Sludge ozone coupling catalytic oxidation treatment test system and method

Abstract

The application discloses a sludge ozone coupling catalytic oxidation treatment test system, which comprises an oxygen generator, an ozone fission device, a micro-nano bubble generating device, a sludge feeding device, an ozone catalytic oxidation reaction kettle, an online Raman spectrum detection device and an ozone concentration online monitoring device; the oxygen generator, the ozone fission device and the micro-nano bubble generating device are sequentially connected, the micro-nano bubble generating device is connected with a micro-nano bubble aeration device; the sludge feeding device is connected with a sludge feeding nozzle; the online Raman spectrum detection device performs non-contact detection on the transparent ozone catalytic oxidation reaction kettle through a high-precision laser probe with a laser signal source, and transmits a signal to a Raman online detector for analysis and calculation; and the ozone concentration online monitoring device is used for online monitoring of the ozone source concentration. The application integrates high-concentration ozone generation, micro-nano bubble mixing, catalytic oxidation reaction and online detection functions, and can realize multi-dimensional data acquisition and process controllability in the sludge wall breaking process.

Description

Technical Field

[0001] This invention relates to the field of activated sludge treatment technology, and in particular to an experimental system and method for ozone-coupled catalytic oxidation treatment of sludge. Background Technology

[0002] Ozone catalytic oxidation of sludge is a cutting-edge technology for the efficient resource utilization of sludge. Its core lies in the synergistic effect of hydroxyl radicals and ozone to break down extracellular polymers in sludge flocs, releasing intracellular organic matter. However, current research still lacks sufficient understanding of key mechanisms such as radical generation pathways, catalytic reaction interfacial behavior, and cell disruption kinetics, primarily due to the lack of simultaneous analysis of multiple parameters in the reaction process. Traditional experimental devices are mostly decentralized with low integration, making it difficult to couple the observation of ozone mass transfer, catalytic action, and sludge structural evolution. Furthermore, they generally lack online detection methods, making it impossible to obtain information on reaction intermediates and dynamic changes. In addition, existing platforms struggle to simultaneously control and monitor key parameters such as ozone concentration, bubble size, mixing intensity, and reaction time, leading to fragmented mechanistic research and hindering technology optimization and engineering transformation. Especially in complex sludge substrates, catalytic efficiency fluctuates greatly, and reaction pathways are unclear, necessitating a multi-parameter, modular, and integrated experimental platform to support systematic research. Summary of the Invention

[0003] The technical problem this invention aims to solve is the lack of understanding of the mechanism caused by the dispersed experimental platforms, lagging monitoring, and lack of multi-parameter synergistic control capabilities in existing research on sludge ozone catalytic oxidation cell wall disruption. This invention provides a sludge ozone-coupled catalytic oxidation treatment experimental system and method. This experimental system integrates high-concentration ozone generation, micro / nano bubble homogenization, catalytic oxidation reaction, and online detection functions, enabling multi-dimensional data acquisition and process control of the sludge cell wall disruption process. This is of great significance for revealing the mechanism of ozone catalytic oxidation cell wall disruption and promoting the quantification and engineering of the technology.

[0004] The technical solution adopted in this invention is: An experimental system for ozone-coupled catalytic oxidation treatment of sludge includes an oxygen generator, an ozone fission device, a micro / nano bubble generator, a sludge feeding device, an ozone catalytic oxidation reactor, an online Raman spectroscopy detection device, and an online ozone concentration monitoring device. The ozone catalytic oxidation reactor comprises a primary reaction chamber, a secondary reaction chamber, and a tertiary reaction chamber arranged sequentially from bottom to top. Catalytic oxidation filling materials are respectively placed in the primary and secondary reaction chambers. A sludge feeding nozzle and a micro / nano bubble aeration device are installed at the bottom of the primary reaction chamber, and a sludge overflow port is provided at the top of the tertiary reaction chamber. The oxygen generator, the ozone fission device, and the micro / nano bubble generator are connected in sequence. The micro-nano bubble generator is connected to the micro-nano bubble aeration device; the sludge feeding device is connected to the sludge feeding nozzle; the online Raman spectroscopy detection device includes an online Raman detector, a lifting bracket, and a high-precision laser probe. The high-precision laser probe is mounted on the lifting bracket and connected to the online Raman detector. The high-precision laser probe transmits the laser signal source through the transparent ozone catalytic oxidation reactor for non-contact detection. The detection signal is transmitted to the online Raman detector for analysis and calculation, thereby obtaining multi-parameter experimental information data; the online ozone concentration monitoring device is installed on the outlet pipeline of the ozone fission device to monitor the ozone source concentration online.

[0005] In the above scheme, the oxygen generator is a benchtop oxygen generator, which includes an air compressor, a No. 1 oil-water dryer filter and an oxygen generation unit. The air compressor is connected to the oxygen generation unit, and the No. 1 oil-water dryer filter is installed on the pipeline between the air compressor and the oxygen generation unit.

[0006] In the above scheme, the ozone fission device includes a No. 2 oil-water drying filter, an ozone fission chamber, and a No. 3 oil-water drying filter; the air inlet pipe of the ozone fission chamber is connected to the air outlet pipe of the oxygen generator, the No. 2 oil-water drying filter is installed on the air inlet pipe of the ozone fission chamber, the No. 3 oil-water drying filter is installed on the ozone oxygen source outlet pipe of the ozone fission chamber, and the ozone oxygen source outlet pipe is connected to the micro-nano bubble generator.

[0007] In the above scheme, the ozone fission device also includes a circulating water pump, an inlet, an outlet pipe, a circulating cooling device, and a cooling water tank. The cooling water tank is connected to the inlet of the ozone fission chamber through the inlet pipe. The circulating water pump is installed on the inlet pipe. The outlet pipe of the ozone fission chamber is connected to the circulating cooling device. The outlet of the circulating cooling device is connected to the cooling water tank.

[0008] In the above scheme, the sludge feeding device includes a sludge storage tank, a pressure pump and a feeding pipe. The sludge storage tank has a built-in stirring device, and the discharge port at the bottom of the sludge storage tank is connected to the pressure pump. The pressure pump is connected to the sludge feed nozzle through the feeding pipe.

[0009] In the above scheme, the upper and lower parts of the catalytic oxidation filling material in the primary and secondary reaction chambers are respectively fixedly installed with porous grids; the middle and lower parts of the tertiary reaction chamber are fixedly installed with porous grids, and the pore size of the porous grids is smaller than the particle size of the catalytic oxidation filling material.

[0010] In the above scheme, adjacent reaction chambers are connected by flange bolts for sealing. A sealing ring is set at the joint of the adjacent reaction chamber cylinders to form a first-level seal. The upper flange, rubber sealing ring and lower flange are connected by bolts to form a second-level seal, thereby forming a sealed reaction cylinder structure.

[0011] In the above scheme, each reaction chamber is equipped with at least one sampling valve for sampling and checking the physicochemical properties of sludge at different stages.

[0012] In the above scheme, each reaction chamber is equipped with at least one backwash feed valve for injecting cleaning fluid; the bottom of the primary reaction chamber is equipped with a discharge valve for discharging wastewater after cleaning.

[0013] Accordingly, this invention also proposes an experimental method for ozone-coupled catalytic oxidation treatment of sludge, employing the aforementioned experimental system, and the experimental method includes: A high-concentration oxygen source is generated by an oxygen generator. This high-concentration oxygen source is then converted into high-purity ozone through an ozone fission device. The high-purity ozone is then efficiently mixed with a small amount of water using a micro-nano bubble generator to form a large volume of micro-nano ozone bubble mixture. This mixture is then transported to the ozone catalytic oxidation reactor via a micro-nano bubble aeration device. Simultaneously, a sludge feeding device delivers highly fluid sludge into the ozone catalytic oxidation reactor through sludge feed nozzles. The activated sludge and micro-nano ozone bubbles converge at the bottom of the ozone catalytic oxidation reactor, undergoing a catalytic oxidation and cell-wall breaking reaction. They then come into full contact with the catalytic oxidation filling materials in the primary and secondary reaction chambers, generating a super catalytic oxidation reaction to achieve cell-wall breaking. The broken-wall sludge mixture is discharged from the sludge overflow port of the tertiary reaction chamber to the next stage for deep dewatering, while the waste gas is discharged to the ozone destruction device through the waste gas valve at the top of the tertiary reaction chamber. During the reaction, the ozone concentration is monitored in real time by an online ozone concentration monitoring device; and the ozone catalytic oxidation cell wall disruption process of sludge is detected online in situ by an online Raman spectroscopy detection device. The characteristic Raman peak intensity changes of intracellular biomacromolecules in microbial cells in sludge are obtained in real time. Combined with the molecular fingerprint information of characteristic pollutants and oxidation intermediates, multi-dimensional synchronous monitoring of intracellular substance release dynamics, organic matter degradation pathways and catalyst action mechanisms is achieved.

[0014] The beneficial effects of this invention are: 1. The sludge ozone coupled catalytic oxidation treatment experimental system of the present invention integrates experimental modules such as an oxygen generator, an ozone fission device, a micro-nano bubble generator, and a high-efficiency homogenizing reactor for sludge catalytic oxidation, and is equipped with high-precision online detection modules such as ozone concentration detection and Raman spectroscopy detection, so as to realize efficient sludge cell disruption and process data acquisition, and provide an integrated experimental platform for mechanism research and technology optimization.

[0015] 2. Modular integrated design enhances experimental efficiency and operational flexibility. This invention employs a highly integrated and modular design, compactly arranging independent units such as oxygen generation, ozone generation, micro / nano bubble preparation, material supply, and reaction detection into a single unit. This design not only significantly saves laboratory space but also reduces the risk of gas leakage through standardized connections. Combined with the modular design of each unit, it enables rapid equipment movement and convenient assembly, significantly improving the smoothness and safety of experimental operations.

[0016] 3. Enhanced gas source quality and mass transfer efficiency ensure a highly reactive reaction environment. The system ensures a high-purity, dry oxygen supply through multi-stage oil-water drying and filtration and a circulating water cooling system at the source, effectively controlling the temperature rise during ozone generation and guaranteeing high-concentration ozone production. Simultaneously, the addition of a micro-nano bubble generator significantly increases the gas-liquid contact area, substantially improving the solubility and mass transfer efficiency of ozone in sludge, providing a highly reactive reaction environment for efficient sludge cell disruption.

[0017] 4. Optimized fluid dynamics structure to solve the problem of high-concentration sludge clogging. Addressing the issue of reduced flow velocity and clogging caused by high-concentration sludge in the catalytic bed, this system innovatively incorporates a multi-stage reaction chamber and a pressurized mixing zone. The synergistic effect of mixing in the primary reaction chamber and pressurization in the secondary reaction chamber provides sufficient power for the slurry to penetrate the catalytic packing layer. Combined with a unique porous grid limiting structure, this effectively fixes the catalyst and prevents bottom accumulation due to excessive flow resistance, ensuring the fluid dynamic stability of the reaction system.

[0018] 5. Multi-parameter online synchronous analysis has been achieved, breaking through the bottleneck of mechanism research. This system integrates online Raman spectroscopy detection and real-time ozone concentration monitoring. This completely changes the traditional experimental lag mode that relies on offline sampling, enabling the simultaneous capture of ozone mass transfer, catalytic reaction interface behavior, and the dynamic evolution of intracellular organic matter (such as proteins and lipids) in sludge at the molecular level, providing precise multi-dimensional data support for revealing the "hydroxyl radical generation pathway" and "cell wall disruption kinetics".

[0019] 6. Equipped with in-situ backwashing function to extend equipment life and catalyst activity. Considering the difficulties in cleaning sludge after experiments and the easy deactivation of catalysts, the system is designed with a convenient backwashing function. After the experiment, there is no need to disassemble the complex reactor; simply inject cleaning fluid through the backwash feed valve to thoroughly remove residual sludge and impurities from the inner wall and catalytic packing under pressure. This design is not only easy to operate, but more importantly, it can quickly restore the active surface of the catalyst, ensuring the accuracy of subsequent experimental data and the long-term reusability of the catalyst. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a schematic diagram of the overall structure of the sludge ozone coupled catalytic oxidation treatment experimental system of the present invention; Figure 2 This is a schematic diagram of the structure of an ozone catalytic oxidation reactor; Figure 3 This is a three-dimensional structural diagram of an ozone catalytic oxidation reactor, where the left-hand diagram is a schematic diagram of the internal structure and the right-hand diagram is a schematic diagram of the external structure. Figure 4 This is a schematic diagram of the sealed connection structure between adjacent reaction chambers; Figure 5 This is a schematic diagram of the porous grid structure.

[0022] In the diagram: 100, Oxygen generator; 101, Air compressor; 102, #1 oil-water dryer filter; 103, Oxygen generating unit; 200. Ozone fission device; 201. No. 2 oil-water dryer filter; 202. Ozone fission chamber; 203. No. 3 oil-water dryer filter; 204. Ozone gas source outlet pipe; 205. Circulating water pump; 206. Water inlet; 207. Water outlet pipe; 208. Circulating cooling device; 209. Cooling water tank; 210. Cooling fan; 300. Micro / nano bubble generator; 301. Micro / nano bubble output pipe; 400. Sludge feeding device; 401. Sludge storage tank; 402. Pressure pump; 403. Feeding pipe; 500. Ozone catalytic oxidation reactor; 501. Primary reaction chamber; 502. Secondary reaction chamber; 503. Tertiary reaction chamber; 504. Micro-nano bubble aeration device; 505. Sludge feed nozzle; 506. Exhaust gas valve; 507. Porous bar; 508. Limiting step; 509. Catalytic oxidation packing material; 510. Micro-nano bubble feed pipeline; 511. Sludge feed pipeline; 512. Discharge valve; 513. Sludge overflow port; 514. Sampling valve; 515. Backwash feed valve; 516. Upper flange; 517. Lower flange; 518. Rubber sealing ring; 519. O-ring seal; 520. Base; 521. Limiting sleeve; 600. Online Raman spectroscopy detection device; 601. Online Raman detector; 602. Lifting support; 603. High-precision laser probe; 700. Online ozone concentration monitoring device. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0024] It should be noted that the illustrations provided in the embodiments of the present invention are only schematic representations of the basic concept of the present invention. Therefore, the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation. In actual implementation, the form, quantity and proportion of each component can be arbitrarily changed, and the layout of the components may also be more complex.

[0025] In this invention, it should also be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application. Furthermore, the terms "first" and "second" are used only for descriptive and distinguishing purposes and should not be construed as indicating or implying relative importance.

[0026] Furthermore, it should be noted that the features of the various embodiments of the present invention can be combined or integrated in whole or in part, and as those skilled in the art will understand, they can interact and operate in different ways. Each embodiment can be implemented independently of each other or in association with one another.

[0027] like Figure 1As shown, the present invention proposes a sludge ozone coupled catalytic oxidation treatment experimental system, including an oxygen generator 100, an ozone fission device 200, a micro-nano bubble generator 300, a sludge feeding device 400, an ozone catalytic oxidation reactor 500, an online Raman spectroscopy detection device 600, and an online ozone concentration monitoring device 700.

[0028] See also Figure 1 The primary function of the oxygen generator 100 is to produce a dry, high-concentration oxygen source. It is a benchtop oxygen generator, comprising an air compressor 101, a #1 oil-water dryer filter 102, and an oxygen production unit 103. The air compressor 101 is connected to the oxygen production unit 103, and the #1 oil-water dryer filter 102 is installed on the pipeline between the air compressor 101 and the oxygen production unit 103. The air compressor 101 compresses the air, providing a certain flow rate and pressure. The air then passes through the #1 oil-water dryer filter 102, which absorbs and filters out the moisture and oil generated during the air compression process, forming a dry air source. This air source enters the oxygen production unit 103 through pipelines, where it is enriched to form a high-concentration oxygen source. Other gases are safely discharged separately from the waste outlet. The oxygen generator 100 is composed of these components arranged and connected in a rational layout, and is equipped with an electrical control system integrated inside the equipment housing, forming an independent modular device. The bottom of the equipment housing is designed with casters for easy movement.

[0029] See also Figure 1 The ozone fission device 200 is used to convert the high-concentration oxygen source generated by the oxygen generator 100 into high-purity ozone (O3) through fission and recombination. The ozone fission device 200 includes a #2 oil-water drying filter 201, an ozone fission chamber 202, and a #3 oil-water drying filter 203. The inlet pipe of the ozone fission chamber 202 is connected to the outlet pipe of the oxygen generator 100. The #2 oil-water drying filter 201 is installed on the inlet pipe of the ozone fission chamber 202, and the #3 oil-water drying filter 203 is installed on the ozone oxygen source outlet pipe 204 of the ozone fission chamber 202. The ozone oxygen source outlet pipe 204 is connected to the micro / nano bubble generator 300. First, the oxygen source passes through the #2 oil-water drying filter 201 for deep drying and oil removal before entering the ozone fission chamber 202. A high-frequency, high-voltage electric field "tears" the oxygen molecules into oxygen atoms, and the highly reactive oxygen atoms recombine with the oxygen molecules to form high-purity ozone. Before being transported outward from the ozone source outlet pipe 204, the high-purity ozone is filtered and purified by the No. 3 oil-water drying filter 203.

[0030] The process of converting oxygen source into high-purity ozone (O3) through fission and recombination generates high temperatures, posing challenges to the structure and material lifespan of the ozone fission chamber 202. Cooling measures are necessary. Therefore, this invention designs a circulating water cooling system, which efficiently cools the inside of the ozone fission chamber 202 using circulating cooling water. The ozone fission device 200 also includes a circulating water pump 205, an inlet 206, an outlet pipe 207, a circulating cooling device 208, and a cooling water tank 209. The cooling water tank 209 is connected to the inlet 206 of the ozone fission chamber 202 via the inlet pipe. The circulating water pump 205 is installed on the inlet pipe. The outlet pipe 207 of the ozone fission chamber 202 is connected to the circulating cooling device 208, and the outlet of the circulating cooling device 208 is connected to the cooling water tank 209. First, the circulating water pump 205 pumps cooling water from the cooling water tank 209 to the inlet 206, which then enters the ozone fission chamber 202. The chamber is filled with water, rapidly cooling the water and carrying away the heat. The hot water exits through the outlet pipe 207, is cooled by the circulating cooling device 208, and then returned to the cooling water tank 209, forming a cooling water circulation system. The circulating cooling device 208 features curved circulating water pipes and heat sinks to increase the heat dissipation area, and is equipped with a cooling fan 210 that blows away heat by delivering high-speed air. The entire cooling system is simple and flexible in structure, has good heat dissipation, and low energy consumption.

[0031] The complete ozone fission device 200 is composed of the above components arranged and connected in a reasonable manner, and is equipped with an electrical control system. It is integrated into the equipment box to form an independent modular device. The bottom of the equipment box is designed with a pulley device for easy movement.

[0032] See also Figure 1 The high-concentration ozone generated by the ozone fission device 200 enters the micro-nano bubble generator 300. Simultaneously, an online ozone concentration monitoring device 700 is installed to monitor the ozone source concentration online, providing data support for equipment process operation. The micro-nano bubble generator 300 efficiently mixes the high-concentration ozone source with a small amount of clean water to form a large amount of micro-nano ozone bubble mixture, providing a highly active and highly soluble ozone source for the subsequent ozone catalytic oxidation reaction. This mixture is output through the micro-nano bubble output pipe 301 to the ozone catalytic oxidation reactor 500, providing a high-concentration ozone source for subsequent sludge ozone catalysis.

[0033] See also Figure 1This invention includes a sludge feeding device 400 to provide highly fluid activated sludge for wastewater treatment throughout the entire process. The sludge feeding device 400 includes a sludge storage tank 401, a pressure pump 402, and a feeding pipe 403. The sludge storage tank 401 has a built-in stirring device to ensure that the highly fluid sludge remains uniform and to prevent large particles from settling and clogging the bottom. The discharge port at the bottom of the sludge storage tank 401 is connected to the pressure pump 402. The sludge is pressurized by the pressure pump 402 and connected to the sludge feed pipeline 511 via the feeding pipe 403, allowing it to enter from the bottom of the ozone catalytic oxidation reactor 500. The sludge feed pipeline 511 is equipped with a manual valve, the end of which is connected to a sludge feed nozzle 505. The flow rate at the outlet of the sludge feed nozzle 505 can be finely adjusted by controlling the opening and closing of the valve.

[0034] like Figure 1-2 As shown, activated sludge and high-concentration ozone converge from the bottom of the ozone catalytic oxidation reactor 500 to undergo a catalytic oxidation and cell-wall-breaking reaction. (See also...) Figure 2-3 The ozone catalytic oxidation reactor 500 includes a primary reaction chamber 501, a secondary reaction chamber 502, and a tertiary reaction chamber 503 arranged sequentially from bottom to top. Catalytic oxidation filling material 509 is installed in the primary and secondary reaction chambers 501 and 502, respectively. The primary reaction chamber 501 is mounted on a base 520, and a sludge feed nozzle 505 and a micro-nano bubble aeration device 504 are installed at its bottom. The sludge feed nozzle 505 is connected to a sludge feed pipe 511, and the micro-nano bubble aeration device 504 is connected to a micro-nano bubble feed pipe 510. Sludge and high-concentration ozone are collected and mixed in a high-jet state. The tertiary reaction chamber 503 is equipped with a sludge overflow port 513 and a waste gas valve 506 at its upper part.

[0035] Further optimization resulted in the three reaction chambers being designed with transparent acrylic material, offering high transparency while ensuring good corrosion resistance. Adjacent reaction chambers are connected by flange bolts for a sealed reaction chamber structure. Figure 4 As shown, the present invention designs a two-stage sealing structure. When the upper and lower cylinder flanges are connected, an O-ring 519 is designed at the cylinder connection to form the first stage of sealing; the upper flange 516, the rubber sealing ring 518 and the lower flange 517 are connected by bolts to form the second stage of sealing.

[0036] Further optimization involves designing the connection between the reaction chamber cylinder and the flange as a cylinder-flange sleeve structure. The cylinder passes through the flange hole, retaining a 0.5mm step, and is then welded together to form a sealed assembly. The thickness of the rubber sealing ring 518 must be greater than the gap thickness between the upper flange 516 and the lower flange 517 to achieve a filling and pre-tightening sealing effect.

[0037] Further optimization involves dividing the primary reaction chamber 501, secondary reaction chamber 502, and tertiary reaction chamber 503 into upper and lower zones using detachable porous grids 507. The lower half of the primary reaction chamber 501 serves as a sludge mixing zone, while the upper half is a catalytic packing zone, forming the core area for the sludge ozone catalytic cell disruption reaction. To confine the catalytic material within a limited space, a porous grid 507 is installed above the catalytic material to prevent large particles from moving upwards. Similarly, the secondary reaction chamber 502 has two sets of porous grids 507 installed, one above the other, with catalytic packing filling in between, forming a second-stage catalytic packing zone. The lower part of this second-stage zone, together with the top of the primary reaction chamber 501, creates a pressurized mixing zone. Because the high-jet mixed slurry encounters resistance and its flow rate decreases as it passes through the first-stage catalytic packing zone, sludge particles are prone to clogging. The innovative design of the pressurization zone provides a certain discharge space for the material passing through the first-stage catalytic packing zone. After the sludge is filled, the internal flow reaches a stable equilibrium, which can accumulate a certain fluid pressure, providing a certain power for smooth upward conveying and passing through the second-stage catalytic packing zone. The tertiary reaction chamber 503 mainly receives the sludge mixture after ozone catalytic oxidation and cell wall breaking. A porous grid 507 is installed in the tertiary reaction chamber 503, which can play a defoaming role and at the same time prevent large particles of catalytic material from moving upward.

[0038] Further optimization involves a waste gas valve 506 at the top of the three-stage reaction chamber 503, with a sludge overflow port 513 at the top. The sludge mixture after cell wall disruption is discharged from the sludge overflow port 513 to enter the next process for deep dewatering, while the waste gas involved is discharged to the ozone destruction device through the waste gas valve 506. Sufficient space is left between the sludge overflow port 513 and the waste gas valve 506 to prevent sludge from quickly filling the three-stage reaction chamber 503 and rushing out through the waste gas valve 506, thus contaminating the downstream exhaust pipe and the exhaust gas destruction device.

[0039] Further optimization, such as Figure 5 As shown, the porous grid 507 is designed as a cylindrical structure with a porous bottom. The outer diameter of the cylindrical structure is fitted with the inner wall of the reaction chamber, allowing for convenient assembly and positioning. The pores at the bottom of the porous grid 507 are smaller than the particle size of the catalytic packing material; in this embodiment, the pore size is designed to be 3mm, and the particle size of the catalytic packing material is designed to be 5mm. The bottom of the porous grid 507 is limited by positioning steps 508, which are welded to the inner wall of the reaction chamber.

[0040] Further optimization, such as Figure 2 As shown, at the flange connection of the adjacent reaction chamber, the upper part of the porous grid 507 is limited by the limiting sleeve 521.

[0041] Further optimization involves installing at least one sampling valve 514 in each reaction chamber to sample and test materials from different reaction zones, and to check the physicochemical properties of sludge at different stages.

[0042] Further optimization involves installing at least one backwash inlet valve 515 in each reaction chamber for injecting cleaning fluid, providing a backwashing function. The bottom of the primary reaction chamber 501 is equipped with a discharge valve 512 for discharging wastewater after cleaning. When the test is stopped, without disassembling any components, the discharge valve 512 is opened, and cleaning fluid is injected from the backwash inlet valve 515 to achieve the cleaning function. Simultaneously, the cleaning fluid is designed with a certain pressure to thoroughly remove sludge and impurities from the inner wall of the device and the catalytic packing material, increasing the reusability of the catalytic material. Wastewater after cleaning is discharged from the discharge valve 512.

[0043] like Figure 1 As shown, this invention features an online Raman spectroscopy detection device 600, which innovatively employs Raman spectroscopy technology for online in-situ detection of the cell wall disruption process during ozone catalytic oxidation of sludge. By acquiring real-time changes in the intensity of characteristic Raman peaks of intracellular biomolecules such as polyphosphates, proteins, lipids, nucleic acids, and glycogen in sludge microbial cells, and combining this with the molecular fingerprint information of characteristic pollutants and oxidation intermediates, it achieves multi-dimensional synchronous monitoring of intracellular substance release dynamics, organic matter degradation pathways, and catalyst action mechanisms. This not only accurately characterizes cell wall disruption efficiency and degradation progress but also enables intelligent control of process parameters based on dynamic feedback at the molecular level. It overcomes the technical bottleneck of traditional methods that struggle to acquire sludge biochemical composition and pollutant degradation information online, non-destructively, and synchronously, significantly improving the accuracy and scientific rigor of process control. It boasts outstanding advantages such as non-invasiveness, high real-time performance, and rich information content. The online Raman spectroscopy detection device 600 includes an online Raman detector 601, a lifting bracket 602, and a high-precision laser probe 603. The high-precision laser probe 603 is mounted on the lifting bracket 602 and connected to the online Raman detector 601 via a signal line. The online Raman spectroscopy detection is non-contact, using an external high-precision laser probe 603 to transmit the laser signal through a transparent ozone catalytic oxidation reactor 500 for non-contact detection. The feedback signal is transmitted via a signal line to the online Raman detector 601 system platform for analysis and calculation, thereby obtaining multi-parameter experimental information data. The detection position of the high-precision laser probe 603 can be easily adjusted using the lifting bracket 602, improving the flexibility of the experimental platform.

[0044] The sludge ozone-coupled catalytic oxidation treatment experimental system of the present invention integrates experimental modules such as an oxygen generator 100, an ozone fission device 200, a micro-nano bubble generator 300, and a high-efficiency homogenizing reactor for sludge catalytic oxidation, and is equipped with high-precision online detection modules such as ozone concentration detection and Raman spectroscopy detection, so as to realize efficient sludge cell disruption and process data acquisition, and provide an integrated experimental platform for mechanism research and technology optimization.

[0045] Accordingly, the present invention also proposes an experimental method for ozone-coupled catalytic oxidation treatment of sludge, employing the above-mentioned experimental system. This experimental method includes: A high-concentration oxygen source is generated by an oxygen generator 100. This high-concentration oxygen source is then converted into high-purity ozone through an ozone fission and recombination device 200. The high-purity ozone is then efficiently mixed with a small amount of water by a micro-nano bubble generator 300 to form a large volume of micro-nano ozone bubble mixture. This mixture is then transported to the ozone catalytic oxidation reactor 500 through a micro-nano bubble feed pipe 510. Simultaneously, a sludge feeding device 400 feeds highly fluid sludge into the ozone catalytic oxidation reactor 500 through a sludge feed nozzle 505. Sludge and micro-nano ozone bubbles gather at the bottom of the ozone catalytic oxidation reactor 500 for catalytic oxidation and cell wall breaking reaction; and then come into full contact with the catalytic oxidation filling material 509 in the primary reaction chamber 501 and the secondary reaction chamber 502 in sequence to generate a super catalytic oxidation reaction to achieve cell wall breaking; the sludge mixture after cell wall breaking is discharged from the sludge overflow port 513 of the tertiary reaction chamber 503 to enter the next process for deep dewatering, while the waste gas involved is discharged to the ozone destruction device through the waste gas valve 506 at the top of the tertiary reaction chamber 503.

[0046] During the reaction, the ozone concentration is monitored in real time by an online ozone concentration monitoring device 700; and the sludge ozone catalytic oxidation cell wall disruption process is detected online and in situ by an online Raman spectroscopy detection device 600. This allows for real-time acquisition of the characteristic Raman peak intensity changes of intracellular biomolecules in the sludge microorganisms. Combined with the molecular fingerprint information of characteristic pollutants and oxidation intermediates, multi-dimensional synchronous monitoring of intracellular substance release dynamics, organic matter degradation pathways, and catalyst action mechanisms is achieved. Sampling valve 514 can also be used to sample and test materials from different reaction zones.

[0047] It should be noted that, depending on the implementation needs, the various steps / components described in this application can be broken down into more steps / components, or two or more steps / components or parts of the operation of steps / components can be combined into new steps / components to achieve the purpose of this invention.

[0048] The order of the steps in the above embodiments does not imply the order of execution. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0049] It should be understood that those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A sludge ozone-coupled catalytic oxidation treatment experimental system, characterized in that, This includes oxygen generators, ozone fission devices, micro-nano bubble generators, sludge feeding devices, ozone catalytic oxidation reactors, online Raman spectroscopy detection devices, and online ozone concentration monitoring devices. The ozone catalytic oxidation reactor includes a primary reaction chamber, a secondary reaction chamber, and a tertiary reaction chamber arranged sequentially from bottom to top. Catalytic oxidation filling materials are respectively installed in the primary and secondary reaction chambers. A sludge feeding nozzle and a micro-nano bubble aeration device are installed at the bottom of the primary reaction chamber. A sludge overflow port is provided at the top of the tertiary reaction chamber. The oxygen generator, ozone fission device, and micro-nano bubble generator are connected in sequence, and the micro-nano bubble generator is connected to the micro-nano bubble aeration device; the sludge feeding device is connected to the sludge feeding nozzle. The online Raman spectroscopy detection device includes an online Raman detector, a lifting bracket, and a high-precision laser probe. The high-precision laser probe is mounted on the lifting bracket and connected to the online Raman detector. The high-precision laser probe transmits the laser signal source through the transparent ozone catalytic oxidation reactor for non-contact detection. The detection signal is transmitted to the online Raman detector for analysis and calculation, thereby obtaining multi-parameter experimental information data. The ozone concentration online monitoring device is installed on the outlet pipeline of the ozone fission device to monitor the ozone source concentration online.

2. The sludge ozone-coupled catalytic oxidation treatment experimental system according to claim 1, characterized in that, The oxygen generator is a benchtop oxygen generator, which includes an air compressor, a No. 1 oil-water dryer filter, and an oxygen generation unit. The air compressor is connected to the oxygen generation unit, and the No. 1 oil-water dryer filter is installed on the pipeline between the air compressor and the oxygen generation unit.

3. The sludge ozone-coupled catalytic oxidation treatment experimental system according to claim 1, characterized in that, The ozone fission device includes a No. 2 oil-water drying filter, an ozone fission chamber, and a No. 3 oil-water drying filter. The air inlet pipe of the ozone fission chamber is connected to the air outlet pipe of the oxygen generator. The No. 2 oil-water drying filter is installed on the air inlet pipe of the ozone fission chamber, and the No. 3 oil-water drying filter is installed on the ozone oxygen source outlet pipe of the ozone fission chamber. The ozone oxygen source outlet pipe is connected to the micro-nano bubble generator.

4. The sludge ozone-coupled catalytic oxidation treatment experimental system according to claim 3, characterized in that, The ozone fission device also includes a circulating water pump, an inlet, an outlet pipe, a circulating cooling device, and a cooling water tank. The cooling water tank is connected to the inlet of the ozone fission chamber through the inlet pipe. The circulating water pump is installed on the inlet pipe. The outlet pipe of the ozone fission chamber is connected to the circulating cooling device, and the outlet of the circulating cooling device is connected to the cooling water tank.

5. The sludge ozone-coupled catalytic oxidation treatment experimental system according to claim 1, characterized in that, The sludge feeding device includes a sludge storage tank, a pressure pump, and a feeding pipe. The sludge storage tank has a built-in stirring device, and the discharge port at the bottom of the sludge storage tank is connected to the pressure pump. The pressure pump is connected to the sludge inlet nozzle through the feeding pipe.

6. The sludge ozone-coupled catalytic oxidation treatment experimental system according to claim 1, characterized in that, Porous grids are fixedly installed on the upper and lower parts of the catalytic oxidation filling material in the primary and secondary reaction chambers, respectively; a porous grid is fixedly installed on the middle and lower part of the tertiary reaction chamber, and the pore size of the porous grid is smaller than the particle size of the catalytic oxidation filling material.

7. The sludge ozone-coupled catalytic oxidation treatment experimental system according to claim 1, characterized in that, Adjacent reaction chambers are connected by flange bolts for sealing. A sealing ring is installed at the joint of the adjacent reaction chamber cylinders to form a first-level seal. The upper flange, rubber sealing ring and lower flange are connected by bolts to form a second-level seal, thus forming a sealed reaction cylinder structure.

8. The sludge ozone-coupled catalytic oxidation treatment experimental system according to claim 1, characterized in that, Each reaction chamber is equipped with at least one sampling valve for sampling and checking the physicochemical properties of sludge at different stages.

9. The sludge ozone-coupled catalytic oxidation treatment experimental system according to claim 1, characterized in that, Each reaction chamber is equipped with at least one backwash feed valve for injecting cleaning fluid; the bottom of the primary reaction chamber is equipped with a discharge valve for discharging wastewater after cleaning.

10. A test method for ozone-coupled catalytic oxidation treatment of sludge, characterized in that, The test system using any one of claims 1-9, the test method comprising: A high-concentration oxygen source is generated by an oxygen generator. This high-concentration oxygen source is then converted into high-purity ozone through an ozone fission device. The high-purity ozone is then efficiently mixed with a small amount of water using a micro-nano bubble generator to form a large volume of micro-nano ozone bubble mixture. This mixture is then transported to the ozone catalytic oxidation reactor via a micro-nano bubble aeration device. Simultaneously, a sludge feeding device delivers highly fluid sludge into the ozone catalytic oxidation reactor through sludge feed nozzles. The activated sludge and micro-nano ozone bubbles converge at the bottom of the ozone catalytic oxidation reactor, undergoing a catalytic oxidation and cell-wall breaking reaction. They then come into full contact with the catalytic oxidation filling materials in the primary and secondary reaction chambers, generating a super catalytic oxidation reaction to achieve cell-wall breaking. The broken-wall sludge mixture is discharged from the sludge overflow port of the tertiary reaction chamber to the next stage for deep dewatering, while the waste gas is discharged to the ozone destruction device through the waste gas valve at the top of the tertiary reaction chamber. During the reaction, the ozone concentration is monitored in real time by an online ozone concentration monitoring device; and the ozone catalytic oxidation cell wall disruption process of sludge is detected online in situ by an online Raman spectroscopy detection device. The characteristic Raman peak intensity changes of intracellular biomacromolecules in microbial cells in sludge are obtained in real time. Combined with the molecular fingerprint information of characteristic pollutants and oxidation intermediates, multi-dimensional synchronous monitoring of intracellular substance release dynamics, organic matter degradation pathways and catalyst action mechanisms is achieved.

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