Fluidization device for catalytic purification of wastewater by combining functional adsorption with O3 and application of fluidization device

Abstract

The invention discloses a fluidization device for catalytic purification of wastewater by combining functional adsorption with O3 and application of the fluidization device. The device comprises a reactor main body, and the reactor main body is defined by an outer cylinder, a bottom plate and a top cover; a guide cylinder is arranged in the outer cylinder, an ascending area is formed in the guide cylinder, and a descending area is formed between the outer side of the guide cylinder and the outer cylinder; a water inlet pipe, an ozone inlet pipe, a gas collecting cover, an argillaceous catalyst fixed bed and a bionic adsorbent fixed bed are sequentially arranged in the descending area from top to bottom; water flow of the water inlet pipe is in countercurrent contact with ozone from top to bottom, the ozone is forced to move downwards to be dissolved and react with wastewater, mixed fluid sequentially passes through the catalytic fixed bed layer and the bionic adsorbent fixed bed layer, passes through the bottom gap area and then ascends and circulates along the ascending area, and clear water separated in the separation area is discharged through overflow holes. According to the invention, catalytic oxidation, bionic adsorption, valence conversion and gas stripping separation functions of various pollutants in wastewater can be realized, high-efficiency synergistic removal is realized, and the method belongs to the field of complex industrial wastewater treatment and water reuse.

Description

Technical Field

[0001] This invention relates to the field of complex industrial wastewater treatment and water reuse, specifically to a fluidized bed device for purifying wastewater by functional adsorption combined with O3 catalysis and its application. Background Technology

[0002] Coking wastewater treatment and resource recovery typically employ a combined process including physicochemical units, biological units, advanced treatment, and membrane separation for water reuse. Physicochemical processes (such as phenol removal and ammonia removal, extraction separation, coagulation and sedimentation) primarily remove suspended solids and some organic pollutants, providing treatability for subsequent biological reactions. Biological processes (such as AO, AAO, OHO, or SBR) decompose degradable organic matter through microbial metabolism, removing nutrient pollutants. Advanced treatment (such as advanced oxidation and activated carbon adsorption) further removes residual COD, color, hardness, and persistent organic pollutants (such as polycyclic aromatic hydrocarbons), creating influent conditions for water reuse technologies. Water resource recovery includes membrane separation (softening, decolorization, microfiltration, ultrafiltration, nanofiltration, reverse osmosis) and salt purification (evaporation, crystallization, recrystallization).

[0003] However, existing deep treatment processes for coking wastewater generally suffer from the following problems: (1) Lengthy process and repetitive units. Conventional processes often include multiple stages such as coagulation and sedimentation, lime softening, ozone oxidation, and activated carbon adsorption, coupled with secondary biochemical and re-physicochemical units, resulting in operating costs as high as 10 yuan / m³. 3 above.

[0004] (2) The ozone utilization rate is low (usually less than 50%), the activated carbon is not fully utilized, and its function cannot be fully realized. The main reason is that the gas-liquid contact efficiency in the reactor is low, the mass transfer is limited, the reaction kinetics are not effectively utilized, and the difference between hydrophilic and hydrophobic organic matter cannot be identified.

[0005] (3) In traditional reactors, the gas-liquid or gas-liquid-solid contact mode is singular, and the flow is mostly in the same direction. The gas distribution is uneven and the bubble residence time is short, which leads to the oxidant escaping before it fully reacts, resulting in high energy consumption, high cost, and common short-flow phenomenon.

[0006] Current research focuses primarily on reactor optimization to enhance mass transfer efficiency. One approach involves fluidized bed devices using porous plates or silica sand packing to achieve gas-liquid velocity equilibrium and circulation distribution, thereby improving gas distribution uniformity. Another approach utilizes microbubble reaction systems, which significantly increase specific surface area, vapor pressure, and gas-liquid contact time by generating bubbles with an average diameter of less than 45 μm. Their volumetric mass transfer coefficient is far higher than that of conventional bubbles. However, their structure typically fails to fully utilize fluid dynamics characteristics, making it difficult to enhance reaction kinetics and fully utilize ozone and oxygen molecules.

[0007] In addition, the biological treatment effluent from coking wastewater still contains a large amount of recalcitrant organic matter, such as polycyclic aromatic hydrocarbons (PAHs) like naphthalene, anthracene, phenanthrene, and pyrene; heterocyclic compounds like pyridine, quinoline, indole, and carbazole; and microbial metabolites (soluble inert organic matter), BOD5 / COD ratio. Cr A concentration below 0.1 indicates extremely poor biodegradability. The water also often contains cyanide / thiocyanate complexes, fluorides, silicates, and Fe. 3+ Ca 2+ Inorganic ions and chromatic substances, etc.

[0008] In high-salt environments (such as nanofiltration / reverse osmosis concentrate), the interactions between these pollutants are enhanced, making it difficult for biological methods to function effectively. Therefore, there is an urgent need for a new type of deep purification system that combines adsorption, catalysis, and enhanced mass transfer. Summary of the Invention

[0009] To address the technical problems existing in the prior art, the purpose of this invention is to provide a fluidized bed device for the combined functional adsorption and O3 catalytic purification of wastewater. This device can realize the catalytic oxidation, biomimetic adsorption, valence state conversion and gas stripping separation of various pollutants in wastewater. It can be used for biological treatment effluent of coking wastewater or nanofiltration / reverse osmosis concentrate for advanced treatment, achieving efficient synergistic removal.

[0010] To achieve the above objectives, the present invention adopts the following technical solution: a fluidized bed device for functional adsorption combined with O3 catalysis to purify wastewater, comprising a reactor body, the reactor body being formed by an outer cylinder, a bottom plate, and a top cover; a guide tube is provided inside the outer cylinder, forming an ascending zone inside the guide tube, and a descending zone is formed between the outer side of the guide tube and the outer cylinder; the descending zone is provided with, from top to bottom, a water inlet pipe, an ozone inlet pipe, a gas collection hood, a sludge catalyst fixed bed, and a biomimetic adsorbent fixed bed; the water inlet pipe is used to introduce wastewater, the ozone inlet pipe is used to input ozone, and the gas collection hood is used to collect aggregates in the descending zone. The reactor contains a gas chamber, a catalytic fixed bed filled with metal-loaded biochar catalyst, and a biomimetic adsorbent fixed bed filled with surface polymer-modified biochar biomimetic adsorbent. A bottom gap zone is formed between the lower end of the guide tube and the bottom plate, and a separation zone is formed between the upper end of the guide tube and the top cover. The separation zone includes an effluent separation zone below the liquid surface and a gas collection zone above the liquid surface. The top cover is equipped with an exhaust port, through which the gas in the gas collection zone is discharged. An overflow port is provided at the top of the reactor body, through which the clear water separated in the separation zone is discharged. A gas distribution pipe is provided in the bottom gap zone, directly opposite the rising zone, and the gas distribution pipe is connected to an external gas supply device.

[0011] With this structure, inorganic reducing pollutants in wastewater are first oxidized by ozone at the beginning of the descending zone, recalcitrant organic matter is transformed through free radical reactions in the catalytic bed, and small molecule organic matter and hydrophobic organic matter are further removed in the biomimetic adsorbent, achieving deep purification driven by countercurrent mass transfer and kinetics.

[0012] As a preferred embodiment, the reactor body is filled with powdered activated carbon, which circulates with the fluid between the descending zone, the bottom gap zone, the rising zone, and the separation zone.

[0013] As a preferred embodiment, it also includes an activated carbon control component, which includes a reflux pipe, a discharge pipe, and a replenishment pipe; the effluent separation zone includes a powdered activated carbon settling zone, and the top cover is cylindrical and surrounds the outer periphery and top of the outer cylinder. The powdered activated carbon settling zone is formed between the outer side of the outer cylinder and the top cover. One end of the reflux pipe is connected to the powdered activated carbon settling zone, and the other end is connected to the settling zone. The reflux pipe is connected to the discharge pipe and the replenishment pipe through a three-way valve. The replenishment pipe is connected to an external activated carbon feed tank through a fluid pump.

[0014] As a preferred embodiment, it also includes a bend, the gas collection hood has a cross-section in the shape of a ∧, and the bend connects the inner top of the gas collection hood and the rising area; there are gaps between the two sides of the gas collection hood and the outer cylinder and the inner cylinder for fluid to pass through, and baffles are installed on the inner wall of the outer cylinder and the outer wall of the guide tube, with the baffles located below the gaps.

[0015] As a preferred embodiment, an outlet weir is provided on the outside of the reactor body, the separation zone is connected to the outlet weir through an overflow hole, and a drain pipe is connected to the bottom of the outlet weir.

[0016] As a preferred option, the bottom gap region is also provided with a cross-shaped baffle for rectification, which is located above the air distribution pipe.

[0017] As a preferred embodiment, the bottom gap area is connected to a drain pipe that communicates with the outside. The drain pipe is equipped with a control valve and is used to discharge wastewater during the shutdown phase.

[0018] As a preferred embodiment, both the biochar catalyst and the surface polymer-modified biochar biomimetic adsorbent are honeycomb structure packing materials, which are fixed by a support frame and a screen; the biochar catalyst is bimetallic supported biochar, and the bimetal is a composite of Fe and other transition metals; the surface polymer-modified biochar biomimetic adsorbent is modified activated carbon with polyhydroxybutyrate attached to its surface.

[0019] As a preferred option, the outer cylinder has a manhole for replenishing and removing carbonaceous materials in the fixed bed.

[0020] The above-mentioned fluidized bed device for purifying wastewater by combining functional adsorption with O3 catalysis adjusts the ozone dosage, gas-liquid ratio, reaction time, and temperature according to the different water quality of the wastewater to be treated. When treating biological treatment tailwater of coking wastewater, the reaction time is 0.5 to 1 hour; when treating nanofiltration concentrate, the reaction time is 3 to 5 hours; and when treating reverse osmosis concentrate, the reaction time is 8 to 10 hours. When the fluidized bed device is used in conjunction with a membrane separation system, the water purified by the fluidized bed device enters the membrane separation unit after being filtered through effluent micropores.

[0021] In summary, the present invention has the following advantages: 1. Enhanced gas-liquid-solid three-phase countercurrent design improves ozone utilization and pollutant reaction efficiency. This invention employs a composite reaction system with countercurrent contact in the descending zone and plug-flow circulation in the ascending zone. Ozone and wastewater come into countercurrent contact from top to bottom in the descending zone, forcing small bubbles to dissolve, thus improving the ozone mass transfer coefficient and dissolution rate. In the ascending zone, a gas collection hood enables secondary gas circulation, enhancing gas residence time and reuse rate. Compared to traditional co-current reactors, this device can increase ozone utilization from 50% to over 95%, effectively reducing ozone escape loss, enhancing multiphase mass transfer and reaction kinetic matching in the gas-liquid-solid three-phase system, and significantly improving the oxidative degradation rate and mineralization degree of organic matter.

[0022] 2. The synergistic effect of bifunctional carbonaceous materials combining catalysis and biomimetic adsorption enhances the deep purification of pollutants. The device features a two-stage functional fixed bed: the upper catalytic fixed bed is filled with Fe-based bimetallic supported biochar derived from coking sludge, which can activate ozone to generate •OH and O2. •– Strong oxidizing free radicals promote chain scission and mineralization reactions of recalcitrant organic matter. The lower layer of biomimetic adsorbent fixed bed is filled with biomimetic biochar with surface modification and PHB attachment, mimicking the selective adsorption characteristics of biofilms, and has preferential enrichment and slow-release adsorption functions for hydrophobic and moderately polar organic matter. This dual-function synergistic mode can achieve stratified removal of various pollutants (such as polycyclic aromatic hydrocarbons, quinoline, phenols, chromogenic substances, etc.), and has functions such as catalytic oxidation, biomimetic adsorption, and valence state conversion, improving the overall effluent COD removal rate by 30%~50%.

[0023] 3. Fluidized circulation and reflux regeneration design of powdered activated carbon extends the lifespan of carbonaceous materials. A powdered activated carbon settling zone is located at the top of the reactor, connected to the descending zone via a reflux pipe. This allows the fine activated carbon to circulate with the fluid between the descending, ascending, and separation zones, achieving a dynamic cycle of adsorption-oxidation-reactivation. The activated carbon can self-regenerate in an ozone oxidation environment, maintaining its adsorption performance and avoiding the drawbacks of frequent replacement required in traditional systems. This fluidized circulation system extends the lifespan of carbonaceous materials by 3-5 times, reduces operating and maintenance costs by approximately 40%, and maintains stable adsorption and catalytic performance of the system.

[0024] 4. Adjustable operating parameters ensure strong engineering compatibility and significant energy savings. The device's operating parameters (ozone dosage, gas-liquid ratio, residence time, reaction temperature, etc.) can be flexibly adjusted according to different types of wastewater (water concentration and salinity). Furthermore, the reactor body can be selected as a circular steel structure or a square concrete structure depending on the treatment scale, and seamlessly connected to the membrane separation system. After pretreatment by this device, the flux of wastewater entering the membrane system can be increased by more than 3 times, and operating costs can be reduced by approximately 50%. This achieves a highly efficient combined process of "enhanced oxidation + biomimetic adsorption + membrane filtration," combining engineering feasibility with economic efficiency. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the internal structure of the fluidized bed device for the functional adsorption combined with O3 catalytic purification of wastewater in Example 1.

[0026] Figure 2 This is a top view of the separation zone of the fluidized bed device for the combined functional adsorption and O3 catalytic purification of wastewater in Example 1.

[0027] Figure 3 This is a top view of the gas collection hood of the fluidization device for the functional adsorption combined with O3 catalytic purification of wastewater in Example 1.

[0028] Figure 4 This is a top view of the bottom air intake structure of the fluidization device for the functional adsorption combined with O3 catalytic purification of wastewater in Example 1.

[0029] Figure 5 This is a continuous effluent photograph taken during the implementation of the fluidized bed device for purifying wastewater using functional adsorption combined with O3 catalysis, as shown in Example 1.

[0030] Figure 6 This is a graph showing the continuous operation of the fluidized bed device for purifying wastewater using functional adsorption combined with O3 catalysis, as described in Example 1.

[0031] Figure 7 This is a schematic diagram of the internal structure of the fluidized bed device for the functional adsorption combined with O3 catalytic purification of wastewater in Example 4.

[0032] Figure 8 This is a top view of the separation zone of the fluidized bed device for the functional adsorption combined with O3 catalytic purification of wastewater in Example 4.

[0033] Figure 9 This is a top view of the gas collection hood of the fluidization device for the functional adsorption combined with O3 catalytic purification of wastewater in Example 4.

[0034] Figure 10 The image shows a three-view diagram of the cross-shaped baffle of the fluidization device for the combined functional adsorption and O3 catalytic purification of wastewater in Example 4.

[0035] The components include: 1. Gas supply device; 101. Ozone generator; 102. Air pump; 103. Activated carbon feeding tank; 104. Gas pressure gauge; 105. Rotor flow meter; 106-1. First shut-off valve; 106-2. Second shut-off valve; 106-3. Third shut-off valve; 201. Reactor body; 202. Outer cylinder; 203. Bottom plate; 204. Top cover; 205. Guide tube; 206. Manhole; 301. Descending zone; 302. Ascending zone; 303. Bottom clearance zone; 304. Separation zone; 305. Effluent separation zone; 306. Gas collection zone; 307. Powdered activated carbon settling zone; 401, water inlet pipe; 402, water inlet distributor; 403, ozone air inlet pipe; 404, titanium alloy microporous aeration pipe; 405, air distribution pipe; 406, central air intake structure; 407, bottom air intake structure; 408, return pipe; 409, three-way valve; 410, fluid pump; 411, elbow; 501, cross-shaped baffle; 502, underwater thruster; 503, sludge catalyst fixed bed; 504, biomimetic adsorbent fixed bed; 505, support frame; 506, screen; 507, gas collection hood; 508, baffle plate; 601, overflow hole; 602, effluent weir; 603, drain pipe; 604, vent hole; 605, empty pipe; 606, liquid drain pipe. Detailed Implementation

[0036] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0037] Example 1 A fluidized bed reactor for wastewater purification using functional adsorption combined with O3 catalysis includes a reactor body, which is formed by an outer cylinder, a bottom plate, and a top cover. Inside the outer cylinder is a guide tube, forming an ascending zone, and outside the guide tube forms a descending zone between it and the outer cylinder. From top to bottom, the descending zone includes a water inlet pipe, an ozone inlet pipe, a gas collection hood, a sludge catalyst fixed bed, and a biomimetic adsorbent fixed bed. The water inlet pipe is used to introduce wastewater, the ozone inlet pipe is used to introduce ozone, the gas collection hood is used to collect the coalesced gas in the descending zone, and the catalyst fixed bed is filled with… The reactor is equipped with a biochar catalyst loaded with metal and a fixed bed of biomimetic adsorbent filled with surface polymer-modified biochar biomimetic adsorbent. A bottom gap zone is formed between the lower end of the guide tube and the bottom plate, and a separation zone is formed between the upper end of the guide tube and the top cover. The separation zone includes an effluent separation zone below the liquid surface and a gas collection zone above the liquid surface. The top cover is equipped with an exhaust port, through which the gas in the gas collection zone is discharged. An overflow port is provided at the top of the reactor body, through which the clear water separated in the separation zone is discharged. A gas distribution pipe is provided in the bottom gap zone, directly facing the rising zone, and the gas distribution pipe is connected to an external gas supply device.

[0038] The ozone inlet pipe is equipped with a titanium alloy microporous aeration pipe, which is connected to an external ozone generator. The water inlet pipe is equipped with a water distributor, which is located at the upper end of the descending zone and above the microporous aeration pipe. This allows the high-concentration influent wastewater and high-concentration ozone to preferentially contact and react at the beginning of the reactor, thereby achieving concentration kinetic matching.

[0039] The air supply system includes an air pump and an air distribution pipe forming a bottom air intake structure. It connects to an external air supply device (power / raw material supply) via a bottom air supply pipe, and the air supply device also connects to the central air intake structure via a central air supply pipe. Both the bottom and central air supply pipes are equipped with rotor flow meters and a first shut-off valve. Large bubbles formed by the air distribution pipe are supplied by the air supply system, and air rises from the bottom, forming a gas-liquid-solid three-phase flow, promoting mass transfer and reaction. In the descending zone, the influent flow and ozone come into counter-current contact from top to bottom. The ozone is forced to descend, dissolve, and react with the wastewater. The mixed fluid sequentially passes through the catalytic fixed bed and the biomimetic adsorbent fixed bed, then circulates upwards along the ascending zone after passing through the bottom gap zone. The separated water in the separation zone flows into the effluent weir through the overflow hole and is finally discharged through the drain pipe. In the above process, dissolved reducing inorganic pollutants in the wastewater are preferentially oxidized by ozone molecules in the initial stage of the descending zone; recalcitrant organic matter is decomposed by ozone in the catalytic fixed bed, producing active oxygen (•OH, O2). •– The organic molecules are further oxidized into smaller organic molecules; while extremely low concentrations of hydrophobic organic molecules are adsorbed by biomimetic adsorbents and then oxidized. The final products of the reaction are mainly CO2 and SO4. 2− NO3 − Stable salts and some volatile components (including VOCs) are collected in the gas collection area and then subjected to secondary purification treatment. Through this countercurrent mass transfer reaction process, the synergistic removal and thorough purification of multiple pollutants in the wastewater are achieved.

[0040] The vent is connected to a vent pipe, and a gas pressure gauge is installed on the vent pipe.

[0041] Specifically, the reactor body is filled with powdered activated carbon, which circulates with the fluid between the descending zone, the bottom void zone, the rising zone, and the separation zone. The reactor is filled with 10% to 15% powdered activated carbon (100 to 150 mesh). The powdered carbon circulates repeatedly with the fluid in the descending zone, the bottom void zone, the rising zone, and the separation zone, achieving a synergistic effect of dynamic adsorption and catalytic reaction.

[0042] Specifically, it also includes an activated carbon control component, which comprises a return pipe, a discharge pipe, and a replenishment pipe. The effluent separation zone includes a powdered activated carbon settling zone. The top cover is cylindrical and surrounds the outer periphery and top of the outer cylinder. The powdered activated carbon settling zone is formed between the outer side of the outer cylinder and the top cover. One end of the return pipe connects to the powdered activated carbon settling zone, and the other end connects to the descending zone. The return pipe is connected to the discharge pipe and the replenishment pipe via a three-way valve. The replenishment pipe is connected to an external activated carbon feeding tank via a fluid pump. In the activated carbon feeding tank, the powdered activated carbon is mixed with water to form a slurry with a content of 10%~15% (by weight), and then transported by a fluid pump. Second shut-off valves are installed on the return pipe, discharge pipe, and replenishment pipe, as well as between the return pipe and the three-way valve. After the powdered activated carbon is separated in the settling zone by a fluid of equal flow rate to the influent, the fluid flows into the effluent weir through the overflow hole. The powdered activated carbon then naturally flows back to the descending zone based on its specific gravity difference, achieving reuse. Saturated activated carbon can be discharged from the discharge pipe through a three-way valve, while fresh activated carbon is added through a fluid pump, thereby realizing the discharge and replenishment of activated carbon.

[0043] Specifically, this also includes a bend in the gas collection hood, whose cross-section is ∧-shaped. The bend connects the inner top of the gas collection hood to the rising zone. Gaps for fluid passage are left between the two edges of the gas collection hood and the outer and inner cylinders. Baffles are installed on the inner wall of the outer cylinder and the outer wall of the guide tube, located below these gaps. Some small bubbles in the descending zone coalesce and rise, transferring to the rising zone through the gas collection hood and the bend, thus achieving flow propulsion, enhanced mass transfer, and reduced resistance in the descending zone. The specific process is as follows: Submerged dissolved gas or some small bubbles coalesce and rise in the descending zone. The gas collection hood, combined with the bend, transfers them to the rising zone, acting as a flow propulsion and mixing agent, while simultaneously reducing the internal resistance of the descending zone and enhancing the fluid stability of the reactor.

[0044] Specifically, an outlet weir is provided on the outside of the reactor body, the separation zone is connected to the outlet weir through an overflow hole, and a drain pipe is connected to the bottom of the outlet weir.

[0045] Specifically, the bottom gap region is also equipped with a cross-shaped baffle for flow rectification, located above the air distribution pipe. An underwater thruster can also be installed in the bottom gap region to enhance flow propulsion.

[0046] Specifically, the bottom clearance area is connected to a drain pipe that leads to the outside. The drain pipe is equipped with a control valve and is used to discharge wastewater during the shutdown phase. The control valve is a third shut-off valve.

[0047] Specifically, both the biochar catalyst and the surface polymer-modified biochar biomimetic adsorbent are honeycomb structure packings with a size of 15-20 mm and an inner pore size of 5-8 mm. They are fixed by a support frame and a screen, allowing fluid and powdered activated carbon to pass through freely. The biochar catalyst is bimetallic supported biochar, and the bimetal is a composite of Fe and other transition metals. The surface polymer-modified biochar biomimetic adsorbent is modified activated carbon with polyhydroxybutyrate (PHB) attached to its surface.

[0048] Specifically, the outer cylinder has a manhole for replenishing and removing carbonaceous material from the fixed bed. Maintenance and replacement of the carbonaceous material in the fixed bed can be performed through the manhole.

[0049] The above-mentioned fluidized bed device for purifying wastewater by combining functional adsorption with O3 catalysis adjusts the ozone dosage, gas-liquid ratio, reaction time, and temperature according to the different water quality of the wastewater to be treated. When treating biological treatment tailwater of coking wastewater, the reaction time is 0.5 to 1 hour; when treating nanofiltration concentrate, the reaction time is 3 to 5 hours; and when treating reverse osmosis concentrate, the reaction time is 8 to 10 hours. When the fluidized bed device is used in conjunction with a membrane separation system, the water purified by the fluidized bed device enters the membrane separation unit after being filtered through effluent micropores.

[0050] This device achieves enhanced gas-liquid-solid three-phase countercurrent reaction through the structural assembly and functional coupling design of fluidized and fixed beds. It combines functional adsorption with the fluidized bed adsorption of powdered activated carbon and the hydrophobic modified adsorption of biomimetic carbon, along with the synergistic effect of catalytic oxidation and multiphase mass transfer processes. This enables highly efficient and deep purification of coking wastewater, nanofiltration concentrate, and reverse osmosis concentrate, ensuring stable water quality compliance (for reclaimed water reuse or restricted discharge). By controlling the proportion of material flow within the reactor and optimizing fluid dynamics parameters, the device achieves matching between gas-liquid mass transfer and reaction kinetics. Through the synergistic effect of multifunctional adsorption-catalysis, it achieves deep purification of most pollutants in a single reactor, eliminating membrane resistance factors and significantly improving reactor efficiency to reduce operating costs. This invention demonstrates significant innovation and advancements in reactor structural design, continuous feeding methods, continuous discharge methods, fluid dynamics control, utilization of carbonaceous functions, and handling of different water qualities.

[0051] In practical implementation, square reinforced concrete reactors and circular steel structure reactors can be selected for construction based on the water quality characteristics and treatment requirements of different wastewater types. In this embodiment, the above-mentioned device is used for the effluent deep treatment unit. Since the effluent treatment volume is large, the reaction time is short, and the corrosiveness is relatively low, a square reinforced concrete structure is preferred. This type of structure has good overall integrity, high impermeability, is suitable for large-volume construction and equipment layout, and is beneficial for subsequent operation, maintenance, and repair.

[0052] In specific implementation, such as Figures 1-4As shown, a square reinforced concrete structure is used, with fluidized bed dimensions of L×B×H = 10 m × 5 m × 10 m. The wastewater treatment capacity is approximately 50 m³. 3 / h, when the influent COD = 80~120 mg∙L −1 NH4 + -N = 2~4mg∙L −1 TN = 12~18 mg∙L −1 Total cyanide 0.6 mg∙L −1 Ozone concentration = 12 mg∙L −1 The hydraulic retention time of the reactor is 0.5~1.0 h; the reactor's COD and NH4+ content are... + The removal rates of -N, TN, and total cyanide were 66.7%–75.0%, 45.0%–60.0%, 60.0%–66.0%, and 35.0%–55.0%, respectively. This was achieved when the ozone concentration was controlled at 10–14 mg∙L⁻¹. −1 At that time, the operating cost, including ozone dosage, activated carbon loss rate, and power for stirring and conveying, averaged approximately 4.3 yuan / m³. 3 . Figure 5 The leftmost water bottle represents the water inlet, and the others represent the water outlet. Specific inlet and outlet water quality monitoring data are as follows: Figure 6 As shown in Table 1, the average influent COD concentration during the test period was 95.85 mg / L, the average effluent COD concentration was 31.56 mg / L, and the average removal rate was 67.07%.

[0053] Table 1 Comparison of influent and effluent water quality indicators before and after treatment

[0054]

[0055] Implementation Case 2: Building upon Example 1, this example proposes a combined biomimetic adsorption and atomic catalysis technique to further improve the removal efficiency of low-concentration hydrophobic organic pollutants. This principle draws inspiration from the enrichment mechanism of hydrophobic organic matter by microorganisms in nature. Based on biochar produced from coking sludge, PHB is loaded onto its surface in an evaporation reactor, significantly enhancing its adsorption performance for low-concentration hydrophobic organic matter. This PHB is then applied as a biomimetic adsorbent in a fluidized bed reaction system.

[0056] This biomimetic adsorption process is based on van der Waals forces and similar-to-similarity interactions between the micro / nano pore structure and the liquid-solid interface. Through a biomimetic design of a fat-like cavity structure, an instantaneous negative pressure is created under active (vacuuming) or passive (pressing) conditions, achieving efficient adsorption and controllable desorption switching, exhibiting bio-like response characteristics. Approximately 30% of the volume area in the descending region is filled with the prepared biomimetic adsorbent particles, forming a functional coupling with the catalyst region.

[0057] The preparation and synergistic mechanism of carbonaceous catalyst and biomimetic adsorbent are as follows: (1) PHB-biochar is prepared using coking sludge as raw material and loaded with bimetallic Fe / Cu and Fe / Co respectively to form Fe / Cu-biochar and Fe / Co-biochar catalysts; (2) The synergistic effect between Fe and Co in Fe / Co-biochar constructs multiple transition channels of electronic energy levels and improves electron transfer efficiency; (3) Fe and Co coexist in different valence states, which accelerates the cyclic conversion process of Fe(II) / Fe(III) and Co(II) / Co(III) and enhances the generation capacity of active oxygen; (4) Quinoline and biological effluent from coking wastewater are used as target pollutants to verify the catalytic oxidation performance and economic feasibility of the system and evaluate the industrial application potential of the Fe / Co-biochar / O3 system.

[0058] By combining the above-mentioned biomimetic adsorption and atomic catalysis system with the reaction kinetics driven by countercurrent mass transfer, we can achieve efficient oxidation and deep purification of recalcitrant organic pollutants. At the same time, it has the functions of adsorption, catalysis, gas stripping and separation, providing an engineering solution for the efficient treatment of highly polluted water bodies.

[0059] Implementation Case 3: This embodiment is based on the structure and countercurrent mass kinetics reaction principle of the combined catalytic and biomimetic adsorption purification of wastewater described in Example 1. It achieves variable parameter reaction control and optimized operation for different wastewaters such as biological treatment tailwater of coking wastewater, nanofiltration concentrate and reverse osmosis concentrate.

[0060] The water quality characteristics of biological treatment effluent from coking wastewater have a significant impact on the selection and operating conditions of subsequent advanced treatment units. Typical water quality parameters are as follows: influent COD is 120~200 mg∙L. −1 After deep processing, the concentration can be reduced to 20-40 mg∙L. −1 ; Inlet water NH4 + -N approximately 5 mg∙L −1 The effluent concentration can be reduced to 2 mg∙L. −1 The influent total nitrogen (TN) is as follows: 16~18 mg∙L. −1 After treatment, the concentration can be reduced to 4-10 mg∙L. −1 The influent cyanide content is 0.4~0.8 mg∙L. −1After treatment, the level can be below 0.2 mg∙L. −1 ; Volatile phenols in the influent: 0.1~0.3 mg∙L −1 The effluent is completely undetectable; the color removal rate reaches 70%~90%; and the suspended solids (SS) can be controlled below 10 mg∙L. −1 The following are the main harmful components remaining after biochemical treatment: aromatic compounds, humic acids, and soluble microbial metabolites, which are difficult to biodegrade organic matter. These substances are the main reasons for the high COD and color of the effluent, and further removal is required by advanced oxidation and coupled adsorption technologies.

[0061] To address the characteristics and reaction requirements of different types of wastewater, this embodiment constructs a variable operating mode by adjusting key parameters such as catalyst type, activated carbon particle size, and reaction time in the fluidized bed system. (1) Biological wastewater treatment mode: 200-mesh powdered activated carbon is added to the fluidized bed reactor (1) and combined with the ozone and air aeration system. The reaction time is controlled at 0.5~1 h to achieve efficient ozone dissolution and dynamic adsorption of powdered activated carbon, promote the rapid oxidation and removal of low-to-medium concentration organic pollutants, and have the functions of color reduction and turbidity purification.

[0062] (2) Nanofiltration Concentrate Treatment Mode: Addressing the characteristic of high concentrations of organic matter and inorganic ions coexisting in the concentrated wastewater generated by nanofiltration, a bimetallic Fe / Cu-supported biochar catalyst (Fe / Cu-biochar) was selected as the packing material for the catalytic fixed bed (503), combined with a second type of activated carbon (30-50 mesh) with a high specific surface area to enhance adsorption and electron transfer effects. The reaction time was controlled at 3-5 h, and the active oxygen (O2) in the catalytic ozone system was utilized. •− Through the action of OH radicals, deep mineralization and structural destruction of complex organic pollutants are achieved.

[0063] (3) Reverse osmosis concentrate treatment mode: Addressing the characteristics of high salt content, high toxicity, and extremely difficult-to-degrade organic matter in reverse osmosis concentrate, a bimetallic Fe / Co-supported biochar catalyst (Fe / Co-biochar) is selected as the fixed-bed catalytic packing material, combined with high-porosity activated carbon particles (60-80 mesh) to enhance mass transfer performance and adsorption retention time. The reaction time is extended to 8-10 h to ensure full utilization of ozone and continuous action of catalytic active sites. Through the electron cycle and free radical chain reaction mechanism between multivalent Fe and Co, the complete oxidation and decolorization of organic pollutants are accelerated.

[0064] By setting the above-mentioned variable operating parameters, the reactor can flexibly adjust the reaction time, catalyst type and adsorption medium according to the differences in the properties of the tailwater or concentrate, thereby reducing energy consumption and operating costs while ensuring removal efficiency.

[0065] Implementation Case 4: Depending on the treatment scale and water quality characteristics, the main body of the reactor can be selected as a circular steel structure reactor or a square concrete structure. When treating wastewater with large volume, low corrosivity, and short retention time, square reinforced concrete structures are preferred. When treating highly corrosive concentrated water, circular steel structure reactors or reactors made of other antioxidant materials are preferred.

[0066] Compared to Example 1, this example uses a circular stainless steel reactor for the treatment of high-concentration, highly corrosive concentrated wastewater. This reactor offers uniform stress distribution, high manufacturing precision, and the ability to be prefabricated in the factory and quickly assembled on-site, facilitating corrosion protection construction and maintenance. It also performs exceptionally well in applications requiring high pressure resistance and leak-proofing.

[0067] like Figures 7-10 As shown, this embodiment uses a circular stainless steel structure, with fluidized bed dimensions of φ×H = 2.6m×10m and an effective volume of approximately 50 m³. 3 The reverse osmosis concentrate treatment capacity is 5 m³. 3 / h, HRT=10 h; influent COD = 600~800 mg∙L −1 The effluent COD is 130~150 mg∙L. −1 Phenol and cyanide were undetectable in the effluent; NH4 was undetectable in the influent. + -N = 30~50 mg∙L −1 TN = 130~160 mg∙L −1 At that time; NH4 in the effluent + -N = 3~6 mg∙L −1 TN = 60~80 mg∙L −1 During the 24-day test period, the activated carbon dosage was 0.38~0.64 kg / m³. 3 The cost is 2.36~3.64 yuan / m. 3 Ozone treatment cost: 2.87~4.45 yuan / m³ 3 The air-to-water ratio is 4:1 to 6:1, and the power cost is 0.88 to 1.28 yuan / m³. 3 The total processing cost is approximately RMB 5.91 to 9.37 per cubic meter. 3 It has demonstrated significant effectiveness.

[0068] The above embodiments are preferred embodiments of the invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A fluidized bed device for purifying wastewater by functional adsorption combined with O3 catalysis, characterized in that: The reactor body consists of an outer cylinder, a bottom plate, and a top cover. The outer cylinder has a guide tube inside, and the inside of the guide tube forms an ascending zone, while the outside of the guide tube and the outer cylinder form a descending zone. The descending zone is equipped with, from top to bottom, a water inlet pipe, an ozone inlet pipe, a gas collection hood, a clay catalyst fixed bed, and a biomimetic adsorbent fixed bed; The inlet pipe is used to introduce wastewater, the ozone inlet pipe is used to input ozone, the gas collection hood is used to collect the gas aggregated in the descending zone, the catalytic fixed bed is filled with metal-loaded biochar catalyst, and the biomimetic adsorbent fixed bed is filled with surface polymer-modified biochar biomimetic adsorbent. A bottom gap area is formed between the lower end of the guide tube and the bottom plate, and a separation area is formed between the upper end of the guide tube and the top cover. The separation area includes an outlet water separation area below the liquid surface and a gas collection area above the liquid surface. The top cover is equipped with an exhaust hole, and the gas in the gas collection area is discharged through the exhaust hole. An overflow hole is provided at the top of the reactor body, and the clear water separated in the separation area is discharged through the overflow hole. The bottom gap area is equipped with an air distribution pipe that faces the rising area and is connected to an external air supply device.

2. The fluidized bed device for functional adsorption combined with O3 catalytic purification of wastewater according to claim 1, characterized in that: The reactor body is filled with powdered activated carbon, which circulates with the fluid between the descending zone, the bottom gap zone, the rising zone, and the separation zone.

3. The fluidized bed device for functional adsorption combined with O3 catalysis to purify wastewater according to claim 2, characterized in that: It also includes activated carbon control components, which include a return pipe, an outlet pipe, and a replenishment pipe. The effluent separation zone includes a powdered activated carbon settling zone. The top cover is cylindrical and surrounds the outer periphery and top of the outer cylinder. The powdered activated carbon settling zone is formed between the outer side of the outer cylinder and the top cover. One end of the return pipe is connected to the powdered activated carbon settling zone, and the other end is connected to the descending zone. The return pipe is connected to the discharge pipe and the replenishment pipe through a three-way valve. The replenishment pipe is connected to the external activated carbon feeding tank through a fluid pump.

4. The fluidized bed device for functional adsorption combined with O3 catalysis for purifying wastewater according to claim 1, characterized in that: It also includes a bend, the gas collection hood has a cross-section in the shape of a ∧, and the bend connects the inner top of the gas collection hood and the rising area; The gas collection hood has gaps between its two sides and the outer and inner cylinders for fluid to pass through. The inner wall of the outer cylinder and the outer wall of the guide tube are equipped with baffles, which are located below the gaps.

5. The fluidized bed device for functional adsorption combined with O3 catalytic purification of wastewater according to claim 1, characterized in that: The outer side of the reactor body is provided with an outlet weir, and the separation zone is connected to the outlet weir through an overflow hole. The bottom end of the outlet weir is connected to a drain pipe.

6. The fluidized bed device for functional adsorption combined with O3 catalytic purification of wastewater according to claim 1, characterized in that: The bottom clearance area is also equipped with a cross-shaped baffle for rectification, which is located above the air distribution pipe.

7. The fluidized bed device for functional adsorption combined with O3 catalytic purification of wastewater according to claim 1, characterized in that: The bottom gap area is connected to a drain pipe that connects to the outside. The drain pipe is equipped with a control valve and is used to discharge wastewater during the shutdown phase.

8. The fluidized bed device for functional adsorption combined with O3 catalytic purification of wastewater according to claim 1, characterized in that: Both the biochar catalyst and the surface polymer-modified biochar biomimetic adsorbent are honeycomb structure packing materials, which are fixed by a support frame and a screen. The biochar catalyst is bimetallic supported biochar, where the bimetal is a composite of Fe and other transition metals; The surface polymer-modified biochar biomimetic adsorbent is a modified activated carbon with polyhydroxybutyrate attached to its surface.

9. The fluidized bed device for functional adsorption combined with O3 catalytic purification of wastewater according to claim 1, characterized in that: The outer cylinder has a manhole for replenishing and removing carbonaceous materials in the fixed bed.

10. The application of the fluidized bed device for functional adsorption combined with O3 catalytic purification of wastewater as described in any one of claims 1-9, characterized in that: Adjust the ozone dosage, gas-liquid ratio, reaction time, and temperature according to the different qualities of the wastewater to be treated. When treating coking wastewater effluent through biological treatment, the reaction time is 0.5 to 1 hour; When treating nanofiltration concentrate, the reaction time is 3 to 5 hours; When treating reverse osmosis concentrate, the reaction time is 8 to 10 hours; The fluidization device is used in conjunction with a membrane separation system. The water purified by the fluidization device is filtered through the effluent micropores and then enters the membrane separation unit for operation.

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