A device for removing refractory organic matter in wastewater and recycling materials

Abstract

The application belongs to the technical field of wastewater treatment devices, and particularly relates to a device for removing refractory organic matter in wastewater and recycling materials. The technical scheme is as follows: a device for removing refractory organic matter in wastewater and recycling materials, comprising, from bottom to top, a water inlet adjusting unit, a liquid inlet pressurizing and distributing unit, a rectifying unit, an electro-catalytic core treatment unit and a material recycling device; the water inlet adjusting unit is provided with an S-ZVI feeding port, a wastewater feeding port and an oxidant feeding port; the material recycling device comprises a collecting cylinder, the bottom of the collecting cylinder is provided with a material negative pressure recycling unit, the upper part of the collecting cylinder is connected with a treated wastewater collecting unit, and the top of the collecting cylinder is connected with a waste gas collecting cover. The application provides a device for removing refractory organic matter in wastewater and recycling materials by using electro-catalytic enhanced sulfidized zero-valent iron.

Description

Technical Field

[0001] This invention belongs to the technical field of wastewater treatment devices, and specifically relates to a device for removing recalcitrant organic matter from wastewater and for material recovery. Background Technology

[0002] This invention relates to a process and apparatus for removing recalcitrant organic matter from wastewater using electrocatalytically enhanced zero-valent iron sulfide, primarily aimed at addressing key technological bottlenecks in the field of advanced industrial wastewater treatment. Wastewater generated in industries such as semiconductors, petrochemicals, and pesticides typically exhibits characteristics including fluoride ion concentrations of 500–2000 mg / L, conductivity as high as 20–50 mS / cm, COD concentrations of 1000–5000 mg / L, BOD concentrations of 500–1000 mg / L, and SS concentrations of 800–1000 mg / L. These complex water quality conditions severely limit the application of traditional treatment processes.

[0003] Currently, mainstream technologies face numerous challenges in treating this type of wastewater. While chemical precipitation is simple to operate, its removal efficiency for recalcitrant organic matter is unsatisfactory, and it generates large amounts of chemical sludge requiring secondary treatment. Traditional Fenton oxidation processes require continuous addition of large amounts of hydrogen peroxide, resulting in high operating costs and significantly reduced oxidation efficiency in high-salt environments. Biological treatment processes suffer from the dual inhibition of high salt and high fluoride ion levels, making it difficult to maintain microbial activity. Membrane separation technology, due to membrane fouling and scaling issues, requires frequent cleaning and replacement, leading to excessively high operating and maintenance costs.

[0004] The closest approach, the sulfidation-based zero-valent iron / hydrogen peroxide treatment system, while improving the stability of zero-valent iron through sulfidation modification, still fails to completely solve the problem of material deactivation under high-salt conditions. Furthermore, the continuous increase in hydrogen peroxide dosage significantly increases operating costs. This technology also has limited effectiveness in removing fluoride ions, failing to meet stringent emission standards. Simultaneously, the reaction process lacks precise control, making it difficult to adapt to fluctuations in influent water quality.

[0005] In summary, the existing technology has the following disadvantages:

[0006] First, there are issues with poor material stability and short lifespan: In existing technologies, zero-valent iron is prone to passivation and agglomeration under high-salt conditions, leading to a reduction in active sites and a rapid decline in reaction efficiency. Although traditional surface modification methods can improve material stability to some extent, the effect is not ideal, and the catalyst lifespan is generally short.

[0007] Secondly, there are problems with low treatment efficiency and high energy consumption: Traditional processes such as Fenton oxidation and electrochemical oxidation often require the addition of large amounts of oxidant or the application of high voltage to achieve the desired treatment effect when treating high-salt and high-fluoride wastewater. This not only results in high energy consumption but also low treatment efficiency.

[0008] Third, the technology suffers from poor adaptability to water quality and weak resistance to interference: Existing technologies are highly sensitive to fluctuations in influent water quality, especially under complex water conditions such as high salinity and high fluoride, where the treatment effect is often not stable enough.

[0009] Fourth, the problem of poor fluoride ion removal efficiency: Conventional processes are generally not ideal for removing fluoride ions, especially in high-salt environments, where the removal rate of fluoride ions often fails to meet emission standards.

[0010] Fifth, poor waste gas treatment effect, which easily leads to secondary pollution problems: Existing technologies often generate a large amount of toxic and harmful waste gas during the treatment process, and the treatment effect is not ideal.

[0011] Sixth, high operating and maintenance costs: Existing technologies generally suffer from problems such as high consumption of reagents and frequent equipment maintenance, resulting in persistently high operating costs. Summary of the Invention

[0012] In order to solve the above-mentioned problems in the prior art, the purpose of this invention is to provide an apparatus for removing refractory organic matter from wastewater and recovering materials by electrocatalytically enhanced zero-valent iron sulfide.

[0013] The technical solution adopted in this invention is as follows:

[0014] A device for removing recalcitrant organic matter from wastewater and recovering materials includes, from bottom to top, an inlet regulating unit, an inlet pressurizing and spreading unit, a rectifier unit, an electrocatalytic core treatment unit, and a material recovery device. The inlet regulating unit is equipped with an S-ZVI inlet, a wastewater inlet, and an oxidant inlet. The material recovery device includes a collection cylinder, with a material negative pressure recovery unit at the bottom, a wastewater collection unit connected to the top of the collection cylinder, and a waste gas collection hood connected to the top of the collection cylinder.

[0015] This invention aims to develop an integrated treatment process capable of efficiently removing recalcitrant organic matter under high-salt and high-fluoride conditions, exhibiting good material stability, low operating costs, high intelligence, and waste gas resource recovery capabilities. This process aims to meet the increasingly stringent environmental and economic requirements in the industrial wastewater treatment field. During wastewater treatment, nano-S-ZVI material is added through the S-ZVI inlet, wastewater is added through the wastewater inlet, and oxidant is added through the oxidant inlet. The mixed liquid is then sequentially processed through an inlet regulating unit, an inlet pressurizing and distributing unit, a rectification unit, and an electrocatalytic core treatment unit, effectively removing recalcitrant organic matter from the wastewater.

[0016] This invention utilizes a negative pressure material recovery unit to extract nano-S-ZVI material from the collection cylinder, enabling the collection and reuse of this material. Wastewater from which the nano-S-ZVI material is separated by centrifugation is collected from the top of the collection cylinder by a wastewater collection unit. Exhaust gas is collected by an exhaust gas collection hood and then sent to a downstream exhaust gas treatment device for processing. This invention can recover nano-S-ZVI material, wastewater, and exhaust gas separately, reducing wastewater treatment costs through resource utilization.

[0017] This invention successfully solves the material stability problem through an innovative sulfidation-modified zero-valent iron process and a new processing device, thereby increasing the catalyst's service life by more than 50% and significantly reducing operating costs.

[0018] This invention organically combines zero-valent iron sulfide with electrocatalytic technology. By optimizing the electrode structure and process parameters, it can achieve efficient COD removal under low energy consumption conditions, improving the treatment efficiency by more than 30%.

[0019] Through innovative process design, this invention enables the system to have strong resistance to shock loads. Even when the influent water quality fluctuates greatly, it can still maintain a stable treatment effect, and all indicators of the effluent can consistently meet the standards.

[0020] This invention significantly improves the removal efficiency of fluoride ions through sulfidation modification and electrocatalytic enhancement, achieving a removal rate of over 85%, which is far higher than that of traditional processes.

[0021] This invention innovatively designs a multi-stage composite waste gas treatment system, which not only achieves efficient treatment of waste gas, but also reduces treatment costs through resource utilization.

[0022] This invention significantly increases the number of times the catalyst can be reused, extends the equipment maintenance cycle, and reduces the overall operating cost by more than 30% by optimizing process design and material properties.

[0023] In a preferred embodiment of the present invention, the water inlet regulating unit includes a water inlet regulating cylinder, which is connected to the lower side of the liquid inlet pressurization and dispensing unit. The S-ZVI inlet, wastewater inlet, and oxidant inlet are all connected to the water inlet regulating cylinder, and an ultrasonic disperser is installed inside the water inlet regulating cylinder. The ultrasonic disperser can fully disperse and mix the S-ZVI, wastewater, and oxidant added to the water inlet regulating cylinder.

[0024] In a preferred embodiment of the present invention, the liquid inlet pressurizing and distributing unit includes a pressurizing and distributing cylinder connected between the water inlet regulating unit and the rectifying unit. A nozzle fixing plate is installed inside the pressurizing and distributing cylinder. A pressurizing impeller is rotatably connected to the lower side of the nozzle fixing plate, and several oblique nozzles are arranged on the upper side of the nozzle fixing plate, with the flow rate decreasing sequentially from the inner to the outer ring of the oblique nozzles. The pressurizing impeller rotates in a fixed direction, generating upward pressure on the wastewater; simultaneously, it further mixes the wastewater. The liquid swirls within the cavity through the oblique nozzles, allowing the materials to mix more thoroughly and flow upwards.

[0025] In a preferred embodiment of the present invention, the rectifying unit includes a rectifying cylinder connected between the liquid inlet pressurization and dispensing unit and the electrocatalytic core treatment unit. A water pipe is provided in the middle of the cylinder, and rectifying spirals are arranged on the outer wall of the water pipe. The number of rectifying spiral layers is determined according to the average wastewater treatment flow rate, and the material is rectified by the determined number of rectifying spiral layers. The flow rate and velocity are larger at the edge, while the flow rate and velocity are smaller in the middle. By providing a water pipe in the middle to directly connect the middle section, the head loss in the middle section is reduced.

[0026] As a preferred embodiment of the present invention, the electrocatalytic core processing unit includes an electrocatalytic cylinder, a cathode is installed in the middle of the electrocatalytic cylinder, a drain outlet is located at the top of the cathode, and an anode assembly is provided on the outer sleeve of the cathode; the anode assembly includes two layers of anode plate supports, an inner anode plate is installed on the inner anode plate support, and an outer anode plate is installed on the outer anode plate support.

[0027] The interaction between the cathode liquid and the anode assembly enables thorough electrocatalytic treatment of wastewater. This invention organically combines zero-valent iron sulfide with electrocatalytic technology. By optimizing the electrode structure and process parameters, it achieves highly efficient COD removal under low energy consumption conditions, increasing treatment efficiency by more than 30%. Through sulfide modification and enhanced electrocatalysis, this invention significantly improves the removal efficiency of fluoride ions, achieving a removal rate of over 85%, far exceeding the level of traditional processes.

[0028] As a preferred embodiment of the present invention, a heating pipe is wound around the outer wall of the electrocatalytic cylinder, a wastewater inlet is connected to a wastewater pipe, one end of the heating pipe is connected to the wastewater pipe, and the other end of the heating pipe is connected to a first liquid-distributing valve, which is connected to a new wastewater inlet pipe; the treated wastewater collection unit is connected to a second liquid-distributing valve, which is connected to a treated wastewater direct discharge pipe, and a return pipe is connected between the first liquid-distributing valve and the second liquid-distributing valve.

[0029] The electrocatalytic unit releases heat, which is used to heat the heating pipes, thereby heating the wastewater entering the influent regulating unit and improving the wastewater treatment effect. The second separating valve controls the reflux ratio based on parameters such as the COD and BOD compliance rates of the treated wastewater. If the standards are met in one go, the wastewater is directly discharged through the treated wastewater direct discharge pipe. The first separating valve controls the ratio of newly entering wastewater to reflux liquid.

[0030] As a preferred embodiment of the present invention, a spiral collection groove is provided on the inner wall of the collection cylinder, and a magnetic component is built into the spiral collection groove. The magnetic field strength of the magnetic component is 0.1 to 0.5T. A centrifugal stirring unit is installed inside the collection cylinder, and a probe unit is installed inside the exhaust gas collection hood. The probe unit includes a probe lifting rod, which is installed inside the exhaust gas collection hood. A 360° probe is connected to the lower end of the probe lifting rod, and a high-pressure water nozzle is provided on the 360° probe.

[0031] The centrifugal mixing unit generates centrifugal force in the treated wastewater, causing the nano-S-ZVI material to be thrown into the spiral collection tank. A 360° probe is used to identify the presence of nano-S-ZVI material in the spiral collection tank. The high-pressure water nozzles are powered by the treated wastewater.

[0032] As a preferred embodiment of the present invention, the centrifugal stirring unit includes a support rod connected to the collection cylinder, a lifting mechanism installed on the support rod, a transmission rod connected to the output end of the lifting mechanism, and a wastewater stirrer connected to the transmission rod; a drain outlet is provided at the bottom of the collection cylinder, and a drain outlet plug is connected to the bottom of the wastewater stirrer.

[0033] A transmission rod drives the wastewater agitator to rotate, generating centrifugal force that centrifuges the nano-S-ZVI material into the spiral collection tank. A lifting mechanism raises and lowers the entire assembly consisting of the transmission rod, wastewater agitator, and drain plug, thus sealing the drain outlet. When the 360° probe is operating, the wastewater agitator stops agitating, and the drain plug moves down to seal the outlet.

[0034] In a preferred embodiment of the present invention, the material negative pressure recovery unit includes a material recovery collection pipe disposed at the bottom of the collection cylinder. The material recovery collection pipe is annular in shape and connected to a negative pressure device. The material recovery collection pipe is also connected to a material discharge pipe, the other end of which extends out of the collection cylinder. After the negative pressure device is activated, the nano-S-ZVI material sliding down from the spiral collection groove is drawn into the material recovery collection pipe and collected through the material discharge pipe.

[0035] As a preferred embodiment of the present invention, the top of the exhaust gas collection hood is connected to an exhaust gas collection pipe, and the other end of the exhaust gas collection pipe is connected to a chlorine treatment and reuse device, which is connected to other exhaust gas treatment devices through a pipe.

[0036] The chlorine treatment and reuse device uses a water ring vacuum pump to create a negative pressure environment and circulating cooling water (5-10℃) as the absorption medium. Because chlorine has a much higher solubility than other gases, it can be selectively enriched at this stage. The enriched chlorine-containing solution is then filtered through a precision filter and connected to a sodium hypochlorite generator to convert the recovered chlorine into sodium hypochlorite, a product with high market value. The product has an effective chlorine content of 10-12% and a conversion rate of over 85%.

[0037] Other waste gas treatment devices are used to treat VOCs and other waste gases. These devices employ a novel porous titanium-based catalytic composite material, prepared via a sol-gel method, with a specific surface area of ​​800–1000 m². 2 / g, pore size distribution 3-5nm. The material surface is loaded with a bimetallic (Cu-Mn) oxide catalyst, exhibiting highly efficient catalytic oxidation performance for VOCs. Under normal temperature and pressure, the VOCs removal rate can reach over 95%. The innovation lies in the proton exchange resin loaded on the catalyst surface, which can adsorb acidic gases generated during the conversion process, extending the catalyst's lifespan to 8-10 months. The residence time of waste gas in this unit is controlled at 2-3 seconds, and the gas flow rate is 0.5-1.0 m / s.

[0038] The beneficial effects of this invention are as follows:

[0039] 1. The present invention, with its sequentially arranged inlet water regulating unit, inlet pressurization and dispensing unit, rectification unit, and electrocatalytic core treatment unit, successfully solves the material stability problem through an innovative sulfide-modified zero-valent iron process and a novel treatment device, increasing catalyst lifespan by more than 50% and significantly reducing operating costs. The present invention also innovatively designs a multi-stage composite waste gas treatment system, which not only achieves efficient waste gas treatment but also reduces treatment costs through resource utilization.

[0040] 2. This invention incorporates nano-S-ZVI material into the influent conditioning unit and performs electrocatalytic treatment on the wastewater through an electrocatalytic core treatment unit. It organically combines zero-valent iron sulfide with electrocatalytic technology. By optimizing the electrode structure and process parameters, it achieves highly efficient COD removal under low energy consumption conditions, increasing treatment efficiency by more than 30%. This invention significantly improves the removal efficiency of fluoride ions through sulfide modification and electrocatalytic enhancement, achieving a removal rate of over 85%, far exceeding the level of traditional processes.

[0041] 3. This invention is equipped with an inlet water regulating unit, an inlet liquid pressurization and dispensing unit, and a rectification unit. Through innovative process design, the system has a strong resistance to shock loads. Even when the inlet water quality fluctuates greatly, it can still maintain a stable treatment effect, and all indicators of the effluent can stably meet the standards.

[0042] 4. This invention uses a negative pressure material recovery unit to extract the nano-S-ZVI material from the collection cylinder, enabling the collection and reuse of the nano-S-ZVI material. Wastewater after centrifugation to separate the nano-S-ZVI material is collected from the top of the collection cylinder by a wastewater collection unit. Exhaust gas is collected by an exhaust gas collection hood and then sent to a downstream exhaust gas treatment device for treatment. This invention can recover nano-S-ZVI material, wastewater, and exhaust gas separately, reducing wastewater treatment costs through resource utilization.

[0043] 5. The waste gas collection pipeline of the present invention is sequentially connected to a chlorine treatment and reuse device and other waste gas treatment devices, and innovatively designs a multi-stage composite waste gas treatment system, which not only achieves efficient treatment of waste gas, but also reduces treatment costs through resource utilization. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the structure of the present invention;

[0045] Figure 2 This is a partial structural diagram of the present invention;

[0046] Figure 3 This is a cross-sectional view of a portion of the structure of the present invention in the first direction;

[0047] Figure 4 This is a cross-sectional view of a portion of the structure of the present invention in the second direction;

[0048] Figure 5 This is a schematic diagram of the water inlet regulating unit;

[0049] Figure 6 This is a schematic diagram of the liquid inlet pressurization and dispensing unit in the first direction;

[0050] Figure 7 This is a schematic diagram of the second direction of the liquid inlet pressurization and dispensing unit;

[0051] Figure 8 This is a cross-sectional view of the rectifier unit;

[0052] Figure 9 This is a schematic diagram of the electrocatalytic core processing unit;

[0053] Figure 10 This is a schematic diagram of the cathode and anode assembly.

[0054] Figure 11 This is a cross-sectional structural diagram of the material recycling device.

[0055] In the diagram: 1-Inlet water regulating unit; 2-Inlet pressurization and spreading unit; 3-Rectification unit; 4-Electrocatalytic core treatment unit; 5-Material recovery device; 6-Outer frame of treatment device; 11-Inlet water regulating cylinder; 12-S-ZVI inlet; 13-Wastewater inlet; 14-Oxidant inlet; 15-Wastewater pipeline; 16-Ultrasonic disperser; 17-First liquid separator valve; 18-New wastewater pipeline; 19-Return pipeline; 21-Pressure and spreading cylinder; 22-Nozzle fixing plate; 23-Pressure impeller; 24-Angled nozzle; 31-Rectification cylinder; 32-Water pipeline; 33-Rectification spiral; 41-Electrocatalytic cylinder; 42-Cathode; 43-Drain outlet; 44-Anode plate support; 45-Inner anode plate; 46-Outer anode plate; 47-Integrated water quality detection probe; 48-Temporary drain outlet; 49-Heating pipe; 51-Collection cylinder; 52-Spiral collection trough; 53-Material negative pressure recovery unit; 54-Wastewater collection unit; 55-Centrifugal stirring unit; 56-Waste gas collection hood; 57-Probe unit; 58-Chlorine treatment and reuse device; 59-Other waste gas treatment devices; 61-Shell; 62-Device support plate; 63-Device support frame; 531-Material recovery and collection pipe; 532-Material discharge pipe; 541-Wastewater collection ring pipe; 542-Wastewater collection pipe; 543-Second liquid separator valve; 544-Wastewater direct discharge pipe; 551-Support rod; 552-Transmission rod; 553-Wastewater agitator; 554-Drain plug; 561-Waste gas collection pipe; 571-Probe lifting rod; 572-360° probe; 573-High-pressure water nozzle. Detailed Implementation

[0056] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0057] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention. It should be noted that, unless otherwise specified, the embodiments and features described in the embodiments of the invention can be combined with each other.

[0058] like Figures 1-4 As shown, the device for removing recalcitrant organic matter from wastewater and recovering materials in this embodiment includes a treatment device frame 6, which includes a shell 61. A device support plate 62 is provided at the bottom of the shell 61, and a device support frame 63 is connected to the bottom of the device support plate 62. The treatment device frame 6 is arranged sequentially from bottom to top as follows: a water inlet regulating unit 1, a liquid inlet pressurizing and spreading unit 2, a rectifier unit 3, an electrocatalytic core treatment unit 4, and a material recovery device 5. The water inlet regulating unit 1 is provided with an S-ZVI inlet 12, a wastewater inlet 13, and an oxidant inlet 14. The material recovery device 5 includes a collection cylinder 51, a material negative pressure recovery unit 53 is provided at the bottom of the collection cylinder 51, a treated wastewater collection unit 54 is connected to the upper part of the collection cylinder 51, and a waste gas collection hood 56 is connected to the top of the collection cylinder 51.

[0059] This invention aims to develop an integrated treatment process capable of efficiently removing recalcitrant organic matter under high-salt and high-fluoride conditions, exhibiting good material stability, low operating costs, high intelligence, and waste gas resource recovery capabilities, to meet the increasingly stringent environmental and economic requirements in the field of industrial wastewater treatment. During wastewater treatment, nano-S-ZVI material is added through the S-ZVI inlet 12, wastewater is added through the wastewater inlet 13, and oxidant is added through the oxidant inlet 14. The mixed liquid is then sequentially processed through the inlet regulating unit 1, the inlet pressurizing and spreading unit 2, the rectification unit 3, and the electrocatalytic core treatment unit 4, effectively removing recalcitrant organic matter from the wastewater.

[0060] This invention utilizes a negative pressure recovery unit 53 to extract nano-S-ZVI material from the collection cylinder 51, enabling the collection and reuse of this material. Wastewater from which the nano-S-ZVI material is separated by centrifugation is collected from the top of the collection cylinder 51 by a wastewater collection unit 54. Exhaust gas is collected by an exhaust gas collection hood 56 and then sent to a downstream exhaust gas treatment device for processing. This invention can recover nano-S-ZVI material, wastewater, and exhaust gas respectively, reducing wastewater treatment costs through resource utilization.

[0061] This invention successfully solves the material stability problem through an innovative sulfidation-modified zero-valent iron process and a new processing device, thereby increasing the catalyst's service life by more than 50% and significantly reducing operating costs.

[0062] This invention organically combines zero-valent iron sulfide with electrocatalytic technology. By optimizing the electrode structure and process parameters, it can achieve efficient COD removal under low energy consumption conditions, improving the treatment efficiency by more than 30%.

[0063] Through innovative process design, this invention enables the system to have strong resistance to shock loads. Even when the influent water quality fluctuates greatly, it can still maintain a stable treatment effect, and all indicators of the effluent can consistently meet the standards.

[0064] This invention significantly improves the removal efficiency of fluoride ions through sulfidation modification and electrocatalytic enhancement, achieving a removal rate of over 85%, which is far higher than that of traditional processes.

[0065] This invention innovatively designs a multi-stage composite waste gas treatment system, which not only achieves efficient treatment of waste gas, but also reduces treatment costs through resource utilization.

[0066] This invention significantly increases the number of times the catalyst can be reused, extends the equipment maintenance cycle, and reduces the overall operating cost by more than 30% by optimizing process design and material properties.

[0067] Specifically, such as Figure 5 As shown, the inlet regulating unit 1 includes an inlet regulating cylinder 11, which is connected to the lower side of the liquid inlet pressurization and dispensing unit 2. The S-ZVI inlet 12, wastewater inlet 13, and oxidant inlet 14 are all connected to the inlet regulating cylinder 11. An ultrasonic disperser 16 is installed inside the inlet regulating cylinder 11. The ultrasonic disperser 16 can fully disperse and mix the S-ZVI, wastewater, and oxidant added to the inlet regulating cylinder 11.

[0068] The nano-S-ZVI material is pre-mixed in deionized water to facilitate subsequent ultrasonic dispersion. The dosage is 2-5% of the wastewater COD, and a stepped dosing strategy is recommended. Initial stage (0-30 min): COD < 2000 mg / L: 2%; COD 2000-3500 mg / L: 2.5%; COD > 3500 mg / L: 3%. Intermediate stage (30-60 min): Adjust according to COD removal rate; removal rate < 40%: increase by 0.5%; removal rate > 60%: decrease by 0.3%. Late stage (> 60 min): Maintain the minimum effective dosage; monitor COD trends; it is recommended not to exceed 50% of the initial dosage.

[0069] The treated / untreated wastewater first passes through the electrocatalytic reaction zone, and after being appropriately heated, it enters the water distribution zone through the wastewater inlet 13.

[0070] The oxidant can be hydrogen peroxide, persulfate, perdisulfate, periodate, etc. Simultaneously, HCl or NaOH is added according to the pH of the influent wastewater to maintain the pH of the wastewater in the influent adjustment zone between 3 and 4.

[0071] Specifically, such as Figure 6 and Figure 7As shown, the liquid inlet pressurization and dispensing unit 2 includes a pressurization and dispensing cylinder 21, which is connected between the water inlet regulating unit 1 and the rectifier unit 3. A nozzle fixing plate 22 is installed inside the pressurization and dispensing cylinder 21. A pressurization impeller 23 is rotatably connected to the lower side of the nozzle fixing plate 22, and a plurality of oblique nozzles 24 are provided on the upper side of the nozzle fixing plate 22.

[0072] The pressure impeller 23 rotates in a fixed direction, generating upward pressure on the wastewater; at the same time, it further mixes the wastewater. The liquid swirls within the cavity through several angled nozzles 24, allowing the materials to mix more thoroughly and flow upwards.

[0073] Several angled nozzles 24 have flow rates that decrease sequentially from the inner to the outer ring. Based on empirical parameters: the flow rate of the first ring nozzle is Q; the flow rate of the second ring nozzle is 1.05 to 1.1Q; the flow rate of the third ring nozzle is 1.2 to 1.4Q; and the flow rate of the fourth ring nozzle is 1.3 to 1.5Q.

[0074] Specifically, such as Figure 8 As shown, the rectifying unit 3 includes a rectifying cylinder 31, which is connected between the liquid inlet pressurization and dispensing unit 2 and the electrocatalytic core treatment unit 4. A water pipe 32 is provided in the middle of the cylinder, and rectifying spirals 33 are arranged on the outer wall of the water pipe 32. The number of rectifying spirals 33 is determined according to the average wastewater treatment flow rate, and the material is rectified by the determined number of rectifying spirals 33. The flow rate and velocity at the edge are larger, while the flow rate and velocity in the middle are smaller. By setting a water pipe 32 in the middle to directly connect the middle, the head loss in the middle is reduced.

[0075] The optimization of the number of 33 layers of the rectifier spiral is determined based on the hydraulic residence time (HRT):

[0076] Less than 5m 3 Daily processing capacity:

[0077] 1st floor: HRT = 4-6 hours, suitable for low pollution;

[0078] 2-layer: HRT = 6-8 hours, suitable for moderate pollution;

[0079] 3-layer: HRT = 8-10 hours, suitable for high pollution levels.

[0080] 5~10m 3 Daily processing capacity:

[0081] 3 layers: HRT = 3-4 hours, to ensure basic treatment effect;

[0082] 4 layers: HRT = 4-5 hours, improving processing efficiency;

[0083] 5 layers: HRT = 5-6 hours, for treating recalcitrant pollutants.

[0084] 10~20m 3 Daily processing capacity:

[0085] 6 floors: HRT = 2.5-3 hours, meeting basic needs;

[0086] 7 layers: HRT = 3-4 hours, improving processing efficiency;

[0087] 8 layers: HRT = 4-5 hours to ensure deep processing.

[0088] Specifically, such as Figure 9 and Figure 10 As shown, the electrocatalytic core processing unit 4 includes an electrocatalytic cylinder 41, a cathode 42 is installed in the middle of the electrocatalytic cylinder 41, a drain outlet 43 connected to the material recovery device 5 is provided on the top of the cathode 42, and an anode assembly is provided on the outer sleeve of the cathode 42.

[0089] The cathode 42 is made of graphite with millimeter-sized pores, used to collect treated wastewater.

[0090] The current density of the anode assembly is 5–20 mA / cm². 2 :

[0091] The system is divided into sections based on different water quality conditions:

[0092] Low concentration pollutants (COD < 2000 mg / L): 5–8 mA / cm² 2 It avoids energy waste, reduces electrode wear, and is suitable for the degradation of common pollutants.

[0093] Medium concentration (COD 2000~3500mg / L): 8~15mA / cm 2 It provides sufficient oxidation capacity, maintains good current efficiency, and is suitable for most industrial wastewater.

[0094] High concentration pollutants (COD>3500mg / L): 15~20mA / cm 2 Ensures sufficient oxidative degradation capacity, suitable for treating recalcitrant organic matter, and recommends temperature control (35-40℃).

[0095] Specific selection criteria: Conductivity: For every 5 mS / cm increase, the conductivity can be reduced by 2–3 mA / cm. 2 Fluoride ion concentration: For every 500 mg / L increase, it is recommended to increase by 2–3 mA / cm². 2 Water temperature: For every 5°C increase, the flow rate decreases by 1–2 mA / cm². 2 .

[0096] The interaction between cathode 42 and the anode assembly enables thorough electrocatalytic treatment of wastewater. This invention organically combines zero-valent iron sulfide with electrocatalytic technology. By optimizing the electrode structure and process parameters, it achieves highly efficient COD removal under low energy consumption conditions, increasing treatment efficiency by more than 30%. Through sulfide modification and enhanced electrocatalysis, this invention significantly improves the removal efficiency of fluoride ions, achieving a removal rate of over 85%, far exceeding the level of traditional processes.

[0097] The anode assembly includes two anode plate supports 44. An inner anode plate 45 is mounted on the inner anode plate support 44, and an outer anode plate 46 is mounted on the outer anode plate support 44. The inner anode plate 45 is made of titanium-based conductive material; the outer anode plate 46 is made of RuO2-IrO2 / Ti, a titanium-based conductive material. Both the outer anode plate 46 and the inner anode plate 45 are arc-shaped, and their angles are adjustable.

[0098] The upper section of the electrocatalytic cylinder 41 is connected to two integrated water quality detection probes 47. These probes detect the pH, DO, and temperature of the treated wastewater. The upper section of the electrocatalytic cylinder 41 is also connected to two temporary drain ports 48. These ports allow for the discharge of liquid in cases of excessive flow.

[0099] Furthermore, a heating pipe 49 is wound around the outer wall of the electrocatalytic cylinder 41, and a wastewater inlet 13 is connected to a wastewater pipe 15. One end of the heating pipe 49 is connected to the wastewater pipe 15, and the other end of the heating pipe 49 is connected to a first liquid-distributing valve 17. A new wastewater inlet pipe 18 is connected to the first liquid-distributing valve 17. The treated wastewater collection unit 54 is connected to a second liquid-distributing valve 543, and a treated wastewater direct discharge pipe 544 is connected to the second liquid-distributing valve 543. A return pipe 19 is connected between the first liquid-distributing valve 17 and the second liquid-distributing valve 543.

[0100] The electrocatalytic unit releases heat, which is used to heat the heating pipe 49, thereby heating the wastewater fed into the influent regulating unit 1 and improving the wastewater treatment effect. The second separating valve 543 controls the reflux ratio based on parameters such as the COD and BOD compliance rates of the treated wastewater. If the standards are met in one go, the wastewater is directly discharged through the treated wastewater direct discharge pipe 544. The first separating valve 17 controls the ratio of newly entering wastewater to reflux liquid.

[0101] Furthermore, such as Figure 11 As shown, a spiral collection groove 52 is provided on the inner wall of the collection cylinder 51. The spiral collection groove 52 has a built-in magnetic component with a magnetic field strength of 0.1 to 0.5T. A centrifugal stirring unit 55 is installed inside the collection cylinder 51, and a probe unit 57 is installed inside the exhaust gas collection hood 56.

[0102] The probe unit 57 includes a probe lifting rod 571, which is installed inside the exhaust gas collection hood 56. A 360° probe 572 is connected to the lower end of the probe lifting rod 571. The 360° probe 572 is used to identify whether there is nano-S-ZVI material in the spiral collection trough 52. When the 360° probe 572 is working, the drain plug 554 seals the drain outlet 43. A high-pressure water nozzle 573 is installed on the 360° probe 572. The water source for the high-pressure water nozzle 573 is treated wastewater.

[0103] Centrifugal stirring unit 55 generates centrifugal force in the treated wastewater, causing the nano-S-ZVI material to be thrown into the spiral collection tank 52. A 360° probe 572 is used to identify the presence of nano-S-ZVI material in the spiral collection tank 52. The high-pressure water nozzle 573 receives its water from the treated wastewater.

[0104] Specifically, the wastewater collection unit 54 includes a wastewater collection annular pipe 541, which is sleeved outside the collection cylinder 51. Several wastewater collection pipes 542 are connected to the wastewater collection annular pipe 541, extending from the upper part of the collection cylinder 51. After centrifugal separation, the wastewater in the upper part contains less nano-S-ZVI material. The wastewater enters the wastewater collection annular pipe 541 through the several wastewater collection pipes 542, thus achieving wastewater collection.

[0105] Specifically, the centrifugal stirring unit 55 includes a support rod 551, which is connected to the inside of the collection cylinder 51. A lifting mechanism is installed on the support rod 551, and the output end of the lifting mechanism is connected to a transmission rod 552. A wastewater agitator 553 is connected to the transmission rod 552. A drain outlet 43 is provided at the bottom of the collection cylinder 51, and a drain outlet plug 554 is connected to the bottom of the wastewater agitator 553.

[0106] The transmission rod 552 drives the wastewater agitator 553 to rotate, generating centrifugal force in the wastewater and causing the nano-S-ZVI material to be centrifuged into the spiral collection tank 52. The lifting mechanism can drive the entire assembly of the transmission rod 552, wastewater agitator 553, and drain plug 554 to rise and fall, thereby sealing the drain outlet 43 with the drain plug 554. When the 360° probe 572 is working, the wastewater agitator 553 stops agitating, and the drain plug 554 moves down to the drain outlet 43 to seal it.

[0107] Specifically, the material negative pressure recovery unit 53 includes a material recovery collection pipe 531, which is located at the bottom inside the collection cylinder 51. The material recovery collection pipe 531 is annular in shape and is connected to a negative pressure device. A material discharge pipe 532 is also connected to the material recovery collection pipe 531, with the other end of the discharge pipe 532 extending out of the collection cylinder 51. After the negative pressure device is activated, the nano-S-ZVI material sliding down from the spiral collection groove 52 is drawn into the material recovery collection pipe 531 and collected through the material discharge pipe 532.

[0108] Furthermore, the top of the exhaust gas collection hood 56 is connected to an exhaust gas collection pipe 561, and the other end of the exhaust gas collection pipe 561 is connected to a chlorine treatment and reuse device 58. The chlorine treatment and reuse device 58 is connected to other exhaust gas treatment devices 59 through pipes.

[0109] The chlorine treatment and reuse device 58 uses a water ring vacuum pump to create a negative pressure environment and circulating cooling water (5-10℃) as the absorption medium. Because chlorine has a much higher solubility than other gases, it can be selectively enriched at this stage. The enriched chlorine-containing solution is then filtered through a precision filter and connected to a sodium hypochlorite generator to convert the recovered chlorine into sodium hypochlorite, a product with high market value. The product has an effective chlorine content of 10-12% and a conversion rate of over 85%.

[0110] Other waste gas treatment device 59 is used to treat VOCs and other waste gases. This device 59 employs a novel porous titanium-based catalytic composite material, prepared via a sol-gel method, with a specific surface area of ​​800–1000 m². 2 / g, pore size distribution 3-5nm. The material surface is loaded with a bimetallic (Cu-Mn) oxide catalyst, exhibiting highly efficient catalytic oxidation performance for VOCs. Under normal temperature and pressure, the VOCs removal rate can reach over 95%. The innovation lies in the proton exchange resin loaded on the catalyst surface, which can adsorb acidic gases generated during the conversion process, extending the catalyst's lifespan to 8-10 months. The residence time of waste gas in this unit is controlled at 2-3 seconds, and the gas flow rate is 0.5-1.0 m / s.

[0111] Example 1 (Treatment of Low-Concentration Pollutants):

[0112] Influent water quality (sampled 3 times every 2 hours, average value): COD: 1832±127 mg / L; BOD: 587±43 mg / L; Fluoride ion: 778±65 mg / L; Conductivity: 24.7±1.8 mS / cm; SS: 863±72 mg / L; pH: 6.3~6.8

[0113] Operating parameters: S-ZVI dosage: 35.8±2.1 mg / L; Current density: 6.2±0.4 mA / cm² 2 ; Rectifier unit 3: 2 layers; HRT: 5.8 ± 0.3 hours; Temperature: 22~26℃.

[0114] Treatment results (continuous operation for 72 hours, sampling every 8 hours): COD: 162±28 mg / L (removal rate 91.2±1.8%); BOD: 35±5.2 mg / L (removal rate 94.1±1.2%); fluoride ions: 101±12 mg / L (removal rate 87.0±2.1%); SS: 42±6.8 mg / L (removal rate 95.1±1.4%).

[0115] Example 2 (Treatment of moderate concentrations of pollutants):

[0116] Influent water quality: COD: 3267±186mg / L; BOD: 812±58mg / L; Fluoride ion: 1478±112mg / L; Conductivity: 34.8±2.3mS / cm; SS: 938±81mg / L; pH: 7.0~7.5.

[0117] Operating parameters: S-ZVI dosage: 82.3±4.7 mg / L; Current density: 11.8±0.6 mA / cm² 2 Rectifier unit: 3-4 layers; HRT: 4.6 ± 0.2 hours; Temperature: 24~28℃.

[0118] Treatment results: COD: 408±45 mg / L (removal rate 87.5±2.2%); BOD: 89±11 mg / L (removal rate 89.1±1.8%); fluoride ions: 238±26 mg / L (removal rate 83.9±2.4%); SS: 62±8.9 mg / L (removal rate 93.4±1.6%).

[0119] Example 3 (Treatment of High Concentration Recalcitrant Pollutants):

[0120] Influent water quality: COD: 4756±243mg / L; BOD: 968±82mg / L; Fluoride ion: 1823±156mg / L; Conductivity: 44.3±3.1mS / cm; SS: 992±93mg / L; pH: 7.8~8.2.

[0121] Operating parameters: S-ZVI dosage: 142±7.8 mg / L; Current density: 17.6±0.9 mA / cm² 2 Rectifier unit 3: 6 layers; HRT: 3.2 ± 0.3 hours; Temperature: 37~39℃.

[0122] Treatment results: COD: 747±68 mg / L (removal rate 84.3±2.8%); BOD: 138±18.5 mg / L (removal rate 85.7±2.3%); fluoride ions: 327±34 mg / L (removal rate 82.1±2.7%); SS: 86±11.2 mg / L (removal rate 91.3±1.9%).

[0123] This invention is not limited to the above-described optional embodiments. Anyone can derive other various forms of products under the guidance of this invention. However, regardless of any changes made in their shape or structure, any technical solution that falls within the scope of the claims of this invention shall be protected by this invention.

Claims

1. A device for removing recalcitrant organic matter from wastewater and recovering materials, characterized in that: The system includes, from bottom to top, an inlet water regulating unit (1), an inlet pressurizing and spreading unit (2), a rectifier unit (3), an electrocatalytic core treatment unit (4), and a material recovery device (5); the inlet water regulating unit (1) is provided with an S-ZVI inlet (12), a wastewater inlet (13), and an oxidant inlet (14); the material recovery device (5) includes a collection cylinder (51), a material negative pressure recovery unit (53) is provided at the bottom of the collection cylinder (51), a wastewater collection unit (54) is connected to the upper part of the collection cylinder (51), and a waste gas collection hood (56) is connected to the top of the collection cylinder (51); The liquid inlet pressurization and dispensing unit (2) includes a pressurization and dispensing cylinder (21), which is connected between the water inlet regulating unit (1) and the rectifier unit (3). A nozzle fixing plate (22) is installed inside the pressurization and dispensing cylinder (21). A pressurization impeller (23) is rotatably connected to the lower side of the nozzle fixing plate (22), and several oblique nozzles (24) are provided on the upper side of the nozzle fixing plate (22). The rectifier unit (3) includes a rectifier cylinder (31), which is connected between the liquid inlet pressurization and spreading unit (2) and the electrocatalytic core treatment unit (4). A water pipe (32) is provided in the middle of the cylinder, and a rectifier spiral (33) is arranged on the outer wall of the water pipe (32). The electrocatalytic core processing unit (4) includes an electrocatalytic cylinder (41), a cathode (42) is installed in the middle of the electrocatalytic cylinder (41), and an anode assembly is provided on the outer sleeve of the cathode (42); the anode assembly includes two anode plate supports (44), an inner anode plate (45) is installed on the inner anode plate support (44), and an outer anode plate (46) is installed on the outer anode plate support (44). A heating pipe (49) is wound around the outer wall of the electrocatalytic cylinder (41), and a wastewater inlet (13) is connected to a wastewater pipe (15). One end of the heating pipe (49) is connected to the wastewater pipe (15).

2. The apparatus for removing recalcitrant organic matter from wastewater and recovering materials according to claim 1, characterized in that: The water inlet regulating unit (1) includes a water inlet regulating cylinder (11), which is connected to the lower side of the liquid inlet pressurization and spreading unit (2). The S-ZVI inlet (12), wastewater inlet (13) and oxidant inlet (14) are all connected to the water inlet regulating cylinder (11), and an ultrasonic disperser (16) is installed inside the water inlet regulating cylinder (11).

3. The apparatus for removing recalcitrant organic matter from wastewater and recovering materials according to claim 1, characterized in that: The other end of the heating pipe (49) is connected to a first liquid distribution valve (17), and a new wastewater inlet pipe (18) is connected to the first liquid distribution valve (17); the wastewater collection unit (54) is connected to a second liquid distribution valve (543), and a wastewater discharge pipe (544) is connected to the second liquid distribution valve (543); a return pipe (19) is connected between the first liquid distribution valve (17) and the second liquid distribution valve (543).

4. The apparatus for removing recalcitrant organic matter from wastewater and recovering materials according to claim 1, characterized in that: The inner wall of the collection cylinder (51) is provided with a spiral collection groove (52), a centrifugal stirring unit (55) is installed inside the collection cylinder (51), and a probe unit (57) is installed inside the exhaust gas collection hood (56); the probe unit (57) includes a probe lifting rod (571), the probe lifting rod (571) is installed inside the exhaust gas collection hood (56), the lower end of the probe lifting rod (571) is connected to a 360° probe (572), and a high-pressure water nozzle (573) is provided on the 360° probe (572).

5. The apparatus for removing recalcitrant organic matter from wastewater and recovering materials according to claim 4, characterized in that: The centrifugal stirring unit (55) includes a support rod (551), which is connected to the inside of the collection cylinder (51). A lifting mechanism is installed on the support rod (551), and a transmission rod (552) is connected to the output end of the lifting mechanism. A wastewater stirrer (553) is connected to the transmission rod (552). A drain outlet (43) is provided between the collection cylinder (51) and the electrocatalytic core treatment unit (4). A drain outlet plug (554) is connected to the bottom of the wastewater stirrer (553).

6. The apparatus for removing recalcitrant organic matter from wastewater and recovering materials according to claim 1, characterized in that: The material negative pressure recovery unit (53) includes a material recovery collection pipe (531), which is located at the bottom of the inside of the collection cylinder (51). The material recovery collection pipe (531) is annular in shape. The material recovery collection pipe (531) is connected to a negative pressure device and a material discharge pipe (532). The other end of the material discharge pipe (532) extends out of the collection cylinder (51).

7. The apparatus for removing recalcitrant organic matter from wastewater and recovering materials according to any one of claims 1 to 6, characterized in that: The top of the exhaust gas collection hood (56) is connected to an exhaust gas collection pipe (561), and the other end of the exhaust gas collection pipe (561) is connected to a chlorine treatment and reuse device (58). The chlorine treatment and reuse device (58) is connected to other exhaust gas treatment devices (59) through a pipe.

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