Membrane catalytic ozone oxidation reactor

Abstract

The present invention relates to the technical field of wastewater treatment, and specifically discloses a membrane catalytic ozone oxidation reactor, comprising a reactor body (100), wherein a wastewater addition component (200) and a catalyst addition pipe (300) are respectively provided on the upper side of the reactor body (100), and a catalyst suspension is introduced into the catalyst addition pipe (300); a micro-nano bubble generator (400) is provided at the bottom of the reactor body (100), and the micro-nano bubble generator (400) is connected to an ozone source; and at least one membrane catalytic component (600) is connected in a closed loop on the reactor body (100). The present invention has the characteristics of sufficient contact reaction between hydroxyl radicals and organic matter and high utilization rate of ozone catalytic oxidation.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, in particular to a membrane catalytic ozone oxidation reactor. Background Art

[0002] Ozone catalytic oxidation technology is a highly efficient advanced wastewater treatment technology and has been a hot topic in wastewater treatment in recent years. Compared to ozone as a single oxidant, the hydroxyl radicals (·OH) formed by ozone in the presence of a catalyst react more quickly with organic matter and are more oxidizing, capable of oxidizing almost all organic matter. The catalyst can catalyze ozone to directly oxidize organic matter in water into CO2 and H2O, or oxidize and decompose large organic molecules into small molecules, making them more susceptible to degradation. Compared to other advanced oxidation technologies, the ozone catalytic oxidation process has the advantages of not requiring the addition of any reagents, resulting in no secondary pollution, a short process flow, and ease of operation.

[0003] The ozone reactor is the core of the ozone catalytic oxidation process and directly affects its efficiency. Patent publication number "CN105000627A" discloses an ozone oxidation reactor comprising a tank body and a water inlet pipe connected to the tank body. The water inlet pipe is provided with a water inlet and an ozone inlet, the ozone inlet is supplied with ozone, and a hydraulic cavitation device is installed in the water inlet pipe to cause hydrodynamic cavitation between water and ozone. An ultrasonic oscillator is installed in the tank body to cause ultrasonic cavitation between water and ozone, and the ultrasonic oscillator is connected to an ultrasonic generator. The cavity of the tank body is filled with a catalyst that excites ozone to produce hydroxyl radicals. By generating hydrodynamic cavitation and ultrasonic cavitation, the ozone oxidation effect is enhanced. The patent document with publication number "CN112811572A" discloses an ozone oxidation reactor and sewage treatment system, which are designed using the principle of impinging flow. A sewage input chamber, a reaction chamber and a gas input chamber are formed inside the main body. The reaction chamber is located between the sewage input chamber and the gas input chamber. A blocking structure is provided between the sewage input chamber and the reaction chamber, and between the reaction chamber and the gas input chamber. Each blocking structure is provided with a micron-sized hole. The sewage and ozone are first passed through the micron-sized holes at a higher rate to form micron-sized liquid flow and air flow, and the ozone and sewage are fully contacted through impact, thereby improving the oxidation effect. Patent document with publication number "CN112850876A" discloses a three-phase reactor for ozone catalytic oxidation, including a reactor body and an internal circulation component arranged therein; the reactor body is provided with a distribution plate, a catalyst support plate and a gas-liquid separator in sequence from bottom to top; the internal circulation component includes a guide plate and a reflux pipe; the guide plate is funnel-shaped, located above the catalyst support plate and below the gas-liquid separator, with the middle portion connected to the top of the reflux pipe, and the bottom of the reflux pipe extends below the distribution plate to ensure that the reflux liquid can enter the mixing zone A along the reflux pipe; the interior of the reactor body is divided into a mixing zone A, a reaction zone B and a separation zone C in sequence along the water inlet direction by the distribution plate, the guide plate and the gas-liquid separator; the catalyst support plates are arranged in a group in sequence in the reaction zone B; the ozone catalytic reactor, which integrates a gas-liquid mixing zone, a catalytic reaction zone and a gas-liquid separation zone, has the advantages of complete functions, less supporting equipment and a small footprint.Patent document with publication number "CN110002576A" discloses an ozone catalytic oxidation reactor and its sewage treatment method. The wastewater to be treated enters a microbubble generator and is mixed with ozone generated by the ozone generator. An ultraviolet lamp tube, an aeration plate, a catalyst layer and a water distribution device are arranged in sequence from top to bottom in the reactor body. A second ozone exhaust pipe and a first ozone exhaust pipe are connected between the ozone generator, the aeration plate and the microbubble generator respectively. The microbubble generator is connected to the water distribution device through a water inlet pipe. The water distribution device is also connected to a backwash water inlet pipe. The upper part of the reactor body is connected to a drain pipe with a drain valve and a backwash drain valve respectively. The top of the reactor body is connected to an exhaust gas exhaust pipe with an exhaust destructor. The ozone catalytic oxidation reactor has a reasonable structural layout, so that ozone is dispersed in the form of tiny bubbles, fully contacts the wastewater, and is added at multiple points. Under the catalytic action of the catalyst and the synergistic action of ultraviolet light, the ozone utilization rate and reaction efficiency are improved. The ozone catalytic oxidation reactor introduces ultraviolet light to cooperate with ozone catalytic oxidation, which can effectively improve ozone oxidation efficiency. The above disclosed reactors are mainly aimed at improving the gas-liquid mixing effect and the ozone conversion rate, but there is still the problem that the generated hydroxyl radicals are difficult to react with organic matter and are easily quenched.

[0004] Therefore, existing ozone catalytic oxidation treatment devices for wastewater have problems such as insufficient contact reaction between hydroxyl radicals and organic matter and low ozone catalytic oxidation utilization rate. Summary of the Invention

[0005] In order to solve the above technical problems existing in the existing ozone catalytic oxidation treatment devices for wastewater, the present invention provides a membrane catalytic ozone oxidation reactor, which has the characteristics of sufficient contact reaction between hydroxyl radicals and organic matter and high ozone catalytic oxidation utilization rate.

[0006] The technical solution of the present invention: a membrane catalytic ozone oxidation reactor comprises a reactor body, wherein a wastewater addition component and a catalyst addition pipe are respectively provided on the upper side of the reactor body, and a catalyst suspension is introduced into the catalyst addition pipe; a micro-nano bubble generator is provided at the bottom inner side of the reactor body, and the micro-nano bubble generator is connected to an ozone source; and at least one membrane catalytic component is connected in a closed loop on the reactor body. The reactor body in the present invention provides a stable reaction environment for the full reaction between wastewater, catalyst suspension and ozone; the wastewater addition component is used to add wastewater to be treated; the catalyst addition pipe is used to add catalyst suspension; the micro-nano bubble generator is used to fully mix the wastewater to be treated with ozone; the catalyst suspension and ozone in the reactor body fully react with the wastewater, so that the organic matter in the wastewater is reduced from a high level to a lower level, and the ozone catalytic oxidation has a higher utilization rate; the membrane catalytic component in the present invention provides another reaction site for the treatment of wastewater, and the catalytic action of the second catalyst in the membrane catalytic component Hydroxyl radicals are generated and fully contacted with organic matter in the membrane pores, reducing the wastewater entering the reactor body after treatment from a lower level to an even lower level, thereby improving the utilization rate of hydroxyl radicals; the wastewater to be treated in the present invention enters from the wastewater adding component on the upper part of the reactor body, and is countercurrently mixed with the ozone from the micro-nano bubble generator, and is sucked by the circulating pump in the membrane catalytic component. The wastewater to be treated flows from top to bottom, and a part of it finally enters the membrane pores and flows out as produced water, and the other part flows back to the reactor body to continue the reaction, and promotes turbulence of the fluid in the reactor, thereby improving the adequacy of the mixing reaction.

[0007] Preferably, the wastewater addition assembly includes a wastewater pipe, which is connected to the upper portion of the reactor body and has a water distribution hood at one end of the wastewater pipe located within the reactor body. The wastewater pipe is used to feed wastewater, and the water distribution hood is used to evenly distribute the fed wastewater into the reactor body.

[0008] Preferably, a guide funnel is provided at the upper portion of the reactor body, and the guide funnel is located below the water distribution hood. The guide funnel is used to better guide the wastewater evenly distributed by the water distribution hood to a more appropriate position in the reactor body.

[0009] Preferably, one end of the catalyst addition tube located within the reactor body is connected to a guide funnel. The catalyst addition tube is connected to the guide funnel to deliver the catalyst suspension to the evenly distributed wastewater. The guide funnel guides the catalyst suspension and the evenly distributed wastewater to a suitable location within the reactor body, allowing them to more fully mix with the ozone and initiate a catalytic oxidation reaction.

[0010] Preferably, the catalyst suspension is introduced into the catalyst addition pipe via a metering pump, which can accurately control the amount of catalyst suspension added into the reactor body, thereby ensuring that the entire catalytic oxidation reaction proceeds more fully.

[0011] Preferably, the catalyst suspension is made from a first catalyst, nanocarbon, and water. Nanocarbon has a large specific surface area, and the first catalyst is loaded onto the nanocarbon, which can adsorb organic matter in the wastewater onto the catalyst surface for reaction. Ozone in the water is converted into hydroxyl radicals by the nanocarbon surface catalyst, which can react rapidly and efficiently with the adsorbed organic matter and also with organic matter in the water. The catalyst suspension can also be directly and evenly distributed within the reactor body and mixed with the wastewater after distribution, thereby expanding the scope of the catalytic reaction and making the entire reactor body a reaction zone.

[0012] Preferably, the first catalyst is at least one of magnesium oxide, calcium oxide, manganese dioxide, aluminum oxide, zinc oxide, iron oxide, or titanium dioxide. The first catalyst is preferably capable of better adsorbing organic matter in the wastewater onto the catalyst surface for reaction, and ozone in the water is better converted into hydroxyl radicals under the action of the nanocarbon surface catalyst.

[0013] Preferably, the loading amount of the first catalyst on the nano-carbon is 0.5% to 20% of the mass of the nano-carbon. More preferably, the loading amount of the first catalyst on the nano-carbon is 1% to 18% of the mass of the nano-carbon. More preferably, the loading amount of the first catalyst on the nano-carbon is 5% to 15% of the mass of the nano-carbon. More preferably, the loading amount of the first catalyst on the nano-carbon is 8% to 12% of the mass of the nano-carbon. More preferably, the loading amount of the first catalyst on the nano-carbon is 10% of the mass of the nano-carbon. The loading amount of the first catalyst is limited so as to ensure that organic matter in the wastewater is fully adsorbed onto the catalyst surface for reaction without being excessive.

[0014] Preferably, the micro-nano bubble generator includes an ozone tube, which is connected to the bottom of the reactor body. The ozone tube is provided with a generator body at one end of the ozone tube located within the reactor body, and an ozone source is connected to the other end of the ozone tube located outside the reactor body. The ozone tube is used to guide ozone from an external ozone source into the reactor body; ozone enters the reactor body from the bottom of the reactor body through the generator body, and a large number of micro-nano bubbles are generated under the action of the generator body. On the one hand, this increases the solubility of ozone in the wastewater, and on the other hand, it slows the rising rate of the ozone gas, thereby improving the utilization rate of ozone and increasing the wastewater treatment capacity of the reactor body.

[0015] Preferably, the membrane catalytic assembly includes a cylindrical shell, the lower end of the cylindrical shell is connected to a drain pipe, and the end of the drain pipe away from the cylindrical shell is connected to the lower part of the reactor body; a circulation pump is provided on the drain pipe; the upper end of the cylindrical shell is connected to a water inlet pipe, and the end of the water inlet pipe away from the cylindrical shell is connected to the upper part of the reactor body; a catalytic membrane tube is provided inside the cylindrical shell, and the space between the outer wall of the catalytic membrane tube and the inner wall of the cylindrical shell forms an annular cavity; the membrane pores of the catalytic membrane tube are loaded with a second catalyst. The cylindrical shell provides installation space for the catalytic membrane tube, through a stable second reaction place; the drain pipe is used to guide the wastewater after the initial reaction of the reactor body into the catalytic membrane tube for re-reaction treatment; the circulating pump provides power for the wastewater after the initial reaction of the reactor body to enter the catalytic membrane tube for re-reaction; the water inlet pipe is used to guide the flowing water in the membrane tube of the catalytic membrane tube again into the reactor body for further treatment; the catalytic membrane tube can well carry out good re-reaction treatment on the incoming water in the reactor body; the circulating water enters through the membrane tube of the catalytic membrane tube, part of the circulating water flows out from the membrane tube, and part flows out from the membrane pores. The water flowing out of the membrane pores is oxidation water; when the wastewater passes through the membrane pores, ozone, the second catalyst and organic matter fully react in the narrow membrane pores, realizing the efficient removal of organic matter, and the organic matter in the wastewater can be removed to a lower level.

[0016] Preferably, the membrane pores have a pore diameter of 10 nm to 200 nm. More preferably, the membrane pores have a pore diameter of 30 nm to 180 nm. More preferably, the membrane pores have a pore diameter of 50 nm to 150 nm. More preferably, the membrane pores have a pore diameter of 70 nm to 130 nm. More preferably, the membrane pores have a pore diameter of 90 nm to 120 nm. More preferably, the membrane pores have a pore diameter of 100 nm to 110 nm. The defined membrane pore diameter enables ozone, the second catalyst, and the organic matter to react more fully within the narrow membrane pores.

[0017] Preferably, the second catalyst is a metal oxide catalyst, which can be stably loaded in the membrane pores and can better initiate a sufficient catalytic oxidation reaction with ozone and organic matter in the narrow membrane pores.

[0018] Preferably, the second catalyst is composed of at least two of CuO, CeO2, NiFe2O4, Co2O3 and MnO2. The limited second catalyst type can better react with ozone and organic matter to produce a sufficient catalytic oxidation reaction in the narrow membrane pores.

[0019] Preferably, the particle size of the metal oxide catalyst is less than 18,000 mesh. The limited particle size of the metal oxide catalyst can be more stably loaded in the membrane pores, and a more complete catalytic oxidation reaction occurs with ozone and organic matter in the narrow membrane pores.

[0020] Preferably, outer clamping rings are provided at the top and bottom of the cylindrical shell, and the outer clamping rings are sleeved on the catalytic membrane tube to ensure the stability of the catalytic membrane tube in the cylindrical shell.

[0021] Preferably, the top and bottom of the cylindrical shell are both provided with conical hollow covers, and a connecting rod is provided between the two conical hollow covers. The connecting rod is located inside the catalytic membrane tube, and a plurality of inverted cones are provided on the connecting rod along the length direction, and the diameter of the inverted cones gradually increases from bottom to top. On the one hand, the conical hollow cover can help limit the stability of the catalytic membrane tube working inside the cylindrical shell, and on the other hand, it can allow the wastewater in the membrane tube to smoothly enter the water inlet pipe from the hollow part; the connecting rod provides a stable installation position for the plurality of inverted cones, ensuring the stability of the operation of the plurality of inverted cones; the plurality of inverted cones are used to better guide the incoming water after the first treatment of the reactor body directly to the catalytic membrane tube for secondary treatment; the inverted cone structure with a diameter gradually increasing from bottom to top is adapted to the direction of water flow inside the catalytic membrane tube, and can better guide the water flow inside the catalytic membrane tube.

[0022] Preferably, the upper portion of the cylindrical shell is connected to a drainage joint, which can discharge the oxidized water that meets the standards after secondary treatment through the catalytic membrane tube.

[0023] Preferably, a tail gas pipe is connected to the top of the reactor body, and a tail gas destroyer is connected to the end of the tail gas pipe away from the reactor body. The tail gas pipe is used to discharge ozone tail gas that has not participated in the reaction; the tail gas destroyer is used to heat up and quickly decompose the ozone into oxygen for discharge into the atmosphere.

[0024] Preferably, the reactor body is provided with connectors at both the top and bottom. The connector at the top of the reactor body is connected to the end of the water inlet pipe away from the cylindrical shell. The connector at the bottom of the reactor body is connected to the end of the drain pipe away from the cylindrical shell. The generator body is located below the connector at the bottom of the reactor body. The connectors at the top and bottom of the reactor body are used to connect to the water inlet pipe and drain pipe of the membrane catalytic assembly, forming a circulation system between the membrane catalytic assembly and the reactor body. The generator body is located below the connector at the bottom of the reactor body, so that ozone at the generator body can better enter the catalytic membrane tube under the action of the circulation pump.

[0025] Preferably, the inner wall of the reactor body is provided with a plurality of obstructions extending from top to bottom. The obstructions can change the fluid flow at the inner wall of the reactor body from laminar flow to turbulent flow, thereby enhancing the mixing effect. The upward flow generated by the micro-nano bubble generator, the suction and reflux of the circulating pump, and the obstructions of the reactor body work together to fully mix the fluid within the reactor body, slow the rise of ozone, and enhance the ozone catalytic oxidation effect.

[0026] Preferably, the blocking portion is a blocking block or a blocking ring, which is easy to prepare and can effectively change the fluid state at the inner wall of the reactor body from laminar flow to turbulent flow.

[0027] Preferably, the bottom of the reactor body is connected to a sludge discharge assembly, which is used to discharge insoluble matter that may be produced during the organic matter reaction from the reactor body.

[0028] Preferably, the sludge discharge assembly includes a sludge discharge pipe, which is connected to the bottom of the reactor body and has multiple filter holes formed on the pipe, each of which is located outside the reactor body. The sludge discharge pipe is used to discharge insoluble matter from the reactor body; the multiple filter holes are used to compress the insoluble matter and squeeze out water when the insoluble matter is discharged, ensuring that the insoluble sludge discharged from the sludge discharge pipe is relatively low in water.

[0029] Preferably, the mud discharge pipe is provided with two annular flanges, which are located outside the reactor body and between the multiple filter holes. A motor is provided at one end of the mud discharge pipe away from the reactor body. A rotating shaft is provided at the driving end of the motor, which extends into the mud discharge pipe. The rotating shaft is rotatably arranged relative to the mud discharge pipe. A spiral blade is provided on the rotating shaft, and a mud outlet is provided near the motor. The two annular flanges define the location of the multiple filter holes on the mud discharge pipe, ensuring a better dehydration effect on insoluble matter. The motor provides power for the discharge of insoluble matter from the reactor body. The rotating shaft drives the spiral blade to rotate, smoothly transporting the insoluble sludge in the reactor body to the mud outlet of the mud discharge pipe.

[0030] Preferably, the pitch of the spiral blade 1 gradually decreases as it moves away from the reactor body. The specific pitch of the spiral blade 1 is set to ensure that the insoluble sludge in the reactor body is smoothly transported and discharged to the mud outlet of the mud discharge pipe, while being able to effectively squeeze and dehydrate the insoluble sludge therein.

[0031] Preferably, the sludge discharge assembly is provided with a filter assembly, which can effectively filter the water discharged from the filter holes to prevent insoluble sludge from being discharged from the filter holes.

[0032] Preferably, the filtration assembly includes a water storage tank, which is mounted on the mud discharge pipe, and the multiple filter holes are located in the water storage tank; a tank cover is hingedly connected to the top of the water storage tank, and the tank cover is provided with two support seats, and the tank cover is provided with two avoidance grooves, and two filter rollers are provided between the two support seats, and the two filter rollers are provided with filter nets, and the filter nets pass through the two avoidance grooves and fit the bottom of the mud discharge pipe. The water storage tank is used to uniformly store the water filtered at the filter holes; the tank cover hinged on the top of the water storage tank can prevent external debris from falling into the water storage tank; the two support seats are used to support the filter rollers and other components; the two avoidance grooves are used for the filter net to pass through after being wound; the two filter rollers are used to connect the two ends of the filter net, and the degree of closeness of the filter net relative to the mud discharge pipe can be adjusted; the filter net can effectively filter the squeezed water passing through the filter holes.

[0033] Preferably, a return pipe is provided at the bottom of the water storage tank, with one end of the return pipe, distal from the water storage tank, connected to the upper portion of the reactor body. A water pump is provided on the return pipe. The return pipe is used to direct filtered water from the water storage tank back into the reactor body for further processing and reuse; the water pump provides power to transport the filtered water from the water storage tank into the reactor body.

[0034] Preferably, the two filter rollers are each provided with at least one ridge on one end away from the reactor body; the support base away from the reactor body has two mounting holes, into which sleeves 1 and 2 are rotatably inserted, respectively; the inner walls of sleeves 1 and 2 are each provided with at least one slot, which mates with the corresponding ridge. The combination of the ridge and slot allows the two filter rollers to be well restrained within sleeves 1 and 2 as needed; the two mounting holes provide a movable mounting position for sleeves 1 and 2 on the support base; and sleeves 1 and 2 can well restrain the two filter rollers on the support base as needed.

[0035] Preferably, a chute is provided on the support seat away from the reactor body, and a slider is provided on the sleeve. The slider slides within the chute. A spring is provided between the slider and the inner wall of the chute, with both ends of the spring connected to the slider and the inner wall of the chute, respectively. The chute effectively limits the horizontal movement of the slider. The combination of the slider, chute, and spring allows the filter roller of the sleeve to be flexibly adjusted left and right as needed, ensuring that the filter fits snugly within the sludge discharge pipe and ensuring smooth filtration.

[0036] Preferably, a support seat away from the reactor body is provided with an arcuate groove, within which a second slider slides. A second spring is provided between the second slider and the inner wall of the arcuate groove, with the two ends of the second spring respectively connected to the second slider and the inner wall of the arcuate groove. A pivot arm is provided on the second sleeve, and the second slider abuts against the pivot arm. The arcuate groove provides a guide for the movement of the second slider. The arcuate groove, the second slider, the second spring, and the pivot arm cooperate as a whole, allowing the filter screen to fit snugly within the sludge discharge pipe, ensuring smooth filtration.

[0037] Preferably, a pushing assembly is provided at the bottom of the reactor body, corresponding to the sludge discharge assembly. The pushing assembly is used to efficiently deliver the insoluble sludge in the reactor body to the spiral blades of the sludge discharge pipe, ensuring that the insoluble sludge in the reactor body can be smoothly discharged from the sludge discharge pipe; wherein the rotating shaft and the spiral blades extend into the reactor body together.

[0038] Preferably, the pushing assembly includes a rotating tube, which is rotatably arranged at the bottom of the reactor body; the rotating tube is provided with a second spiral blade, which is located in the reactor body; the rotating tube is provided with a first gear, which is located outside the reactor body; the reactor body is provided with a second motor, and the driving end of the second motor is provided with a second gear, which is engaged with the first gear; the end of the sludge discharge pipe located in the reactor body is opposite to the second spiral blade. The rotating tube drives the second spiral blade to rotate together, and smoothly delivers the insoluble sludge in the reactor body to the inlet of the sludge discharge pipe; the first gear is used to receive the driving force to rotate the rotating tube; the second motor provides a stable driving force for the rotation of the rotating tube; the second gear is used to stably transmit the driving force of the second motor to the first gear.

[0039] Preferably, the rotating tube is sleeved on the ozone tube.

[0040] The present invention has the following beneficial effects:

[0041] (1) The reactor body provides a stable reaction environment for the full reaction between wastewater, catalyst suspension and ozone; the wastewater addition component is used to add wastewater to be treated; the catalyst addition tube is used to add catalyst suspension; the micro-nano bubble generator is used to fully mix the wastewater to be treated with ozone; the catalyst suspension and ozone in the reactor body fully react with the wastewater, reducing the organic matter in the wastewater from a high level to a low level, and the ozone catalytic oxidation has a high utilization rate;

[0042] (2) The membrane catalytic component provides another reaction site for wastewater treatment. Hydroxyl radicals are generated under the catalytic action of the second catalyst in the membrane catalytic component and are fully in contact with organic matter in the membrane pores, reducing the wastewater entering the reactor body from a low level to an even lower level, thereby improving the utilization rate of hydroxyl radicals.

[0043] (3) The wastewater to be treated enters from the wastewater addition component on the upper part of the reactor body, is counter-currently mixed with the ozone from the micro-nano bubble generator, and is sucked by the circulation pump in the membrane catalytic component. The wastewater to be treated flows from top to bottom, and a part of it eventually enters the membrane pores and flows out as produced water, while the other part flows back to the reactor body to continue the reaction, and promotes turbulence of the fluid in the reactor, thereby improving the adequacy of the mixing reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 is a first structural diagram of the present invention;

[0045] Figure 2 This is a flow diagram of treated water in the catalytic membrane tube of the present invention;

[0046] Figure 3 It is a three-dimensional structural diagram of the present invention;

[0047] Figure 4 It is a three-dimensional cutaway view of the reactor body of the present invention;

[0048] Figure 5 It is a three-dimensional assembly diagram of the wastewater addition component, catalyst addition pipe and guide funnel of the present invention;

[0049] Figure 6 It is a three-dimensional cutaway view of the membrane catalytic component of the present invention;

[0050] Figure 7 This is a structural expansion diagram of the membrane catalyst assembly of the present invention;

[0051] Figure 8 This is a structural expansion diagram of the micro-nano bubble generator and the pushing component of the present invention;

[0052] Figure 9 This is a structural expansion diagram of the sludge discharge component and the filter component of the present invention;

[0053] Figure 10 It is a structural expansion diagram of the water storage tank of the present invention;

[0054] Figure 11 It is a structural expansion diagram of the sleeve 1, sleeve 2 and filter roller of the present invention.

[0055] The markings in the accompanying drawings are: 100-reactor body; 200-wastewater addition component; 300-catalyst addition pipe; 400-micro-nano bubble generator; 500-exhaust pipe; 600-membrane catalytic component; 700-sludge discharge component; 800-filtration component; 900-pushing component; 101-connector; 102-guide funnel; 103-blocking part; 201-wastewater pipe; 202-water distribution cover; 401-ozone tube; 402-generator body; 601-cylindrical shell; 602-drain pipe; 603-circulation pump; 604-water inlet pipe; 605-catalytic membrane tube; 606-drainage connector; 607-outer clamping ring; 608-conical hollow cover; 609-connecting rod; 610-inverted cone; 611-membrane hole ;612-second catalyst;701-mud discharge pipe;702-annular flange;703-filter hole;704-rotating shaft;705-threaded blade one;706-motor one;801-water storage tank;802-tank cover;803-support seat;804-avoidance groove;805-filter screen roller;806-return pipe;807-water pump;808-convex strip;809-mounting hole;810-sleeve one;811-slider one;812-slide groove;813-spring one;814-sleeve two;815-rotating arm;816-arc groove;817-slider two;818-spring two;819-slot;901-rotating tube;902-spiral blade two;903-gear one;904-gear two;905-motor two. DETAILED DESCRIPTION

[0056] The present invention will be further described below with reference to the accompanying drawings and examples, but they are not intended to limit the present invention.

[0057] like Figure 1 The membrane catalytic ozone oxidation reactor shown includes Figure 3 The reactor body 100 shown in FIG. 1 has a wastewater addition assembly 200 and a catalyst addition pipe 300 respectively provided on the upper side of the reactor body 100. The catalyst suspension is introduced into the catalyst addition pipe 300. The bottom of the reactor body 100 is provided with a wastewater addition assembly 200 and a catalyst addition pipe 300 respectively. Figure 4 The micro-nano bubble generator 400 shown is connected to an ozone source; at least one membrane catalytic component 600 is closed-loop connected to the reactor body 100 .

[0058] The wastewater adding assembly 200 includes a wastewater pipe 201, which is connected to the upper part of the reactor body 100. One end of the wastewater pipe 201 located in the reactor body 100 is provided with a Figure 5The water distribution hood 202 is shown. A guide funnel 102 is provided at the upper portion of the reactor body 100, and the guide funnel 102 is located below the water distribution hood 202. One end of the catalyst addition pipe 300 located in the reactor body 100 is connected to the guide funnel 102. The catalyst suspension is introduced into the catalyst addition pipe 300 through a metering pump. The catalyst suspension is made of a first catalyst, nanocarbon and water; the first catalyst is at least one of magnesium oxide, calcium oxide, manganese dioxide, aluminum oxide, zinc oxide, iron oxide or titanium dioxide; the loading amount of the first catalyst on the nanocarbon is 0.5% to 20% of the mass of the nanocarbon.

[0059] The micro-nano bubble generator 400 includes an ozone tube 401, which is connected to the bottom of the reactor body 100. The end of the ozone tube 401 located inside the reactor body 100 is provided with a generator body 402, and the end of the ozone tube 401 located outside the reactor body 100 is connected to an ozone source.

[0060] The membrane catalytic assembly 600 includes a cylindrical shell 601, the lower end of which is connected to a drain pipe 602, the end of which away from the cylindrical shell 601 is connected to the lower part of the reactor body 100; a circulation pump 603 is provided on the drain pipe 602; the upper end of the cylindrical shell 601 is connected to a water inlet pipe 604, the end of which away from the cylindrical shell 601 is connected to the upper part of the reactor body 100; the interior of the cylindrical shell 601 is provided with the following Figure 6 The catalyst membrane tube 605 shown in FIG. 6 forms an annular cavity between the outer wall of the catalyst membrane tube 605 and the inner wall of the cylindrical shell 601; the membrane hole 611 of the catalyst membrane tube 605 is loaded with Figure 2 The second catalyst 612 is shown. The pore size of the membrane pore 611 is 10nm to 200nm. The second catalyst 612 is a metal oxide catalyst. The second catalyst is composed of at least two of CuO, CeO2, NiFe2O4, Co2O3 and MnO2. The particle size of the metal oxide catalyst is less than 18,000 mesh. The top and bottom of the cylindrical shell 601 are provided with an outer clamping ring 607, and the outer clamping ring 607 is sleeved on the catalytic membrane tube 605. The top and bottom of the cylindrical shell 601 are provided with a conical hollow cover 608, and a hollow cover 608 is provided between the two conical hollow covers 608. Figure 7 Connecting rod 609 is shown, located within catalytic membrane tube 605. Connecting rod 609 is provided with several inverted tapered portions 610 along its length, with the diameter of these tapered portions increasing gradually from bottom to top. A drain connector 606 is connected to the top of cylindrical shell 601. The top of reactor body 100 is connected to tail gas pipe 500, with the tail gas disruptor connected to the end away from reactor body 100.

[0061] The reactor body 100 is provided with connectors 101 at both its top and bottom. The top connector 101 connects to the end of the water inlet pipe 604 away from the cylindrical shell 601. The bottom connector 101 connects to the end of the drain pipe 602 away from the cylindrical shell 601. The generator body 402 is located below the bottom connector 101 of the reactor body 100. Several blocking portions 103 are provided on the inner wall of the reactor body 100 from top to bottom. These blocking portions 103 are either blocking blocks or blocking rings.

[0062] A sludge discharge assembly 700 is connected to the bottom of the reactor body 100. The sludge discharge assembly 700 includes a sludge discharge pipe 701, which is connected to the bottom of the reactor body 100 and has multiple filter holes 703 located outside the reactor body 100. Two annular flanges 702 are provided on the sludge discharge pipe 701, which are located outside the reactor body 100. The multiple filter holes 703 are located between the two annular flanges 702. A motor 706 is provided at the end of the sludge discharge pipe 701 away from the reactor body 100. A rotating shaft 704 is provided at the drive end of the motor 706. The rotating shaft 704 extends into the interior of the sludge discharge pipe 701 and is rotatably arranged relative to the sludge discharge pipe 701. The rotating shaft 704 is provided with a spiral blade 705. A sludge discharge hole is provided on the sludge discharge pipe 701 near the motor 706. The pitch of the spiral blade 1 705 gradually decreases as it moves away from the reactor body 100 .

[0063] The sludge discharge assembly 700 is provided with a filter assembly 800. The filter assembly 800 includes: Figure 10 The water tank 801 shown in the figure is mounted on the mud discharge pipe 701, and a plurality of filter holes 703 are located in the water tank 801; a cover 802 is hinged on the top of the water tank 801, and the cover 802 is provided with a Figure 11 There are two support bases 803 shown in the figure, and two avoidance grooves 804 are provided on the box cover 802. Figure 9Two filter rollers 805 are shown, each equipped with a filter screen. The filter screen passes through two avoidance grooves 804 and then abuts against the bottom of the sludge discharge pipe 701. A return pipe 806 is connected to the bottom of the water tank 801. The end of the return pipe 806, away from the water tank 801, is connected to the upper part of the reactor body 100 and is equipped with a water pump 807. Each end of the two filter rollers 805, away from the reactor body 100, is provided with at least one protrusion 808. The support base 803, away from the reactor body 100, has two mounting holes 809, into which a first sleeve 810 and a second sleeve 814 are rotatably inserted, respectively. The inner walls of each sleeve 810 and sleeve 814 are each provided with at least one slot 819, which mates with the corresponding protrusion 808. A slide groove 812 is provided on the support base 803 away from the reactor body 100. A slider 1 811 is provided on the sleeve 1 810. Slider 1 811 slides within the slide groove 812. A spring 1 813 is provided between slider 1 811 and the inner wall of the slide groove 812. The ends of spring 1 813 are connected to slider 1 811 and the inner wall of the slide groove 812, respectively. An arcuate groove 816 is provided on the support base 803 away from the reactor body 100. A slider 2 817 slides within the arcuate groove 816. A spring 2 818 is provided between slider 2 817 and the inner wall of the arcuate groove 816. The ends of spring 2 818 are connected to slider 2 817 and the inner wall of the arcuate groove 816, respectively. A rotating arm 815 is provided on the sleeve 2 814. Slider 2 817 abuts against the rotating arm 815.

[0064] The bottom of the reactor body 100 is provided with a push assembly 900, which corresponds to the sludge discharge assembly 700. The push assembly 900 includes a rotating tube 901, which is rotatably arranged at the bottom of the reactor body 100; Figure 8 The second spiral blade 902 is shown, located within the reactor body 100. A gear 903 is provided on the rotating tube 901, located outside the reactor body 100. A second motor 905 is provided on the reactor body 100, and a second gear 904 is provided at the drive end of the motor 905, which meshes with the first gear 903. The end of the sludge discharge pipe 701 located within the reactor body 100 faces the second spiral blade 902. The rotating tube 901 is sleeved onto the ozone tube 401.

[0065] Membrane catalytic ozone oxidation reactor, including reactor body 100, reactor body 100 side upper part runs through fixed wastewater addition assembly 200 and catalyst addition pipe 300, wastewater addition assembly 200 is used to add wastewater, catalyst addition pipe 300 is used to add catalyst, catalyst is added in reactor body 100 from catalyst addition pipe 300 by metering pump, catalyst is a suspension, mainly containing nano-carbon and water of catalytic components. This nano-carbon has a large specific surface area, and a loaded catalyst, and can adsorb organic matter in wastewater to the catalyst surface for reaction. When the ozone in the water body is converted into hydroxyl radicals under the action of nano-carbon surface catalyst, it can react rapidly with the organic matter adsorbed on the one hand, and on the other hand it can also react with the organic matter in the water body. The catalyst in this reactor can be evenly distributed in the reactor, expands the catalytic reaction range, and makes the whole reactor a reaction zone.

[0066] A micro-nano bubble generator 400 runs through the bottom of the reactor body 100. This is used to input ozone. Ozone flows upward from the bottom, while the added wastewater flows downward from the top, creating convection currents that ensure full contact between the wastewater and the ozone. Ozone enters the reactor through the micro-nano bubble generator 400, generating a large number of micro-nano bubbles. This increases ozone's solubility in the wastewater and slows its rise rate, thereby improving ozone utilization and increasing the reactor's processing capacity.

[0067] A tail gas pipe 500 is fixedly installed on the top of the reactor body 100, and the other end of the tail gas pipe 500 is connected to a tail gas destroyer through a pipe. The ozone tail gas is discharged from the top of the reactor into the tail gas destroyer. A membrane catalytic assembly 600 is set on both sides of the reactor body 100. The membrane catalytic assembly 600 is used to drive the wastewater in the lower layer of the reactor body 100 to pass through the membrane catalytic assembly 600 and flow back from the top of the membrane catalytic assembly 600 to the upper layer of the reactor body 100. The membrane catalytic assembly 600 is also used to perform membrane catalytic treatment on the wastewater; a sludge discharge assembly 700 is set on the side of the bottom of the reactor body 100, and a filter assembly 800 is set on the surface of the sludge discharge assembly 700. A pushing assembly 900 is set through the bottom of the reactor body 100. The pushing assembly 900 is used to push the sludge at the bottom of the reactor body 100 into the sludge discharge assembly 700. The sludge discharge assembly 700 is used to discharge the sludge, and the filter assembly 800 is used to filter the water in the sludge.

[0068] Two sets of connectors 101, distributed vertically, are fixedly mounted on both sides of the reactor body 100. These connectors 101 are connected to the membrane catalyst assembly 600. A guide funnel 102 is fixedly mounted on the inner wall of the upper half of the reactor body 100. The guide funnel 102 is used to guide the wastewater added by the wastewater addition assembly 200 and the catalyst added by the catalyst addition pipe 300. The wastewater and catalyst are added together into the guide funnel 102, undergo preliminary mixing, and are then discharged into the interior of the reactor body 100. The inner wall of the middle portion of the reactor body 100 is arrayed with barrier portions 103 along its length. The barrier portions 103 block the wastewater and ozone inside the reactor body 100, forming turbulent flow and further ensuring the mixing effect of the wastewater and ozone. The wastewater addition assembly 200 includes a wastewater pipe 201 that extends through and is fixed to the side of the reactor body 100. A water distribution hood 202 is fixedly mounted at the end of the wastewater pipe 201. The bottom of the hood 202 has multiple holes and is located directly above the guide funnel 102. The catalyst addition pipe 300 extends through and is fixed to the side of the guide funnel 102. The micro-nano bubble generator 400 includes an ozone tube 401 that extends through the center of the bottom of the reactor body 100. The generator body 402 is fixedly mounted at the top of the ozone tube 401 and is located below the connector 101.

[0069] The membrane catalytic assembly 600 includes two groups of cylindrical shells 601 arranged on the left and right sides of the reactor body 100. A drain pipe 602 is fixedly installed at the bottom of the cylindrical shell 601, and a circulation pump 603 is arranged in the middle of the drain pipe 602. An inlet pipe 604 is fixedly installed at the top of the cylindrical shell 601. The inlet pipe 604 and the drain pipe 602 are respectively connected to two groups of connectors 101 distributed above and below. Catalytic membrane tubes 605 are arranged inside the cylindrical shell 601 and the drain pipe 602. An annular cavity is formed between the outer wall of the catalytic membrane tube 605 and the inner wall of the cylindrical shell 601. The wastewater is sucked from the lower part of the reactor body 100 by the circulation pump 603 and the drain pipe 602. Part of the wastewater flows through the middle of the catalytic membrane tube 605 and flows back into the reactor body 100 through the water inlet pipe 604. The membrane pores 611 of the catalytic membrane tube 605 have diameters between 10 nm and 200 nm. These pores are loaded with a catalyst, primarily a metal oxide. As wastewater passes through the pores, ozone, the catalyst, and organic matter react fully within the narrow membrane pores, effectively removing organic matter from the wastewater to a low level. A drainage connector 606 is fixedly mounted on the top side of the cylindrical shell 601. Wastewater passes through the pores, forming oxidation product water that enters the annular cavity and is then discharged through the drainage connector 606.

[0070] External clamping rings 607 are fixedly mounted on the top and bottom walls of the cylindrical shell 601. These rings are fitted around the outside of the ends of the catalytic membrane tubes 605. Conical hollow covers 608 are also fixedly mounted on the top and bottom walls of the cylindrical shell 601. These hollow covers are tapered and feature an array of slots on their sides. These hollow covers 608 are inserted into the inside of the ends of the catalytic membrane tubes 605. The outer clamping rings 607 and hollow covers 608 cooperate to clamp onto the ends of the catalytic membrane tubes 605, securing them in place. A connecting rod 609 is fixedly mounted between the centers of the two sets of hollow covers 608. The connecting rods 609 have inverted tapered sections 610 arrayed along their lengths, increasing in diameter from bottom to top. These inverted tapered sections 610 guide wastewater toward the surfaces of the catalytic membrane tubes 605.

[0071] The pushing assembly 900 includes a rotating tube 901 that extends through and rotatably connects to the center of the bottom of the reactor body 100. Rotating tube 901 is sleeved on the outside of the ozone tube 401. Spiral blade 2 902 is fixedly mounted on the surface of rotating tube 901 located inside the reactor body 100. Spiral blade 2 902 is attached to the bottom wall of the reactor body 100. Gear 1 903 is fixedly mounted on the surface of rotating tube 901 located outside the reactor body 100. Gear 1 903 is meshed with gear 2 904. Gear 2 904 is rotatably connected to the bottom of the reactor body 100. Motor 2 905 is fixedly mounted at the center of the bottom of gear 2 904. Insoluble matter in the wastewater and ozone reaction process docks within the bottom end of the reactor body 100, forming sludge. Motor 2 905 drives gear 2 904 to rotate, driving gear 1 903 to rotate, thereby driving the rotating tube 901 and spiral blade 2 902 assembly to rotate, thereby pushing the sludge downward.

[0072] The sludge discharge assembly 700 includes a sludge discharge pipe 701 fixedly mounted on the side of the bottom end of the reactor body 100. Sludge is pushed by spiral blade 2 902 into the interior of the sludge discharge pipe 701. Two sets of annular flanges 702 are fixedly mounted on the outer wall of the sludge discharge pipe 701. Multiple filter holes 703 are formed in the lower half of the sludge discharge pipe 701, located between the two sets of annular flanges 702. A rotating shaft 704 is rotatably connected to the interior of the sludge discharge pipe 701. Spiral blade 1 705 is fixedly mounted on the surface of the rotating shaft 704. The pitch of the spiral blade 1 705 gradually decreases from right to left. A motor 1 706 is fixedly mounted on the end of the rotating shaft 704. The motor 1 706 drives the assembly of the rotating shaft 704 and spiral blade 1 705 to rotate, pushing the sludge inside the sludge discharge pipe 701 to the left. The pitch of the spiral blade 1 705 gradually decreases, gradually increasing the pressure on the sludge, squeezing out water from the sludge and discharging it through the filter holes 703.

[0073] The filter assembly 800 includes a water tank 801 fixedly mounted outside the sludge discharge pipe 701. The water tank 801 is sleeved outside two sets of annular flanges 702. Water discharged from the filter holes 703 accumulates inside the water tank 801. A lid 802 is hingedly attached to the top of the water tank 801. Support bases 803 are fixedly mounted on the top of each end of the lid 802. Two sets of escape grooves 804 are formed through the surface of the lid 802. A filter roller 805 is positioned between the two sets of support bases 803. The filter screen on one of the filter rollers 805 is released, passes around the bottom of the sludge discharge pipe 701, and is wound around the surface of the other filter roller 805. The escape grooves 804 allow the filter screen to pass through the lid 802. The hinged connection between the lid 802 and the water tank 801 allows the lid 802 to be opened, facilitating the filter screen's passage around the bottom of the sludge discharge pipe 701. The two sets of annular flanges 702 also serve to limit the filter screen's position on both sides. A return pipe 806 is fixedly installed at the bottom of the water tank 801, and the other end of the return pipe 806 is fixedly installed on the upper half surface of the reactor body 100. A water pump 807 is provided on the return pipe 806. The assembly of the water pump 807 and the return pipe 806 is used to suck the water inside the water tank 801 and transport it to the reactor body 100.

[0074] The left ends of both sets of filter rollers 805 are fixed with an array of raised strips 808. Two sets of mounting holes 809 are formed through the surface of the left support base 803. Sleeves 1 810 and 2 814 are inserted into these mounting holes 809, respectively. Sleeves 1 810 and 2 814 are respectively designed to be fitted over the left ends of the two sets of filter rollers 805. The inner walls of both sleeves 810 and 814 have slots corresponding to the array of raised strips 808. Once fitted over the left ends of the filter rollers 805, sleeves 1 810 and 814 rotate synchronously with the filter rollers 805.

[0075] A slider 811 is fixedly installed on the left end surface of the sleeve 810, and a slide groove 812 is fixedly installed on the surface of the left support seat 803. The slider 811 is slidably connected in the slide groove 812. A spring 813 is fixedly installed between the slider 811 and the inner wall of the slide groove 812. The spring 813 is used to drive the slider 811 to move toward the support seat 803; the slide groove 812 limits the slider 811 to inhibit the sleeve 810 from rotating, so that when the sleeve 810 is sleeved on the left end of the filter roller 805, the filter roller 805 is inhibited from rotating.

[0076] A pivot arm 815 is fixedly mounted on the left end of sleeve 814. The left support base 803 has an arcuate groove 816 formed on its surface. A second slider 817 is slidably connected within this groove. A second spring 818 is fixedly mounted between slider 817 and the inner wall of this groove. This spring 818 drives slider 817 to slide upward and rearward along this groove, where it abuts against the front of pivot arm 815. Slider 817 is U-shaped, ensuring that pivot arm 815 remains stably positioned within it. When sleeve 814 is positioned over the left end of filter roller 805, the elasticity of spring 818 causes slider 817 to push upward and rearward, causing filter roller 805 to rotate clockwise, thereby winding the filter screen.

[0077] The working principle of the present invention is:

[0078] During use, the first catalyst is added from the catalyst addition pipe 300 to the interior of the guide funnel 102 via a metering pump. The wastewater pipe 201 and the water distribution cover 202 add wastewater to the interior of the guide funnel 102. The wastewater and the first catalyst are mixed in the guide funnel 102 and then enter the interior of the reactor body 100. At the same time, ozone is added to the interior of the reactor body 100 via the micro-nano bubble generator 400, forming a large number of microbubbles that flow from bottom to top, and the wastewater flows from top to bottom, forming convection, so that the ozone and wastewater are fully in contact and react.

[0079] Wastewater is sucked from the lower portion of the reactor body 100 by a circulation pump 603 in conjunction with a drain pipe 602 and transported into the interior of the cylindrical shell 601. Guided by the inverted cone 610, the wastewater flows toward the catalytic membrane tubes 605, reacting with the second catalyst 612 within the membrane pores of the catalytic membrane tubes 605 to form oxidized water, which is then discharged through the drain connector 606. Some wastewater passes directly through the middle of the catalytic membrane tubes 605 and flows back into the interior of the reactor body 100 through the water inlet pipe 604.

[0080] The motor 2 905 drives the gear 2 904 to rotate, driving the gear 1 903 to rotate, and then driving the assembly of the rotating tube 901 and the spiral blade 2 902 to rotate, pushing the sludge inside the reactor body 100 downward, so that the sludge enters the interior of the sludge discharge pipe 701; then the motor 1 706 drives the assembly of the rotating shaft 704 and the spiral blade 1 705 to rotate, pushing the sludge inside the sludge discharge pipe 701 to the left, and during the movement of the sludge, the pressure exerted by the spiral blade 1 705 on the sludge gradually increases, so that the water inside the sludge is squeezed out, and the water is filtered through the filter screen released by the filter roller 805 and enters the interior of the water tank 801. Finally, the water inside the water tank 801 is sucked into the interior of the reactor body 100 through the cooperation of the reflux pipe 806 and the water pump 807.

[0081] The reactor body 100 provides a stable reaction environment for the full reaction between wastewater, catalyst suspension and ozone; the wastewater addition component 200 is used to add wastewater to be treated; the catalyst addition pipe 300 is used to add catalyst suspension; the micro-nano bubble generator 400 is used to fully mix the wastewater to be treated with ozone; the catalyst suspension and ozone in the reactor body fully react with the wastewater, reducing the organic matter in the wastewater from a high level to a low level, and the ozone catalytic oxidation has a high utilization rate; the membrane catalytic component 600 provides another reaction site for the treatment of wastewater, and the catalytic activity of the second catalyst 612 in the membrane catalytic component Under the action of the ozone layer, hydroxyl radicals are generated and fully contacted with organic matter in the membrane pores 611, reducing the wastewater entering the reactor body after treatment from a lower level to an even lower level, thereby improving the utilization rate of hydroxyl radicals; the wastewater to be treated enters from the wastewater addition component 200 on the upper part of the reactor body, and is counter-currently mixed with the ozone from the micro-nano bubble generator 400, and is sucked by the circulation pump 603 in the membrane catalytic component. The wastewater to be treated flows from top to bottom, and a part of it eventually enters the membrane pores and flows out as produced water, while the other part flows back to the reactor body to continue the reaction, and promotes turbulence of the fluid in the reactor, thereby improving the adequacy of the mixing reaction.

[0082] The wastewater pipe 201 is used to feed wastewater; the water distribution cover 202 is used to evenly sprinkle the fed wastewater into the reactor body 100; the guide funnel 102 is used to better guide the wastewater evenly distributed by the water distribution cover to a more appropriate position in the reactor body; the catalyst addition pipe 300 is connected to the guide funnel 102, and the catalyst suspension is fed into the evenly distributed wastewater, so that the catalyst suspension and the evenly distributed wastewater are better guided to the appropriate position in the reactor body under the guidance of the guide funnel, and the catalytic oxidation reaction occurs after being more fully mixed with the ozone; the metering pump can accurately control the catalyst entering the reactor body. The amount of the added catalyst suspension is reduced, thereby ensuring that the entire catalytic oxidation reaction proceeds more fully; the nanocarbon has a large specific surface area, and the first catalyst is loaded on the nanocarbon, which can adsorb organic matter in the wastewater to the catalyst surface for reaction. When the ozone in the water body is converted into hydroxyl radicals under the action of the nanocarbon surface catalyst, on the one hand, it can quickly and efficiently react with the adsorbed organic matter, and on the other hand, it can also react with the organic matter in the water body; the catalyst suspension can also be directly and evenly distributed in the reactor body and mixed with the wastewater after distribution, thereby expanding the scope of the catalytic reaction and making the entire reactor body a reaction zone.

[0083] The ozone tube 401 is used to guide the ozone from the external ozone source into the reactor body 100; the ozone enters the reactor body from the bottom of the reactor body through the generator body 402, and a large number of micro-nano bubbles are generated under the action of the generator body, which increases the solubility of ozone in wastewater on the one hand and slows down the rising rate of ozone gas on the other hand, thereby improving the utilization rate of ozone and increasing the wastewater treatment capacity of the reactor body; the cylindrical shell 601 provides an installation space for the catalytic membrane tube 605, which passes through a stable second reaction site; the drain pipe 602 is used to drain the initial part of the reactor body. The wastewater after the first step of the reaction is guided into the catalytic membrane tube for re-reaction treatment; the circulation pump 603 provides power for the wastewater after the initial reaction in the reactor body to enter the catalytic membrane tube for re-reaction; the water inlet pipe 604 is used to guide the water in the membrane tube of the catalytic membrane tube back into the reactor body for further treatment; the catalytic membrane tube 605 can well perform good re-reaction treatment on the water in the reactor body; the circulating water enters through the membrane tube of the catalytic membrane tube, part of the circulating water flows out from the membrane tube, and part flows out from the membrane hole 611. The water flowing out of the membrane hole is the oxidation water; when the wastewater passes through the membrane hole, Ozone, the second catalyst and organic matter fully react in the narrow membrane pores, achieving efficient removal of organic matter, and can remove organic matter in wastewater to a lower level; the limited membrane pore size can make ozone, the second catalyst and organic matter react more fully in the narrow membrane pores; the metal oxide catalyst can be stably loaded in the membrane pores, and can better undergo a full catalytic oxidation reaction with ozone and organic matter in the narrow membrane pores; the outer clamping ring 607 can ensure the stability of the catalytic membrane tube working in the cylindrical shell; the conical hollow cover 608 can, on the one hand, assist in limiting the catalytic membrane tube 605 working in the cylindrical shell 601 On the one hand, it can ensure the stability of the operation, and on the other hand, it can make the wastewater in the membrane tube smoothly enter the water inlet pipe from the hollow part; the connecting rod 609 provides a stable installation position for the several inverted cones 610, ensuring the stability of the operation of the several inverted cones; the several inverted cones are used to better guide the incoming water after the first treatment of the reactor body directly to the catalytic membrane tube for secondary treatment; the inverted cone structure with a diameter gradually increasing from bottom to top is adapted to the direction of water flow in the catalytic membrane tube, and can better guide the water flow in the catalytic membrane tube; the drain joint 606 can discharge the qualified oxidized water after the secondary treatment of the catalytic membrane tube.

[0084] The tail gas pipe 500 is used to discharge the ozone tail gas that has not participated in the reaction; the tail gas destroyer is used to heat up and quickly decompose the ozone into oxygen and discharge it into the atmosphere; the connectors 101 located at the upper and lower parts of the reactor body 100 are used to connect with the water inlet pipe 604 and the drain pipe 602 of the membrane catalytic component 600, forming a circulation between the membrane catalytic component 600 and the reactor body; the generator body is located below the connector at the lower part of the reactor body, so that the ozone at the generator body 402 can better enter the catalytic membrane tube 605 under the action of the circulation pump 603; a number of blocking parts 103 can change the fluid morphology at the inner wall of the reactor body from laminar flow to turbulent flow, thereby enhancing the mixing effect; the upward flow generated by the micro-nano bubble generator 400, the suction and reflux of the circulation pump 603 and the blocking part of the reactor body work together to fully mix the fluid in the reactor body, and slow down the rising speed of ozone, thereby enhancing the ozone catalytic oxidation effect; the blocking block or blocking ring is easy to prepare and can also well change the reaction The fluid form at the inner wall of the reactor body changes from laminar flow to turbulent flow; the sludge discharge component 700 is used to discharge insoluble matter that may be produced during the organic matter reaction from the reactor body; the sludge discharge pipe 701 is used to discharge the insoluble matter in the reactor body 100; multiple filter holes 703 are used to compress and squeeze out the water in the insoluble matter when discharging the insoluble matter, ensuring that the insoluble sludge discharged from the sludge discharge pipe is in a relatively low-water state; the two annular flanges 702 limit the setting positions of the multiple filter holes on the sludge discharge pipe to ensure a better dehydration effect on the insoluble matter; the motor 1 706 provides power for the insoluble matter to be discharged from the reactor body; the rotating shaft 704 drives the spiral blade 1 705 to rotate, and the insoluble sludge in the reactor body is smoothly transported and discharged to the sludge outlet of the sludge discharge pipe; the specific pitch of the spiral blade 1 is set to ensure that the insoluble sludge in the reactor body is smoothly transported and discharged to the sludge outlet of the sludge discharge pipe, while being able to well squeeze and dehydrate the insoluble sludge therein.

[0085] The filter assembly 800 can filter the water discharged from the filter holes 703 well, and prevent insoluble sludge from being discharged from the filter holes; the water storage tank 801 is used to uniformly store the water filtered at the filter holes; the box cover 802 hinged on the top of the water storage tank can prevent external debris from falling into the water storage tank; the two support seats 803 are used to support components such as the filter roller 805; the two avoidance grooves 804 are used for the filter screen to pass through after winding; the two filter rollers are used to connect the two ends of the filter screen, and the degree of closeness of the filter screen relative to the mud discharge pipe 701 can be adjusted; the filter screen can well filter the squeezed water passing through the filter holes 703; the return pipe 806 is used to guide the filtered water in the water storage tank back into the reactor body 100 for further processing and reuse; the water pump 807 provides power for sending the filtered water in the water storage tank into the reactor body; the cooperation of the ridges 808 and the slots 819 can make the two The filter screen roller 805 can be well confined in the sleeve one 810 and the sleeve two 814 in a manner as needed; the two mounting holes 809 provide a movable mounting position for the sleeve one and the sleeve two on the support seat 803; the sleeve one and the sleeve two can well confine the two filter screen rollers on the support seat in a manner as needed; the slide groove 812 can well limit the horizontal and appropriate movement of the slider one 811; the cooperation of the slider one 811, the slide groove 812 and the spring one 813 enables the filter screen roller of the sleeve one to be flexibly adjusted left and right as needed, so that the filter screen can fit well in the mud discharge pipe, ensuring the smooth progress of the entire filtering work; the arc groove 816 provides a guide for the movement of the slider two 817; the arc groove 816, the slider two 817, the spring two 818 and the rotating arm 815 cooperate as a whole, so that the filter screen can fit well in the mud discharge pipe 701, ensuring the smooth progress of the entire filtering work.

[0086] The pushing assembly 900 is used to deliver the insoluble sludge in the reactor body 100 to the spiral blade 1 705 of the sludge discharge pipe 701, ensuring that the insoluble sludge in the reactor body can be discharged smoothly from the sludge discharge pipe; wherein the rotating shaft 704 and the spiral blade 1 705 extend into the reactor body together; the rotating tube 901 drives the spiral blade 2 902 to rotate together, and smoothly delivers the insoluble sludge in the reactor body to the entrance of the sludge discharge pipe 701; gear 1 903 is used to receive the driving force to make the rotating tube rotate; motor 2 905 provides a stable driving force for the rotation of the rotating tube; gear 2 904 is used to stably transmit the driving force of motor 2 to gear 1.

[0087] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. Membrane catalytic ozone oxidation reactor, characterized by: The invention comprises a reactor body (100), wherein a wastewater addition component (200) and a catalyst addition pipe (300) are respectively provided on the upper side of the reactor body (100), and a catalyst suspension is introduced into the catalyst addition pipe (300); a micro-nano bubble generator (400) is provided at the bottom of the reactor body (100), and the micro-nano bubble generator (400) is connected to an ozone source; and at least one membrane catalyst component (600) is connected to the reactor body (100) in a closed loop. The bottom of the reactor body (100) is connected to a sludge discharge assembly (700); the sludge discharge assembly (700) comprises a sludge discharge pipe (701), the sludge discharge pipe (701) is connected to the bottom of the reactor body (100), a plurality of filter holes (703) are provided on the sludge discharge pipe (701), and the plurality of filter holes (703) are located outside the reactor body (100); the sludge discharge pipe (701) is provided with two annular flanges (702), and the two annular flanges (702) are located outside the reactor body (100). The plurality of filter holes (703) are located between the two annular flanges (702); a motor (706) is provided at one end of the mud discharge pipe (701) away from the reactor body (100); a rotating shaft (704) is provided at the driving end of the motor (706); the rotating shaft (704) extends into the mud discharge pipe (701); the rotating shaft (704) is rotatably arranged relative to the mud discharge pipe (701); a spiral blade (705) is provided on the rotating shaft (704); and a mud outlet hole is provided on the mud discharge pipe (701) at a position close to the motor (706); The sludge discharge assembly (700) is provided with a filter assembly (800); the filter assembly (800) comprises a water tank (801), the water tank (801) is sleeved on the sludge discharge pipe (701), and the plurality of filter holes (703) are located in the water tank (801); a box cover (802) is hingedly connected to the top of the water tank (801), two support seats (803) are provided on the box cover (802), two avoidance grooves (804) are provided on the box cover (802), two filter screen rollers (805) are provided between the two support seats (803), and filter screens are provided on the two filter screen rollers (805), and the filter screens pass through the two avoidance grooves (804) and are attached to the bottom of the sludge discharge pipe (701); The two filter screen rollers (805) are each provided with at least one convex strip (808) at one end away from the reactor body (100); two mounting holes (809) are provided on the support base (803) away from the reactor body (100), and a sleeve 1 (810) and a sleeve 2 (814) are respectively rotatably inserted into the two mounting holes (809); the inner walls of the sleeve 1 (810) and the sleeve 2 (814) are each provided with at least one slot (819), and the slot (819) matches the corresponding convex strip (808); A slide groove (812) is provided on the support seat (803) away from the reactor body (100), and a slider (811) is provided on the sleeve (810), and the slider (811) is slidably arranged in the slide groove (812); a spring (813) is provided between the slider (811) and the inner wall of the slide groove (812), and the two ends of the spring (813) are respectively connected to the slider (811) and the inner wall of the slide groove (812); away from the reactor body (100) The support seat (803) is provided with an arc-shaped groove (816), a slider (817) is provided in the arc-shaped groove (816), a spring (818) is provided between the slider (817) and the inner wall of the arc-shaped groove (816), and the two ends of the spring (818) are respectively connected to the slider (817) and the inner wall of the arc-shaped groove (816); a rotating arm (815) is provided on the sleeve (814), and the slider (817) is in contact with the rotating arm (815).

2. The membrane catalytic ozone oxidation reactor according to claim 1, characterized in that: The wastewater addition component (200) comprises a wastewater pipe (201), the wastewater pipe (201) being arranged in communication with the upper part of the reactor body (100), and a water distribution cover (202) being provided at one end of the wastewater pipe (201) located inside the reactor body (100); the micro-nano bubble generator (400) comprises an ozone tube (401), the ozone tube (401) being connected to the bottom of the reactor body (100), the ozone tube (401) being provided with a generator body (402) at one end located inside the reactor body (100), and an ozone source being connected at one end of the ozone tube (401) located outside the reactor body (100); and a plurality of blocking portions (103) being provided on the inner wall of the reactor body (100) from top to bottom.

3. The membrane catalytic ozone oxidation reactor according to claim 1, characterized in that: The catalyst suspension is made of a first catalyst, nanocarbon and water; the first catalyst is at least one of magnesium oxide, calcium oxide, manganese dioxide, aluminum oxide, zinc oxide, iron oxide or titanium dioxide; and the loading amount of the first catalyst on the nanocarbon is 0.5% to 20% of the mass of the nanocarbon.

4. The membrane catalytic ozone oxidation reactor according to claim 1, characterized in that: The membrane catalytic assembly (600) includes a cylindrical shell (601), the lower end of the cylindrical shell (601) is connected to a drain pipe (602), and the end of the drain pipe (602) away from the cylindrical shell (601) is connected to the lower part of the reactor body (100); a circulation pump (603) is provided on the drain pipe (602); the upper end of the cylindrical shell (601) is connected to a water inlet pipe (604), and the end of the water inlet pipe (604) away from the cylindrical shell (601) is connected to the upper part of the reactor body (100); a catalytic membrane tube (605) is provided inside the cylindrical shell (601), and the space between the outer wall of the catalytic membrane tube (605) and the inner wall of the cylindrical shell (601) forms an annular cavity; the membrane pores (611) of the catalytic membrane tube (605) are loaded with a second catalyst (612).

5. The membrane catalytic ozone oxidation reactor according to claim 4, characterized in that: The top and bottom of the cylindrical shell (601) are both provided with outer clamping rings (607), and the outer clamping rings (607) are sleeved on the catalytic membrane tube (605); the top and bottom of the cylindrical shell (601) are both provided with conical hollow covers (608), and a connecting rod (609) is provided between the two conical hollow covers (608), and the connecting rod (609) is located in the catalytic membrane tube (605). The connecting rod (609) is provided with a plurality of inverted cones (610) along the length direction, and the diameter of the inverted cones (610) gradually increases from bottom to top.

6. The membrane catalytic ozone oxidation reactor according to claim 1, characterized in that: The bottom of the reactor body (100) is provided with a pushing assembly (900), and the pushing assembly (900) corresponds to the sludge discharge assembly (700); the pushing assembly (900) includes a rotating tube (901), and the rotating tube (901) is rotatably arranged at the bottom of the reactor body (100); the rotating tube (901) is provided with a second spiral blade (902), and the second spiral blade (902) is located inside the reactor body (100); the rotating tube (901) is provided with a first gear (903), and the first gear (903) is located outside the reactor body (100); the reactor body (100) is provided with a second motor (905), and the driving end of the second motor (905) is provided with a second gear (904), and the second gear (904) is meshed with the first gear (903); one end of the sludge discharge pipe (701) located inside the reactor body (100) is opposite to the second spiral blade (902).

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