Fenton-like membrane reactor

Abstract

The utility model discloses a Fenton-like membrane reactor. Comprising a membrane reaction tank, a catalytic membrane assembly located in the membrane reaction tank, a water inlet system used for introducing water to be treated into the membrane reaction tank, a membrane filtration system used for discharging water treated by the catalytic membrane assembly, and an air aeration system used for carrying out air aeration on the interior of the membrane reaction tank, the ozone aeration system is used for carrying out ozone aeration on the membrane reaction tank; the online dosing system is used for adding an oxidizing agent into the membrane reaction tank; the membrane backwashing system is used for adding a backwashing agent into the membrane reaction tank; and the membrane off-line cleaning system is used for carrying out off-line cleaning on the catalytic membrane component and introducing the cleaned liquid into the membrane reaction tank. The Fenton-like membrane reactor disclosed by the utility model can be used for realizing efficient and environment-friendly cleaning of the membrane and improving the removal of pollutants, particularly new pollutants, in water at the same time.

Description

TECHNICAL FIELD

[0001] The utility model relates to the membrane reactor in water treatment especially relates to a kind of fenton-like membrane reactor. BACKGROUND

[0002] With the high-speed development of global economy, water pollution problem represented by new pollutant pollution has received the attention and emphasis of countries around the world. Fenton-like reaction based on transition metal oxide can oxidize new pollutants by active oxygen species generated by Fenton system, and is considered as a new pollutant treatment technology with promising application prospect in new water treatment era. However, the existing water treatment membrane reactor has problems such as low pollutant removal efficiency and difficulty in membrane cleaning and maintenance.

[0003] It should be noted that the information disclosed in the above BACKGROUND section is only for understanding the background of the present application, and therefore can include information that does not constitute prior art known to those of ordinary skill in the art. SUMMARY

[0004] In order to make up for the deficiencies of the prior art, the utility model provides a kind of fenton-like membrane reactor.

[0005] The utility model adopts the following technical solutions:

[0006] A kind of fenton-like membrane reactor, including membrane reaction pool, catalytic membrane assembly, water inlet system, membrane filtration system, air aeration system, ozone aeration system, on-line dosing system, membrane backwash system and membrane offline cleaning system;The catalytic membrane assembly is located in the membrane reaction pool, for treating water to be handled;The water inlet system is communicated with the membrane reaction pool, for the water to be handled into the membrane reaction pool;The membrane filtration system is connected with the catalytic membrane assembly, for the water after being treated by the catalytic membrane assembly is discharged;The air aeration system is communicated with the membrane reaction pool, for the air aeration in the membrane reaction pool, the ozone aeration system is communicated with the membrane reaction pool, for the ozone aeration in the membrane reaction pool;The on-line dosing system is communicated with the membrane reaction pool, for adding oxidant to the membrane reaction pool;The membrane backwash system is connected with the catalytic membrane assembly, for the backwash of the catalytic membrane assembly;The membrane offline cleaning system is used for the offline cleaning of the catalytic membrane assembly and the liquid after cleaning is introduced into the membrane reaction pool.

[0007] Further, the catalytic membrane assembly includes a catalytic membrane, the catalytic membrane includes a porous ceramic membrane support, a halloysite nanotube layer, and a catalyst with Fenton-like catalytic activity, the halloysite nanotube layer is attached to the surface of the porous ceramic membrane support, the catalyst is loaded on the surface and pores of the porous ceramic membrane support, and the catalyst is also loaded on the surface and pores of the halloysite nanotube layer.

[0008] Further, the thickness of the halloysite nanotube layer is 10-50 μm; the pore size of the central hole of the halloysite nanotube in the halloysite nanotube layer is 10-30 nm, the outer diameter of the tube of the halloysite nanotube is 30-190 nm, and the tube length of the halloysite nanotube is 0.02-30 μm; the spacing between the wall sheet layers of the halloysite nanotube is

[0009] Further, the thickness of the porous ceramic membrane support is 1-2 mm, and the pore size of the porous ceramic membrane support is 1-3 μm.

[0010] Further, the material of the porous ceramic membrane support is aluminum oxide; and the material of the catalyst is one of CuMnO, FeMnO, TiMnO, ZnMnO, CuFeMnO, CuZnMnO, CuTiMnO, and TiMnFeO.

[0011] Further, the membrane reaction tank comprises a membrane tank, a sludge discharge valve, and a water level gauge, the sludge discharge valve is located at the bottom of the membrane tank, and the water level gauge is located at the upper part of the membrane tank; the water inlet system comprises a water inlet pump, a water inlet flow meter, and a water inlet valve arranged in sequence along the water inlet direction; the membrane filtration system comprises a transmembrane pressure gauge, a first time relay, a membrane outlet pump, a water outlet flow meter, a water outlet valve, and a membrane outlet tank arranged in sequence along the water outlet direction, and is used for discharging the water treated by the catalytic membrane assembly into the membrane outlet tank.

[0012] Further, the air aeration system comprises an air pump, an air gas flow meter, an air aeration valve, and an air aeration rod arranged in sequence along the air entering direction, and the air aeration rod is located below the catalytic membrane assembly in the membrane reaction tank; the ozone aeration system comprises an ozone generator, an ozone concentration monitoring gauge, an ozone gas flow meter, an ozone aeration valve, and an ozone aeration rod arranged in sequence along the ozone entering direction, and the ozone aeration rod is located below the catalytic membrane assembly in the membrane reaction tank.

[0013] Further, the online dosing system comprises a medicament tank, a dosing pump, a dosing flow meter, and a dosing valve arranged in sequence along the oxidant adding direction, and is used for adding the oxidant in the medicament tank into the membrane reaction tank through the dosing pump, the dosing flow meter, and the dosing valve in sequence.

[0014] Further, the membrane backwashing system comprises a backwashing agent tank, an agent backwashing valve, a second time relay, a backwashing pump, a backwashing agent flow meter and an agent backwashing valve arranged in sequence along the adding direction of the backwashing agent, for passing the backwashing agent in the backwashing agent tank into the catalytic membrane assembly; the membrane backwashing system further comprises a clean water backwashing valve, one end of which is connected to the membrane water outlet pool, and the other end of which is connected between the agent backwashing valve and the second time relay.

[0015] Further, the membrane offline cleaning system comprises a membrane offline cleaning pool, a backflow pump, a backflow flow meter and a backflow valve arranged in sequence along the backflow direction of the cleaning waste liquid, the membrane offline cleaning pool being used for offline cleaning of the catalytic membrane assembly, and the cleaned cleaning waste liquid in the membrane offline cleaning pool being arranged to backflow to the membrane reaction pool through the backflow pump, the backflow flow meter and the backflow valve for treatment.

[0016] The Fenton-like membrane reactor has the following beneficial effects: the Fenton-like membrane reactor comprises a membrane reaction pool, a catalytic membrane assembly, a water inlet system, a membrane filtration system, an air aeration system, an ozone aeration system, an online dosing system, a membrane backwashing system and a membrane offline cleaning system, the catalytic membrane assembly can be effectively cleaned through the cooperation of the air aeration system, the ozone aeration system, the membrane backwashing system and the membrane offline cleaning system, good membrane pollution control is achieved, the Fenton-like membrane reactor can not only save the cost of the agent but also improve the efficiency of the membrane pollution control, the membrane offline cleaning system passes the cleaned liquid into the membrane reaction pool for water treatment after offline cleaning of the catalytic membrane assembly, careful secondary collection and special treatment are not needed, the Fenton-like membrane reactor is green and environmentally friendly, the Fenton-like membrane reactor can realize efficient and environmentally friendly cleaning of the membrane and improve the removal of pollutants in water, especially new pollutants. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The Fenton-like membrane reactor in Example 1 of the utility model has the structure as shown in the schematic view.

[0018] Figure 2 The Fenton-like membrane reactor in Example 2 of the utility model removes ofloxacin in water.

[0019] Figure 3 The Fenton-like membrane reactor in Example 3 of the utility model removes paracetamol in water. DETAILED DESCRIPTION

[0020] The embodiments of the utility model are described in detail as follows. It should be emphasized that the following description is only exemplary and is not intended to limit the scope and application of the utility model, and the embodiments in the application and the features in the embodiments can be combined with each other without conflict.

[0021] The utility model discloses a kind of Fenton-like membrane reactors, it includes membrane reaction pool, catalytic membrane assembly, water inlet system, membrane filtration system, air aeration system, ozone aeration system, on-line dosing system, membrane backwash system and membrane offline cleaning system;The catalytic membrane assembly is located in the membrane reaction pool, for treating water to be handled;The water inlet system is communicated with the membrane reaction pool, for the water to be handled is passed into the membrane reaction pool;The membrane filtration system is connected with the catalytic membrane assembly, for water after being treated by the catalytic membrane assembly is discharged;The air aeration system is communicated with the membrane reaction pool, for air aeration is carried out in the membrane reaction pool, the ozone aeration system is communicated with the membrane reaction pool, for ozone aeration is carried out in the membrane reaction pool;The on-line dosing system is communicated with the membrane reaction pool, for adding oxidant to the membrane reaction pool;The membrane backwash system is connected with the catalytic membrane assembly, for the catalytic membrane assembly is backwashed;The membrane offline cleaning system is used to carry out offline cleaning to the catalytic membrane assembly and pass the liquid after cleaning into the membrane reaction pool.

[0022] In some embodiments, the catalytic membrane assembly is a Fenton-like catalytic membrane assembly, comprising a catalytic membrane, the catalytic membrane comprising a porous ceramic membrane support, a layer of halloysite nanotubes attached to the surface of the porous ceramic membrane support, and a catalyst having Fenton-like catalytic activity, the catalyst being loaded on the surface of the porous ceramic membrane support and within the pores thereof, and also being loaded on the surface of the layer of halloysite nanotubes and within the pores thereof.

[0023] Halloysite, as a natural hollow tubular nanomaterial, has the advantages of natural abundance, low cost, high biocompatibility, strong thermal stability, high specific surface area, and extremely strong hydrophilicity. The catalytic membrane constructed by halloysite nanotubes not only has low preparation cost, but also has higher porosity and higher membrane flux than granular packed ceramic membranes. The multi-walled halloysite has a central nanoscale confinement space (the pore size of the central cavity of the halloysite nanotube is nanoscale) and a multi-walled interlayer angstrom-scale (the spacing between the wall layers of the halloysite nanotube is angstrom-scale) confinement space, which can provide multiple confinement reaction spaces for catalytic reactions, improve the molecular mass transfer efficiency and new pollutant removal rate in the Fenton-like catalytic reaction process, and more stably load the catalyst in the nanoscale confinement space of the halloysite nanotube, thereby improving the catalytic stability of the catalytic membrane. The catalytic membrane in the above preferred embodiment of the utility model has the advantages of extremely strong hydrophilicity, high membrane flux, stronger catalyst stability, and catalyst not easy to fall off, and can be widely applied in various water treatment such as medical wastewater.

[0024] In some embodiments, the thickness of the halloysite nanotube layer is 10-50 μm; the pore size of the central hole of the halloysite nanotube in the halloysite nanotube layer is 10-30 nm, the outer diameter of the tube of the halloysite nanotube is 30-190 nm, and the tube length of the halloysite nanotube is 0.02-30 μm; the spacing between the wall sheet layers of the tube of the halloysite nanotube is

[0025] In some embodiments, the thickness of the porous ceramic membrane support is 1-2 mm, and the pore size of the porous ceramic membrane support is 1-3 μm.

[0026] In some embodiments, the material of the porous ceramic membrane is aluminum oxide; and the material of the catalyst is one of CuMnO, FeMnO, TiMnO, ZnMnO, CuFeMnO, CuZnMnO, CuTiMnO, and TiMnFeO.

[0027] In some embodiments, the membrane reaction tank comprises a membrane tank, a sludge discharge valve at the bottom of the membrane tank, and a water level gauge at the upper part of the membrane tank.

[0028] In some embodiments, the water inlet system comprises a water inlet pump, a water inlet flow meter, and a water inlet valve arranged in sequence along the water inlet direction. The water to be treated passes through the water inlet pump, the water inlet flow meter, and the water inlet valve in sequence and enters the membrane reaction tank.

[0029] In some embodiments, the membrane filtration system comprises a transmembrane pressure gauge, a first time relay, a membrane water outlet pump, a water outlet flow meter, a water outlet valve, and a membrane water outlet tank arranged in sequence along the water outlet direction. The membrane filtration system is used to discharge the water treated by the catalytic membrane assembly into the membrane water outlet tank. Specifically, the water treated by the catalytic membrane assembly passes through the transmembrane pressure gauge, the time relay, the membrane water outlet pump, the water outlet flow meter, the water outlet valve, and the membrane water outlet tank in sequence and enters the membrane water outlet tank.

[0030] In some embodiments, the air aeration system comprises an air pump, an air gas flow meter, an air aeration valve, and an air aeration rod arranged in sequence along the air inlet direction. The air aeration rod is located below the catalytic membrane assembly in the membrane reaction tank. Air passes through the air pump, the air gas flow meter, the air aeration valve, and the air aeration rod in sequence and is aerated in the membrane reaction tank.

[0031] In some embodiments, the ozone aeration system comprises, in sequence along the ozone entering direction, an ozone generator, an ozone concentration monitoring meter, an ozone gas flow meter, an ozone aeration valve, and an ozone aeration rod, the ozone aeration rod being located below the catalytic membrane assembly in the membrane reaction tank, and the ozone generated by the ozone generator being sequentially passed through the ozone concentration monitoring meter, the ozone gas flow meter, the ozone aeration valve, and the ozone aeration rod for ozone aeration in the membrane reaction tank.

[0032] In-situ air aeration and ozone aeration are performed at the bottom of the catalytic membrane assembly, the gas-water ratio can be controlled to be 3:1-8:1, and the in-situ ozone gaseous dosage can be 0.5-10 mg / L, so as to further strengthen the removal of new pollutants in water by Fenton-like reaction, and simultaneously control the membrane pollution.

[0033] In some embodiments, the online dosing system comprises, in sequence along the oxidant adding direction, a dosing tank, a dosing pump, a dosing flow meter, and a dosing valve, for sequentially adding the oxidant in the dosing tank into the membrane reaction tank through the dosing pump, the dosing flow meter, and the dosing valve. The added oxidant includes but is not limited to hydrogen peroxide, ozone, persulfate, ozone / hydrogen peroxide, hydrogen peroxide / persulfate, etc. The oxidant dosage is 0.01-10 mM, but is not limited to this oxidant dosage, and the residual amount of the oxidant in the membrane effluent needs to be within the range required by the local water quality standard. Under the action of aeration, the oxidant is uniformly mixed with the water to be treated to perform oxidation reaction.

[0034] In some embodiments, the membrane backwashing system comprises, in sequence along the adding direction of the backwashing agent, a backwashing agent tank, an agent backwashing valve, a second time relay, a backwashing pump, a backwashing agent flow meter, and an agent backwashing valve, the membrane backwashing system being used for passing the backwashing agent in the backwashing agent tank into the catalytic membrane assembly, specifically, the backwashing agent in the backwashing agent tank is sequentially passed through the agent backwashing valve, the time relay, the backwashing pump, the backwashing agent flow meter, and the agent backwashing valve to be passed into the inside of the catalytic membrane assembly for agent backwashing of the catalytic membrane; the membrane backwashing system further comprises a clean water backwashing valve, one end of the clean water backwashing valve being connected to the membrane effluent tank, and the other end of the clean water backwashing valve being connected between the agent backwashing valve and the second time relay, clean water in the membrane effluent tank being passed into the catalytic membrane assembly via the clean water backwashing valve, the time relay, the backwashing pump, the backwashing agent flow meter, and the agent backwashing valve for clean water backwashing of the catalytic membrane.

[0035] In some embodiments, the membrane off-line cleaning system comprises, in sequence along the direction of backflow of the cleaning waste liquid, a membrane off-line cleaning tank for off-line cleaning of the catalytic membrane assembly, a backflow pump, a backflow flow meter, and a backflow valve, wherein the cleaned cleaning waste liquid in the membrane off-line cleaning tank is backflowed to the membrane reaction tank for treatment through the backflow pump, the backflow flow meter, and the backflow valve.

[0036] The Fenton-like membrane reactor can realize efficient and environmentally friendly cleaning of the membrane, and thus can realize efficient removal of pollutants in water treatment, especially efficient removal of new pollutants in water (the removal rate can be more than 99%). The new pollutants include, but are not limited to, the following common new pollutant species in natural water bodies: ofloxacin, ciprofloxacin, tylosin, paracetamol, salicylic acid, ibuprofen, erythromycin, tetracycline, oxytetracycline, roxithromycin, clarithromycin, azithromycin, etc.

[0037] The specific embodiments of the utility model are further described below.

[0038] Example 1

[0039] A Fenton-like membrane reactor comprises a membrane reaction tank, a catalytic membrane assembly 7 located in the membrane reaction tank, and the following 7 systems combined with the membrane reaction tank: a water inlet system, a membrane filtration system, an air aeration system, an ozone aeration system, an online dosing system, a membrane backwashing system, and a membrane off-line cleaning system.

[0040] The catalytic membrane assembly 7 comprises a catalytic membrane containing a catalyst with Fenton-like catalytic activity. The membrane reaction tank comprises a membrane tank 4, a sludge discharge valve 5 located at the bottom of the membrane tank 4, and a water level meter 6 located at the upper part of the membrane tank 4. The water inlet system comprises a water inlet pump 1, a water inlet flow meter 2, and a water inlet valve 3, and the water to be treated enters the membrane tank 4 in sequence through the water inlet pump 1, the water inlet flow meter 2, and the water inlet valve 3.

[0041] The membrane filtration system is connected with the water outlet at the top of the catalytic membrane assembly 7, and comprises a transmembrane pressure gauge 8, a first time relay 9, a membrane water outlet pump 10, a water outlet flow meter 11, a water outlet valve 12, and a membrane water outlet tank 13, and the water treated by the catalytic membrane assembly 7 enters the membrane water outlet tank 13 in sequence through the transmembrane pressure gauge 8, the first time relay 9, the membrane water outlet pump 10, the water outlet flow meter 11, and the water outlet valve 12.

[0042] The air aeration system comprises an air pump 14, an air gas flow meter 15, an air aeration valve 16 and an air aeration rod 17 located below the catalytic membrane assembly 7 in the membrane tank 4, and air is aerated in the membrane tank 4 in sequence through the air pump 14, the air gas flow meter 15, the air aeration valve 16 and the air aeration rod 17.

[0043] The ozone aeration system comprises an ozone generator 18, an ozone concentration monitoring meter 19, an ozone gas flow meter 20, an ozone aeration valve 21 and an ozone aeration rod 22 located below the catalytic membrane assembly 7 in the membrane tank 4, and ozone generated by the ozone generator 18 is aerated in the membrane tank 4 in sequence through the ozone concentration monitoring meter 19, the ozone gas flow meter 20, the ozone aeration valve 21 and the ozone aeration rod 22.

[0044] The online dosing system comprises a dosing tank 23, a dosing pump 24, a dosing flow meter 25 and a dosing valve 26, and the oxidant in the dosing tank 23 is added into the membrane tank 4 in sequence through the dosing pump 24, the dosing flow meter 25 and the dosing valve 26.

[0045] The membrane backwashing system is connected with a backwashing interface at the bottom of the catalytic membrane assembly 7 (the backwashing interface and the water outlet are at different sides of the catalytic membrane assembly and are in a diagonal position), and comprises a dosing backwashing valve 27, a backwashing dosing flow meter 28, a backwashing pump 29, a second time relay 30, a dosing backwashing valve 31, a backwashing dosing tank 32 and a clean water backwashing valve 33, and the backwashing dosing agent in the backwashing dosing tank 32 is introduced into the catalytic membrane assembly 7 in sequence through the dosing backwashing valve 31, the second time relay 30, the backwashing pump 29, the backwashing dosing flow meter 28 and the dosing backwashing valve 27 to perform dosing backwashing on the catalytic membrane assembly 7. One end of the clean water backwashing valve 31 is connected to the membrane water outlet tank 13, and the other end is connected between the dosing backwashing valve 21 and the second time relay 30, and the clean water in the membrane water outlet tank 13 is introduced into the catalytic membrane assembly 7 through the clean water backwashing valve 21, the second time relay 30, the backwashing pump 29, the backwashing dosing flow meter 28 and the dosing backwashing valve 31 to perform clean water backwashing on the catalytic membrane assembly 7.

[0046] The membrane offline cleaning system comprises a backflow valve 34, a backflow flow meter 35, a backflow pump 36 and a membrane offline cleaning tank 37, and the membrane offline cleaning tank 37 is used for offline cleaning of the catalytic membrane assembly 7, and the cleaned liquid in the membrane offline cleaning tank 37 is introduced into the membrane tank 4 through the backflow pump 36, the backflow flow meter 37 and the backflow valve 34 for treatment.

[0047] In this example, the catalytic membrane module 7 in the membrane tank can be subjected to efficient membrane filtration under the suction of the membrane effluent pump 10, with a membrane flux of 20-120 L / (m 2 ·h), using a suction-stop mode of 9 min suction and 1 min stop; the oxidant is introduced into the membrane tank through an online dosing system simultaneously with the water to be treated through the water inlet system (the dosage of the oxidant is 0.01-10 mM), to start the Fenton-like advanced oxidation reaction of the catalytic membrane module 7, to strengthen the removal of pollutants, especially new pollutants, in the water and to control membrane fouling. The pressure gauge monitors the change in the transmembrane pressure difference during membrane filtration, and the catalytic membrane module 7 is controlled to operate within a transmembrane pressure difference increase of 35-40 kPa.

[0048] In this example, in-situ air aeration and ozone aeration can be performed at the bottom of the catalytic membrane module 7 during membrane filtration, with a gas-water ratio of 3:1-8:1 and an in-situ ozone gaseous dosage of 0.5-10 mg / L, to further strengthen the removal of new pollutants in the water based on the Fenton-like reaction of the catalytic membrane module 7 and to simultaneously strengthen membrane fouling control.

[0049] In this example, the catalytic membrane module 7 is backwashed online every half hour during membrane filtration to control membrane fouling, i.e., every half hour, the catalytic membrane module 1 is backwashed for 1 min using 2 times the membrane flux of the membrane effluent (water in the membrane effluent tank 13) (backwashing is performed during the 1 min stop of the membrane suction filtration cycle); during membrane filtration, if the transmembrane pressure difference of the ceramic membrane increases by 35-40 kPa, the membrane filtration is stopped, the catalytic membrane module 7 is backwashed using 50-1000 mM hydrogen peroxide solution (oxidant solution in the backwashing reagent tank 32) through the online backwashing system; during membrane filtration, if the transmembrane pressure difference recovery rate of the ceramic membrane after online dosing cleaning is less than 30% and the transmembrane pressure difference exceeds the set threshold value (35-40 kPa), the membrane filtration is stopped, the catalytic membrane module 7 is removed from the membrane tank to the membrane offline cleaning tank of the offline cleaning system, and the catalytic membrane module 7 is cleaned by offline soaking with 1000 mM hydrogen peroxide solution until the transmembrane pressure difference of the catalytic membrane is recovered by more than 99%. The hydrogen peroxide offline cleaning solution of the catalytic membrane can be returned to the membrane tank after the hydrogen peroxide and the eluted membrane pollutants are completely reacted, and then discharged through the membrane filtration system, thereby realizing a green and environmentally friendly cleaning method of the catalytic membrane without secondary treatment of the membrane cleaning solution.

[0050] The off-line cleaning is specifically that the cleaning solution in the membrane off-line cleaning tank 37 is hydrogen peroxide solution, and the hydrogen peroxide off-line soaking cleaning method can realize efficient cleaning of the contaminated catalytic membrane assembly after long-term operation of the Fenton-like membrane reactor. The hydrogen peroxide membrane cleaning solution does not need secondary treatment, but only needs to be simply refluxed to the membrane tank. Specifically, the Fenton-like membrane reactor provided by the utility model is used for continuous treatment of actual medical wastewater, and when the transmembrane pressure difference of the catalytic membrane assembly 7 increases by 35 kPa, the contaminated catalytic membrane assembly 7 is removed from the membrane tank and placed in the membrane off-line cleaning tank. The catalytic membrane assembly 7 can be cleaned by soaking in 1000 mM hydrogen peroxide solution for 6 hours, so that the transmembrane pressure difference of the catalytic membrane assembly 7 is restored by more than 99.5%, and efficient membrane cleaning effect is realized. Only a certain concentration of hydrogen peroxide and oxidized organic matter eluted from the catalytic membrane is left in the hydrogen peroxide membrane cleaning solution, and there is no toxic and harmful reaction byproduct. The residual concentration of hydrogen peroxide in the membrane cleaning solution gradually decreases with the extension of the reaction time, and when the concentration of hydrogen peroxide tends to be stable, the membrane cleaning solution can be refluxed to the membrane reactor without additional secondary complex treatment.

[0051] Example 1 can realize efficient and environmentally friendly cleaning of the membrane, and at the same time improve the removal of pollutants in water, especially new pollutants.

[0052] Example 2

[0053] The Fenton-like membrane reactor in Example 2 is different from that in Example 1 in that the catalytic membrane comprises a porous ceramic membrane support, a halloysite nanotube layer and a catalyst having Fenton-like catalytic activity, the halloysite nanotube layer is attached to the surface of the porous ceramic membrane support, the catalyst is loaded on the surface and pores of the porous ceramic membrane support, and the catalyst is also loaded on the surface and pores of the halloysite nanotube layer. The thickness of the halloysite nanotube layer is 10-50 μm; the pore diameter of the central hole of the halloysite nanotube in the halloysite nanotube layer is 10-30 nm, the outer diameter of the halloysite nanotube is 30-190 nm, and the length of the halloysite nanotube is 0.02-30 μm; the spacing between the halloysite nanotube wall lamellas is 0.5-2 nm. The thickness of the porous ceramic membrane support is 1-2 mm, and the pore diameter of the porous ceramic membrane support is 1-3 μm. The material of the porous ceramic membrane support is aluminum oxide; the material of the catalyst is CuFeMnO, and the loading amount of the catalyst in the catalytic membrane is 0.5 wt%-10 wt%, and the particle size of the catalyst is 5-20 nm.

[0054] The Fenton-like membrane reactor provided in the example is used for water treatment, as shown in Figure 2 The constant flux dead-end filtration method is used, and the transmembrane pressure difference is controlled to be 0.1-0.3 kPa. 2A continuous membrane filtration experiment was conducted at a membrane flux of ·h) to treat water containing 1 mg / L ofloxacin. When the dosage of hydrogen peroxide added through the online dosing system was 5 mM, the removal rate of ofloxacin in the membrane effluent exceeded 99%. After 24 hours of continuous membrane filtration, the removal rate of ofloxacin in the membrane effluent was still over 99%.

[0055] Example 3

[0056] Water treatment is carried out using the Fenton-like membrane reactor provided in Example 2, such as... Figure 3 As shown, a constant flux dead-end filtration method is used, with a flow rate of 40 L / (m³). 2 A continuous membrane filtration experiment was conducted at a membrane flux of ·h) to treat water containing 1.5 mg / L acetaminophen. With a hydrogen peroxide dosage of 5 mM, over 99.9% of acetaminophen was removed from the effluent. Even after 48 hours of continuous membrane filtration, the removal rate of acetaminophen in the effluent remained above 99.9%.

[0057] The above description, in conjunction with specific / preferred embodiments, provides a further detailed explanation of the present invention and should not be construed as limiting the specific implementation of the present invention to these descriptions. For those skilled in the art, various substitutions or modifications can be made to these described embodiments without departing from the concept of the present invention, and all such substitutions or modifications should be considered within the protection scope of the present invention. In the description of this specification, the reference to terms such as "an embodiment," "some embodiments," "preferred embodiment," "example," "specific example," or "some examples," etc., indicates that the specific features, structures, materials, or characteristics described in connection with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the described specific features, structures, materials, or characteristics can be combined in a suitable manner in any one or more embodiments or examples. Without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification and the features of different embodiments or examples. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations may be made herein without departing from the scope of protection of the patent application.

Claims

1. A Fenton-like membrane reactor, characterized in that, The Fenton-like membrane reactor comprises a membrane reaction tank, a catalytic membrane assembly, a water inlet system, a membrane filtration system, an air aeration system, an ozone aeration system, an online dosing system, a membrane backwashing system and a membrane offline cleaning system.

2. The Fenton-like membrane reactor of claim 1, wherein: The catalytic membrane assembly is located in the membrane reaction tank and used for treating the water to be treated.

3. The Fenton-like membrane reactor of claim 2, wherein: The thickness of the halloysite nanotube layer is 10-50 μm; the pore size of the central hole of the halloysite nanotube in the halloysite nanotube layer is 10-30 nm, the outer diameter of the tube of the halloysite nanotube is 30-190 nm, and the tube length of the halloysite nanotube is 0.02-30 μm; the spacing between the wall sheet layers of the tube of the halloysite nanotube is 4. The Fenton-like membrane reactor of claim 2, wherein: The thickness of the porous ceramic membrane support is 1-2 mm, and the pore size of the porous ceramic membrane support is 1-3 μm.

5. The Fenton-like membrane reactor of claim 2, wherein: The material of the porous ceramic membrane support is aluminum oxide, and the catalyst is one of CuMnO, FeMnO, TiMnO, ZnMnO, CuFeMnO, CuZnMnO, CuTiMnO and TiMnFeO.

6. The Fenton-like membrane reactor of claim 1, wherein: The membrane reaction tank comprises a membrane tank, a sludge discharge valve and a water level gauge, the sludge discharge valve is located at the bottom of the membrane tank, and the water level gauge is located at the upper part of the membrane tank; the water inlet system comprises a water inlet pump, a water inlet flowmeter and a water inlet valve which are sequentially arranged along the water inlet direction; the membrane filtration system comprises a transmembrane pressure gauge, a first time relay, a membrane outlet pump, a water outlet flowmeter, a water outlet valve and a membrane outlet tank which are sequentially arranged along the water outlet direction, and is used for discharging the water treated by the catalytic membrane assembly into the membrane outlet tank.

7. The Fenton-like membrane reactor of claim 1, wherein: The air aeration system comprises an air pump, an air gas flowmeter, an air aeration valve and an air aeration rod which are sequentially arranged along the air entering direction, and the air aeration rod is located below the catalytic membrane assembly in the membrane reaction tank; the ozone aeration system comprises an ozone generator, an ozone concentration monitor, an ozone gas flowmeter, an ozone aeration valve and an ozone aeration rod which are sequentially arranged along the ozone entering direction, and the ozone aeration rod is located below the catalytic membrane assembly in the membrane reaction tank.

8. The Fenton-like membrane reactor of claim 1, wherein: The online dosing system comprises a medicament tank, a dosing pump, a dosing flow meter and a dosing valve arranged in sequence along the direction of the oxidant addition, and is used for adding the oxidant in the medicament tank into the membrane reaction tank through the dosing pump, the dosing flow meter and the dosing valve in sequence.

9. The Fenton-like membrane reactor of claim 6, wherein: The membrane backwashing system comprises a backwashing medicament tank, a medicament backwashing valve, a second time relay, a backwashing pump, a backwashing flow meter and a medicament backwashing valve arranged in sequence along the direction of the backwashing medicament addition, and is used for passing the backwashing medicament in the backwashing medicament tank into the catalytic membrane assembly. The membrane backwashing system further comprises a clean water backwashing valve, one end of which is connected to the membrane water outlet tank, and the other end of which is connected between the medicament backwashing valve and the second time relay.

10. The Fenton-like membrane reactor of claim 1, wherein: The membrane offline cleaning system comprises a membrane offline cleaning tank, a backflow pump, a backflow flow meter and a backflow valve arranged in sequence along the direction of the cleaning waste liquid backflow, the membrane offline cleaning tank is used for offline cleaning of the catalytic membrane assembly, and the cleaned cleaning waste liquid in the membrane offline cleaning tank is arranged to backflow into the membrane reaction tank through the backflow pump, the backflow flow meter and the backflow valve for treatment.

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