example on organic matters, wherein the removal rate of the organic matters in 15min is recorded in table 1.
Example 1 was compared to comparative examples 1 and 2: as shown in figure 1, the effect of treating the p-chlorobenzoic acid by adopting single electrochemical oxidation is very poor, and the removal rate of the p-chlorobenzoic acid in 15min reaction time is not up to 10%; the effect is better when the p-chlorobenzoic acid is treated by the single ozone catalytic oxidation, and the removal rate of the p-chlorobenzoic acid reaches about 40 percent within 15min of reaction time; when the coupled degradation device and the degradation method are adopted to treat the p-chlorobenzoic acid, the removal rate of the p-chlorobenzoic acid reaches about 80 percent within 15min of treatment time. In addition, as can be seen from fig. 2, the removal rate of the pentafluorouracil in 15min reaction time is about 60% by adopting single electrochemical oxidation treatment of the pentafluorouracil; the single ozone catalytic oxidation treatment of the pentafluorouracil is adopted, and the removal rate of the pentafluorouracil reaches about 50% within 15min of reaction time; when the coupling degradation device and the degradation method are adopted to treat the pentafluorouracil, the removal rate of the pentafluorouracil reaches over 95 percent within 15min of treatment time. Therefore, the tubular membrane electrode is coupled with the heterogeneous ozone catalyst, and the synergistic effect between electrochemical oxidation and ozone catalytic oxidation can be generated, so that the benzene ring or heterocyclic organic matters can be effectively degraded.
Comparative example 2
The present comparative example provides a degradation device and a degradation method for a tubular membrane electrode, and the specific implementation manner is basically the same as that of example 1, and the main differences are as follows: the tubular membrane electrode is not added, and the ozone catalytic oxidation is independently carried out.
In this comparative example, separate degradation experiments were carried out for p-chlorobenzoic acid at a concentration of 40mg/L and a volume of 500mL and for pentafluorouracil at a concentration of 50mg/L and a volume of 200mL, respectively, and the electrolyte was anhydrous sodium sulfate at a concentration of 2 g/L. In order to understand the degradation conditions of the chlorobenzoic acid and the pentafluorouracil in the experimental process, a sample is taken in the running time of 15min in the degradation experiment, and a target pollutant in a water sample is detected to evaluate the degradation performance of the degradation device of the comparative example on organic matters, wherein the removal rate of the organic matters in 15min is recorded in table 1.
Comparative example 3
The present comparative example provides a degradation device and a degradation method for a tubular membrane electrode, and the specific implementation manner is basically the same as that of example 2, and the main differences are as follows: in the degradation method, a first stage is carried out by single electrochemical oxidation, and a second stage is carried out by single ozone catalytic oxidation.
In the embodiment, separate degradation experiments are respectively carried out on p-chlorobenzoic acid with the concentration of 40mg/L and the volume of 500mL and pentafluorouracil with the concentration of 50mg/L and the volume of 200mL, and the electrolyte is anhydrous sodium sulfate with the concentration of 2 g/L. In order to understand the removal condition of the TOC in the experimental process, the degradation experiment was performed with sampling within 90min of operation time, and the target pollutants in the water sample were detected to evaluate the removal performance of the coupling degradation device of the present invention on the TOC, wherein the TOC removal rate at 90min is recorded in table 1.
Comparative example 4
The present comparative example provides a degradation device and a degradation method for a tubular membrane electrode, and the specific implementation manner is basically the same as that of example 2, and the main differences are as follows: the ozone aeration unit is arranged outside the tubular membrane cathode, and the aeration direction of the ozone aeration unit is still upward.
In the embodiment, separate degradation experiments are respectively carried out on p-chlorobenzoic acid with the concentration of 40mg/L and the volume of 500mL and pentafluorouracil with the concentration of 50mg/L and the volume of 200mL, and the electrolyte is anhydrous sodium sulfate with the concentration of 2 g/L. In order to understand the removal condition of the TOC in the experimental process, the degradation experiment was performed with sampling within 90min of operation time, and the target pollutants in the water sample were detected to evaluate the removal performance of the coupling degradation device of the present invention on the TOC, wherein the TOC removal rate at 90min is recorded in table 1. Ozone exposed by the aeration unit is mainly distributed outside the tubular membrane cathode, so that the concentration of the ozone between the tubular membrane cathode and the tubular membrane anode is reduced, the ozone cannot effectively contact with a catalytic oxidation layer on the surface of the tubular membrane anode, the synergistic effect of electrochemical oxidation and ozone catalytic oxidation is reduced, and the degradation performance is reduced.
Comparative example 5
The present comparative example provides a degradation device and a degradation method for a tubular membrane electrode, and the specific implementation manner is basically the same as that of example 2, and the main differences are as follows: the ozone aeration unit is arranged at the top between the tubular membrane cathode and the tubular membrane anode, and the aeration direction of the ozone aeration unit is downward.
In the embodiment, separate degradation experiments are respectively carried out on p-chlorobenzoic acid with the concentration of 40mg/L and the volume of 500mL and pentafluorouracil with the concentration of 50mg/L and the volume of 200mL, and the electrolyte is anhydrous sodium sulfate with the concentration of 2 g/L. In order to understand the removal condition of the TOC in the experimental process, the degradation experiment was performed with sampling within 90min of operation time, and the target pollutants in the water sample were detected to evaluate the removal performance of the coupling degradation device of the present invention on the TOC, wherein the TOC removal rate at 90min is recorded in table 1.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. When mass, concentration, temperature, time, current density, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction. "

Claims (10)

1. A tubular membrane electrode and heterogeneous ozone catalyst coupling degradation device is characterized in that the device is used for degrading organic matters in wastewater and comprises a tubular membrane electrode, a heterogeneous ozone catalyst and an ozone aeration unit; the tubular membrane electrode comprises a tubular membrane cathode and a tubular membrane anode, wherein the tubular membrane cathode is sleeved outside the tubular membrane anode, and the tubular membrane anode comprises a titanium-based tubular membrane anode; the ozone aeration unit is arranged at the bottom of the tubular membrane electrode, and the aeration direction of the ozone aeration unit is upward; the heterogeneous ozone catalyst includes a carbon-based material supporting a transition metal or a transition metal oxide, which is disposed in wastewater.
2. The tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device according to claim 1, wherein the ozone aeration unit is disposed at the bottom between the tubular membrane cathode and the tubular membrane anode and used for driving the wastewater between the tubular membrane cathode and the tubular membrane anode to flow upwards; the concentration of ozone in the aeration of the ozone aeration unit is 2 mg/L-50 mg/L, and the aeration flow is 0.5L/min-5L/min.
3. The tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device of claim 1, wherein a plating layer is arranged on the surface of the titanium-based tubular membrane anode, and the plating layer comprises lead dioxide or ruthenium dioxide; the titanium-based tubular membrane anode has the length of 80-800 mm, the outer diameter of 30-300 mm and the inner diameter of 26-260 mm; the tubular membrane cathode comprises a metal tubular membrane electrode or a carbon-based tubular membrane electrode, and the diameter of the tubular membrane cathode is 80-800 mm; the tubular membrane cathode and the tubular membrane anode are coaxially arranged.
4. The tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device according to claim 3, wherein the tubular membrane anode is Ti/PbO2A tubular membrane electrode; the tubular membrane cathode is a stainless steel tubular membrane electrode; the heterogeneous ozone catalyst is Fe3O4the/MWCNTs composite ozone catalyst.
5. The tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device according to claim 4, further comprising a fluidized bed reactor; the heterogeneous ozone catalyst is filled in a fluidized bed reactor, the fluidized bed reactor is arranged in the degradation device, the length of the fluidized bed reactor is 100 mm-1000 mm, and the outer diameter of the fluidized bed reactor is 200 mm-2000 mm.
6. A degradation method is based on the tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device of any one of claims 1 to 5, and is characterized in that a tubular membrane anode and a heterogeneous ozone catalyst are prepared, and then the heterogeneous ozone catalyst, a tubular membrane cathode, the tubular membrane anode and an ozone aeration unit are assembled into a tubular membrane electrode and heterogeneous ozone catalyst coupled reaction system; introducing wastewater into a reaction system, electrifying a tubular membrane cathode and a tubular membrane anode for electrochemical oxidation in the first stage, and simultaneously starting an ozone aeration unit to carry out ozone catalysis on the aeration of the reaction system, wherein the reaction time in the first stage is T1; then stopping electrochemical oxidation in the second stage, and independently carrying out ozone catalysis, wherein the reaction time in the second stage is T2; and (T1+ T2) T1 is 1-20.
7. A degradation method according to claim 6, characterized in that the tubular membrane anode is prepared by the steps of:
(1) preparing PbO2Coating liquid: firstly, 0.1 mol/L-1.5 mol/L Pb2+Dissolving salt in distilled water until Pb2+After the salt is completely dissolved, 0.01 mol/L-1.5 mol/L NaF is dissolved in distilled water;
(2) preparation of Ti/PbO2Tubular membrane electrode: immersing the porous titanium tube in the PbO by an inflatable electrodeposition method2Taking the film coating liquid as an anode and a stainless steel ring as a cathode; one end of the porous titanium tube is sealed by silica gel, the other end of the porous titanium tube is continuously introduced with air, the air flow is 0.1L/min-5L/min until the electrodeposition is finished to prepare Ti/PbO2Tubular membrane electrode.
8. A degradation method according to claim 7, characterized in that said heterogeneous ozone catalyst is prepared by the steps of:
(1) preparing modified MWCNTs: preparing a mixed solution of nitric acid and sulfuric acid, soaking the MWCNTs in the mixed solution for reaction, and drying the MWCNTs after the reaction is finished to obtain modified MWCNTs;
(2) preparation of Fe3O4MWCNTs composite ozone catalyst: uniformly dispersing the modified MWCNTs in deionized water to obtain a modified MWCNTs dispersion liquid, transferring the dispersion liquid to a heat collection type constant-temperature magnetic stirrer at the temperature of 30-120 ℃, stirring for 20-120 min, adding ferric ion salt and ferrous ion salt into the dispersion liquid, and simultaneously introducing argon to stir for 20-120 min; slowly adding 2-20 wt% of ammonia water, and placing the flask at the constant temperature of 30-200 ℃ for reacting for 1-10 h; cooling to room temperature after the reaction is finished, separating supernatant through magnetic separation, washing the supernatant for multiple times through deionized water and ethanol, and drying the washed material in a drying oven for 4-24 h to finally obtain Fe3O4the/MWCNTs composite ozone catalyst.
9. A degradation method according to claim 8, characterized in that, in the step (1), the ratio of deionized water, concentrated sulfuric acid and concentrated nitric acid in the mixed solution of nitric acid and sulfuric acid is 1: (1-20): 1, the reaction conditions are as follows: soaking MWCNTs in the mixed solution, stirring for 2-h 20h, heating to 50-250 ℃, performing reflux reaction for 2-12 h, centrifuging to remove the mixed solution after the reflux reaction is finished, washing the precipitate with deionized water to be neutral, washing the precipitate with absolute ethyl alcohol for 1-8 times, transferring the washed precipitate to a vacuum oven at 30-150 ℃, and drying for 4-24 h to finally obtain modified MWCNTs;
in the step (2), the concentration of the modified MWCNTs dispersion liquid is 1 g/L-20 g/L, and the concentrations of the ferric ion salt and the ferrous ion salt added into the dispersion liquid are 0.01 mol/L-0.35 mol/L and 0.01 mol/L-0.3 mol/L respectively.
10. A degradation method according to claim 9, wherein said Ti/PbO is in said Ti/PbO2Tubular membrane electrode and Fe3O4After the preparation of the/MWCNTs composite ozone catalyst is finished, the specific operation steps are as follows:
(1) mixing Ti/PbO2The tubular membrane electrode is used as a tubular membrane anode and embedded in a tubular membrane cathode made of stainless steel materials, and the tubular membrane electrode is placed in an electrolytic bath and externally connected with a stabilized voltage power supply;
(2) adding Fe to an electrolytic cell3O4The MWCNTs composite ozone catalyst is arranged at the bottom of the catalyst, and an ozone aeration unit with an upward aeration direction is arranged at the bottom of the catalyst;
(3) preparing a solution to be degraded, pouring the solution to be degraded into an electrolytic bath, starting a stabilized voltage power supply and aerating ozone for reaction; the solution to be degraded comprises an organic matter to be degraded and an electrolyte, wherein the electrolyte comprises anhydrous sodium sulfate with the concentration of 1 g/L-20 g/L; the current density of the stabilized voltage supply is 2mA/cm2～100mA/cm2。
CN202111072954.XA 2021-09-14 2021-09-14 Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method Pending CN113683234A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111072954.XA CN113683234A (en) 2021-09-14 2021-09-14 Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111072954.XA CN113683234A (en) 2021-09-14 2021-09-14 Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method

Publications (1)

Publication Number Publication Date
CN113683234A true CN113683234A (en) 2021-11-23

Family

ID=78586288

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111072954.XA Pending CN113683234A (en) 2021-09-14 2021-09-14 Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method

Country Status (1)

Country Link
CN (1) CN113683234A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115140809A (en) * 2022-07-28 2022-10-04 中电环保股份有限公司 Tubular membrane electrode catalytic reaction device and oxidative decomposition method
CN117819770A (en) * 2024-01-29 2024-04-05 青岛海发环保产业控股有限公司 A deep treatment process for effluent from a municipal sewage treatment plant
WO2024229971A1 (en) * 2023-05-10 2024-11-14 天津工业大学 Electrochemical double-membrane reactor and wastewater treatment method
PL448448A1 (en) * 2024-04-29 2025-11-03 Instytut Biotechnologii I Medycyny Molekularnej Ceramic-carbon foam electrodes enriched with oxides, method of their preparation and application in photo-electro-oxidation reactors of organic compounds

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1600699A (en) * 2004-09-29 2005-03-30 浙江大学 A device and method for synergistic electrocatalytic treatment of organic wastewater with negative and positive electrodes
CN102489252A (en) * 2011-12-19 2012-06-13 南京大学 Ferroferric oxide nano crystal loaded on acid-modified carbon nano tube and preparation method thereof
CN202400887U (en) * 2011-11-10 2012-08-29 中国石油化工股份有限公司 Three-dimensional particle electrolytic catalytic oxidation sewage treating device
CN105565442A (en) * 2014-10-09 2016-05-11 南京理工大学 Titanium-based lead dioxide porous tubular membrane electrode and its preparation method and use
CN205603403U (en) * 2016-02-02 2016-09-28 南京理工大学 Advanced treatment unit of nitrogenous heterocyclic compound chemical industry tail water and electricity chemical oxidation unit thereof
CN108358350A (en) * 2018-02-07 2018-08-03 北京交通大学 The advanced treatment apparatus and method of high ferro defecate collection waste water
GB201913584D0 (en) * 2019-06-26 2019-11-06 Univ Central South Method and device for sewage treatment
CN113336373A (en) * 2021-06-21 2021-09-03 浙江工商大学 Organic wastewater deep degradation reaction device and application

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1600699A (en) * 2004-09-29 2005-03-30 浙江大学 A device and method for synergistic electrocatalytic treatment of organic wastewater with negative and positive electrodes
CN202400887U (en) * 2011-11-10 2012-08-29 中国石油化工股份有限公司 Three-dimensional particle electrolytic catalytic oxidation sewage treating device
CN102489252A (en) * 2011-12-19 2012-06-13 南京大学 Ferroferric oxide nano crystal loaded on acid-modified carbon nano tube and preparation method thereof
CN105565442A (en) * 2014-10-09 2016-05-11 南京理工大学 Titanium-based lead dioxide porous tubular membrane electrode and its preparation method and use
CN205603403U (en) * 2016-02-02 2016-09-28 南京理工大学 Advanced treatment unit of nitrogenous heterocyclic compound chemical industry tail water and electricity chemical oxidation unit thereof
CN108358350A (en) * 2018-02-07 2018-08-03 北京交通大学 The advanced treatment apparatus and method of high ferro defecate collection waste water
GB201913584D0 (en) * 2019-06-26 2019-11-06 Univ Central South Method and device for sewage treatment
CN113336373A (en) * 2021-06-21 2021-09-03 浙江工商大学 Organic wastewater deep degradation reaction device and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
田小军: "改性Fe3O4/碳纳米管复合材料的制备及在废水处理中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115140809A (en) * 2022-07-28 2022-10-04 中电环保股份有限公司 Tubular membrane electrode catalytic reaction device and oxidative decomposition method
WO2024229971A1 (en) * 2023-05-10 2024-11-14 天津工业大学 Electrochemical double-membrane reactor and wastewater treatment method
CN117819770A (en) * 2024-01-29 2024-04-05 青岛海发环保产业控股有限公司 A deep treatment process for effluent from a municipal sewage treatment plant
PL448448A1 (en) * 2024-04-29 2025-11-03 Instytut Biotechnologii I Medycyny Molekularnej Ceramic-carbon foam electrodes enriched with oxides, method of their preparation and application in photo-electro-oxidation reactors of organic compounds

Similar Documents

Publication Publication Date Title
CN113683234A (en) Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method
Xiao et al. Fenton‐like reaction: recent advances and new trends
Sirés et al. Upgrading and expanding the electro-Fenton and related processes
Oturan et al. Electro-fenton process: Background, new developments, and applications
CN109896598B (en) Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water
Chen et al. A mini-review of the electro-peroxone technology for wastewaters: Characteristics, mechanism and prospect
CN105439258A (en) A Wastewater Treatment Method Using In-situ Electric Generation of H2O2 and O3 Oxidation
CN102092820A (en) Method and device for removing organic matters from water by using double-pool double-effect visible light in response to photo-electro-Fenton reaction
CN111977751A (en) Cathode electric field enhanced ozone oxidation breaking and metal synchronous recovery device and method
CN102070230A (en) Method for removing organic matters in water by utilizing three-dimensional electrode electro-fenton and device thereof
CN101423266A (en) Wastewater treatment device of horizontal polar plate multi-electrodes electrocatalysis reactor
CN101665300A (en) Catalytic electrolysis coupling reactor used for treating organic wastewater
CN101913693B (en) Device and method for treating refractory organic wastewater by activating molecular oxygen through electrocatalysis
CN101186361A (en) Three-dimensional electrode reactor and its method for treating chlorobenzene wastewater
Ma et al. A review on three-dimensional electrochemical technology for the antibiotic wastewater treatment
CN101555080A (en) Method and device for treating wastewater containing dimethylformamide and dimethylformamide
CN114604943B (en) Wastewater treatment device and wastewater treatment method by cathode electro-Fenton coupling anodic oxidation
CN101302050A (en) Normal temperature and pressure catalytic oxidation sewage disposal reaction tank and combined device
CN105731604A (en) Advanced treatment method for electroplating wastewater
CN109626518B (en) Magnetic graphene-based Fen+Method for treating printing and dyeing wastewater by three-dimensional electrode heterogeneous electro-Fenton
CN116655068B (en) Internal aeration type electro-Fenton device and method for treating antibiotic wastewater
CN110563093A (en) Membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device and process
CN211946615U (en) Electrochemical coupling ozone micro-nano bubble processing system
CN218231992U (en) Sewage treatment system with fixed bed heterogeneous catalysis and bipolar electrocatalysis
CN106830457A (en) Electrode couples ozone oxidation integral reactor

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: 20211123

RJ01 Rejection of invention patent application after publication