Device for removing refractory organic matters in wastewater and recycling materials

Abstract

The invention belongs to the technical field of wastewater treatment devices, and particularly relates to a device for removing refractory organic matters in wastewater and recycling materials. According to the technical scheme, the device for removing the refractory organic matters in the wastewater and recycling the materials comprises a water inlet adjusting unit, a liquid inlet pressurizing and scattering unit, a rectifying unit, an electro-catalysis core treatment unit and a material recycling device which are sequentially arranged from bottom to top; an S-ZVI feed port, a wastewater feed port and an oxidant feed port are formed in the water inlet adjusting unit; the material recovery device comprises a collection barrel, a material negative pressure recovery unit is arranged at the bottom of the collection barrel, the upper part of the collection barrel is connected with a treated wastewater collection unit, and the top of the collection barrel is connected with a waste gas collection cover. The invention provides a device for removing refractory organic matters in wastewater and recycling materials by electro-catalysis reinforced sulfurized zero-valent iron.

Description

Technical Field

[0001] The invention belongs to the technical field of wastewater treatment devices, and in particular relates to a device for removing refractory organic matter in wastewater and recycling materials. Background Art

[0002] The process and device for removing refractory organic matter from wastewater by electrocatalytically enhanced zero-valent iron sulfide is mainly dedicated to solving the key technical bottlenecks in the field of deep treatment of industrial wastewater. In the wastewater generated by industries such as semiconductors, petrochemicals and pesticides, there are generally characteristics of fluoride ion concentrations of 500-2000 mg / L, conductivity of 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. Such complex water quality conditions severely restrict the application of traditional treatment processes.

[0003] At present, mainstream technologies face many difficulties in treating this type of wastewater. Although the chemical precipitation method is easy to operate, it is not ideal for removing difficult-to-degrade organic matter, and it will produce a large amount of chemical sludge that requires secondary treatment. The traditional Fenton oxidation process requires the continuous addition of a large amount of hydrogen peroxide, which not only has high operating costs, but also significantly reduces the oxidation efficiency in a high-salt environment. The biological treatment process encounters dual inhibition from high salt and high fluoride ions, making it difficult to maintain microbial activity. Membrane separation technology requires frequent cleaning and replacement due to membrane fouling and scaling problems, resulting in excessively high operating and maintenance costs.

[0004] The closest zero-valent iron sulfide / hydrogen peroxide treatment system, although it improves the stability of zero-valent iron through sulfide modification, still fails to completely solve the problem of material deactivation under high-salt conditions, and the continuous increase in hydrogen peroxide greatly increases the operating cost. The technology is also relatively limited in its effect on the removal of fluoride ions and cannot meet the strict emission standards. At the same time, the control accuracy of the reaction process is insufficient, making it difficult to adapt to the fluctuations in the quality of the influent water.

[0005] In summary, the prior art has the following disadvantages:

[0006] First, the material has poor stability and short service life: In the existing technology, zero-valent iron is very easy to passivate and agglomerate under high salt conditions, resulting in a reduction in active sites and a rapid decrease in reaction efficiency. Although traditional surface modification methods can improve material stability to a certain extent, the effect is not ideal and the service life of the catalyst is generally short.

[0007] Second, the problem of low treatment efficiency and high energy consumption: When treating high-salt and high-fluoride wastewater, traditional Fenton oxidation, electrochemical oxidation and other processes often require the addition of a large amount of oxidant or the application of a higher voltage to achieve the ideal treatment effect, which not only has high energy consumption but also has low treatment efficiency.

[0008] Third, the problem of poor adaptability to water quality and weak anti-interference ability: the existing technology is very sensitive to fluctuations in influent water quality, especially under complex water quality conditions such as high salt and high fluoride, the treatment effect is often not stable enough.

[0009] Fourth, the problem of poor fluoride ion removal effect: The conventional process is generally not ideal for fluoride ion removal, especially in a high-salt environment, the fluoride ion removal rate is often difficult to meet emission standard requirements.

[0010] Fifth, the waste gas treatment effect is poor, and secondary pollution problems are easily generated: the existing technology often produces a large amount of toxic and harmful waste gas during the treatment process, and the treatment effect is not ideal.

[0011] Sixth, the problem of high operating and maintenance costs: The existing technology generally has problems such as large consumption of reagents and frequent equipment maintenance, which leads to high operating costs. Summary of the invention

[0012] In order to solve the above problems existing in the prior art, the purpose of the present invention is to provide a device for removing refractory organic matter in wastewater and recovering materials by electrocatalytically enhancing zero-valent iron sulfide.

[0013] The technical solution adopted by the present invention is:

[0014] A device for removing refractory organic matter from wastewater and recovering materials, comprising a water inlet regulating unit, a liquid inlet pressurizing and spreading unit, a rectifying unit, an electrocatalytic core processing unit, and a material recovery device, which are arranged in sequence from bottom to top; the water inlet regulating unit is provided with an S-ZVI feed port, a wastewater feed port and an oxidant feed port; the material recovery device comprises a collecting cylinder, a material negative pressure recovery unit is provided at the bottom of the collecting cylinder, a treated wastewater collection unit is connected to the upper part of the collecting cylinder, and an exhaust gas collection cover is connected to the top of the collecting cylinder.

[0015] The present invention is committed to developing an integrated treatment process that can achieve efficient removal of refractory organic matter under high-salt and high-fluorine conditions, has good material stability, low operating cost, high intelligence, and has the function of waste gas resource utilization, so as to meet the increasingly stringent environmental protection requirements and economic needs in the field of industrial wastewater treatment. During wastewater treatment, nano S-ZVI material is added through the S-ZVI feed port, wastewater is added through the wastewater feed port, and oxidant is added through the oxidant feed port. The mixed liquid is processed in turn by the water inlet regulating unit, the liquid inlet pressurization and spreading unit, the rectifier unit, and the electrocatalytic core treatment unit to effectively remove refractory organic matter in the wastewater.

[0016] The present invention extracts the nano S-ZVI material in the collection cylinder through the material negative pressure recovery unit, so as to realize the collection and reuse of the nano S-ZVI material. The wastewater after the nano S-ZVI material is centrifugally separated is collected from the upper part of the collection cylinder by the wastewater treatment collection unit. The waste gas is collected by the waste gas collection cover and sent to the downstream waste gas treatment device for treatment. The present invention can recycle the nano S-ZVI material, waste water and waste gas respectively, and can reduce the cost of wastewater treatment through resource utilization.

[0017] The present invention successfully solves the problem of material stability through an innovative sulfurized modified zero-valent iron process + a new treatment device, thereby increasing the service life of the catalyst by more than 50% and significantly reducing operating costs.

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

[0019] Through innovative process design, the present invention enables the system to have a strong ability to resist 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.

[0020] The present invention significantly improves the removal efficiency of fluoride ions through sulfurization modification and electrocatalytic strengthening, and the removal rate can reach more than 85%, which is much higher than the traditional process level.

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

[0022] The present invention significantly increases the number of catalyst reuses, extends the equipment maintenance cycle, and reduces the overall operating cost by more than 30% by optimizing process design and material properties.

[0023] As 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 pressurizing and spreading unit, and the S-ZVI feed port, the wastewater feed port and the oxidant feed port are all connected to the water inlet regulating cylinder, and an ultrasonic disperser is installed in 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] As a preferred embodiment of the present invention, the liquid inlet pressurization and spreading unit includes a pressurization and spreading cylinder, which is connected between the water inlet regulating unit and the rectifier unit. A nozzle fixing plate is installed in the pressurization and spreading cylinder, and a pressurization impeller is rotatably connected to the lower side of the nozzle fixing plate. A plurality of oblique nozzles are arranged on the upper side of the nozzle fixing plate, and the flow rates of the plurality of oblique nozzles decrease successively from the inner circle to the outer circle. The pressurization impeller rotates in a fixed direction, generating upward pressure on the wastewater; at the same time, it plays a role of further mixing. The liquid generates a swirl in the cavity through a plurality of oblique nozzles, so that the materials are more fully mixed and flow upward.

[0025] As a preferred embodiment of the present invention, the rectification unit includes a rectification cylinder, which is connected between the liquid inlet pressurization and spreading unit and the electrocatalytic core treatment unit. A water pipeline is provided in the middle of the overall cylinder, and a rectification spiral is arranged on the outer wall of the water pipeline. The number of rectification spiral layers is determined according to the average wastewater treatment flow rate, and the material is rectified by the rectification spirals with a determined number of layers. The edge flow rate and flow velocity are relatively large, while the middle flow rate and flow velocity are relatively small. By arranging a water pipeline in the middle, the middle part is directly connected to reduce the head loss in the middle part.

[0026] As a preferred embodiment of the present invention, the electrocatalytic core treatment unit includes an electrocatalytic cylinder, a cathode is installed in the middle of the electrocatalytic cylinder, a drain outlet is arranged at the top of the cathode, and an anode assembly is arranged on the cathode outer shell; the anode assembly includes two layers of anode plate brackets, an inner anode plate is installed on the inner anode plate bracket, and an outer anode plate is installed on the outer anode plate bracket.

[0027] The cathode liquid and anode components interact with each other to fully electrocatalytically treat the wastewater. The present invention organically combines sulfide zero-valent iron with electrocatalytic technology, and by optimizing the electrode structure and process parameters, it can achieve efficient removal of COD under low energy consumption conditions, and the treatment efficiency is improved by more than 30%. The present invention significantly improves the removal efficiency of fluoride ions through sulfidation modification and electrocatalytic enhancement, and the removal rate can reach more than 85%, which is much higher than the traditional process level.

[0028] As a preferred embodiment of the present invention, a heating pipeline is wound around the outer wall of the electrocatalytic cylinder, the wastewater feed port is connected to the wastewater pipeline, one end of the heating pipeline is connected to the wastewater pipeline, and the other end of the heating pipeline is connected to a first liquid separation valve, and the first liquid separation valve is connected to a new wastewater pipeline; the treated wastewater collection unit is connected to a second liquid separation valve, and the second liquid separation valve is connected to a treated wastewater direct discharge pipeline, and a reflux pipeline is connected between the first liquid separation valve and the second liquid separation valve.

[0029] The electrocatalytic unit will release heat, which is used to heat the heating pipeline, so that the wastewater sent to the water inlet regulating unit is heated, improving the wastewater treatment effect. The second liquid separation valve controls the reflux ratio according to parameters such as the COD and BOD compliance rate of the treated wastewater. If the standards are met at one time, it will be directly discharged through the treated wastewater direct discharge pipeline. The first liquid separation valve controls the ratio of wastewater newly entering the system and reflux liquid.

[0030] As a preferred embodiment of the present invention, a spiral collecting groove is provided on the inner wall of the collecting cylinder, and a magnetic component is built in the spiral collecting groove, and the magnetic field strength of the magnetic component is 0.1 to 0.5 T; a centrifugal stirring unit is installed in the collecting cylinder, and a probe unit is installed in the exhaust gas collection cover; the probe unit includes a probe lifting rod, which is installed in the exhaust gas collection cover, and 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 stirring unit generates centrifugal force in the treated wastewater, and the nano-S-ZVI material is thrown into the spiral collection tank under the action of centrifugal force. The 360° probe is used to identify whether there is nano-S-ZVI material in the spiral collection tank. The water source of the high-pressure water nozzle comes from the treated wastewater.

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

[0033] The transmission rod drives the wastewater agitator to rotate, so that the wastewater generates centrifugal force, and the nano S-ZVI material is centrifuged into the spiral collection tank. The lifting mechanism can drive the transmission rod, the wastewater agitator and the drain plug to lift and lower the whole structure, so that the drain plug can block the drain. When the 360° probe is working, the wastewater agitator stops stirring, and the drain plug moves down to the drain to block it.

[0034] As a preferred embodiment of the present invention, the material negative pressure recovery unit includes a material recovery collection pipe, which is arranged at the bottom of the collection cylinder, is annular in shape, is connected to a negative pressure device, is connected to a material discharge pipe, and the other end of the material discharge pipe extends out of the collection cylinder. After the negative pressure device is started, the nano S-ZVI material sliding down from the spiral collection trough is sucked 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 waste gas collection hood is connected to a waste gas collection pipeline, the other end of the waste gas collection pipeline is connected to a chlorine treatment and reuse device, and the chlorine treatment and reuse device is connected to other waste gas treatment devices through pipelines.

[0036] The chlorine treatment and recycling device uses a water ring vacuum pump to create a negative pressure environment and uses circulating cooling water (5-10°C) as the absorption medium. Since the solubility of chlorine is much higher than that of other gases, chlorine can be selectively enriched at this stage. The enriched chlorine-containing solution is connected to the sodium hypochlorite generator after precision filtration to convert the recovered chlorine into a sodium hypochlorite product with high market value. The effective chlorine content of the product can reach 10-12%, and the conversion rate can reach more than 85%.

[0037] Other waste gas treatment devices are used to treat VOCs and other waste gases. Other waste gas treatment devices use a new porous titanium-based catalytic composite material, which is prepared by the sol-gel method and has a specific surface area of ​​800-1000m 2 / g, pore size distribution 3 ~ 5nm. The material surface is loaded with bimetallic (Cu ~ Mn) oxide catalyst, which has high catalytic oxidation performance for VOCs. At normal temperature and pressure, the VOCs removal rate can reach more than 95%. The innovation lies in that the catalyst surface is also loaded with proton exchange resin, which can adsorb the acidic gas generated during the conversion process and extend the service life of the catalyst to 8 to 10 months. The residence time of the exhaust gas in this unit is controlled at 2 to 3 seconds, and the gas flow rate is 0.5 to 1.0 m / s.

[0038] The beneficial effects of the present invention are:

[0039] 1. The water inlet regulating unit, liquid inlet pressurizing and spreading unit, rectifying unit and electrocatalytic core processing unit are sequentially arranged in the present invention. Through the innovative sulfurized modified zero-valent iron process + new processing device, the material stability problem is successfully solved, the service life of the catalyst is increased by more than 50%, and the operating cost is greatly reduced. The present invention innovatively designs a multi-stage composite exhaust gas treatment system, which not only realizes the efficient treatment of exhaust gas, but also reduces the treatment cost through resource utilization.

[0040] 2. The present invention adds nano S-ZVI material to the water inlet regulating unit, and electrocatalytically treats the wastewater through the electrocatalytic core treatment unit, organically combines sulfide zero-valent iron with electrocatalytic technology, and optimizes the electrode structure and process parameters to achieve efficient removal of COD under low energy consumption conditions, and the treatment efficiency is improved by more than 30%. The present invention significantly improves the removal efficiency of fluoride ions through sulfidation modification and electrocatalytic enhancement, and the removal rate can reach more than 85%, which is much higher than the traditional process level.

[0041] 3. The present invention is provided with a water inlet regulating unit, a liquid inlet pressurizing and spreading unit, and a rectifying unit. Through innovative process design, the system has a strong ability to resist shock loads. Even when the inlet water quality fluctuates greatly, it can still maintain a stable treatment effect, and various indicators of the effluent can stably meet the standards.

[0042] 4. The present invention extracts the nano S-ZVI material in the collection cylinder through the negative pressure material recovery unit, so as to realize the collection and reuse of the nano S-ZVI material. The wastewater after the nano S-ZVI material is centrifugally separated is collected from the upper part of the collection cylinder by the wastewater treatment collection unit. The waste gas is collected by the waste gas collection hood and sent to the downstream waste gas treatment device for treatment. The present invention can recycle the nano S-ZVI material, waste water and waste gas respectively, and can reduce the cost of wastewater treatment through resource utilization.

[0043] 5. The waste gas collection pipeline of the present invention is connected in sequence with a chlorine gas treatment and recycling device and other waste gas treatment devices, and an innovative multi-stage composite waste gas treatment system is designed, which not only realizes efficient waste gas treatment, but also reduces treatment costs through resource utilization. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0046] Figure 3 It is a cross-sectional structural diagram of a part of the structure of the present invention in the first direction;

[0047] Figure 4 It is a cross-sectional structural diagram of a part of the structure of the present invention in the second direction;

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

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

[0050] Figure 7 It is a schematic diagram of the structure of the second direction of the liquid inlet pressurization and spreading unit;

[0051] Figure 8 It is a cross-sectional structural diagram of the rectifier unit;

[0052] Fig. 9 is a schematic diagram of the structure of the electrocatalytic core processing unit;

[0053] Fig.10 is a schematic diagram of the structure of the cathode and anode components;

[0054] Fig.11 This is a cross-sectional structural diagram of a material recovery device.

[0055] In the figure: 1-water inlet regulating unit; 2-liquid pressurizing and spreading unit; 3-rectifier unit; 4-electrocatalytic core treatment unit; 5-material recovery device; 6-treatment device frame; 11-water inlet regulating cylinder; 12-S-ZVI feed port; 13-wastewater feed port; 14-oxidant feed port; 15-wastewater pipeline; 16-ultrasonic disperser; 17-first liquid separation valve; 18-new wastewater pipeline; 19-return pipeline; 21-pressurizing and spreading cylinder; 22-nozzle fixing plate; 23-pressurizing impeller; 24-oblique nozzle; 31-rectifier cylinder; 32-water pipeline; 33-rectifier spiral; 41-electrocatalytic cylinder; 42-cathode; 43-drainage outlet; 44-anode plate bracket; 45-inner anode plate; 46-outer anode plate; 47-integrated water quality detection probe; 48-temporary drainage outlet; 49-heating pipeline; 51-collecting cylinder; 52-spiral collecting tank; 53-material negative pressure recovery unit; 54-wastewater collection unit; 55-centrifugal stirring unit; 56-waste gas collection cover; 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 collection pipe; 532-material discharge pipe; 541-wastewater collection annular pipe; 542-wastewater collection pipe; 543-second liquid separation valve; 544-wastewater direct discharge pipeline; 551-support rod; 552-transmission rod; 553-wastewater agitator; 554-drainage outlet plug; 561-waste gas collection pipeline; 571-probe lifting rod; 572-360° probe; 573-high-pressure water nozzle. DETAILED DESCRIPTION

[0056] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0057] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

[0058] like Figure 1 to Figure 4 As shown, the device for removing difficult-to-degrade organic matter in wastewater and recovering materials in this embodiment includes a treatment device outer frame 6, the treatment device outer frame 6 includes a shell 61, a device support plate 62 is arranged at the bottom of the shell 61, and the bottom of the device support plate 62 is connected to a device support frame 63; the treatment device outer frame 6 is provided with a water inlet regulating unit 1, a liquid pressurizing and spreading unit 2, a rectifying unit 3 and an electrocatalytic core treatment unit 4, and a material recovery device 5 from bottom to top; the water inlet regulating unit 1 is provided with an S-ZVI feed port 12, a wastewater feed port 13 and an oxidant feed port 14; the material recovery device 5 includes a collecting cylinder 51, a material negative pressure recovery unit 53 is arranged at the bottom of the collecting cylinder 51, the upper part of the collecting cylinder 51 is connected to a treated wastewater collection unit 54, and the top of the collecting cylinder 51 is connected to an exhaust gas collection cover 56.

[0059] The present invention is committed to developing an integrated treatment process that can achieve efficient removal of refractory organic matter under high-salt and high-fluorine conditions, has good material stability, low operating cost, high intelligence, and has the function of waste gas resource utilization, so as to meet the increasingly stringent environmental protection requirements and economic needs in the field of industrial wastewater treatment. During wastewater treatment, nano S-ZVI material is added through the S-ZVI feed port 12, wastewater is added through the wastewater feed port 13, and oxidant is added through the oxidant feed port 14. The mixed liquid is sequentially treated by the water inlet regulating unit 1, the liquid inlet pressurization and spreading unit 2, the rectification unit 3 and the electrocatalytic core treatment unit 4 to effectively remove refractory organic matter in the wastewater.

[0060] The present invention extracts the nano S-ZVI material in the collection cylinder 51 through the material negative pressure recovery unit 53, so that the nano S-ZVI material can be collected and reused. The wastewater after the nano S-ZVI material is centrifugally separated is collected from the upper part of the collection cylinder 51 by the treated wastewater collection unit 54. The waste gas is collected by the waste gas collection cover 56 and sent to the downstream waste gas treatment device for treatment. The present invention can recycle the nano S-ZVI material, waste water and waste gas respectively, and can reduce the cost of wastewater treatment through resource utilization.

[0061] The present invention successfully solves the problem of material stability through an innovative sulfurized modified zero-valent iron process + a new treatment device, thereby increasing the service life of the catalyst by more than 50% and significantly reducing operating costs.

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

[0063] Through innovative process design, the present invention enables the system to have a strong ability to resist 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.

[0064] The present invention significantly improves the removal efficiency of fluoride ions through sulfurization modification and electrocatalytic strengthening, and the removal rate can reach more than 85%, which is much higher than the traditional process level.

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

[0066] The present invention significantly increases the number of catalyst reuses, extends the equipment maintenance cycle, and reduces the overall operating cost by more than 30% by optimizing process design and material properties.

[0067] Specifically, Figure 5 As shown, the water inlet regulating unit 1 includes a water inlet regulating cylinder 11, which is connected to the lower side of the liquid inlet pressurizing and spreading unit 2, and the S-ZVI feed port 12, the wastewater feed port 13 and the oxidant feed port 14 are all connected to the water inlet regulating cylinder 11, and an ultrasonic disperser 16 is installed in the water inlet regulating cylinder 11. The ultrasonic disperser 16 can fully disperse and mix the S-ZVI, wastewater and oxidant added to the water inlet regulating cylinder 11.

[0068] Among them, the nano-S-ZVI material is mixed in deionized water in advance to facilitate subsequent ultrasonic dispersion. The dosage is 2-5% of the wastewater COD. A step-by-step dosage strategy is recommended. Initial stage (0-30min): COD <2000mg / L: 2%; COD2000-3500mg / L: 2.5%; COD>3500mg / L: 3%. Intermediate stage (30-60min): adjust according to COD removal rate; removal rate <40%: increase 0.5%; removal rate >60%: reduce 0.3%. Late stage (>60min): maintain the minimum effective dose; monitor the COD change trend; it is recommended not to exceed 50% of the initial dosage.

[0069] Treated / untreated wastewater first passes through the electrocatalytic reaction zone, and after being appropriately heated, enters the water distribution zone through the wastewater feed port 13 .

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

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

[0072] The pressurizing impeller 23 rotates in a fixed direction, generating upward pressure on the wastewater and further mixing the wastewater. The liquid generates a swirl in the cavity through a plurality of oblique nozzles 24, so that the materials are more fully mixed and flow upward.

[0073] The flow rates of the plurality of oblique nozzles 24 decrease from the inner circle to the outer circle. According to empirical parameters: the flow rate of the nozzles in the first circle is Q; the flow rate of the nozzles in the second circle is 1.05-1.1Q; the flow rate of the nozzles in the third circle is 1.2-1.4Q; and the flow rate of the nozzles in the fourth circle is 1.3-1.5Q.

[0074] Specifically, Figure 8 As shown, the rectifying unit 3 includes a rectifying 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 arranged in the middle of the whole cylinder, and a rectifying spiral 33 is arranged on the outer wall of the water pipe 32. According to the average treatment flow of the wastewater, the number of layers of the rectifying spiral 33 is determined, and the material is rectified by the rectifying spiral 33 with a determined number of layers. The edge flow and flow velocity are larger, while the middle flow and flow velocity are smaller. By arranging a water pipe 32 in the middle, the middle is directly connected to reduce the head loss in the middle.

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

[0076] Less than 5m 3 / Daily processing volume:

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

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

[0079] Layer 3: HRT = 8 to 10 hours, suitable for high pollution.

[0080] 5~10m 3 / Daily processing volume:

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

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

[0083] 5th layer: HRT = 5 to 6 hours, for treating difficult-to-degrade pollutants.

[0084] 10~20m 3 / Daily processing volume:

[0085] Level 6: HRT = 2.5 to 3 hours, meeting basic needs;

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

[0087] 8th layer: HRT = 4-5 hours, to ensure deep treatment.

[0088] Specifically, Fig. 9 and Fig.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 port 43 connected to the material recovery device 5 is arranged on the top of the cathode 42, and an anode assembly is arranged on the outer shell of the cathode 42.

[0089] The cathode 42 is made of graphite material, has a millimeter-level pore size, and collects treated wastewater.

[0090] The current density of the anode assembly is 5-20 mA / cm 2 :

[0091] Segment settings according to different water quality conditions:

[0092] Low concentration pollutants (COD < 2000 mg / L): 5-8 mA / cm 2 : Avoid energy waste, reduce electrode loss, and be suitable for degradation of conventional pollutants.

[0093] Medium concentration (COD 2000~3500mg / L): 8~15mA / cm 2 : 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 : Ensure sufficient oxidative degradation capacity, suitable for the treatment of difficult-to-degrade organic matter, and it is recommended to cooperate with temperature control (controlled at 35-40℃).

[0095] Specific selection basis: Conductivity: Every increase of 5mS / cm can reduce 2~3mA / cm 2 ; Fluoride ion concentration: For every 500mg / L increase, it is recommended to increase 2-3mA / cm 2 ; Water temperature: Every 5℃ increase can reduce 1~2mA / cm 2 .

[0096] The cathode 42 interacts with the anode assembly to fully electrocatalytically treat the wastewater. The present invention organically combines sulfide zero-valent iron with electrocatalytic technology, and by optimizing the electrode structure and process parameters, it can achieve efficient removal of COD under low energy consumption conditions, and the treatment efficiency is improved by more than 30%. The present invention significantly improves the removal efficiency of fluoride ions through sulfidation modification and electrocatalytic enhancement, and the removal rate can reach more than 85%, which is much higher than the traditional process level.

[0097] The anode assembly includes two layers of anode plate brackets 44, an inner layer anode plate 45 is mounted on the inner layer anode plate bracket 44, and an outer layer anode plate 46 is mounted on the outer layer anode plate bracket 44. The inner layer anode plate 45 is a titanium-based conductive material; the outer layer anode plate 46 is RuO2-IrO2 / Ti, a titanium-based conductive material. The outer layer anode plate 46 and the inner layer anode plate 45 are in an arc shape, and their angles can be adjusted.

[0098] The upper section of the electrocatalytic cylinder 41 is connected to two integrated water quality detection probes 47. The integrated water quality detection probes 47 detect the pH, DO, temperature, etc. of the treated wastewater. The upper section of the electrocatalytic cylinder 41 is connected to two temporary drain ports 48. The temporary drain ports 48 can discharge liquid when the flow rate is too large.

[0099] Furthermore, a heating pipeline 49 is wound around the outer wall of the electrocatalytic cylinder 41, the wastewater feed port 13 is connected to the wastewater pipeline 15, one end of the heating pipeline 49 is connected to the wastewater pipeline 15, and the other end of the heating pipeline 49 is connected to the first liquid-dividing valve 17, and the first liquid-dividing valve 17 is connected to the new wastewater pipeline 18; the treated wastewater collection unit 54 is connected to the second liquid-dividing valve 543, and the second liquid-dividing valve 543 is connected to the treated wastewater direct discharge pipeline 544, and a reflux pipeline 19 is connected between the first liquid-dividing valve 17 and the second liquid-dividing valve 543.

[0100] The electrocatalytic unit releases heat, which is used to heat the heating pipeline 49, so that the wastewater sent to the water inlet regulating unit 1 is heated, thereby improving the wastewater treatment effect. The second liquid separation valve 543 controls the reflux ratio according to parameters such as the COD and BOD compliance rate of the treated wastewater. If the wastewater meets the standards at one time, it is directly discharged through the treated wastewater direct discharge pipeline 544. The first liquid separation valve 17 controls the ratio of wastewater newly entering the system and the reflux liquid.

[0101] Furthermore, Fig.11 As shown, a spiral collecting groove 52 is provided on the inner wall of the collecting cylinder 51 , and a magnetic component is built in the spiral collecting groove 52 , and the magnetic field strength of the magnetic component is 0.1 to 0.5 T; a centrifugal stirring unit 55 is installed in the collecting cylinder 51 , and a probe unit 57 is installed in the exhaust gas collecting cover 56 .

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

[0103] The centrifugal stirring unit 55 generates centrifugal force on the treated wastewater, and the nano S-ZVI material is thrown into the spiral collecting tank 52 under the action of the centrifugal force. The 360° probe 572 is used to identify whether there is nano S-ZVI material in the spiral collecting tank 52. The water source of the high-pressure water nozzle 573 comes from the treated wastewater.

[0104] Specifically, the treated wastewater collection unit 54 includes a treated wastewater collection annular pipe 541, which is sleeved outside the collection cylinder 51, and is connected to a plurality of treated wastewater collection pipes 542, which extend from the upper part of the collection cylinder 51. After centrifugal separation, the sewage in the upper part contains less nano-S-ZVI materials. The wastewater enters the treated wastewater collection annular pipe 541 through the plurality of treated wastewater collection pipes 54242 to achieve wastewater collection.

[0105] Specifically, the centrifugal stirring unit 55 includes a support rod 551, which is connected to the collecting cylinder 51, and a lifting mechanism is installed on the support rod 551. The output end of the lifting mechanism is connected to a transmission rod 552, and the transmission rod 552 is connected to a wastewater agitator 553; a drain outlet 43 is provided at the bottom of the collecting 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, so that the wastewater generates centrifugal force, and the nano S-ZVI material is centrifuged into the spiral collection tank 52. The lifting mechanism can drive the transmission rod 552, the wastewater agitator 553 and the drain plug 554 to rise and fall as a whole, so that the drain plug 554 blocks the drain 43. When the 360° probe 572 is working, the wastewater agitator 553 stops stirring, and the drain plug 554 moves down to the drain 43 to block it.

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

[0108] Furthermore, the top of the waste gas collecting hood 56 is connected to a waste gas collecting pipeline 561, the other end of the waste gas collecting pipeline 561 is connected to a chlorine gas treatment and recycling device 58, and the chlorine gas treatment and recycling device 58 is connected to other waste gas treatment devices 59 through pipelines.

[0109] The chlorine treatment and recycling device 58 uses a water ring vacuum pump to create a negative pressure environment and uses circulating cooling water (5-10°C) as the absorption medium. Since the solubility of chlorine is much higher than that of other gases, chlorine can be selectively enriched at this stage. The enriched chlorine-containing solution is connected to the sodium hypochlorite generator after precision filtration to convert the recovered chlorine into a sodium hypochlorite product with high market value. The effective chlorine content of the product can reach 10-12%, and the conversion rate can reach more than 85%.

[0110] Other waste gas treatment device 59 is used to treat other waste gases such as VOCs. Other waste gas treatment device 59 adopts a new porous titanium-based catalytic composite material, which is prepared by sol-gel method and has a specific surface area of ​​800-1000m 2 / g, pore size distribution 3 ~ 5nm. The material surface is loaded with bimetallic (Cu ~ Mn) oxide catalyst, which has high catalytic oxidation performance for VOCs. At normal temperature and pressure, the VOCs removal rate can reach more than 95%. The innovation lies in that the catalyst surface is also loaded with proton exchange resin, which can adsorb the acidic gas generated during the conversion process and extend the service life of the catalyst to 8 to 10 months. The residence time of the exhaust gas in this unit is controlled at 2 to 3 seconds, and the gas flow rate is 0.5 to 1.0 m / s.

[0111] Example 1 (low concentration pollutant treatment):

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

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

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

[0115] Example 2 (Medium Concentration Pollutant Treatment):

[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±4.7mg / L; current density: 11.8±0.6mA / cm 2 ; Rectification unit 3: 4 layers; HRT: 4.6±0.2 hours; Temperature: 24~28℃.

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

[0119] Example 3 (treatment of high concentration refractory 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±7.8mg / L; current density: 17.6±0.9mA / cm 2 ; Rectification unit 3: 6 layers; HRT: 3.2±0.3 hours; Temperature: 37~39℃.

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

[0123] The present invention is not limited to the above-mentioned optional implementation modes. Anyone can derive other various forms of products under the inspiration of the present invention. However, no matter what changes are made in the shape or structure, all technical solutions that fall within the scope defined by the claims of the present invention fall within the protection scope of the present invention.

Claims

1. A device for removing refractory organic matter from wastewater and recycling materials, characterized in that: The invention comprises a water inlet regulating unit (1), a liquid inlet pressurizing and spreading unit (2), a rectifying unit (3), an electrocatalytic core processing unit (4), and a material recovery device (5) which are arranged in sequence from bottom to top; the water inlet regulating unit (1) is provided with an S-ZVI feed port (12), a wastewater feed port (13), and an oxidant feed port (14); the material recovery device (5) comprises a collecting cylinder (51), a material negative pressure recovery unit (53) is arranged at the bottom of the collecting cylinder (51), a treated wastewater collection unit (54) is connected to the upper part of the collecting cylinder (51), and a waste gas collection cover (56) is connected to the top of the collecting cylinder (51).

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

3. The device for removing refractory organic matter from wastewater and recovering materials according to claim 1, characterized in that: The liquid inlet pressurizing and spreading unit (2) comprises a pressurizing and spreading cylinder (21), the pressurizing and spreading cylinder (21) is connected between the water inlet regulating unit (1) and the rectifying unit (3), a nozzle fixing plate (22) is installed in the pressurizing and spreading cylinder (21), a pressurizing impeller (23) is rotatably connected to the lower side of the nozzle fixing plate (22), and a plurality of oblique nozzles (24) are arranged on the upper side of the nozzle fixing plate (22).

4. The device for removing refractory organic matter from wastewater and recycling materials according to claim 1, characterized in that: The rectifying unit (3) comprises a rectifying cylinder (31), the rectifying cylinder (31) being connected between the liquid inlet pressurizing and spreading unit (2) and the electrocatalytic core processing unit (4), a water pipeline (32) being arranged in the middle of the whole cylinder, and a rectifying spiral (33) being arranged on the outer wall of the water pipeline (32).

5. The device for removing refractory organic matter from wastewater and recycling materials according to claim 1, characterized in that: The electrocatalytic core processing unit (4) comprises an electrocatalytic cylinder (41), a cathode (42) is installed in the middle of the electrocatalytic cylinder (41), and an anode assembly is arranged outside the cathode (42); the anode assembly comprises two layers of anode plate brackets (44), an inner layer anode plate (45) is installed on the inner layer anode plate bracket (44), and an outer layer anode plate (46) is installed on the outer layer anode plate bracket (44).

6. The device for removing refractory organic matter from wastewater and recovering materials according to claim 5, characterized in that: A heating pipeline (49) is wound around the outer wall of the electrocatalytic cylinder (41); the wastewater feed port (13) is connected to the wastewater pipeline (15); one end of the heating pipeline (49) is connected to the wastewater pipeline (15); the other end of the heating pipeline (49) is connected to a first liquid separation valve (17); the first liquid separation valve (17) is connected to a new wastewater pipeline (18); the treated wastewater collection unit (54) is connected to a second liquid separation valve (543); the second liquid separation valve (543) is connected to a treated wastewater direct discharge pipeline (544); a reflux pipeline (19) is connected between the first liquid separation valve (17) and the second liquid separation valve (543).

7. The device for removing refractory organic matter from wastewater and recycling materials according to claim 1, characterized in that: A spiral collecting groove (52) is provided on the inner wall of the collecting cylinder (51), a centrifugal stirring unit (55) is installed in the collecting cylinder (51), and a probe unit (57) is installed in the exhaust gas collecting cover (56); the probe unit (57) comprises a probe lifting rod (571), the probe lifting rod (571) is installed in the exhaust gas collecting cover (56), the lower end of the probe lifting rod (571) is connected to a 360° probe (572), and a high-pressure water spray head (573) is provided on the 360° probe (572).

8. The device for removing refractory organic matter from wastewater and recycling materials according to claim 7, characterized in that: The centrifugal stirring unit (55) comprises a support rod (551), the support rod (551) is connected to the inside of the collection cylinder (51), a lifting mechanism is installed on the support rod (551), the output end of the lifting mechanism is connected to a transmission rod (552), and the transmission rod (552) is connected to a wastewater stirrer (553); a drain outlet (43) is provided between the collection cylinder (51) and the electrocatalytic core treatment unit (4), and a drain outlet plug (554) is connected to the bottom of the wastewater stirrer (553).

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

10. A device for removing refractory organic matter from wastewater and recycling materials according to any one of claims 1 to 9, characterized in that: The top of the waste gas collection hood (56) is connected to a waste gas collection pipeline (561), the other end of the waste gas collection pipeline (561) is connected to a chlorine gas treatment and recycling device (58), and the chlorine gas treatment and recycling device (58) is connected to other waste gas treatment devices (59) through pipelines.

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