CN-121974444-A - Preparation method and application of electro-Fenton curtain type composite cathode assembly based on hydrophilic/hydrophobic hollow fiber membrane

Abstract

The invention provides a preparation method and application of an electro-Fenton curtain type composite cathode component based on a hydrophilic/hydrophobic hollow fiber membrane, belonging to the technical field of electrochemistry, comprising the steps of cutting a conductive material, a hydrophilic hollow fiber membrane and a hydrophobic hollow fiber membrane into equal lengths respectively, sequentially placing the conductive material, the hydrophilic hollow fiber membrane and the hydrophobic hollow fiber membrane in pretreatment solution and deionized water for ultrasonic cleaning, and drying to obtain a pretreated conductive material, a hydrophilic membrane material and a hydrophobic membrane material; and inserting a supporting material into the conductive material to obtain the conductive material with supporting property, fixing the conductive material on the hydrophobic membrane material to obtain a conductive material coupling hydrophobic hollow fiber membrane composite body, connecting the conductive material coupling hydrophobic hollow fiber membrane composite body with a membrane assembly shell, and alternately arranging the hydrophilic membrane material and the composite body according to a preset interval to obtain the composite cathode assembly. The invention solves the problems of low oxygen utilization rate, large mass transfer resistance, low contact efficiency of H 2 O 2 and ferrous ions and high system energy consumption in the existing electro-Fenton technology.

Inventors

• ZHAO XUEHUI
• ZHEN SIYUAN

Assignees

• 天津工业大学

Dates

Publication Date

20260505

Application Date

20260203

Claims (10)

1. 1. The preparation method of the electro-Fenton curtain type composite cathode component based on the hydrophilic/hydrophobic hollow fiber membrane is characterized by comprising the following steps of: s1, cutting a conductive material into equal lengths, sequentially placing the conductive material into a pretreatment solution and deionized water for ultrasonic cleaning, and drying to obtain a pretreated conductive material; s2, cutting the hydrophilic hollow fiber membrane and the hydrophobic hollow fiber membrane to be equal in length, sequentially placing the hydrophilic hollow fiber membrane and the hydrophobic hollow fiber membrane in pretreatment solution and deionized water for ultrasonic cleaning, and respectively obtaining a pretreated hydrophilic membrane material and a pretreated hydrophobic membrane material after drying; s3, inserting a supporting material into the pretreated conductive material to obtain a conductive material with supporting property; S4, fixing the conductive material with the supporting property on the pretreated hydrophobic membrane material to obtain a conductive material coupling hydrophobic hollow fiber membrane complex; and S5, connecting the conductive material coupling hydrophobic hollow fiber membrane composite with a membrane component shell, and alternately arranging the hydrophilic membrane material and the composite according to preset intervals to finally obtain the electro-Fenton curtain type composite cathode component based on the hydrophilic/hydrophobic hollow fiber membrane.
2. 2. The method according to claim 1, wherein in S1, the conductive material is selected from one of carbon felt, woven tube, plastic conductive material.
3. 3. The preparation method of claim 1, wherein in S1 and S2, the pretreatment solution is a mixed solution of ethanol and water, the volume ratio of the ethanol to the water is 1:1, the drying temperature is 80-100 ℃, and the drying time is 2-3 h.
4. 4. The preparation method of the porous membrane according to claim 1, wherein in the step S2, the hydrophilic hollow fiber membrane is made of one or more of polysulfone, polyvinylidene fluoride and polypropylene, the hydrophobic hollow fiber membrane is made of one or more of polytetrafluoroethylene, polyvinylidene fluoride and polypropylene, and the membrane lengths of the hydrophilic hollow fiber membrane and the hydrophobic hollow fiber membrane are 6-15 cm.
5. 5. The method according to claim 1, wherein in S3, the supporting material is a conductive wire, and the conductive wire is one or more selected from a titanium wire and a nickel wire.
6. 6. The method according to claim 1, wherein in S4, the conductive material with support is fixed on the pretreated hydrophobic film material in a form including, but not limited to, winding or wrapping, and in S5, the preset distance is 4-10 mm.
7. 7. The method of claim 1, wherein in S5, the membrane module housing comprises a membrane housing intake header in communication with the hydrophobic membrane material and a membrane housing feed base in communication with the hydrophilic membrane material.
8. 8. A hydrophilic/hydrophobic hollow fiber membrane-based electro-Fenton curtain type composite cathode assembly prepared by the preparation method according to any one of claims 1 to 7, which is characterized by being formed by alternately arranging hollow fiber hydrophobic membranes and hollow fiber hydrophilic membranes of coupling conductive materials.
9. 9. Use of an electro-Fenton curtain-type composite cathode assembly based on hydrophilic/hydrophobic hollow fiber membranes according to claim 8 for treating pollutants in an intensive electro-Fenton reaction.
10. 10. The use according to claim 9, characterized in that the electro-Fenton system used in the use comprises a Fenton degradation unit, an oxygen supply unit, a reducing agent dosing unit and a stirring unit; The degradation tank of the Fenton degradation unit is internally provided with an anode component, the composite cathode component and the anode component are respectively connected with a current voltmeter, a magnetic rotor of the stirring unit is positioned in the degradation tank, an oxygen tank of the oxygen supply unit is communicated with an air inlet top cover of the membrane shell through an oxygen supply pipeline, a gas flowmeter is arranged on the oxygen supply pipeline, an oxygen pressure gauge is arranged on the oxygen tank, a reducing agent container of the reducing agent adding unit is communicated with an air inlet base of the membrane shell through a peristaltic pump, and a liquid flowmeter is arranged on a pipeline of the peristaltic pump.

Description

Preparation method and application of electro-Fenton curtain type composite cathode assembly based on hydrophilic/hydrophobic hollow fiber membrane Technical Field The invention relates to the technical field of electrochemistry, in particular to a preparation method and application of an electro-Fenton curtain type composite cathode component based on a hydrophilic/hydrophobic hollow fiber membrane. Background The electro-Fenton technology is used as a high-efficiency and environment-friendly advanced oxidation technology, the principle is that hydrogen peroxide is synthesized by oxygen in situ at a cathode (H 2O2）,H2O2 is contacted with an iron-based catalyst to generate hydroxyl free radicals with strong oxidability so as to efficiently remove organic pollutants which are difficult to degrade, and the technology has wide application prospect in the sewage treatment fields of pharmacy, printing and dyeing, chemical industry, textile industry and the like because the reaction condition is mild and a large amount of chemical oxidizing agents are not required to be added: the efficiency of cathode electrosynthesis H 2O2, and the mass transfer contact efficiency of H 2O2 and ferrous ions (Fe 2+) directly determine the pollutant degradation effect; the power consumption of cathode oxygen supply and the energy consumption of Fe 2+ addition and mixing form the main part of the energy consumption of system operation, and become the main bottleneck for restricting the technology to fall to the ground. To improve the performance of the electro-Fenton technology, a series of patent technologies have been developed and disclosed in the related art. For example, an electro-Fenton cathode membrane material with aeration function and a preparation method and application thereof are disclosed in publication No. CN110255672A, carbon black and polyethylene wax are dispersed into polyphenylene sulfide ultrafine fiber base cloth in a spraying manner, a cloth-shaped cathode membrane material is prepared through heat setting and hot rolling treatment, the combination of membrane side aeration and H 2O2 in-situ synthesis is realized, a preparation method and application thereof for a carbon nanotube integrated electro-Fenton membrane are disclosed in publication No. CN109678225A, an iron-modified carbon nanotube and multilevel pore carbon are loaded on a flat ceramic membrane by adopting a suction filtration and high-pressure fixing method, an integrated electro-Fenton membrane structure is constructed, nano particles containing an iron catalyst are dispersed into an electrostatic spinning solution, electrostatic fibers are coated on a conductive carbon material through an electrostatic spinning technology, and in addition, a conductive film electro-Fenton cathode electro-Fenton sewage treatment device based on iron circulation and a method and application thereof are disclosed in publication No. CN119612702A, and a flat conductive electro-Fenton membrane structure is designed, and a vacuum filtration and a vacuum 2+/Fe3+ is combined with an active layer of Fe 2+/Fe3+. These developments have all been around the goals of improving oxygen utilization, strengthening catalyst action, etc., driving the development of electro-Fenton cathode technology. Despite the advances made in current research and development, there are a number of shortcomings. The efficiency and the energy consumption of the electro-Fenton system are key factors for restricting the popularization of the electro-Fenton system, the efficiency of the electro-Fenton system is influenced by various factors, the efficiency of cathode electro-synthesis of hydrogen peroxide and the mass transfer contact efficiency of the hydrogen peroxide and Fe 2+ are certainly key factors influencing the efficiency of the electro-Fenton system, and the energy consumption of the electro-Fenton system mainly comprises the electricity consumption of cathode oxygen supply and the energy consumption of Fe 2+ adding and mixing. At present, the cathode oxygen supply mostly adopts a mode of separating an external oxygen supply from a cathode, and has the main defects that the utilization rate of the supplied oxygen is lower, so that the energy consumption of a system is higher, the supply of a reducing agent Fe 2+ is in a plurality of modes, fe 2+ is generated by sacrificial anode oxidation, the passivation of an electrode is often accompanied, the transfer efficiency of system electrons is influenced, the energy consumption of the system is increased, fe 2+ is added to a reactor at fixed points, stirring and mixing equipment is required to be added through stirring and mixing mass transfer and hydrogen peroxide contact catalysis, and Fe 2+ is loaded on the cathode in different modes, but as an electro-Fenton system operates, fe 2+ gradually runs off, and the cyclic regeneration of Fe 2+ and Fe 3+ is a key of the stability of the electro-Fenton system, but the complex preparation technology