WO2020124912A1 - 一种防生物污堵滤芯及保安过滤器 - Google Patents

一种防生物污堵滤芯及保安过滤器 Download PDF

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Publication number
WO2020124912A1
WO2020124912A1 PCT/CN2019/083890 CN2019083890W WO2020124912A1 WO 2020124912 A1 WO2020124912 A1 WO 2020124912A1 CN 2019083890 W CN2019083890 W CN 2019083890W WO 2020124912 A1 WO2020124912 A1 WO 2020124912A1
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porous
filter
filter element
electrode
water
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PCT/CN2019/083890
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English (en)
French (fr)
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胡洪营
巫寅虎
刘海
倪欣业
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清华大学
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Publication of WO2020124912A1 publication Critical patent/WO2020124912A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • 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
    • 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
    • C02F1/467—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
    • C02F1/46—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
    • 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
    • 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
    • C02F2303/04—Disinfection

Definitions

  • the invention relates to the field of water treatment, in particular to an anti-biological fouling filter element and a security filter with the filter element.
  • Membrane fouling caused a decrease in membrane flux and a decrease in the quality of produced water, which are the main problems that limit the stable operation of the reverse osmosis process.
  • biological fouling caused by microorganisms is an important cause of reverse osmosis fouling.
  • Reverse osmosis devices are usually equipped with a security filter to retain particulates and other pollutants in the water to protect the reverse osmosis membrane.
  • the filter element of the security filter has almost no trapping effect on microorganisms, and cannot protect the reverse osmosis system from biological fouling.
  • the biological filter clogging often occurs in the filter element of the security filter itself.
  • an object of the present invention is to provide a filter element that can effectively kill microorganisms and prevent biological fouling, and a security filter having the filter element.
  • the bio-fouling blocking filter provided by the present invention includes a hollow cylindrical structure of the filter, including a porous support layer and an electrode filter layer stacked from the inside to the outside, the porous support layer is cylindrical, and the electrode filter layer is coated On the outer circumference of the support layer, it includes a porous anode, a porous electrode separator and a porous cathode stacked from the inside to the outside.
  • the porous anode and the porous cathode are connected to the positive and negative electrodes of the power supply, respectively.
  • the porous anode and the porous cathode are made of conductive material.
  • the porous support layer and the porous electrode separator are made of insulating materials.
  • the anti-biological fouling filter element in the above technical solution can effectively kill microorganisms in water.
  • the anode is placed behind to make the water flow first contact the porous cathode, an electrode reaction occurs, and OH -is generated.
  • the microorganisms in the water flow are negatively charged and easier When contacting the anode, when the water flow contacts the porous anode again, the microorganisms in the water lose electrons when contacting with the anode, and are oxidized and inactivated, and the H + produced by the anode can neutralize the OH - produced by the pre-cathode, further promoting the anode reaction, thereby further reducing It consumes energy and improves the efficiency of current utilization, achieving efficient inactivation of microorganisms and rapid degradation of organic matter at lower voltages and low residence times, while reducing the production of disinfection byproducts (active chlorine byproducts).
  • the output voltage of the power supply is 1-5V.
  • the conductive material used to make the porous anode and the porous cathode has a porosity ⁇ 90% and a pore size ⁇ 100 ⁇ m.
  • the thickness of the porous anode and the porous cathode are both 4-6 mm, the thickness of the porous electrode separator is 0.1-0.3 mm; the height of the filter element is 1-1.2 m, and the hollow inner diameter of the porous support layer is 5-15 cm.
  • the outer circumference of the porous support layer is covered with 1-4 sets of electrode filter layers, and the adjacent two sets of electrode filter layers are separated by a porous electrode separator.
  • the filtration method using any of the above filter elements is to control the flow rate of the water sample to be treated between 40-60L/min, so that the water sample first contacts the porous cathode of the electrode filter layer, and an electrode reaction occurs to generate hydrogen peroxide and hydroxide The ions then contact the porous anode to kill the microorganisms in the water, and finally the produced water flows out from the hollow part of the porous support layer.
  • the present invention provides a security filter, the security filter including any filter element described in the first aspect.
  • the security filter includes a housing and a porous tube plate horizontally installed at the lower part of the inner side of the housing, the housing spaces above and below the porous tube plate respectively form a filtering space and a water storage space, and the porous tube plate is vertically fixed
  • the filter core is connected to the power source outside the shell through a wire wrapped by an insulating layer; the outer wall of the shell of the filter space is provided with a water inlet, and the outer wall of the shell of the water storage space is provided with a water outlet.
  • a plurality of filter core seats are provided on the porous tube plate, a water production port is vertically opened in the center of the filter core seat, the bottom of the filter core is fixed on the filter core seat, the top of the filter core is connected with the fixed pressure plate provided on the upper part of the inner side of the shell, and the fixed pressure plate and the tube are fixed Form filter space between plates;
  • a plurality of water outlet diversion tubes with a porous structure are fixed on the porous tube plate, and the filter core is sheathed on the outside of the water diversion tube.
  • the filtering method when filtering with the above security filter is: controlling the flow rate of the water sample to be treated to 40-60L/min, the water sample enters the filtering space of the security filter from the water inlet, flows into the filter core from the periphery of the filter core, and passes through After the filtering action of the porous anode, porous electrode separator and porous cathode of the filter element extinguishes the microorganisms, it enters the hollow space of the porous support layer, flows out from the bottom end of the porous support layer, flows into the storage below through the holes in the porous tube plate The water space eventually flows out of the water outlet.
  • FIG. 1 is a schematic structural diagram of an anti-biological plugging filter element provided by the present invention
  • FIG. 2 is a partial structural schematic diagram of a filter element when multiple cathodes are paired with a single anode
  • Figure 3 is a schematic diagram of the structure when the filter element adopts a multilayer electrode filter layer
  • Figure 4 is a schematic diagram of the structure of a security filter
  • FIG. 5 is a schematic structural view of the filter element sheathed on the outside of the outlet diversion pipe.
  • the bio-fouling plug filter 1 provided by the present invention is a hollow cylindrical structure, including a porous support layer 11 and an electrode filter layer 12 laminated from the inside to the outside, the porous support layer 11 is cylindrical, and the electrode is filtered
  • the layer 12 is wrapped around the outer circumference of the support layer, and includes a porous anode 121, a porous electrode separator 122 and a porous cathode 123 laminated from the inside to the outside.
  • the porous anode and the porous cathode are connected to the positive and negative electrodes of the power supply through wires, respectively.
  • the voltage of the power supply is 1-5V, preferably 2-3V
  • the porous anode 121 and the porous cathode 123 are both made of a conductive material
  • the porous support layer 11 and the porous electrode separator 122 are made of an insulating material.
  • the wire may be fixed on the upper end or the lower end of the filter element, and the wire is wrapped by the insulating layer.
  • the influent water is passed through the electrode filter layer 12 and the porous support layer 11 in sequence, and after sterilization by the electrode filter layer 12, it finally flows out from the port of the porous support layer 11; when the electrochemical reaction on the surface of the cathode electrode is the most common The accumulation of H + and OH - will seriously inhibit the progress of the reaction.
  • the porous anode 121 connected to the positive electrode of the power supply is located on the inside, and the porous cathode 123 connected to the negative electrode of the power supply is located on the outside.
  • the water flow first contacts the porous cathode 123, an electrode reaction occurs, and OH -is generated, so that the pH value of the solution increases, and the microorganisms in the water flow are negatively charged, thereby making it easier for the microorganisms to contact the anode.
  • the water Microorganisms lose electrons when they come into contact with the anode and are inactivated by oxidation, and the H + produced by the anode can neutralize the OH - produced by the pre-cathode, further promoting the anode reaction, thereby further reducing energy consumption and improving current utilization efficiency, achieving lower voltage, At low residence time, microorganisms are efficiently inactivated and organics are rapidly degraded, while reducing the production of disinfection byproducts (active chlorine byproducts).
  • the anti-biological fouling plug provided by the present invention is an electrochemical oxidation structure that filters water flow from inside the electrode, which can improve the reaction efficiency, reduce energy consumption, and increase the service life of the electrode; electrochemical degradation of organic matter and microbial inactivation Mainly lies in the oxidation of the anode to achieve microbial inactivation and organic matter degradation at low voltage.
  • the porosity of the conductive material used for making the porous anode and the porous cathode is ⁇ 90%, and the pore size is ⁇ 100 ⁇ m.
  • the setting of the pore size is much larger than the pore size of the general microfiltration or ultrafiltration membranes. With high operating pressure, bacteria can be inactivated due to the pore size is too large to entrap after being powered, so as to play a disinfecting role.
  • the setting of porosity can improve the water flux and meet the requirements of disinfection.
  • the porous anode 121 and the porous cathode 123 may be made of metal foam (silver nanowires, titanium foam, copper oxide and copper oxide nanowires, etc.), carbon fiber materials (such as graphite fiber felt, carbon fiber felt, carbon fiber cloth, etc.), carbon nanotubes Made of sponge, the thickness is 4-6mm, preferably 5mm; the porous electrode separator 122 can use common porous insulating materials, specifically, the porous electrode separator 122 can be made of PP cotton or quick filter paper, the thickness is 0.1-0.3mm, It is preferably 0.15 mm.
  • the porous support layer may be a hollow cylindrical multi-grid plastic shelf.
  • the height of the filter element is 1-1.2m, and the hollow inner diameter of the porous support layer is 5-15cm.
  • this embodiment provides a combined unit form that uses multiple cathodes paired with a single anode. After multilayer cathode treatment, the resulting strong alkaline treatment liquid will flow into the anode, and microorganisms are easily oxidized directly under alkaline conditions. The reaction can achieve complete inactivation of microorganisms at low voltage ((1-5V).
  • This unit setting method significantly improves the disinfection ability of the unit, greatly shortens the hydraulic retention time of the unit, and can effectively avoid excessive oxidation or fragmentation of microorganisms. The resulting energy waste and subsequent competition for disinfection sites.
  • the combined unit of a multi-cathode paired single anode includes a layer of porous anode 121 and at least two layers of porous cathode 123, between porous anode 121 and porous cathode 123 and between porous cathode 123 and porous cathode 123 They are all separated by an insulating porous electrode separator 122 to prevent short circuits and the effects between the layers.
  • the porous cathode is preferably 3 layers.
  • Example 1 and Example 2 in order to increase the effective water treatment capacity of the filter element, multiple sets (at least two sets) of electrode filter layers 12 may be provided outside the porous support layer 11, as shown in FIG. 3, the electrodes used The more the number of filter layer groups, the greater the amount of water that can be effectively treated.
  • the adjacent two groups of electrode filter layers 12 are separated by a porous electrode separator 122, preferably 2-4 groups of electrode filter layers, each group of electrode filter layers can be used
  • the combination of a single cathode paired with a single anode can also be a combination of multiple cathodes paired with a single anode.
  • Cartridge filter using any of the above methods are: Control sample flow of water to be treated between 40-60L / min, the water sample to the porous cathode electrode in contact with the filtration layer, the electrode reaction occurs, generating H 2 O 2 and OH - Then, it contacts the porous anode to kill the microorganisms in the water, and finally the produced water flows out from the hollow part of the porous support layer.
  • the security filter includes the filter element 1 of any structure of Embodiments 1-3.
  • the filter element 1 is vertically fixedly installed inside the security filter.
  • the security filter includes The housing 3 and the porous tube plate 4 horizontally installed at the lower part of the inner side of the housing 3, the housing spaces above and below the porous tube plate 4 respectively form a filtering space and a water storage space, and a plurality of filter elements 1 are vertically fixed on the porous tube plate 4, For example, 2-10; the water inlet 31 is set on the side wall of the housing 3 of the filter space, and the water outlet 32 is provided on the bottom of the housing 3 of the water storage space, and the top shell of the filter space is sealed to prevent water leakage; The treated influent water sample enters the filter space through the water inlet 31.
  • the filter element 1 After filling the filter space, it flows in from the periphery of the filter element 1 under its own pressure, and is sequentially filtered by the porous anode 121, the porous electrode separator 122, and the porous cathode 123 of the filter element 1. After extinguishing the microorganisms, the microorganism enters the hollow space of the porous support layer 11 and flows out from the bottom end of the porous support layer 11, flows into the water storage space below through the holes in the porous tube sheet 4, and finally flows out from the water outlet 32.
  • a plurality of filter element seats 41 are fixed on the porous tube plate 4, a water production port 42 is vertically opened in the center of the filter element seat 41, and the bottom of the filter element 41 is fixed on the filter element seat 41.
  • the top of the filter element 41 is The fixed pressure plate 5 provided at the upper part of the inner side of the housing is connected, and a closed filter space is formed between the fixed pressure plate 5 and the porous tube plate 4, and the filter element 41 is vertically fixed in the filter space, and the water inlet filtered by the filter element 1 passes through the water outlet 42 1.
  • the holes in the porous tube sheet 4 flow into the water storage space; or, the porous tube sheet 4 is fixed with a number of porous structure outlet guide tubes 6, and the filter element 1 is sheathed outside the outlet guide tube 6, as shown in FIG. 5,
  • the inlet water filtered by the filter element 1 flows into the water storage space through the holes in the outlet diversion pipe 6 and the holes in the porous tube plate 4.
  • the housing 3, the porous tube plate 4, and the fixed pressure plate 5 are all detachable structures.
  • the housing 3 includes an upper housing 33, a middle housing 34, which are sequentially connected by flanges.
  • the lower shell 35, the porous tube plate 4, and the fixed pressure plate 5 are fixed to the top and bottom of the middle shell through flange rings.
  • the upper and lower ends of the filter element 1 are installed with end caps 2, specifically, the end cap 2 includes an upper end cap 21 and a lower end cap 22; one end of the lower end cap 22 has a chevron structure , The other end is provided with a mounting shaft 221, the outer circumference of the mounting shaft 221 is an external thread, which matches the internal thread inside the water outlet 42 of the filter element seat 41, the mounting shaft 221 is threadedly connected to the filter element seat 41, and the bottom of the filter element 1 is clipped on the lower end cover
  • the center of the lower end cover 22 is provided with a through hole 222 that communicates with the water outlet 42 to facilitate the flow of water samples;
  • the structure of the upper end cover 21 is basically the same as the structure of the lower end cover 22, and the center of the upper end cover 21 does not need to be provided. Hole, the mounting shaft on the upper end cover 21 is inserted into the mounting hole 51 opened on the fixed pressure plate 5 and connected
  • the wires of the porous anode 121 and the porous cathode 123 are provided on the top of the filter element, the upper end cover 21 is provided with a wire hole A211 for threading the wire, and the fixed pressure plate 5 is provided with a threading hole
  • the wire hole B52 of the wire, the upper housing 33 is provided with a wire hole C331 for threading the wire, the wire is threaded in the rubber plug and then sealed and fixed in each wire hole, the wire passes through the wire hole A, the wire hole B, the wire hole C is connected to the power supply outside the casing.
  • An insulation box 7 for installing the power supply may be provided outside the casing.
  • the box 7 may be provided outside the upper casing 33 or the middle casing 34.
  • the filtering method when filtering with the above security filter is: controlling the flow rate of the water sample to be treated to 40-60L/min, the water sample enters the filtering space of the security filter from the water inlet, flows into the filter core from the periphery of the filter core, and passes through After the filtering action of the porous anode, porous electrode separator and porous cathode of the filter element extinguishes the microorganisms, it enters the hollow space of the porous support layer, flows out from the bottom end of the porous support layer, flows into the storage below through the holes in the porous tube plate The water space eventually flows out of the water outlet.
  • the anti-biofouling filter element provided by the present invention can be used to kill various microorganisms in water (including bacteria: E. coli, Enterococcus faecalis, E. faecalis, Bacillus subtilis, etc.; viruses: MS2, F2, etc.; spores, etc.) and water
  • water including bacteria: E. coli, Enterococcus faecalis, E. faecalis, Bacillus subtilis, etc.; viruses: MS2, F2, etc.; spores, etc.
  • trace organic pollutants antibiotic, scale inhibitor, bacteriostatic agent, etc.
  • the microbial killing efficiency in the water sample is as high as 98% and above; from the experimental data of the serial numbers 1, 2, and 3, it can be seen that when other conditions are consistent, the electrode If the thickness is too high or too low, it will affect the removal rate of microorganisms; from the experimental data of groups 2, 4 and 5, it can be seen that the thickness of the electrode separator is too high or too low, it will also affect the removal rate of microorganisms;
  • the experimental data of groups 2, 6 and 7 shows that the more cathode layers, the greater the water flux that can be used for disinfection under the condition of ensuring the removal rate of microorganisms; from the experimental data of groups 8, 9, and 10, The greater the height of the filter element and the diameter of the hollow part, the larger the size of the filter element.
  • microorganism killing effect is good, and it has good killing effect on the common pathogenic microorganisms in water;

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Abstract

一种防生物污堵滤芯（1），滤芯（1）为中空圆柱体结构，包括从内到外层叠的多孔支撑层（11）和电极过滤层（12），多孔支撑层（11）呈圆筒状，电极过滤层（12）包覆在多孔支撑层（11）外圆周，包括从内到外层叠的多孔阳极（121）、多孔电极隔层（122）和多孔阴极（123），多孔阳极（121）和多孔阴极（123）均由导电材料制成，多孔支撑层（11）、多孔电极隔层（122）由绝缘材料制成；还公开了一种利用防生物污堵滤芯（1）的过滤方法，水样先接触多孔阴极（123），产生氢氧根离子杀灭水中微生物，然后接触多孔阳极（121），最后产水由多孔支撑层（11）中空部位流出；还公开了一种包括防生物污堵滤芯（1）的保安过滤器。

Description

一种防生物污堵滤芯及保安过滤器 技术领域
本发明涉及水处理领域，尤其涉及一种防生物污堵滤芯以及具有该滤芯的保安过滤器。
背景技术
膜污堵导致的膜通量下降、产水水质下降等现象是限制反渗透工艺稳定运行的主要问题。研究表明，微生物导致的生物污堵是造成反渗透污堵的重要原因，反渗透装置之前通常设有保安过滤器，用于截留水中的颗粒物等污染物以保护反渗透膜，然而，现有的保安过滤器的滤芯对于微生物几乎没有截留作用，不能保护反渗透系统免受生物污堵，同时，保安过滤器的滤芯本身也常常发生生物污堵现象。
发明内容
为了解决上述问题，本发明的目的是提供一种可以有效杀灭微生物、防止生物污堵的滤芯以及具有该滤芯的保安过滤器。
第一方面，本发明提供的防生物污堵滤芯，包括滤芯为中空圆柱体结构，包括从内到外层叠的多孔支撑层和电极过滤层，多孔支撑层呈圆筒状，电极过滤层包覆在支撑层外圆周，包括从内到外层叠的多孔阳极、多孔电极隔层和多孔阴极，多孔阳极和多孔阴极分别与电源的正极和负极连接，多孔阳极和多孔阴极均由导电材料制成，多孔支撑层、多孔电极隔层由绝缘材料制成。
上述技术方案中的防生物污堵滤芯可以有效杀灭水中的微生物，本发明采用阳极后置的方式使水流先接触多孔阴极，发生电极反应，生成OH -，水流中的微生物带负电，更容易接触阳极，当水流再接触多孔阳极时，水中的微生物与阳极接触失去电子，被氧化灭活，并且阳极产生的H +可以中和前置阴极产生的OH -，进一步促进阳极反应，从而进一步降低能耗并提 高电流利用效率，实现更低电压、低停留时间下微生物高效灭活和有机物的迅速降解，同时减少消毒副产物(活性氯副产物)的生成。
优选地，电源的输出电压为1-5V。
优选地，制成多孔阳极和多孔阴极所用导电材料的孔隙率≥90％、孔径≥100μm。
优选地，多孔阳极和多孔阴极的厚度均为4-6mm，多孔电极隔层的厚度为0.1-0.3mm；所述滤芯的高度为1-1.2m，多孔支撑层的中空内径为5-15cm。
优选地，多孔支撑层外圆周包覆有1-4组电极过滤层，相邻两组电极过滤层由多孔电极隔层隔开。
利用上述任一种滤芯的过滤方法为：控制待处理水样流量在40-60L/min之间，使水样先接触电极过滤层的多孔阴极，发生电极反应，生成过氧化氢和氢氧根离子，然后接触多孔阳极，杀灭水中的微生物，最后形成产水由多孔支撑层中空部位流出。
第二方面，本发明提供一种保安过滤器，所述保安过滤器包括第一方面所述的任一种滤芯。
进一步地，所述保安过滤器包括壳体和水平安装在壳体内侧下部的多孔管板，多孔管板上方和下方的壳体空间分别形成过滤空间和储水空间，多孔管板上竖直固定若干上述滤芯，所述滤芯通过由绝缘层包裹的导线与壳体外侧的电源连接；过滤空间的壳体外壁开设进水口，储水空间的壳体外壁开设出水口。
进一步地，多孔管板上设有若干滤芯座，滤芯座中心竖向开设有产水口，所述滤芯底部固定在滤芯座上，滤芯顶部与壳体内侧上部设置的固定压板连接，固定压板与管板之间形成过滤空间；
或者，多孔管板上固定若干多孔结构的出水导流管，滤芯套装在出水导流管外侧。
利用上述保安过滤器进行过滤时的过滤方法为：控制待处理水样的流量为40-60L/min，水样由进水口进入保安过滤器的过滤空间内，由滤芯 四周流入滤芯内，依次经过滤芯的多孔阳极、多孔电极隔层和多孔阴极的过滤作用将微生物灭火后，进入多孔支撑层的中空空间内，并从多孔支撑层的底端流出，经多孔管板上的孔洞流入下方的储水空间，最终从出水口流出。
本发明提供的防生物污堵滤芯及保安过滤器，具有以下有益效果：
(1)结构简单，使用方便；
(2)微生物杀灭效果较好，对水中常见的病原微生物有良好的灭火效果；
(3)不需要投加任何化学试剂，仅需极低的电压即可实现高标准消毒，杀毒效率高，可有效解决保安过滤器易受生物污堵的问题，并保护后端的反渗透单元免受生物污堵。
附图说明
图1为本发明提供的防生物污堵滤芯的结构示意图；
图2为滤芯采用多阴极配对单阳极时的局部结构示意图；
图3为滤芯采用多层电极过滤层时的结构示意图；
图4为保安过滤器的结构示意图；
图5为滤芯套装在出水导流管外侧的结构示意图。
其中，1、滤芯；11、多孔支撑层；12、电极过滤层；121、多孔阳极；122、多孔电极隔层；123、多孔阴极；2、端盖；21、上端盖；211、导线孔A；22、下端盖；221、安装轴；222、通孔；3、壳体；31、进水口；32、出水口；33、上壳体；331、导线孔C；34、中壳体；35、下壳体；4、多孔管板；41、滤芯座；42、产水口；5、固定压板；51、安装孔；52、导线孔B；6、出水导流管；7、盒体。
具体实施方式
为了使本发明的滤芯及保安过滤器的技术方案更加清楚明白，以下结合具体附图和具体实施例，对本发明做进一步详细说明。需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
实施例1
如图1所示，本发明提供的防生物污堵滤芯1为中空圆柱体结构，包括从内到外层叠的多孔支撑层11和电极过滤层12，多孔支撑层11呈圆筒状，电极过滤层12包覆在支撑层外圆周，包括从内到外层叠的多孔阳极121、多孔电极隔层122和多孔阴极123压制而成，多孔阳极和多孔阴极分别通过导线与电源的正极和负极连接，电源的电压为1-5V，优选2-3V，多孔阳极121和多孔阴极123均由导电材料制成，多孔支撑层11、多孔电极隔层122由绝缘材料制成。
具体地，可将导线固定在滤芯的上端或下端，导线由绝缘层包裹。
在具体使用时，使进水依次经过电极过滤层12和多孔支撑层11，经电极过滤层12杀菌后，最终从多孔支撑层11端口流出；阴阳电极表面进行电化学反应时，最常见的是H +和OH -的累积，会严重抑制反应进行，在本发明中，由于与电源正极连接的多孔阳极121位于内侧，与电源负极连接的多孔阴极123位于外侧，这种采用阳极后置的结构，使水流先接触多孔阴极123，发生电极反应，生成OH -，使溶液pH值升高，水流中的微生物带负电，从而使微生物更容易接触阳极，当水流再接触多孔阳极121时，水中的微生物与阳极接触失去电子，被氧化灭活，并且阳极产生的H +可以中和前置阴极产生的OH -，进一步促进阳极反应，从而进一步降低能耗并提高电流利用效率，实现更低电压、低停留时间下微生物高效灭活和有机物的迅速降解，同时减少消毒副产物(活性氯副产物)的生成。同时，当阴极发生电极反应产生过氧氢根(HO 2 -)时，由于过氧氢根具有较强的氧化性，能对微生物直接氧化灭活，进一步提高微生物氧化灭活的程度，实现高效灭活。采用这种阳极后置的方式，其有机物的去除率相较于阴极后置的方式高出30-40％。
本发明提供的防生物污堵滤芯是使水流从电极内部通过的电极内过滤电化学氧化结构，其可提高反应效率，降低能耗，提高电极的使用寿命；电化学对有机物降解和微生物灭活主要在于阳极的氧化作用，实现低电压下微生物灭活和有机物降解。
较佳地，作为一种可实施方式，制成多孔阳极和多孔阴极所用导电材料的孔隙率≥90％、孔径≥100μm，该孔径的设置远大于一般微滤或超滤膜孔径，不需要太高的运行压力，通电之后，即可灭活因孔径太大而无法截留的细菌，从而起到消毒的作用，孔隙率的设置可以提高水通量，满足消毒要求。具体地，多孔阳极121和多孔阴极123可由金属泡沫(银纳米线、钛泡沫、氧化铜及氧化铜纳米线等)、碳纤维材料(例如石墨纤维毡、碳纤维毡、碳纤维布等)、碳纳米管海绵制成，厚度为4-6mm，优选5mm；多孔电极隔层122选用常见的多孔绝缘材料即可，具体地，多孔电极隔层122可采用PP棉或快速滤纸，厚度为0.1-0.3mm，优选0.15mm。具体地，多孔支撑层可选用中空圆柱状的多网格塑料架子。
较佳地，作为一种可实施方式，所述滤芯的高度为1-1.2m，多孔支撑层的中空内径为5-15cm。
实施例2
在实施例1中提供的单阴极配对单阳极的组合单元中，当进水流速变大后，阴极的氢氧根累积效率变低，失去后置阳极的优势，其消毒效果变差，为了解决该技术问题，本实施例提供一种采用多阴极配对单阳极的组合单元形式，经过多层阴极处理后，生成的强碱性处理液将流入阳极，微生物在碱性条件下极易直接发生氧化反应，可在低电压((1-5V)下实现微生物完全灭活，这种单元设置方式使得单元消毒能力显著提升，极大地缩短单元的水力停留时间，亦可有效避免微生物的过度氧化或破碎造成的能量浪费以及后续竞争消毒位点的问题。
具体地，如图2所示，多阴极配对单阳极的组合单元包括一层多孔阳极121和至少两层多孔阴极123，多孔阳极121与多孔阴极123之间以及多孔阴极123与多孔阴极123之间均由绝缘的多孔电极隔层122隔开，防止短路以及层与层之间造成影响，多孔阴极优选3层。
实施例3
在实施例1和实施例2的基础上，为了提高滤芯的有效处理水量，可以在多孔支撑层11的外侧设置多组(至少两组)电极过滤层12，如图3 所示，使用的电极过滤层组数越多，可有效处理的水量越大，相邻两组电极过滤层12之间由多孔电极隔层122隔开，优选2-4组电极过滤层，每组电极过滤层可以采用单阴极配对单阳极的组合形式，也可以采用多阴极配对单阳极的组合形式。
利用上述任一种滤芯的过滤方法为：控制待处理水样流量在40-60L/min之间，使水样先接触电极过滤层的多孔阴极，发生电极反应，生成H 2O 2和OH -，然后接触多孔阳极，杀灭水中的微生物，最后形成产水由多孔支撑层中空部位流出。
实施例4
本实施例提供一种保安过滤器，该保安过滤器包括实施例1-3任一种结构的滤芯1，滤芯1竖直固定安装在保安过滤器内部，如图4所示，保安过滤器包括壳体3和水平安装在壳体3内侧下部的多孔管板4，多孔管板4上方和下方的壳体空间分别形成过滤空间和储水空间，多孔管板4上竖直固定若干滤芯1，例如2-10个；过滤空间的壳体3侧壁开设进水口31，储水空间的壳体3外壳底部开设出水口32，过滤空间顶部的壳体封死，防止漏水；在使用时，待处理的进水水样经进水口31进入过滤空间，充满过滤空间后，在自身压力作用下由滤芯1四周流入，依次经过滤芯1的多孔阳极121、多孔电极隔层122和多孔阴极123的过滤作用将微生物灭火后，进入多孔支撑层11的中空空间内，并从多孔支撑层11的底端流出，经多孔管板4上的孔洞流入下方的储水空间，最终从出水口32流出。
具体地，多孔管板4上固定有若干滤芯座41，滤芯座41中心竖向开设有产水口42，滤芯41底部固定在滤芯座41上，为了保证滤芯的稳固，优选地，滤芯41顶部与壳体内侧上部设置的固定压板5连接，固定压板5与多孔管板4之间形成封闭的过滤空间，将滤芯41竖直固定在过滤空间内，经滤芯1过滤后的进水经产水口42、多孔管板4上的孔洞流入储水空间内；或者，多孔管板4上固定若干多孔结构的出水导流管6，滤芯1套装在出水导流管6外侧，如图5所示，经滤芯1过滤后的进水经出水导流管6上的孔洞、多孔管板4上的孔洞流入储水空间内。
进一步地，为了便于滤芯的拆卸，壳体3、多孔管板4、固定压板5均为可拆卸结构，具体地，壳体3包括依次通过法兰连接的上壳体33、中壳体34、下壳体35，多孔管板4、固定压板5通过法兰圈固定在中壳体顶部和底部。
进一步地，为了便于滤芯1的安装，滤芯1的上、下两端均安装有端盖2，具体地，端盖2包括上端盖21和下端盖22；下端盖22的一端呈山字型结构，另一端设置安装轴221，安装轴221外圆周为外螺纹，与滤芯座41的产水口42内部的内螺纹相匹配，安装轴221与滤芯座41螺纹连接，滤芯1底部卡装在下端盖22山字形的一端，下端盖22中心开设有与产水口42相通的通孔222，便于水样流经；上端盖21的结构与下端盖22的结构基本一致，上端盖21中心不需设置通孔，上端盖21上的安装轴插装在固定压板5上开设的安装孔51内，通过螺纹连接。
较佳地，作为一种可实施方式，多孔阳极121和多孔阴极123的导线设置在滤芯的顶部，上端盖21上开设有用于穿装导线的导线孔A211，固定压板5上开设有用于穿装导线的导线孔B52，上壳体33上开设有用于穿装导线的导线孔C331，导线穿装在橡胶塞内进而密封固定在各导线孔内，导线经导线孔A、导线孔B、导线孔C与壳体外侧的电源连接，壳体外侧可以设置安装电源的绝缘盒体7，盒体7可设置在上壳体33或中壳体34外侧。
利用上述保安过滤器进行过滤时的过滤方法为：控制待处理水样的流量为40-60L/min，水样由进水口进入保安过滤器的过滤空间内，由滤芯四周流入滤芯内，依次经过滤芯的多孔阳极、多孔电极隔层和多孔阴极的过滤作用将微生物灭火后，进入多孔支撑层的中空空间内，并从多孔支撑层的底端流出，经多孔管板上的孔洞流入下方的储水空间，最终从出水口流出。
本发明提供的防生物污堵滤芯可用于杀除水中的多种微生物(包括细菌：大肠杆菌、粪肠球菌、粪大肠杆菌、枯草芽孢杆菌等；病毒：MS2、F2等；芽孢等)以及水中微量有机污染物(抗生素、阻垢剂、抑菌剂等)， 下面针对单个滤芯的具体实验数据(以大肠杆菌为例)进行说明，其中电源的电压均为3V，实验数据如下：
Figure PCTCN2019083890-appb-000001
通过上述实验数据可知，采用本发明的消毒装置进行消毒时，水样中微生物杀除效率高达98％及以上；由序号为1、2、3组的实验数据可知，当其他条件一致时，电极厚度太高或太低，都会影响微生物的去除率；由序号为2、4、5组的实验数据可知，电极隔层的厚度太高或太低，也会影响微生物的去除率；由序号为2、6、7组的实验数据可知，阴极层数越多，在保证微生物去除率的条件下，可用于消毒的水通量越大；由序号为8、9、10组的实验数据可知，滤芯的高度和中空部分的直径越大，滤芯的尺寸越大，在保证微生物去除率的条件下，可用于消毒的水通量越大；由序号为2、11、12组的实验数据可知，电极过滤层数量越多，在保证微生物去除率的条件下，可用于消毒的水通量越大。
本发明提供的滤芯及保安过滤器具有以下有益效果：
(1)结构简单，使用方便；
(2)微生物杀灭效果好，对水中常见的病原微生物有良好的灭活效果；
(3)不需要投加任何化学试剂，仅需极低的电压即可实现高标准消毒，杀毒效率高，并且没有消毒副产物产生。
以上所述实施方式仅表达了本发明的多种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (10)

  1. 一种防生物污堵滤芯，其特征在于，所述滤芯(1)为中空圆柱体结构，包括从内到外层叠的多孔支撑层(11)和电极过滤层(12)，多孔支撑层呈圆筒状，电极过滤层(12)包覆在支撑层外圆周，包括从内到外层叠的多孔阳极(121)、多孔电极隔层(122)和多孔阴极(123)，多孔阳极和多孔阴极分别与电源的正极和负极连接，多孔阳极和多孔阴极均由导电材料制成，多孔支撑层、多孔电极隔层由绝缘材料制成。
  2. 根据权利要求1所述的防生物污堵滤芯，其特征在于，电极过滤层中的多孔阳极为1层，多孔阴极为1-3层，相邻两多孔阴极之间由多孔电极隔层隔离。
  3. 根据权利要求1所述的防生物污堵滤芯，其特征在于，电源的输出电压为1-5V。
  4. 根据权利要求1所述的防生物污堵滤芯，其特征在于，多孔阳极和多孔阴极所用导电材料的孔隙率≥90％、孔径≥100μm。
  5. 根据权利要求1所述的防生物污堵滤芯，其特征在于，多孔阳极和多孔阴极的厚度均为4-6mm，多孔电极隔层的厚度为0.1-0.3mm；所述滤芯的高度为1-1.2m，多孔支撑层的中空内径为5-15cm。
  6. 根据权利要求1所述的防生物污堵滤芯，其特征在于，多孔支撑层外圆周包覆有1-4组电极过滤层，相邻两组电极过滤层由多孔电极隔层隔开。
  7. 一种利用权利要求1-6任一所述滤芯的过滤方法，其特征在于，所述过滤方法为：控制待处理水样流量在40-60L/min之间，使水样先接触电极过滤层的多孔阴极，发生电极反应，生成氢氧根离子，然后接触多孔阳极，利用阴极产生的氢氧根离子杀灭水中的微生物，最后形成产水由多孔支撑层中空部位流出。
  8. 一种保安过滤器，其特征在于，所述保安过滤器包括壳体(3)和水平安装在壳体内侧下部的多孔管板(4)，多孔管板上方和下方的壳体空间分别形成过滤空间和储水空间，多孔管板上竖直固定若干权利要求1-6任一所述的防生物污堵滤芯，所述滤芯通过由绝缘层包裹的导线与壳体外 侧的电源连接；过滤空间的壳体外壁开设进水口(31)，储水空间的壳体外壁开设出水口(32)。
  9. 根据权利要求8所述的保安过滤器，其特征在于，多孔管板上设有若干滤芯座(41)，滤芯座中心竖向开设有产水口(42)，所述滤芯底部固定在滤芯座上，滤芯顶部与壳体内侧上部设置的固定压板(5)连接，固定压板与管板之间形成过滤空间；
    或者，多孔管板上固定若干多孔结构的出水导流管(6)，滤芯套装在出水导流管外侧。
  10. 一种利用权利要求8-9任一所述保安过滤器的过滤方法，其特征在于，所述过滤方法为：控制待处理水样的流量为40-60L/min，水样由进水口进入保安过滤器的过滤空间内，由滤芯四周流入滤芯内，依次经过滤芯的多孔阳极、多孔电极隔层和多孔阴极的过滤作用将微生物灭火后，进入多孔支撑层的中空空间内，并从多孔支撑层的底端流出，经多孔管板上的孔洞流入下方的储水空间，最终从出水口流出。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112919700A (zh) * 2020-12-08 2021-06-08 北京师范大学 一种以多级光电管深度处理高盐有机废水的反应器
CN113526775A (zh) * 2021-07-23 2021-10-22 高凯 一种复合滤芯及使用该复合滤芯的超滤净水器

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109455798B (zh) * 2018-12-21 2022-01-04 清华大学 一种防生物污堵滤芯及保安过滤器
CN111939710A (zh) * 2020-09-03 2020-11-17 中钢集团天澄环保科技股份有限公司 一种顶部垂直进风电袋复合除尘器
CN115010223A (zh) * 2021-03-04 2022-09-06 中国石油化工股份有限公司 一种电催化水处理装置
CN112979104A (zh) * 2021-04-26 2021-06-18 深圳市水务工程检测有限公司 一种用于大型河湖污染水质生态的修复系统及修复方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014767A (en) * 1974-10-18 1977-03-29 Ametek, Inc. Self-contained waste disposal system including self-cleaning filter
GB2177625A (en) * 1985-06-17 1987-01-28 Noboru Inoue Fluid filtering apparatus
DE10013457A1 (de) * 2000-03-17 2001-09-20 Andreas Noack Verfahren und Vorrichtung zur Reinigung von Wasser
CN2659873Y (zh) * 2003-08-25 2004-12-01 中国科学院广州化学研究所 叠网式净水装置
CN105668725A (zh) * 2015-09-20 2016-06-15 大连双迪创新科技研究院有限公司 连续饮用水净水机
CN109354136A (zh) * 2018-12-21 2019-02-19 清华大学 一种基于多孔电极内过滤的消毒方法及消毒装置
CN109368749A (zh) * 2018-12-21 2019-02-22 清华大学 一种高通量消毒装置及消毒方法
CN109455798A (zh) * 2018-12-21 2019-03-12 清华大学 一种防生物污堵滤芯及保安过滤器

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3536092B2 (ja) * 2001-06-11 2004-06-07 群馬大学長 電場を用いた被処理水からのリンの除去方法
CN104030405B (zh) * 2014-06-25 2015-06-10 中国地质大学（武汉） 一种电化学强化砂滤罐除砷方法
CN105540771A (zh) * 2016-01-21 2016-05-04 清华大学 一种纳米线修饰的三维电极电穿孔消毒装置、方法及应用
CN205856075U (zh) * 2016-08-05 2017-01-04 重庆大学 一种用于水处理的电催化膜反应器
CN107162123A (zh) * 2017-04-26 2017-09-15 清华大学 一种电极内过滤消毒方法及装置和应用
CN107445256A (zh) * 2017-09-08 2017-12-08 南开大学 一种连续流过滤式电解臭氧化杀菌消毒方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014767A (en) * 1974-10-18 1977-03-29 Ametek, Inc. Self-contained waste disposal system including self-cleaning filter
GB2177625A (en) * 1985-06-17 1987-01-28 Noboru Inoue Fluid filtering apparatus
DE10013457A1 (de) * 2000-03-17 2001-09-20 Andreas Noack Verfahren und Vorrichtung zur Reinigung von Wasser
CN2659873Y (zh) * 2003-08-25 2004-12-01 中国科学院广州化学研究所 叠网式净水装置
CN105668725A (zh) * 2015-09-20 2016-06-15 大连双迪创新科技研究院有限公司 连续饮用水净水机
CN109354136A (zh) * 2018-12-21 2019-02-19 清华大学 一种基于多孔电极内过滤的消毒方法及消毒装置
CN109368749A (zh) * 2018-12-21 2019-02-22 清华大学 一种高通量消毒装置及消毒方法
CN109455798A (zh) * 2018-12-21 2019-03-12 清华大学 一种防生物污堵滤芯及保安过滤器

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112919700A (zh) * 2020-12-08 2021-06-08 北京师范大学 一种以多级光电管深度处理高盐有机废水的反应器
CN113526775A (zh) * 2021-07-23 2021-10-22 高凯 一种复合滤芯及使用该复合滤芯的超滤净水器

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